IUPAC-NIST Solubility Data Series. 79. Alkali and Alkaline

IUPAC-NIST Solubility Data Series. 79. Alkali and Alkaline Earth MetalPseudohalides

Jiri Ha laa…

Department of Inorganic Chemistry, Masaryk University, Brno, Czech Republic

Contributors „*Evaluator …Jiri Ha la*

Masaryk University, Czech Republic

H. AkaiwaGunma University, Japan

~Received 23 August 2002; accepted 4 November 2002; published online 13 February 2004!

This volume presents solubility data of azides, cyanides, cyanates, and thiocyanates ofalkali metals, alkaline earth metals, and ammonium. Covered are binary and ternarysystems in all solvents. No solubility data have been found for some of the compounds ofalkali metals, alkaline metals, and ammonium. These include beryllium and magnesiumazides, lithium, rubidium cesium, ammonium, and alkaline earth cyanates and cyanides,and beryllium thiocyanate. Likewise, no solubility data seem to exist for selenocyanatesof the mentioned metals and ammonium. The literature has been covered up to the middleof 2001, and there was a great effort to have the literature survey as complete as possible.The few documents which remained unavailable to the editor, and could not be includedin the volume, are listed in the Appendix. For some compounds it was not possible toshow theChemical Abstractsregistry numbers since these have not been assigned. Forthis reason, the registry number index is incomplete. ©2004 American Institute ofPhysics. @DOI: 10.1063/1.1563591#

Key words: alkali metals; alkaline earth metals; ammonia; azides; cyanides; cyanates; organic solvents;thiocyanates; solid-liquie equilibrium; solubility; water.

5

Contents

1. Preface. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32. Introduction to the Solubility Data Series:

Solubility of Solids in Liquids. . . . . . . . . . . . . . . . . 32.1. The Nature of the Project. .. . . . . . . . . . . . . . . 32.2. Compilations and Evaluations. . . . . . . . . . . . . 3

2.2.1. Compilations. . . . . . . . . . . . . . . . . . . . . . 32.2.2. Evaluations. . . . . . . . . . . . . . . . . . . . . . . 3

2.3. Quantities and Units Used in Compilationand Evaluation of Solubility Data. . . .. . . . . . 52.3.1. Mixtures, Solutions, and Solubilities...2.3.2. Physicochemical Quantities and

Units. . . . . . . . . . . . . . . . . . . . . . . . . . . . 52.4. References for the Introduction.. . . . . . . . . . . 7

3. The Solubility of Azides. . . . . . . . . . . . . . . . . . . . . 83.1. Lithium Azide. . . . . . . . . . . . . . . . . . . . . . . . . . 83.2. Sodium Azide. .. . . . . . . . . . . . . . . . . . . . . . . . 93.3. Potassium Azide. . . . . . . . . . . . . . . . . . . . . . . . 15

a!Electronic mail: [email protected]© 2004 American Institute of Physics.

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3.3.1. Evaluation of the KN3– H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 15

3.4. Rubidium Azide. . . . . . . . . . . . . . . . . . . . . . . . 173.5. Cesium Azide. . . . . . . . . . . . . . . . . . . . . . . . . . 183.6. Ammonium Azide. . . . . . . . . . . . . . . . . . . . . . . 183.7. Calcium Azide. .. . . . . . . . . . . . . . . . . . . . . . . . 203.8. Strontium Azide. . . . . . . . . . . . . . . . . . . . . . . . 21

3.8.1. Evaluation of the Sr~N3)2– H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 21

3.9. Barium Azide. . . . . . . . . . . . . . . . . . . . . . . . . . 243.9.1. Evaluation of the Ba~N3)2– H2O

System. . . . . . . . . . . . . . . . . . . . . . . . . . . 244. The Solubility of Cyanides. . . . . . . . . . . . . . . . . . . 25

4.1. Lithium Cyanide. . . . . . . . . . . . . . . . . . . . . . . . 254.2. Sodium Cyanide. . . . . . . . . . . . . . . . . . . . . . . . 26

4.2.1. Evaluation of the NaCN–H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 26

4.2.2. Evaluation of the NaCN–NaOH–H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 29

4.3. Potassium Cyanide. . . . . . . . . . . . . . . . . . . . . . 334.3.1. Evaluation of the KCN–NH3

System. . . . . . . . . . . . . . . . . . . . . . . . . . . 364.3.2. Evaluation of the KCN–Ethanol

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22 IUPAC-NIST SOLUBILITY DATA SERIES

System. . . . . . . . . . . . . . . . . . . . . . . . . . . 375. The Solubility of Cyanates. . . . . . . . . . . . . . . . . . . 46

5.1. Sodium Cyanate. . . . . . . . . . . . . . . . . . . . . . . . 465.1.1. Evaluation of the NaOCN–NH3

System. . . . . . . . . . . . . . . . . . . . . . . . . . . 465.2. Potassium Cyanate. . . . . . . . . . . . . . . . . . . . . . 50

6. The Solubility of Thiocyanates. .. . . . . . . . . . . . . . 526.1. Lithium Thiocyanate. . . . . . . . . . . . . . . . . . . . . 52

6.1.1. Evaluation of the LiSCN–H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 52

6.2. Sodium Thiocyanate. . . . . . . . . . . . . . . . . . . . . 596.2.1. Evaluation of the NaSCN–H2O

System. . . . . . . . . . . . . . . . . . . . . . . . . . . 596.2.2. Evaluation of the NaSCN–Ethanol

System. . . . . . . . . . . . . . . . . . . . . . . . . . . 656.2.3. Evaluation of the NaSCN–Acetone

System. . . . . . . . . . . . . . . . . . . . . . . . . . . 676.3. Potassium Thiocyanate. . . . . . . . . . . . . . . . . . . 82

6.3.1. Evaluation of the KSCN–H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 82

6.3.2. Evaluation of the KSCN–EthanolSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 90

6.3.3. Evaluation of the KSCN–AcetoneSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 91

6.3.4. Evaluation of the KSCN–2-ButanoneSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 93

6.3.5. Evaluation of the KSCN–1-ButanolSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 94

6.3.6. Evaluation of the KSCN–PyridineSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 95

6.4. Rubidium Thiocyanate. . . . . . . . . . . . . . . . . . . 1196.5. Cesium Thiocyanate. . . . . . . . . . . . . . . . . . . . . 1216.6. Ammonium Thiocyanate. . . . . . . . . . . . . . . . . . 122

6.6.1. Evaluation of the NH4SCN–H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . . . . 122

6.7. Magnesium Thiocyanate. . . . . . . . . . . . . . . . . . 1466.8. Calcium Thiocyanate. . . . . . . . . . . . . . . . . . . . . 1486.9. Strontium Thiocyanate. . . . . . . . . . . . . . . . . . . 1546.10. Barium Thiocyanate. . . . . . . . . . . . . . . . . . . . 155

6.10.1. Evaluation of the Ba~SCN)2– H2OSystem. . . . . . . . . . . . . . . . . . . . . . . . . . 155

7. Appendix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168. System Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1649. Registry Number Index. . . . . . . . . . . . . . . . . . . . . . 16810. Author Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170

List of Tables1. Interconversions between quanties used as

measures of solubilities. . . . . . . . . . . . . . . . . . . . . . 7

List of Figures1. Lithium azide–water system. . . . . . . . . . . . . . . . . . 82. Sodium azide–water system. . . . . . . . . . . . . . . . . . 103. Potassium azide–water system. . . . . . . . . . . . . . . . 164. Ammonium azide–ammonia system. . . . . . . . . . . . 195. Sodium cyanide–sodium hydroxide–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3


6. Sodium cyanate–ammonia system. .. . . . . . . . . . . 467. Sodium cyanate–diethylether–methanol

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498. Lithium thiocyanate–water system. . . . . . . . . . . . . 529. Sodium thiocyanate–water system.. . . . . . . . . . . . 6010. Sodium thiocyanate–ammonia system. . . . . . . . . . 6411. Sodium thiocyanate–acetone system. . . . . . . . . . . . 6712. Sodium thiocyanate–methylthiocyanate–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8013. Potassium thiocyanate–water system. . . . . . . . . . . 8214. Potassium thiocyanate–water system. . . . . . . . . . . 8515. Potassium thiocyanate–ammonia system. . . . . . . . 8816. Potassium thiocyanate–potassium carbonate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10717. Potassium thiocyanate–urea–water system. . . . . . . 11118. Potassium thiocyanate–water–acetone system. . . .19. Potassium thiocyanate–polyethylene~1500!–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11520. Potassium thiocyanate–polyethylene~6000!–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11621. Potassium thiocyanate–methylthiocyanate–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1122. Potassium thiocyanate–ethylthiocyanate–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1123. Ammonium thiocyanate–water system. . . . . . . . . . 12224. Ammonium thiocyanate–water system. . . . . . . . . . 12425. Ammonium thiocyanate–ammonia system. . . . . . . 12726. Ammonium thiocyanate–ammonium nitrate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13227. Ammonium thiocyanate–potassium thiocyanate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13428. Ammonium thiocyanate–potassium thiocyanate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13629. Ammonium thiocyanate–ammonium sulfate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13930. Ammonium thiocyanate–triethylamine–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1431. Ammonium thiocyanate–urea–water system.. . . . 14232. Ammonium thiocyanate–methylthiocyanate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14333. Ammonium thiocyanate–aniline–water system. . . 134. Calcium thiocyanate–sodium thiocyanate–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1535. Calcium thiocyanate–potassium thiocyanate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15136. Calcium thiocyanate–ammonium thiocyanate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15237. Calcium thiocyanate–methylthiocyanate–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1538. Barium thiocyanate–sodium thiocyanate–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1539. Barium thiocyanate–potassium thiocyanate–

water system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15740. Barium thiocyanate–methylthiocyanate–water

system. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

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1. Preface

This volume presents solubility data of azides, cyanidcyanates, and thiocyanates of alkali metals, alkaline emetals, and ammonium. Covered are binary and ternarytems in all solvents. No solubility data have been foundsome of the compounds of alkali metals, alkaline metals,ammonium. These include beryllium and magnesium azidlithium, rubidium cesium, ammonium, and alkaline earth canates and cyanides, and beryllium thiocyanate. Likewisesolubility data seem to exist for selenocyanates of the mtioned metals and ammonium. The literature has been cered up to the middle of 2001, and there was a great effohave the literature survey as complete as possible. Thedocuments which remained unavailable to the compiler,could not be included in the volume are listed in the Appedix. For some compounds it was not possible to showChemical Abstractsregistry numbers since these have nbeen assigned. For this reason, the registry number indeincomplete.

In addition to documents that published numerical dasome papers that presented data in graphical form only wincluded as well. They were considered for the volume eitif no other data were available for the system, or if the dwere published in difficult to obtain older literature. Thecriteria led the compiler to include sometimes paperswhich the authors failed to specify conditions such as teperature, equilibrium time, or methods of analysis. Phdiagrams have been included for some of the ternarytems. For binary eutonic systems, phase diagrams werecluded only if no numerical data were reported in the orinal documents and the diagrams were the sole sourcinformation. Of the many systems covered by the volumrelatively few were studied by more than one laboratoThus the opportunity to carry out evaluations has been lited, and only 20 systems have been evaluated. Howebecause of some uncertainty in most of the evaluatedtems, only tentative solubility values could usually be reommended.

Only those published results that report meaningful dwere considered for the volume. Papers that reported qutative results with statements like ‘‘sparingly soluble’’ or ‘‘insoluble,’’ etc., were not considered. However, some doments reported solubility data which, although not includin the volume for one reason or other~e.g., single values ouncertain quality without any supporting informatiosketches of phase diagrams!, may nevertheless be of sominformative value to the potential user of this volume in cathey represent the only information available for a given stem. For this reason, a list of systems for which only sudata exist has been included in the Appendix.

The editor wishes to express his thanks to the followcolleagues from IUPAC for their effort in proving copiespublications, which would otherwise not be available to hiProfessor H. Akaiwa, Gunma, Japan~also for translating theJapanese papers!; D. J. J. Counioux, Lyon, France; Dr. P. GT. Fogg, London, U.K.; Professor Fu Jufu, Beijing, Chin

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2. Introduction to the Solubility Data Series:Solubility of Solids in Liquids

2.1. The Nature of the Project

The Solubility Data project~SDP! has as its aim a comprehensive review of published data for solubilities of gasliquids, and solids in liquids or solids. Data of suitable prcision are compiled for each publication on data sheetsuniform format. The data for each system are evaluated awhere data from independent sources agree sufficiently,ommended values are proposed. The evaluation sheets,ommended values, and compiled data sheets are publion consecutive pages.

2.2. Compilations and Evaluations

The formats for the compilations and critical evaluatiohave been standardized for all volumes. A descriptionthese formats follows.

2.2.1. Compilations

The format used for the compilations is, for the most paself-explanatory. Normally, a compilation sheet is dividinto boxes, with detailed contents described below.

Components

Each component is listed according to IUPAC name, fmula, and Chemical Abstracts~CA! Registry Number. TheChemical Abstracts name is also included if this differs frothe IUPAC name, as are trivial names if appropriate. IUPAand common names are cross-referenced to Chemicalstracts names in the System Index.

The formula is given either in terms of the IUPAC or Hil1

system and the choice of formula is governed by whausual for most current users: i.e., IUPAC for inorganic copounds, and Hill system for organic compounds. Comnents are ordered on a given compilation sheet according

~a! saturating components;~b! non-saturating components;~c! solvents.In each of~a!, ~b! or ~c!, the components are arranged

order according to the IUPAC 18-column periodic table wtwo additional rows:

Columns 1 and 2: H, alkali elements, ammonium, alkalearth elements

Columns 3 to 12: transition elementsColumns 13 to 17: boron, carbon, nitrogen groups; ch

cogenides, halogensColumn 18: noble gasesRow 1: Ce to Lu


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Row 2: Th to the end of the known elements, in orderatomic number.

The same order is followed in arranging the compilatisheets within a given volume.

Original Measurements

References are abbreviated in the forms given by Checal Abstracts Service Source Index~CASSI!. Names origi-nally in other than Roman alphabets are given as translated by Chemical Abstracts. In the case of multiple entr~for example, translations! an asterisk indicates the publication used for compilation of the data.

Variables

Ranges of temperature, pressure, etc., are indicated h

Prepared by

The names of all compilers are given here.

Experimental Data

Components are described as~1!, ~2!, etc., as defined inthe ‘‘Components’’ box. Data are reported in the units usin the original publication, with the exception that modenames for units and quantities are used; e.g., mass pefor weight percent; mol dm23 for molar; etc. Usually, onlyone type of value~e.g., mass percent! is found in the originalpaper, and the compiler has added the other type of v~e.g., mole percent! from computer calculations based o1989 atomic weights.2 Temperatures are expressed ast/°C,t/°F or T/K as in the original; if necessary, conversionsT/K are made, sometimes in the compilations and alwaythe critical evaluation. However, the author’s units arepressed according to IUPAC recommendations3 as far as pos-sible.

Errors in calculations, fitting equations, etc., are noted,where possible corrected. Material inserted by the compis identified by the word ‘‘compiler’’ or by the compiler’sname in parentheses or in a footnote. In addition, compicalculated values of mole or mass fractions are includethe original data do not use these units. If densities areported in the original paper, conversions from concentratito mole fractions are included, but otherwise this is donethe evaluation, with the values and sources of the densbeing quoted and referenced.

Details of smoothing equations~with limits! are includedif they are present in the original publication and if the teperature or pressure ranges are wide enough to justifyprocedure and if the compiler finds that the equationsconsistent with the data.

The precision of the original data is preserved whenrived quantities are calculated, if necessary by the inclusof one additional significant figure. In some cases, compinote that numerical data have been obtained from publisgraphs using digitizing techniques. In these cases, the psion of the data can be determined by the quality of


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original graph and the limitations of the digitizing techniquIn some cases graphs have been included, either to illusdata more clearly, or if this is the only information in thoriginal. Full grids are not usually inserted as it is not itended that users should read data from the graphs.

Method

The apparatus and procedure are mentioned briefly. Abviations used in Chemical Abstracts are often used heresave space, reference being made to sources of further dif these are cited in the original paper.

Source and Purity of Materials

For each component, referred to as~1!, ~2!, etc., the fol-lowing information~in this order and in abbreviated form! isprovided if available in the original paper: source and spefied method of preparation; properties; degree of purity.

Estimated Error

If estimated errors were omitted by the original authoand if relevant information is available, the compilers haattempted to estimate errors~identified by ‘‘compiler’’ or thecompiler’s name in parentheses or in a footnote! from theinternal consistency of data and type of apparatus usMethods used by the compilers for estimating and reporterrors are based on Ku and Eisenhart.4

Comments and Õor Additional Data

Many compilations include this section which providshort comments relevant to the general nature of the woradditional experimental and thermodynamic data whichjudged by the compiler to be of value to the reader.

References

The format for these follows the format for the OriginMeasurements box, except that final page numbers are oted. References~usually cited in the original paper! are givenwhere relevant to interpretation of the compile data, or whcross-reference can be made to other compilations.

2.2.2. Evaluations

The evaluator’s task is to assess the reliability and quaof the data, to estimate errors where necessary, and toommend ‘‘best’’ values. The evaluation takes the form osummary in which all the data supplied by the compiler habeen critically reviewed. There are only three boxes ontypical evaluation sheet, and these are described below.

Components

The format is the same as on the Compilation sheets.

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Evaluator

The name and affiliation of the evaluator~s! and date up towhich the literature was checked.

Critical Evaluation

~a! Critical text. The evaluator checks that the compildata are correct, assesses their reliability and quality, emates errors where necessary, and recommends numevalues based on all the published data~including theses, patents and reports! for each given system. Thus, the evaluareviews the merits or shortcomings of the various data. Opublished data are considered. Documented rejectionsome published data may occur at this stage, and the csponding compilations may be removed.

The solubility of comparatively few systems is knowwith sufficient accuracy to enable a set of recommendedues to be presented. Although many systems have beenied by at least two workers, the range of temperatureoften sufficiently different to make meaningful comparisimpossible.

Occasionally, it is not clear why two groups of workeobtained very different but internally consistent sets ofsults at the same temperature, although both sets of rewere obtained by reliable methods. In such cases, a definassessment may not be possible. In some cases, two orsets of data have been classified as tentative even thougsets are mutually inconsistent.

~b! Fitting equations. If the use of a smoothing equationjustifiable the evaluator may provide an equation represing the solubility as a function of the variables reportedall the compilation sheets, stating the limits within whichshould be used.

~c! Graphical summary. In addition to~b! above, graphicalsummaries are often given.

~d! Recommended values. Data are recommended if thesults of at least two independent groups are availablethey are in good agreement, and if the evaluator has no das to the adequacy and reliability of the applied experimeand computational procedures. Data are reported as tentif only one set of measurements is available, or if the evaator considers some aspect of the computational or expmental method as mildly undesirable but estimates thashould cause only minor error. Data are considered as doful if the evaluator considers some aspect of the comptional or experimental method as undesirable but still coners the data to have some value where the order of magnof the solubility is needed. Data determined by an inadequmethod or under ill-defined conditions are rejected. Hoever, references to these data are included in the evaluatogether with a comment by the evaluator as to the reasontheir rejection.

~e! References. All pertinent references are given here,cluding all those publications appearing in the accompanycompilation sheets and those which, by virtue of their poprecision, have been rejected and not compiled.

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~f! Units. While the original data may be reported in thunits used by the investigators, the final recommended vaare reported in SI units3 when the data can be accurateconverted.

2.3. Quantities and Units Used in Compilation andEvaluation of Solubility Data

2.3.1. Mixtures, Solutions and Solubilities

A mixture5 describes a gaseous, liquid or solid phase ctaining more than one substance, where the substances atreated in the same way.

A solution5 describes a liquid or solid phase containinmore than one substance, when for convenience one osubstances, which is called thesolvent, and may itself be amixture, is treated differently than the other substancwhich are calledsolutes. If the sum of the mole fractions othe solutes is small compared to unity, the solution is cala dilute solution.

The solubility of a solute 1~solid, liquid or gas! is theanalytical composition of a saturated solution, expressedterms of the proportion of the designated solute in a denated solvent.6

‘‘Saturated’’ implies equilibrium with respect to the processes of dissolution and precipitation; the equilibrium mbe stable or metastable. The solubility of a substancemetastable equilibrium is usually greater than that ofsame substance in stable equilibrium.~Strictly speaking, it isthe activity of the substance in metastable equilibrium thagreater.! Care must be taken to distinguish true metastabifrom supersaturation, where equilibrium does not exist.

Either point of view, mixture or solution, may be takendescribing solubility. The two points of view find their expression in the reference states used for definition of acties, activity coefficients and osmotic coefficients.

Note that the composition of a saturated mixture~or solu-tion! can be described in terms of any suitable set of thermdynamic components. Thus, the solubility of a salt hydratewater is usually given as the relative proportions of anhdrous salt in solution, rather then the relative proportionshydrated salt and water.

2.3.2. Physicochemical Quantities and Units

Solubilities of solids have been the subject of researcha long time, and have been expressed in a great many was described below. In each case, specification of the tperature and either partial or total pressure of the saturagaseous component is necessary. The nomenclature andfollow, where possible, IUPAC Green Book.3 A few quanti-ties follow the ISO standards7 or the German standard;8 see areview by Cvitasˇ9 for details.

A Note on Nomenclature

The nomenclature of the IUPACGreen Book3 calls thesolute component B and the solvent component A. In copilations and evaluations, the first-named component~com-


ldm

-

asi

ysco

an

se

re.

he

isolu-

d toor a

e toerly.rriedhise.


ponent 1! is the solute, and the second~component 2 for atwo-component system! is the solvent. The reader shoubear these distinctions in nomenclature in mind when coparing equations given here with those in theGreen Book.

1. Mole fraction of substance 1,x1 or x~1! ~condensedphases!, y1 ~gases!:

x15n1Y (s51

c

ns ~1!

wherens is the amount of substance ofs, andc is the numberof distinct substances present~often the number of thermodynamic components in the system!. Mole percentof sub-stance 1 is 100x1.

2. Ionic mole fractionsof salt i, xi 1, xi 2: For mixture ofs binary saltsi, each of which ionizes completely intoni 1

cations andv i 2 anions, withv i5v i 11v i 2 and a mixture ofp nonelectrolytesk, of which some may be consideredsolvent components, a generalization of the definitionRobinson and Stokes10 gives:

x1 i5v1 ix1 i

11(j 51

s

~v j21!xj

, x2 i5v2 ix1 i

v1 ii 51...s ~2!

xok5xj

11(j 51

s

~v j21!xj

, k5~s11!...c. ~3!

The sum of these mole fractions is unity, so that, withc5s1p,

(i 51

s

~x1 i1x2 i !1 (i 5s11

c

xoi51. ~4!

General conversions to other units in multicomponent stems are complicated. For a three-component systemtaining nonelectrolyte 1, electrolyte 2, and solvent 3,

x15v12xo1

v122~v221!x12x25

x12

v122~v221!x12. ~5!

These relations are used in solubility equations for salts,for tabulation of salt effects on solubilities of gases.

3. Mass fractionof substance 1,w1 or w~1!:

w15g1Y (s51

c

gs ~6!

wheregs is the mass of substances. Mass percentof sub-stance 1 is 100w1. The equivalent termsweight fraction,weight percentandg(1)/100g solutionare no longer used.

4. Solute mole fractionof substance 1,xv,1:

xs,15m1Y (s51

c8

ms5x1Y (s51

c8

xs ~7!

where c8 is the number of solutes in the mixture. Thequantities are sometimes called Ja¨necke mole ~mass!fractions.11,12 Solute mass fractionof substance 1,ws,1, isdefined analogously.


-

n

-n-

d

5. Solvent mole fractionof substance 1,xv,1:

xv,15x1Y (s51

p

xs. ~8!

Here,p is the number of solvent components in the mixtuSolvent mass fractionof substance 1,wv,1, is defined analo-gously.

6. Molality of solute 1 in a solvent 2,m1:

m15n1/n2M2 ~9!

SI base units: mol kg21. Here,M2 is the molar mass of thesolvent.

7. Aquamolality, Solvomolalityof substance 1 in a mixedsolvent with components 2, 3,13 m1

(3):

m1~3!5m1M /M3 ~10!

SI base units: mol kg21. Here, the average molar mass of tsolvent is

M5xv,2M21~12vv,2!M3 ~11!

and xv, is the solvent mole fraction of component 2. Thterm is used most frequently in discussing comparative sbilities in water~component 2! and heavy water~component3! and in their mixtures.

8. Amount concentrationof solute 1 in a solution of vol-umeV, c1:

c15@ formula of solute#5n1/V ~12!

SI base units: mol cm23. The symbolc1 is preferred to@for-mula of solute#, but both are used. The old termsmolarity,molar andmoles per unit volumeare no longer used.

9. Mass concentrationof solute 1 in a solution of volumeV, r1:

r15g1/V5c1M1/V ~13!

SI base units: kg m23.

10. Mole ratio, r A,B ~dimensionless!:9

r n,125n1/n2 . ~14!

Mass ratio, symbolzA,B, may be defined analogously.9

11. Ionic strength, I m ~molality basis!, or I c ~concentrationbasis!:

I m51

2(imizi

2, I c51

2(icizi

2 ~15!

wherezi is the charge number of ioni. While these quantitiesare not used generally to express solubilities, they are useexpress the compositions of nonsaturating components. Fsingle salti with ions of charge numbersz1 andz2,

I m5uz1z2uvmi , I c5uz1z2uvci . ~16!

Mole and mass fractions and mole ratios are appropriateither the mixture of the solution point of view. The othquantities are appropriate to the solution point of view onConversions between pairs of these quantities can be caout using the equation given in Table 1 at the end of tIntroduction. Other useful quantities will be defined in thprefaces to individual volumes or on specific data sheets

77JIRI HALA

TABLE 1. Interconversions between quantities used as measures of solubilitiesc-component systems containingc-1 solutesi and single solventc ~r—densityof solution;Mi—molar masses ofi. For relations for two-component systems, set summations to 0.!

xi wi mi ci

xi5 xi

1

11Mi

McH 1

wi211 (

jÞ1

c21 SMc

Mj21D wj

wiJ

1

111

miMc1(

jÞi

c21mj

mi

1

111

McSr

ci2MiD 1(

jÞi

c21cj

ciS12

Mj

McD

wi5

1

11Mc

MiH1

xi211(

jÞi

c21 SMj

Mc21D xj

xiJ wi

1

111

miMiS11(

jÞi

c21

mjMjDciMi

r

mi5

1

Mc S1

xi212(

jÞi

c21xj

xiD

1

MiS 1

wi212(

jÞi

c21wj

wiD mi

1

1

ciSr2(

jÞi

c21

cjMjD 2Mi

ci5

r

Mi1McH1

xi211(

jÞi

c21 SMj

Mc21D xj

xiJ

rwi

Mi

r

1

miS11(

jÞi

c21

mjMjD1Mj

ci

tiss

CAtrl

ngth

.

roto

anctfs.natoar

pro-the

ure

try

-

d.

a

Salt hydrates are generally not considered to be saturacomponents since most solubilities are expressed in termthe anhydrous salt. The existence of hydrates or solvatenoted carefully in the critical evaluation.

Mineralogical names are also quoted, along with theirRegistry Numbers, again usually in the text and CA RegisNumbers~where available! are given usually in the criticaevaluation.

In addition to the quantities defined above, the followiare useful in conversions between concentrations and oquantities.

12. Density, r:

r5g/V5(s51

c

rs ~17!

SI base units: kg m23. Hereg is the total mass of the system

13. Relative density, d5r/r°: the ratio of the density of amixture at temperaturet, pressurep to the density of a ref-erence substance at temperaturet8, pressurep8. For liquidsolutions, the reference substance is often water at 4 °~C!, 1bar. ~In some cases 1 atm is used instead of 1 bar.! The termspecific gravityis no longer used.

Thermodynamics of Solubility

Thermodynamic analysis of solubility phenomena pvides a rational basis for the construction of functionsrepresent solubility data, and thus aids in evaluation,sometimes enables thermodynamic quantities to be extraBoth these aims are often difficult to achieve because olack of experimental or theoretical activity coefficientWhere thermodynamic quantities can be found, they areevaluated critically, since this task would involve examintion of a large body of data that is not directly relevantsolubility. Where possible, procedures for evaluation

ngofis

y

er

-

ded.a

ot-

e

based on established thermodynamic methods. Specificcedures used in a particular volume will be described inPreface to this volume.

2.4 References for the Introduction

1E. A. Hill, J. Am. Chem. Soc.22, 478 ~1900!.2IUPAC Commission on Atomic Weights and Isotopic Abundances, PAppl. Chem.63, 975 ~1989!.

3I. Mills et al., eds.Quantities, Units and Symbols in Physical Chemis~the Green Book!~Blackwell Scientific Publications, Oxford, U.K., 1993!.

4H. H. Ku, p. 73; C. Eisenhart, p. 69; in H. H. Ku, ed.,Precision Measure-ment and Calibration, NBS Special Publication 300~NBS, Washington,1969!, Vol. 1.

5V. Gold et al., eds.,Compendium of Analytical Nomenclature~the GoldBook! ~Blackwell Scientific Publications, Oxford, U.K., 1987!.

6H. Freiser and G. H. Nancollas, eds.,Compendium of Analytical Nomenclature ~the Orange Book! ~Blackwell Scientific Publications, Oxford,U.K., 1987!, Sect. 9.1.8.

7ISO Standards Handbook,Quantities and Units~International StandardsOrganization, Geneva, 1993!.

8German Standard, DIN 1310,Zusammensetzung von Mischphasen~BeuthVerlag, Berlin, 1984!.

9T. Cvitas, Chem. International17, 123 ~1995!.10R. A. Robinson and R. H. Stokes,Electrolyte Solutions, 2nd ed.~Butter-

worths, London, 1959!.11E. Janecke, Z. Anorg. Chem.51, 132 ~1906!.12H. L. Friedman, J. Chem. Phys.32, 1351~1960!.13J. W. Lorimer, inAlkali Metal and Ammonium Chlorides in Water an

Heavy Water (Binary Systems), edited by R. Cohen-Adad, and J. WLorimer, IUPAC Solubility Data Series, Vol. 47~Pergamon, Oxford, U.K.,1991!, p. 495.

This section was written by:R. Cohen-Adad J. W. Lorimer

Villeurbanne, France London, Ontario, CanadM. Salomon M.-T. Saugier-Cohen Adad

Sea Bright, N.J., USA Villeurbanne, FranceDecember, 1995


Tem

pera

ture

:no

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 T.C

urtiu

s,B

er.2

4,33

41~1

891!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Lith

ium

azid

e;Li

N 3;

@195

97-6

9-4#

Wat

er;

H 2O

;@7

732-

18-5#

A.

P.R

olle

tan

dJ.

Woh

lgem

uth,

Com

pt.

Ren

d.199,

1772

–4

~193

4!.

riabl

es:

Pre

pare

dB

y:

mpe

ratu

rean

dco

mpo

sitio

n.J.

Ha

´ la

Exp

erim

enta

lDat

aP

hase

diag

ram

ofth

eLi

N 3–H

2O

syst

ema

gnifi

cant

poin

tTe

mpe

ratu

re(t

/°C

)Li

N3

(100

w1

/mas

s%

)Li

N3

(m1

/mol

kg2

1)b

Sol

idph

asec

E2

47.5

60.

526

.060.

47.

176

A1B

T1

231

.06

0.5

33.56

0.3

10.2

9B1

C

T2

68.2

60.

148

.060.

318

.85

C1D

esul

tsw

ere

pres

ente

din

grap

hica

lfor

m~Fig

.1!

.N

umer

ical

valu

esw

ere

repo

rted

for

thre

esi

gnifi

cant

poin

tsin

the

phas

edi

agra

m.

alcu

late

dby

com

pile

r.:

Ice;

H2O

;@7

732-

18-5#

;B

:Li

N3•4

H2O

;@

#;C

:Li

N3•H

2O

;@3

4204

-05-

2#;D

:Li

N3

;@1

9597

-69-

4#.

FIG

.1.

Pha

sedi

agra

mof

the

LiN 3–

H2O

syst

em@~

full

circ

les!

poly

ther

mal

mea

sure

men

ts,

~ope

nci

rcle

s!is

othe

rmal

mea

sure

men

ts,

~tria

ngle

s!da

tafr

omC

urtiu

san

dR

isso

m,

1in

clud

edby

auth

ors#.


3.T

heS

olub

ility

ofA

zide

s

3.1.

Lith

ium

Azi

de

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Lith

ium

azid

e;Li

N 3;

@195

97-6

9-4#

~2!

Sol

vent

sT.

Cur

tius

and

J.R

isso

m,

J.P

rakt

.C

hem

.58

,26

1–

309~

1898

!.

Varia

bles

:P

repa

red

By:

T/K

:28

3–

289

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofLi

N3

inw

ater

oret

hano

lat

diffe

rent

tem

pera

ture

sa

Sol

vent

Tem

pera

ture

(t/°

C)

LiN

3

(g/1

00g

solv

ent!

LiN

3

(m1

/mol

kg2

1)b

Wat

er;

H 2O

;@7

732-

18-5#

1036

.12

7.37

7

15.5

62.0

712

.68

1666

.41

13.5

6

Eth

anol

;C 2

H6O

;@6

4-17

-5#

1620

.26

4.14

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:S

atur

ated

solu

tions

ofLi

N3

inw

ater

show

edal

kalin

ere

actio

n.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

salt

was

kept

inco

ntac

tw

ithth

eso

lven

tfo

rse

vera

lwee

ksun

der

occa

sion

alst

irrin

gin

aro

omw

ithco

nsta

ntte

mpe

ratu

re.

Equ

ilibr

ium

tem

pera

ture

was

mea

sure

din

the

satu

rate

dso

lutio

nspr

ior

with

draw

alof

the

sam

ples

.Aw

eigh

edam

ount

ofth

esa

tura

ted

solu

tion

was

then

evap

orat

edin

apl

atin

umdi

sh,

and

drie

din

ade

ssic

ator

until

cons

tant

wei

ght

was

atta

ined

.

LiN

3w

aspr

epar

edfr

omLi 2S

O4

and

Ba~N

3) 2

asco

lorle

sshy

gros

copi

ccr

ysta

ls.T

hepr

oduc

twas

recr

ysta

llize

dfr

omw

ater

,an

dan

alyz

edaf

ter

prol

onge

ddr

ying

over

conc

entr

ated

H2S

O4

ina

vacu

umde

sicc

ator

.F

ound

/cal

cula

ted

for

LiN

3(%

):N

85.6

7–

86.0

2/85

.71,

Li14

.09

–14

.18/

14.2

9.T

heba

rium

azid

eus

edw

aspr

epar

edby

diss

olvi

ngB

a~OH

) 2in

8%aq

ueou

sso

lutio

nof

HN

3.

The

latte

rw

asob

tain

edby

dist

illat

ion

with

dilu

teH

2S

O4

ofei

ther

Pb~N

3) 2

orN

H4N

3ac

cord

ing

toC

urtiu

s.1P

urity

ofw

ater

not

spec

ified

.Abs

olut

eet

hano

lwas

used

.

Est

imat

edE

rror

:

Co

~1!

~2!

Va Te Si

a R b C c A


3.2.

Sod

ium

Azi

de

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#S

olve

nts

T.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

–30

9~18

98!.

riabl

es:

Pre

pare

dB

y:

K:

283

–29

0J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aN3

inw

ater

oret

hano

lat

diffe

rent

tem

pera

ture

sa

Sol

vent

Tem

pera

ture

(t/°

C)

NaN

3

(g/1

00g

solv

ent!

NaN

3

(m1

/mol

kg2

1)b

ater

;H 2

O;

@773

2-18

-5#10

40.1

66.

178

15.2

40.7

6.26

1

1741

.76.

414

hano

l;C 2

H6O

;@6

4-17

-5#

160.

3153

0.04

85

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

ditio

nali

nfor

mat

ion:

Sat

urat

edso

lutio

nsof

NaN 3

inw

ater

show

edal

kalin

ere

actio

n.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

salt

was

kept

innt

act

with

the

solv

ent

for

seve

ralw

eeks

unde

roc

casi

onal

rrin

gin

aro

omw

ithco

nsta

ntte

mpe

ratu

re.

Equ

ilibr

ium

pera

ture

was

mea

sure

din

the

satu

rate

dso

lutio

nspr

ior

thdr

awal

ofth

esa

mpl

es.A

wei

ghed

amou

ntof

the

satu

rate

dlu

tion

was

then

evap

orat

edin

apl

atin

umdi

sh,

and

drie

din

asi

ccat

orun

tilco

nsta

ntw

eigh

tw

asat

tain

ed.

NaN

3w

aspr

epar

edby

neut

raliz

ing

8%aq

ueou

sso

lutio

nof

HN

3

with

NaO

H.T

heso

lutio

nof

the

acid

was

obta

ined

bydi

still

atio

nw

ithdi

lute

H2S

O4

ofei

ther

Pb~N

3) 2

orN

H4N

3ac

cord

ing

toC

urtiu

s.1N

aN3

was

recr

ysta

llize

dfr

omw

ater

,an

ddr

ied

over

conc

entr

ated

H 2SO

4in

ava

cuum

dess

icat

or.

Ana

lysi

s,fo

und/

calc

ulat

edfo

rN

aN3

~%!:

Na

35.3

1–

35.3

5/35

.38.

Pur

ityof

wat

erno

tsp

ecifi

ed.A

bsol

ute

etha

nolw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 T.C

urtiu

s,B

er.2

4,33

41~1

891!

.

99JIRI HALA

. Phys. Chem. Ref. Data, Vol. 33, No. 1, 2004

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Fre

ezin

gcu

rve

was

obta

ined

bypo

lyth

erm

alm

etho

d.T

heso

lubi

lity

curv

ew

asob

tain

edby

isot

herm

alm

etho

d.E

xces

ssa

ltw

aseq

uilib

rate

dw

ithw

ater

ina

ther

mos

tat

for

1da

yin

clos

edve

ssel

s.In

the

satu

rate

dso

lutio

ns,

azid

ew

aspr

ecip

itate

dw

ithA

gNO 3

,an

dsu

bseq

uent

lyde

term

ined

grav

imet

rical

lyas

AgC

l,lit

hium

was

dete

rmin

edgr

avim

etric

ally

asLi 2

SO

4.

Coo

ling

curv

esw

ere

obta

ined

bypo

lyth

erm

alm

etho

d,th

etim

ene

cess

ary

tore

ach

equi

libriu

mw

asno

tsp

ecifi

ed.

Itw

asst

ated

that

equi

libriu

mw

asat

tain

edve

rysl

owly

,an

dth

atth

esy

stem

ssh

owed

cons

ider

able

tend

ency

tosu

pers

atur

atio

nev

enw

hen

inoc

ulat

ed.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

–0.

5K

~aut

hors!

.S

olub

ility

:10

0w

1:6

0.3%

–0.

4%~a

utho

rs!.

Ref

eren

ces:

1 T.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

~189

8!.

Co

~1!

~2!

Va T/ W Et

a S b C Ad

Me

An

co sti

tem

wi

so de

J

FIG

.2.

Pha

sedi

agra

mof

the

NaN 3–

H2O

syst

em@~

full

circ

les!

poly

ther

mal

mea

sure

men

ts;

~ope

nci

rcle

s!is

othe

rmal

mea

sure

men

ts;

~tria

ngle

s!da

tafr

omC

urtiu

san

dR

isso

m,

1in

clud

edby

the

auth

or#.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

efr

eezi

ngcu

rve

was

obta

ined

bypo

lyth

erm

alm

etho

d.T

helu

bilit

ycu

rve

was

obta

ined

byis

othe

rmal

met

hod.

Exc

ess

ltw

aseq

uilib

rate

dw

ithw

ater

ina

ther

mos

tat

for

1da

yin

sed

vess

els.

Insa

mpl

esof

the

satu

rate

dso

lutio

ns,

azid

ew

asec

ipita

ted

with

AgN

O 3,

and

subs

eque

ntly

dete

rmin

edav

imet

rical

lyas

AgC

l,so

dium

was

dete

rmin

edav

imet

rical

lyas

Na 2S

O4

.C

oolin

gcu

rves

wer

eob

tain

edby

lyth

erm

alm

etho

d.E

quili

briu

mtim

ew

asno

tsp

ecifi

ed.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:In

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 T.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

~189

8!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#~2

!W

ater

;H 2

O;

@773

2-18

-5#J.

Woh

lgem

uth,

Com

pt.

Ren

d.198

,601

–3

~193

4!.

Varia

bles

:P

repa

red

By:

Tem

pera

ture

J.H

a´ l

a

Exp

erim

enta

lDat

a

Tem

pera

ture

(t/°

C)

NaN

3

(100

w1

/mas

s%

)N

aN3

(m1

/mol

kg2

1)c

Not

e

220

26.8

5.63

met

asta

ble

eute

ctic

poin

t(i

ce1

NaN

3)

215

.121

.64.

24eu

tect

icpo

int

22.

127

.85.

92tr

ansi

tion

poin

t

028

5.98

100

35.6

8.50

a Res

ults

wer

epr

esen

ted

ingr

aphi

calf

orm~Fig

.2!

.N

umer

ical

valu

esw

ere

repo

rted

for

five

sign

ifica

ntpo

ints

inth

eph

ase

diag

ram

.b S

olid

phas

esw

ere

repo

rted

tobe

NaN 3•3

H2O

,@

#,be

twee

n215

.1°C

and2

2.1

°C,

and

NaN

3,

@266

28-2

2-8#,

abov

e22.

1°C

.c C

alcu

late

dby

com

pile

r.

Me

Th

so sa clo

pr gr gr po


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#E

than

ol;

C 2H

6O

;@6

4-17

-5#

J.A

.C

rans

ton

and

A.

Y.Li

ving

ston

e,J.

Che

m.

Soc

.50

1–

3~1

926!

.

riabl

es:

Pre

pare

dB

y:

K:

273

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aN3

was

repo

rted

tobe

0.22

gsa

ltin

100

gso

lven

tat

0°C

.F

rom

this

valu

eth

eco

mpi

ler

calc

ulat

edm

1

0.03

38m

olkg

21.

Add

ition

alin

form

atio

n:T

heau

thor

sal

sore

port

edth

eso

lubi

lity

ofN

aN3

inbo

iling

etha

nolt

obe

0.46

gsa

ltin

100

gso

lven

t.B

oilin

gin

tof

the

satu

rate

dso

lutio

nan

dat

mos

pher

icpr

essu

reat

whi

chth

em

easu

rem

ent

was

cond

ucte

dw

ere

not

repo

rted

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed,

deta

ilsw

ere

not

repo

rted

.al

ysis

ofth

esa

tura

ted

solu

tions

was

carr

ied

out

bytit

ratin

gid

e1in

wei

ghed

sam

ples

.

No

info

rmat

ion

onN

aN3

repo

rted

.E

than

olus

edha

dde

nsity

of0.

799

gcm

23

at17

°C.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 F.R

asch

ig,

Che

m.

Ztg

.12

03~19

08!.

1111JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#~2

!E

than

ol;

C 2H

6O

;@6

4-17

-5#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

E.

Lieb

er,

C.

N.

R.

Rao

,H

.E

.D

ingl

e,an

dJ.

Teet

sow

,J.

Che

m.

Eng

.D

ata1

1,10

5~1

966!

.

Varia

bles

:P

repa

red

By:

T/K

:29

8C

once

ntra

tion

ofet

hano

l/%~v

/v!:

0–

95.5

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

at25

°Cof

NaN

3in

wat

er–

etha

nols

olut

ionsa

C2H

6O

~%,v

/v!

NaN

3

(g/1

00g

solv

ent!

NaN

3

(m1

/mol

kg2

1)d

043

.60b

6.70

7

4017

.95b

18.1

9c

6011

.17b

10.4

8c

804.

21c

95.5

0.81

b1.

05c

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Syn

thet

icm

etho

d.c Is

othe

rmal

met

hod.

d Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ies

wer

ede

term

ined

bysy

nthe

tican

dis

othe

rmal

met

hods

.In

the

synt

hetic

met

hod,

1th

eso

lutio

nsof

know

nco

mpo

sitio

nsw

ere

prep

ared

,an

dth

eir

satu

ratio

npo

ints

wer

ede

term

ined

byva

ryin

gth

ete

mpe

ratu

re.

Inth

eis

othe

rmal

met

hod,

sam

ples

ofth

esa

tura

ted

solu

tions

wer

eev

apor

ated

,an

dth

ere

sidu

ew

asdr

ied

and

wei

ghed

.T

heau

thor

sco

nsid

ered

the

resu

ltsob

tain

edby

isot

herm

alm

etho

das

mor

eac

cura

tean

dre

liabl

e.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 O.

Fla

schn

eran

dB

.M

acE

wen

,J.

Che

m.

Soc

.93

,10

00~1

908!

.

Co

~1!

~2!

Va T/

5 po Me

An

An

az

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#S

olve

nts

R.

Ale

xand

er,

E.

C.

F.K

o,Y.

C.

Mac

,an

dA

.J.

Par

ker,

J.A

m.

Che

m.

Soc

.89,

3703

–12

~196

7!.

riabl

es:

Pre

pare

dB

y:

K:

273

or29

8J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

prod

uct

ofN

aN3

inth

ree

solv

entsa

Sol

vent

Tem

pera

ture

(t/°

C)

Ksp

bN

aN3

(c1

/mol

dm2

3)c

Met

hano

l;C

H 4O

;@6

7-56

-1#

010

20.

90.

355

ulfin

yl-b

ism

etha

ne;dC

2H

6O

S;@

67-6

8-5#

2510

20.

640.

479

N-d

imet

hylfo

rmam

ide;

C 3H7N

O;

@68-

12-2

#25

102

1.9

0.11

2

olid

phas

ew

asN

aN 3,

@266

28-2

2-8#,

inal

lsol

vent

s.

sp5

@Na1

#@N

32#

alcu

late

dby

com

pile

r.im

ethy

lsul

foxi

de.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Sat

urat

edso

lutio

nsw

ere

epar

edby

shak

ing

the

solid

with

the

solv

ent

ina

stop

pere

dsk

at35

°Cfo

r24

h,an

dth

enfo

rfu

rthe

r24

hat

0°C

etha

nol!or

at25

°C~o

ther

two

solv

ents!.

The

liqui

dph

ases

rean

alyz

edby

pote

ntio

met

rictit

ratio

nw

ithA

gNO

3.

The

lidph

ases

wer

ean

alyz

edaf

ter

dryi

ngat

1m

mH

gfo

r48

hro

omte

mpe

ratu

re.

NaN

3,A

nala

rgr

ade

prod

uct,

sour

ceno

tspe

cifie

d.M

etha

nolw

aspu

rified

acco

rdin

gto

Cla

ree

ta

l.1D

imet

hyls

ulfo

xide

was

apr

oduc

tof

Cro

wn

Zel

lerb

ach

Cor

p.N

,N-d

imet

hylfo

rmam

ide

~sou

rce

not

spec

ified!

was

drie

dw

ithty

pe4A

mol

ecul

arsi

eve,

and

frac

tiona

ted

twic

eun

der

redu

ced

pres

sure

ofdr

yni

trog

en.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1.B

.W.C

lare

,D.C

ook,

E.C

.F.K

o,Y.

C.M

ac,a

ndA

.J.P

arke

r,J.

Am

.C

hem

.S

oc.88

,19

11~1

966!

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#~2

!M

etha

nol;

CH 4

O;

@67-

56-1

#F.

Hud

swel

l,J.

S.

Nai

rn,

and

K.

R.

Gad

sby,

J.A

ppl.

Che

m.,

Sup

pl.

Issu

e.N

o.2,

S13

7–

8~19

51!.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aN3

was

repo

rted

tobe

2.49

1or

2.48

6g

salt

in10

0cm

3of

the

satu

rate

dso

lutio

nat

25°C

,as

dete

rmin

edfr

omw

eigh

tof

the

resi

due

ortit

ratio

n,re

spec

tivel

y.U

sing

the

solu

bilit

yof

NaN

3in

wat

erof

40.8

gsa

ltpe

r10

0g

wat

erat

20°C

,1

and

the

dens

ityof

the

satu

rate

dso

lutio

nof

NaN 3

inm

etha

nolo

f0.

8083

gcm2

3 ,th

eau

thor

sco

rrec

ted

the

expe

rimen

tally

dete

rmin

edso

lubi

lity

inm

etha

nolf

orth

eco

ntrib

utio

nfr

om0.

035

mas

s%

wat

erin

met

hano

luse

d,an

dob

tain

edth

eso

lubi

lity

ofN

aN3

as3.

166

0.01

gN

aN3

in10

0g

anhy

drou

sm

etha

nol,

or2.

48N

aN 3in

100

cm3

ofth

esa

tura

ted

solu

tion.

Fro

mth

efo

rmer

valu

eth

eco

mpi

ler

obta

ined

m1

50.

486

mol

kg2

1.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

solid

was

shak

enm

echa

nica

llyw

ithth

eso

lven

tfo

r5

min

,an

dth

enke

ptin

ath

erm

osta

tfo

r1

h.T

his

proc

edur

ew

asre

peat

edth

ree

times

whi

chw

assu

ffici

ent

tore

ach

equi

libriu

m.

Twen

tym

Lof

the

satu

rate

dso

lutio

nw

asw

ithdr

awn

with

api

pette

thro

ugh

asi

nter

ed/g

lass

filte

r,an

dth

eso

lven

tw

asev

apor

ated

belo

w50

°Cin

aw

eigh

edbe

aker

.T

here

sidu

ew

asdr

ied

at50

°Cto

cons

tant

wei

ght,

and

corr

ecte

dfo

rbl

ank

expe

rimen

t.T

here

sidu

ew

asth

enan

alyz

edfo

rN

aN 3by

reac

ting

itw

ithex

cess

(NH

4) 2

Ce~

NO

3) 6

and

back

-titr

atin

gex

cess

Ce

~IV!

with

FeS

O 4us

ing

the

o-ph

enan

thro

line

–F

e~II

!co

mpl

exas

indi

cato

r.

NaN

3,

sour

ceno

tspe

cifie

d,co

ntai

ned

99.9

%N

aN3

afte

rdr

ying

toco

nsta

ntw

eigh

tat

50°C

.It

was

used

with

out

furt

her

purifi

catio

n.M

etha

nol,

boili

ngpo

int

65°C

,w

asof

high

-gra

depu

rity.

Itco

ntai

ned

0.03

5m

ass

%w

ater

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

60.

2%~a

utho

rs,

base

don

thre

em

easu

rem

ents

;in

divi

dual

resu

ltsno

tre

port

ed!.

Ref

eren

ces:

1 T.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

~189

8!.

Co

~1!

~2!

Va T/ S

N,

a S b K c C d D Me

An

pr fla ~m we

so at


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#S

odiu

mam

ide;

NaN

H 2;

@778

2-92

-5#A

mm

onia

;N

H 3;

@766

4-41

-7#

T.K

awak

ami

and

S.

Mor

oto,

Nag

oya

Kog

yoG

ijuts

uS

hken

sho

Hok

oku

8,79

3–

8~1

959!

.

riabl

es:

Pre

pare

dB

y:

K:

273

–30

3/m

olkg

21:

0–

0.13

H.A

kaiw

aan

dJ.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

aN3–

NaN

H 2–

liqui

dam

mon

iasy

stem

mpe

ratu

re(t

/°C

)N

aNH

2

(g/1

00g

NH 3

)N

aNH

2

(m2

/mol

kg2

1)b

NaN

3

(g/1

00g

NH 3

)N

aN3

(m1

/mol

kg2

1)b

Sol

idph

asea

00.

910.

0233

50.5

7.77

A

0.92

0.02

3148

.57.

46A

2.69

0.06

9051

.47.

91A1

B

2.32

0.05

9543

.46.

68B

1.98

0.05

0834

.45.

29B

1.70

0.04

3634

.75.

34B

1.24

0.03

1822

.13.

40B

0.78

0.02

0012

.61.

94B

0.77

0.01

9711

.41.

75B

100

048

.67.

48A

1.51

0.03

8748

.57.

46A

3.10

0.07

9549

.17.

55A1

B

3.16

0.08

1050

.17.

71A1

B

2.73

0.07

0042

.56.

54B

2.11

0.05

4131

.54.

85B

1.58

0.04

0522

.33.

43B

0.98

0.02

5112

.31.

89B

200.

800.

0205

48.1

7.40

A

2.31

0.05

0949

.57.

62A

3.68

0.09

4348

.47.

45A1

B

2.70

0.06

9235

.85.

51B

2.48

0.06

3631

.24.

80B

1.97

0.05

0525

.73.

95B

1.87

0.04

7923

.13.

55B

1.51

0.03

8719

.93.

06B

1.52

0.03

9019

.32.

97B

1.11

0.02

8512

.41.

91B

0.74

0.01

907.

571.

16B

0.51

0.01

315.

050.

777

B

301.

590.

0408

47.2

7.26

A

3.39

0.08

6948

.67.

48A1

B

5.07

0.13

046

.07.

08B

4.40

0.11

339

.86.

12B

3.44

0.08

8231

.94.

91B

2.72

0.06

9724

.83.

82B

2.32

0.05

9521

.13.

25B

a A:

NaN

3,

@266

628-

22-8#

;B

:N

aNH

2,

@778

2-92

-5#.

b Cal

cula

ted

byco

mpi

ler~J

.H.!.

1313JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#~2

!A

mm

onia

;N

H 3;

@766

4-41

-7#T.

Kaw

akam

ian

dS

.M

orot

o,N

agoy

aK

ogyo

Giju

tsu

Shk

ensh

oH

okok

u8,

793

–8

~195

9!.

Varia

bles

:P

repa

red

By:

T/K

:23

1.7

–26

3.9

H.A

kaiw

aan

dJ.

Ha

´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aN3

inliq

uid

amm

onia

asa

func

tion

ofte

mpe

ratu

re

Tem

pera

ture

(t/°

C)

NaN

3

(g/1

00g

NH 3

)N

aN3

(m1

/mol

kg2

1)a

Sol

idph

aseb

29.

351

.45

7.91

A

218

.052

.51

8.08

A

227

.952

.23

8.03

c

228

.950

.40

7.75

c

232

.844

.69

6.78

c

236

.039

.25

6.03

B

237

.038

.60

5.94

B

241

.532

.14

4.94

B

a Cal

cula

ted

byco

mpi

ler~J

.H.!.

b A:

NaN

3;

@266

28-2

2-8#;

B:

NaN

3•6

NH

3,

@#.

c Not

repo

rted

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Drie

dN

aN3

~2.9

84g!

and

exce

ssof

drie

dliq

uid

amm

onia

wer

ein

trod

uced

into

apr

essu

rebo

ttle.

The

mix

ture

was

tran

sfer

red

into

aD

ewar

flask

and

cool

edw

ithac

eton

e/dr

yic

eco

olan

t.T

heso

lubi

lity

ofN

aN3

was

dete

rmin

edby

the

clou

dm

etho

d.A

tte

mpe

ratu

res

belo

w235

°Cth

eso

lutio

nssh

owed

ate

nden

cyto

war

dsu

pers

atur

atio

n.

NaN

3,

com

mer

cial

lyav

aila

ble

prod

uct~s

ourc

eno

tsp

ecifi

ed!,w

asre

crys

talli

zed

from

liqui

dam

mon

ia.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.2

K~a

utho

rs!.

Sol

ubili

ty:

prec

isio

nno

tre

port

ed.

Co

~1!

~2!

~3!

Va T/

m2

Te

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#6,

7,9,

10,1

7,18

,20,

21-o

ctah

ydro

-dib

enzo

@b,k

#,4

,7,1

0,13

,16#h

exao

xacy

cloo

ctad

ecin

;

0H24

O6

;@1

4187

-32-

7#~1

8-di

benz

o-cr

own-

6!S

olve

nts

L.N

.Y

astr

ebov

,T.

M.

Shu

vaev

a,an

dL.

N.

Kra

vche

nko,

Zh.

Prik

l.K

him

.50,

2107

–8~

1977

!.

riabl

es:

Pre

pare

dB

y:

/mol

dm2

3:

0–

0.15

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aN3

inva

rious

solv

ents

asa

func

tion

of18

-dib

enzo

-cro

wn-

6co

ncen

trat

ion

Sol

vent

Tem

pera

ture

(t/°

C)

C20

H24

O6

(c2

/mol

dm2

3)

NaN

3

(c1

/mol

dm2

3)

ulfin

yl-b

is~m

etha

ne!;

aC

2H

6O

S;@

67-6

8-5#

800

1.1

0.05

1.1

0.10

1.19

0.15

1.66

N-d

imet

hylfo

rmam

ide;

C 3H6N

O;

@68-

12-2

#80

00.

18

0.05

0.19

0.10

0.21

0.15

0.26

Eth

anol

;C 2

H6O

;@6

4-17

-5#

750

0.11

0.05

0.12

0.10

0.17

0.15

0.31

Ace

tone

;C 3

H6O

;@6

7-64

-1#

550

0.00

24

0.05

0.00

58

0.10

0.01

04

0.15

0.01

39

2-B

utan

one;

C 4H

8O

;@7

8-93

-3#

750

0.00

19

0.05

0.00

28

0.10

0.00

70

0.15

0.01

15

Cyc

lohe

xano

ne;

C 6H10

O;

@108

-94-

1#80

0.15

0.00

38

Ace

toni

trile

;C 2

H3N

;@7

5-05

-8#

800.

150.

0092

a Dim

ethy

lsul

foxi

de.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

No

info

rmat

ion

repo

rted

.N

oin

form

atio

nre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

ofso

lids

wer

eeq

uilib

rate

dw

ithliq

uid

amm

onia

atth

ede

sire

dte

mpe

ratu

rein

apr

essu

rebo

ttle

imm

erse

din

ath

erm

osta

ted

Dew

arfla

sk.

Insa

mpl

esof

the

satu

rate

dso

lutio

ns,

amm

onia

was

dete

rmin

edfr

omw

eigh

tlo

ssaf

ter

allo

win

git

toev

apor

ate

from

aw

eigh

edsa

mpl

e.T

heco

nten

tof

NaN

H 2in

the

resi

due

was

dete

rmin

edal

kalim

etric

ally

afte

rde

com

posi

ngth

eam

ide

byad

ding

carb

onat

e-fr

eew

ater

.T

heN

H3

liber

ated

was

abso

rbed

inex

cess

stan

dard

H 2SO

4so

lutio

n,an

dex

cess

acid

was

back

-titr

ated

agai

nst

NaO

Hso

lutio

n.T

hem

etho

dfo

rN

aN3

dete

rmin

atio

nw

asno

tre

port

ed.

NaN

3,

sour

ceno

tsp

ecifi

ed,

was

apr

oduc

tof

99.4

5%–

99.6

5%pu

rity.

NaN

H 2w

aspr

epar

edby

redu

ctio

nof

NaN 3

with

sodi

umm

etal

inliq

uid

amm

onia

,us

ing

iron

pow

der

asa

cata

lyst

.P

urity

ofth

epr

oduc

tw

asno

tre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n60.

2K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

@1 C2

~3!

Va c 2 S N,


Tetr

ahyd

rofu

rane

;C 4H

8O

;@1

09-9

9-9#

650.

153

0.00

21

1,4-

Dio

xane

;C 4

H8O

2;

@123

-91-

1#80

0.15

30.

0042

Ben

zene

;C 6

H6

;@7

1-43

-2#

800.

153

0.00

64

a Dim

ethy

lsul

foxi

de.

b Bas

edon

the

effe

ctof

met

hano

lon

the

solu

bilit

yof

NaN

3,

the

com

pile

ras

sum

edth

isfig

ure

coul

dbe

am

ispr

int.

The

corr

ectv

alue

coul

dbe

eith

er0.

15or

0.05

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.N

othi

ngsp

ecifi

ed.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

3.3.

Pot

assi

umA

zide

3.3.

1.E

valu

atio

nof

the

KN

3–

H2O

Sys

tem

mpo

nent

s:E

valu

ator

:

Pot

assi

umaz

ide;

KN 3;

@207

62-6

0-1#

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

June

2001

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

KN 3

inw

ater

was

mea

sure

dby

isot

herm

alm

etho

din

two

docu

men

ts.

Cur

tius

and

Ris

som

1re

port

edth

ree

valu

estw

een

283.

6an

d29

0.1

K,

whi

leW

ohlg

emut

h2

repo

rted

the

phas

edi

agra

mof

the

KN

3–

H2O

syst

em,

and

num

eric

alda

taon

lyat

273.

1d

373.

1K

.A

lthou

ghth

etw

ose

tsof

data

wer

eob

tain

edun

der

diffe

rent

equi

libra

tion

cond

ition

san

dw

ithun

know

npr

ecis

ion

ofpe

ratu

rem

easu

rem

ent

the

data

seem

tobe

ingo

odag

reem

ent

sinc

eth

eyfa

llon

ast

raig

htlin

e.Le

ast

squa

retr

eatm

ent

ofth

eda

tatw

een

273.

1an

d29

0.1

Kyi

elde

dan

equa

tion

for

the

solu

bilit

yof

KN

3in

wat

eras

afu

nctio

nof

tem

pera

ture

asm

1/m

olkg

215

0.05

94T

211

.11,

ich

can

beus

edto

obta

inte

ntat

ive

solu

bilit

ies

inth

em

entio

ned

tem

pera

ture

rang

e.

fere

nces

:

.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

~189

8!.

.W

ohlg

emut

h,C

ompt

.R

end.1

98,

601

~193

4!.

1515JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

azid

e;N

aN3

;@2

6628

-22-

8#~2

!6,

7,9,

10,1

7,18

,20,

21-o

ctah

ydro

-dib

enzo

@b,k

#@1

,4,7

,10,

13,1

6#he

xaox

acyc

looc

tade

cin;

C20

H24

O6

;@1

4187

-327

#~1

8-di

benz

o-cr

own-

6!~3

!M

etha

nol;

CH 4

O;

@67-

56-1

#~4

!S

olve

nts

L.N

.Y

astr

ebov

,T.

M.

Shu

vaev

a,an

dL.

N.

Kra

vche

nko,

Zh.

Prik

l.K

him

.50,

2107

–8~

1977

!.

Varia

bles

:P

repa

red

By:

Con

cent

ratio

nof

CH 4O

/v/v

%:

1–

3F

orea

chso

lven

tm

easu

rem

ents

wer

eca

rrie

dou

tat

one

tem

pera

ture

and

one

18-d

iben

zo-C

row

n-6

conc

entr

atio

n.

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aN3

inva

rious

solv

ents

inth

epr

esen

ceof

18-d

iben

zo-c

row

n-6

asa

func

tion

ofm

etha

nolc

once

ntra

tion

Sol

vent

Tem

pera

ture

(t/°

C)

C20

H24

O6

(c2

/mol

dm2

3)

Met

hano

l~v

/v%

!N

aN3

(c1

/mol

dm2

3)

Sul

finyl

-bis

met

hane

;C 2H

6O

S;@

67-6

8-5#

a80

0.15

11.

66

21.

71

32.

17

N,N

-dim

ethy

lform

amid

e;C 3H

6N

O;

@68-

12-2

#80

0.05

10.

19

20.

22

30.

39

Ace

tone

;C 3

H6O

;@6

7-64

-1#

550.

11

0.01

2

20.

023

30.

068

2-B

utan

one;

C 4H

8O

;@7

8-93

-3#

750.

5b1

0.01

8

20.

021

30.

038

Cyc

lohe

xano

ne;

C 6H10

O;

@108

-94-

1#80

0.15

10.

0053

20.

014

30.

026

Ace

toni

trile

;C 2

H3N

;@7

5-05

-8#

800.

151

0.01

1

20.

015

30.

025

Hep

tane

;C 7

H16

;@1

42-8

2-5#

800.

153

0.00

53

Co

~1!

~2!

be an tem

be wh

Re

1 T 2 J

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umaz

ide;

KN 3;

@207

62-6

0-1#

Wat

er;

H 2O

;@7

732-

18-5#

J.W

ohlg

emut

h,C

ompt

.R

end.1

98,

601

–3

~193

4!.

riabl

es:

Pre

pare

dB

y:

mpe

ratu

reJ.

Ha

´ la

Exp

erim

enta

lDat

a

mpe

ratu

re(t

/°C

)K

N3a

(100

w1

/mas

s%

)K

N3

(m1

/mol

kg2

1)b

212

.926

.24.

38c

029

.35.

11

100

51.4

13.0

4

bove

eute

ctic

poin

t,K

N 3,

@207

62-6

0-1#,

was

the

equi

libriu

mso

lidph

ase~s

eeF

ig.

3!.al

cula

ted

byco

mpi

ler.

utec

ticpo

int.

FIG

.3.

Pha

sedi

agra

mof

the

KN 3–

H2O

syst

em.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ycu

rve

was

obta

ined

byth

eis

othe

rmal

met

hod.

Exc

ess

salt

was

equi

libra

ted

with

wat

erin

ath

erm

osta

tfo

r1

day

incl

osed

vess

els.

Insa

mpl

esof

the

satu

rate

dso

lutio

ns,

azid

ew

aspr

ecip

itate

dw

ithA

gNO 3,

and

subs

eque

ntly

dete

rmin

edgr

avim

etric

ally

asA

gCl,

pota

ssiu

mw

asde

term

ined

grav

imet

rical

lyas

K 2S

O4

.C

oolin

gcu

rves

wer

eob

tain

edby

poly

ther

mal

met

hod.

Equ

ilibr

ium

time

was

not

spec

ified

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umaz

ide;

KN 3;

@207

62-6

0-1#

~2!

Sol

vent

sT.

Cur

tius

and

J.R

isso

m,

J.P

rakt

.C

hem

.58

,26

1–

309~

1898

!.

Varia

bles

:P

repa

red

By:

T/K

:28

3–

290

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

N3

inw

ater

oret

hano

lat

diffe

rent

tem

pera

ture

sa

Sol

vent

Tem

pera

ture

(t/°

C)

KN

3

(g/1

00g

solv

ent!

KN

3

(m1

/mol

kg2

1)b

Wat

er;

H 2O

;@7

732-

18-5#

10.5

46.5

5.73

15.5

48.9

6.03

1749

.66.

12

Eth

anol

;C 2

H6O

;@6

4-17

-5#

160.

1375

0.01

69

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

salt

was

kept

inco

ntac

tw

ithth

eso

lven

tfo

rse

vera

lwee

ksun

der

occa

sion

alst

irrin

gin

aro

omw

ithco

nsta

ntte

mpe

ratu

re.

Equ

ilibr

ium

tem

pera

ture

was

mea

sure

din

the

satu

rate

dso

lutio

nspr

ior

tow

ithdr

awal

ofth

esa

mpl

es.A

wei

ghed

amou

ntof

the

satu

rate

dso

lutio

nw

asth

enev

apor

ated

ina

plat

inum

dish

,an

ddr

ied

ina

dess

icat

orun

tilco

nsta

ntw

eigh

tw

asat

tain

ed.

KN

3w

aspr

epar

edby

reac

ting

stoi

chio

met

ricam

ount

ofK

OH

with

eith

erN

H 4N

3,

oran

aque

ous

solu

tion

ofH

N 3.

Bot

hN

H4N

3an

dth

eH

N 3so

lutio

nw

ere

obta

ined

acco

rdin

gto

Cur

tius,1

the

latte

rby

dist

illat

ion

with

dilu

teH 2S

O4

ofei

ther

Pb~

N3) 2

orN

H4N

3.

Pur

ityof

wat

erno

tsp

ecifi

ed.

Abs

olut

eet

hano

lwas

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 T.C

urtiu

s,B

er.2

4,33

41~1

891!

.

Co

~1!

~2!

Va Te Te a A b C c E


3.4.

Rub

idiu

mA

zide

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Rub

idiu

maz

ide;

RbN

3;

@227

56-3

6-1#

Sol

vent

s~w

ater

and

etha

nol

!T.

Cur

tius

and

J.R

isso

m,

J.P

rakt

.C

hem

.58

,26

1–

309~

1898

!.

riabl

es:

Pre

pare

dB

y:

K:

289

and

290

J.H

a´ l

a

Exp

erim

enta

lDat

aS

olub

ility

ofR

bN3

inw

ater

oret

hano

lat

two

tem

pera

ture

sa

Sol

vent

Tem

pera

ture

(t/°

C)

RbN

3

(g/1

00g

solv

ent!

RbN

3

(m1

/mol

kg2

1)b

ater

;H 2

O;

@773

2-18

-5#16

107.

18.

40

ater

;H 2

O;

@773

2-18

-5#17

114.

18.

95

hano

l;C 2

H6O

;@6

4-17

-5#

160.

182

0.01

43

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

salt

was

kept

innt

act

with

the

solv

ent

for

seve

ralw

eeks

unde

roc

casi

onal

rrin

gin

aro

omw

ithco

nsta

ntte

mpe

ratu

re.

Equ

ilibr

ium

pera

ture

was

mea

sure

din

the

satu

rate

dso

lutio

nspr

ior

toth

draw

alof

the

sam

ples

.Aw

eigh

edam

ount

ofth

esa

tura

ted

lutio

nw

asth

enev

apor

ated

ina

plat

inum

dish

,an

ddr

ied

ina

sicc

ator

until

cons

tant

wei

ght

was

atta

ined

.

RbN

3w

aspr

epar

edby

doub

lede

com

posi

tion

from

Rb

2S

O4

and

Ba~

N3) 2

.T

hepr

oduc

tw

asre

crys

talli

zed

from

wat

er,

and

anal

yzed

afte

rpr

olon

ged

dryi

ngov

erco

ncen

trat

edH

2S

O4

ina

vacu

umde

ssic

ator

.F

ound

/cal

cula

ted

for

RbN

3~%

!:N

33.1

0–

33.2

0/33

.02,

Rb

66.7

3–

66.8

9/66

.98.

The

bariu

maz

ide

used

was

prep

ared

bydi

ssol

ving

Ba~O

H) 2

in8%

aque

ous

solu

tion

ofH

N3

.T

hela

tter

was

obta

ined

bydi

still

atio

nw

ithdi

lute

H2S

O4

ofei

ther

Pb~N

3) 2

orN

H4N

3ac

cord

ing

toC

urtiu

s.1P

urity

ofw

ater

not

spec

ified

.Abs

olut

eet

hano

lwas

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 T.C

urtiu

s,B

er.2

4,33

41~1

891!

.

1717JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umaz

ide;

KN 3;

@207

62-6

0-1#

~2!

Eth

anol

;C 2

H6O

;@6

4-17

-5#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

J.A

.C

rans

ton

and

A.

Y.Li

ving

ston

e,J.

Che

m.

Soc

.50

1–

3~1

926!

.

Varia

bles

:P

repa

red

By:

T/K

:27

3et

hano

lcon

cent

ratio

n:80

%an

d10

0%~v/

v!J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

N3

at0

°Cin

etha

nola

ndon

eet

hano

l–w

ater

syst

ema

Eth

anol

~%~v

/v!!

KN

3

(g/1

00g

solv

ent!

KN

3

(m1

/mol

kg2

1)b

801.

8

100

0.16

0.02

0

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:A

lso

repo

rted

wer

eth

eso

lubi

litie

sof

KN

3at

boili

ngpo

ints

ofth

esa

tura

ted

solu

tions

as5.

9an

d0.

54g

KN

3pe

r10

0g

solv

ent

for

80%

and

100%

~v/v

!et

hano

l,re

spec

tivel

y.T

hebo

iling

poin

tste

mpe

ratu

res

and

atm

osph

eric

pres

sure

atw

hich

the

mea

sure

men

tsw

ere

perf

orm

edw

ere

not

repo

rted

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

atio

ntim

ew

asno

tsp

ecifi

ed.

Inw

eigh

edsa

mpl

esof

the

satu

rate

dso

lutio

nsth

eaz

ide

cont

ent

was

dete

rmin

edtit

rimet

rical

ly.

1

Sou

rce

and

purit

yof

KN 3

use

wer

eno

tsp

ecifi

ed.

Eth

anol

used

had

dens

ityof

0.79

9g

cm23

at17

°C.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 F.R

asch

ig,

Che

m.

Ztg

.12

03~19

08!.

Co

~1!

~2!

Va T/ W W Et

a S b C Me

An

co sti

tem

wi

so de

J

3.6.

Am

mon

ium

Azi

de

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

azid

e;N

H 4N

3;

@121

64-9

4-2#

Sol

vent

sW

.S.F

rost

,J.C

.Cot

hran

,and

A.W

.Bro

wne

,J.A

m.C

hem

.Soc

.55

,35

16–

8~19

33!.

riabl

es:

Pre

pare

dB

y:

K:

273;

293;

313

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4N

3in

five

solv

ents

atdi

ffere

ntte

mpe

ratu

res

a

Sol

vent

Tem

pera

ture

(t/°

C)

rb

~gcm

23 !

NH

4N

3

(g/1

00g)

cN

H4N

3

(c1

/mol

dm2

3)d

NH

4N

3

(m1

/mol

kg2

1)d

Wat

er;

H 2O

;@7

732-

18-5#

01.

0435

13.8

02.

302.

54

201.

0473

20.1

63.

363.

97

401.

0554

27.0

74.

515.

74

Met

hano

l;C

H 4O

;@6

7-56

-1#

200.

8166

3.26

80.

544

0.69

4

400.

7986

3.98

40.

663

0.87

4

Eth

anol

;C 2

H6O

;@6

4-17

-5#

200.

7972

1.06

00.

176

0.22

4

400.

7803

1.32

50.

221

0.28

8

Ben

zene

;C 6

H6

;@7

1-42

-3#

200.

8778

0.00

320.

000

532

0.00

060

7

400.

8609

0.00

780.

0013

00.

0015

1

ethy

leth

er;

C 4H

10O

;@6

0-29

-7#

200.

7129

0.00

630.

0010

50.

0014

7

olid

phas

esw

ere

not

inve

stig

ated

.en

sity

ofth

esa

tura

ted

solu

tions

.ra

ms

NH 4

N3

per

100

gsa

tura

ted

solu

tion.

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Exp

erim

ents

wer

epe

rfor

med

anap

para

tus

desi

gned

for

syst

ems

cons

istin

gof

vola

tile

thso

lven

tsan

dso

lute

s.D

etai

lsof

the

appa

ratu

sor

anal

ytic

alth

ods

used

wer

eno

tre

port

ed.

NH

4N

3w

aspr

epar

edby

reflu

xing

anet

her

solu

tion

ofH

N3

over

CaC

l 2,

redi

still

ing

the

solu

tion

from

the

desi

ccan

t,an

dne

utra

lizin

git

with

NH 3

gas

until

com

plet

epr

ecip

itatio

nof

NH

4N

3oc

curr

ed.

The

salt

was

free

dfr

omet

her

byst

orag

eov

erH

2S

O4

.T

heet

her

solu

tion

ofH

N 3w

asob

tain

edby

the

reac

tion

ofN

aN3

with

H2S

O4

inth

epr

esen

ceof

ethe

r.S

ourc

ean

dpu

rity

ofth

eso

lven

tsus

edw

ere

not

repo

rted

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

the

auth

ors

stat

edth

atea

chso

lubi

lity

valu

ew

asth

eav

erag

eof

atle

ast

two

satis

fact

orily

conc

orda

ntde

term

inat

ions

.In

divi

dual

resu

ltsw

ere

not

repo

rted

.


3.5.

Ces

ium

Azi

de

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ces

ium

azid

e;C

sN 3;

@227

50-5

7-8#

~2!

Sol

vent

s~w

ater

and

etha

nol

!T.

Cur

tius

and

J.R

isso

m,

J.P

rakt

.C

hem

.58

,26

1–

309~

1898

!.

Varia

bles

:P

repa

red

By:

T/K

:27

3an

d28

9J.

Ha

´ la

Exp

erim

enta

lDat

aS

olub

ility

ofC

sN3

inw

ater

oret

hano

lat

two

tem

pera

ture

sa

Sol

vent

Tem

pera

ture

(t/°

C)

CsN

3

(g/1

00g

solv

ent!

CsN

3

(m1

/mol

kg2

1)b

Wat

er;

H 2O

;@7

732-

18-5#

022

4.2

12.8

2

Wat

er;

H 2O

;@7

732-

18-5#

1630

7.4

17.5

7

Eth

anol

;C 2

H6O

;@6

4-17

-5#

161.

0366

0.05

93

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

salt

was

kept

inco

ntac

tw

ithth

eso

lven

tfo

rse

vera

lwee

ksun

der

occa

sion

alst

irrin

gin

aro

omw

ithco

nsta

ntte

mpe

ratu

re.

Equ

ilibr

ium

tem

pera

ture

was

mea

sure

din

the

satu

rate

dso

lutio

nspr

ior

tow

ithdr

awal

ofth

esa

mpl

es.A

wei

ghed

amou

ntof

the

satu

rate

dso

lutio

nw

asth

enev

apor

ated

ina

plat

inum

dish

,an

ddr

ied

ina

desi

ccat

orun

tilco

nsta

ntw

eigh

tw

asat

tain

ed.

CsN

3w

aspr

epar

edby

doub

lede

com

posi

tion

from

Cs

2S

O4

and

Ba~

N3) 2

.T

hepr

oduc

tw

asre

crys

talli

zed

from

wat

er,

and

anal

yzed

afte

rpr

olon

ged

dryi

ngov

erco

ncen

trat

edH

2S

O4

ina

vacu

umde

ssic

ator

.F

ound

/cal

cula

ted

for

CsN

3~%

!:N

23.9

5–

24.1

3/24

.04,

Cs

75.8

2–

75.8

3/75

.96.

The

bariu

maz

ide

used

was

prep

ared

bydi

ssol

ving

Ba~O

H) 2

in8%

aque

ous

solu

tion

ofH

N3

.T

hela

tter

was

obta

ined

bydi

still

atio

nw

ithdi

lute

H2S

O4

ofei

ther

Pb~N

3) 2

orN

H4N

3ac

cord

ing

toC

urtiu

s.1P

urity

ofw

ater

not

spec

ified

.Abs

olut

eet

hano

lwas

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 T.C

urtiu

s,B

er.2

4,33

41~1

891!

.

Co

~1!

~2!

Va T/

Di

a S b D c G d C Me

An

in bo me


257

.25

36.9

99.

775

C2

5.0

47.3

014

.94

D

254

.737

.33

9.91

8C

20.

447

.60

15.1

3D

251

.337

.73

10.0

9C

16.

948

.10

15.4

3D

247

.438

.23

10.3

1C

a Cal

cula

ted

byco

mpi

ler

from

auth

ors’

mas

s%

NH

3da

ta.

b Cal

cula

ted

byco

mpi

ler.

c A:

NH

3,

@766

4-41

-7#;

B:

NH

4N

3•5

NH

3,

@#;

C:

NH

4N

3•2

NH

3,

@#;

D:

NH

4N

3,

@121

64-9

4-2#.

d Met

asta

ble

syst

em.

The

solid

phas

esin

equi

libriu

mw

ithsa

tura

ted

solu

tions

alon

gth

eva

rious

bran

ches

ofth

ecu

rve

are,

resp

ectiv

ely,

asfo

llow

s:M

N–

NH

3,

NO

–N

H4N

3•5

NH

3,

OP

–N

H 4N

3•2

NH

3,

PQ

–N

H 4N

3~P

P 8-m

etas

tabl

e!~s

eeF

ig.4

!.T

heeu

tect

icpo

into

ccur

sat2

87°C

and

24m

ass

%

NH

4N

3.

Tra

nsiti

onpo

ints

ofco

nver

sion

ofN

H 4N3•5

NH

3to

NH

4N

3•2

NH

3,

and

ofN

H 4N

3•2

NH

3to

NH

4N

3ar

eat

271

and

29

°C,

resp

ectiv

ely.

FIG

.4.

Pha

sedi

agra

mof

the

NH

4N

3–

NH

3sy

stem

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Mea

sure

men

tsw

ere

rfor

med

inan

all-g

lass

vacu

umlin

e.N

H3

gas

was

nden

sed

ona

wei

ghed

amou

ntof

the

salt

inth

ere

actio

nce

llnn

ecte

dto

man

omet

er.

The

tem

pera

ture

ofth

ece

llw

asco

ntro

lled

thro

ugh

asu

itabl

eba

th.

Equ

ilibr

ium

was

atta

ined

byst

irrin

gof

the

bath

,an

dby

agita

tion

ofth

ere

actio

nce

ll.T

hesy

stem

show

eda

stro

ngte

nden

cyto

war

dth

efo

rmat

ion

ofsu

pers

atur

ated

solu

tions

and

met

asta

ble

solid

s.T

his

was

over

com

eby

brin

ging

the

syst

emfo

ra

shor

ttim

eto

the

tem

pera

ture

ofei

ther

liqui

dai

ror

solid

CO

2.

The

met

hod

ofth

ede

term

inat

ion

ofth

eco

mpo

sitio

nof

the

satu

rate

dso

lutio

nsw

asno

tde

scrib

ed.

The

com

posi

tion

ofth

eso

lidph

ases

was

infe

rred

from

the

pres

sure

–co

ncen

trat

ion

mea

sure

men

ts.

NH

4N

3w

aspr

epar

edac

cord

ing

toF

rostet

al.1

byne

utra

lizin

gan

ethe

real

solu

tion

ofH

N 3by

NH

3ga

s.T

hepr

oduc

tw

assu

blim

edin

ase

aled

tube

at13

0°C

and

stor

edov

erco

ncen

trat

edH

2S

O4

.T

heH

N 3so

lutio

nw

asob

tain

edby

the

reac

tion

ofN

aN 3w

ithH

2S

O4

inth

epr

esen

ceof

ethe

r.N

H 3ga

sus

edw

aspa

ssed

thro

ugh

ase

ries

oftu

bes

fille

dw

ithso

dalim

ean

dso

dium

met

al.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 W.

S.

Fro

st,

J.C

.C

othr

an,

and

A.

W.

Bro

wne

,J.

Am

.C

hem

.S

oc.5

5,35

16~1

933!

.

1919JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!A

mm

oniu

maz

ide;

NH 4

N3

;@1

2164

-94-

2#~2

!A

mm

onia

;N

H 3;

@766

4-41

-7#D

.H

.H

owar

d,F.

Frie

dric

hs,

and

A.

W.

Bro

wne

,J.

Am

.C

hem

.S

oc.5

6,23

32–

40~1

934!

.

Varia

bles

:P

repa

red

By:

T/K

:19

5–

280

J.H

a´ la

Exp

erim

enta

lDat

aC

ompo

sitio

nof

satu

rate

dso

lutio

nsas

afu

nctio

nof

tem

pera

ture

Tem

pera

ture

(t/°

C)

NH

4N

3

(100

w1

/mas

s%

)aN

H4N

3

(m1

/mol

kg2

1)b

Sol

idph

asec

Tem

pera

ture

(t/°

C)

NH

4N

3

(100

w1

/mas

s%

)aN

H4N

3

(m1

/mol

kg2

1)b

Sol

idph

asec

277

.70

282

.514

.98

2.93

4A

244

.85

38.7

110

.52

C

283

.016

.03

3.17

9A

241

.239

.19

10.7

3C

283

.817

.79

3.60

3A

27.

739

.76

10.9

9C

284

.418

.80

3.85

5A

235

.65

40.1

611

.17

C

285

.220

.48

4.28

8A

232

.740

.74

11.4

5C

286

.022

.40

4.80

6A

230

.25

41.2

911

.71

C

286

.124

.52

5.40

9B

227

.141

.82

11.9

7C

285

.425

.49

5.69

6B

224

.042

.66

12.3

9C

282

.927

.58

6.34

1B

221

.35

43.2

812

.70

C

280

.929

.20

6.86

7B

218

.65

44.0

213

.09

C

278

.530

.39

7.26

9B

216

.344

.78

13.5

0C

278

.030

.98

7.47

4B

213

.445

.59

13.9

5C

276

.831

.80

7.76

4B

212

.545

.85

14.1

0C

276

.032

.41

7.98

4B

211

.346

.17

14.2

8C

275

.432

.91

8.16

8B

210

.746

.42

14.4

3C

273

.034

.38

8.72

4B

210

.246

.56

14.5

1C

272

.035

.71

9.24

8B

29.

446

.82

14.6

6C

273

.15

35.7

09.

244

B2

28.4

d46

.16

14.2

8D

271

.435

.86

9.30

9B

220

.2d

46.4

614

.45

D

268

.036

.04

9.38

2C

213

.6d

46.8

614

.68

D

265

.836

.23

9.46

0C

29.

047

.00

14.7

7D

263

.836

.43

9.54

2C

28.

947

.03

14.7

8D

260

.536

.73

9.66

6C

28.

447

.15

14.8

5D

Me

An

pe co co

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Cal

cium

azid

e;C

a~N3) 2

;@1

9465

-88-

4#W

ater

;H 2

O;

@773

2-18

-5#K

.To

rkar

,H

.K

irsch

ner,

and

G.

Ern

st,

Mon

atsh

.C

hem

.10

0,20

3–

12~1

969!

.

riabl

es:

Pre

pare

dB

y:

K:

253.

5–

348.

6J.

Ha

´ la

Exp

erim

enta

lDat

aS

olub

ility

ofC

a~N

3) 2

inw

ater

asa

func

tion

ofte

mpe

ratu

re

mpe

ratu

re(t

/°C

)C

a~N

3) 2

(g/1

00g

H 2O

)

Ca~

N3) 2

(100

w1

/m

ass

%)

Ca~

N3) 2

(m1

/mol

kg2

1)a

Tem

pera

ture

(t/°

C)

Ca~

N3) 2

(g/1

00g

H 2O

)C

a~N

3) 2

(100

w1

/mas

s%

)C

a~N

3) 2

(m1

/mol

kg2

1)a

219

.639

.78

28.4

63.

205

24.8

59.7

437

.40

4.81

3

216

.242

.32

29.7

43.

410

26.6

59.6

437

.36

4.80

5

212

.642

.77

29.9

63.

446

29.2

59.6

137

.35

4.80

3

29.

644

.19

30.6

53.

560

29.6

63.0

738

.29

5.08

1

21.

648

.50

32.8

83.

908

32.1

60.0

037

.50

4.83

4

20.

550

.00

33.3

34.

028

33.4

60.7

737

.80

4.89

6

1.7

49.8

033

.24

4.01

236

.863

.71

38.9

25.

133

3.0

50.9

033

.73

4.10

140

.167

.14

40.1

75.

409

8.5

51.0

033

.80

4.10

941

.567

.41

40.2

15.

431

13.4

52.9

234

.61

4.26

442

.368

.06

40.5

05.

484

16.4

54.5

135

.28

4.39

242

.971

.85

41.8

15.

789

20.0

55.4

435

.67

4.46

743

.766

.61

39.9

85.

367

22.3

57.3

536

.45

4.62

153

.966

.97

40.1

15.

396

23.2

60.8

237

.82

4.90

075

.575

.90

43.1

56.

115

alcu

late

dby

com

pile

r.

ditio

nali

nfor

mat

ion:

Exi

sten

cere

gion

sof

the

equi

libriu

mso

lidph

ases

wer

eob

tain

edby

the

auth

ors

byco

mbi

ning

isot

herm

alda

taw

ithez

ing

poin

tde

term

inat

ions

,as

follo

ws:

Ca

~N3) 2

,@1

9465

-88-

4#,ab

ove

41.5

°C;

Ca~N

3) 2•0.

5H2O

,@2

2119

-71-

7#,fr

om25

61

°Cto

.5°C

;C

a~N3) 2•1.

5H2O

,@2

2119

-72-

8#,fr

om06

2to

25°C

;an

dC

a~N3) 2•4

H2O

,@2

2119

-73-

9#,fr

om2

20.8

to0

°C.

Cry

ohyd

ratic

int

was

at2

20.8

60.

5°C

,an

dat

28.3

mas

s%

Ca

~N3) 2

.A

lso

repo

rted

wer

ehe

ats

ofso

lutio

n,va

por

pres

sure

s,an

dst

anda

rden

thal

pies

Ca~

N3) 2

and

itshy

drat

es.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Sys

tem

sw

ere

equi

libra

ted

for

2w

eeks

ina

ther

mos

tat.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

with

afil

terin

gro

d,w

eigh

ed,

and

the

calc

ium

cont

ent

dete

rmin

edtit

rimet

rical

lyw

ithE

DTA

solu

tion.

Sol

idph

ases

wer

eid

entifi

edby

x-ra

ydi

ffrac

tion

mea

sure

men

ts.

1

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 H.

Kris

chne

r,M

onat

sh.

Che

m.98

,21

34~1

968!

.


3.7.

Cal

cium

Azi

de

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Cal

cium

azid

e;C

a~N3) 2

;@1

9465

-88-

4#~2

!S

olve

nts~

wat

eran

det

hano

l!

T.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

–30

9~18

98!.

Varia

bles

:P

repa

red

By:

T/K

:27

3;28

8.2;

289

J.H

a´ l

a

Exp

erim

enta

lDat

aS

olub

ility

ofC

a~N

3) 2

inw

ater

oret

hano

lat

diffe

rent

tem

pera

ture

sa

Sol

vent

Tem

pera

ture

(t/°

C)

Ca~

N3) 2

(g/1

00g

solv

ent!

Ca~

N3) 2

(m1

/mol

kg2

1)b

Wat

er;

H 2O

;@7

732-

18-5#

038

.13.

07

15.2

45.0

3.63

Eth

anol

;C 2

H6O

;@6

4-17

-5#

160.

211

0.01

70

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

salt

was

kept

inco

ntac

tw

ithth

eso

lven

tfo

rse

vera

lwee

ksun

der

occa

sion

alst

irrin

gin

aro

omw

ithco

nsta

ntte

mpe

ratu

re.

Equ

ilibr

ium

tem

pera

ture

was

mea

sure

din

the

satu

rate

dso

lutio

nspr

ior

with

draw

alof

the

sam

ples

.Aw

eigh

edam

ount

ofth

esa

tura

ted

solu

tion

was

then

evap

orat

edin

apl

atin

umdi

sh,

and

drie

din

ade

sicc

ator

until

cons

tant

wei

ght

was

atta

ined

.

Ca~

N3) 2

was

prep

ared

bydi

ssol

ving

Ca

~OH

) 2in

8%aq

ueou

sso

lutio

nof

HN 3

,or

bybo

iling

fres

hly

prec

ipita

ted

Ca~O

H) 2

with

NH

4N

3so

lutio

n.E

xces

sC

a~OH

) 2w

asre

mov

edby

prec

ipita

tion

asC

aCO 3

with

CO

2ga

s,an

dth

esa

ltw

asob

tain

edby

evap

orat

ing

the

filtr

ate.

Afte

rre

crys

talli

zatio

nfr

omw

ater

the

prod

uctc

onta

ined

,in

mas

s%

,31.

97–

32.1

6C

aan

d67

.54

–67

.59

N.

Cal

cula

ted

for

Ca~N

3) 2

:32

.26

Ca,

67.7

4N

.T

heH

N 3so

lutio

nw

asob

tain

edac

cord

ing

toC

urtiu

s.1

Pur

ityof

wat

erno

tsp

ecifi

ed.A

bsol

ute

etha

nolw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 T.C

urtiu

s,B

er.2

4,33

41~1

891!

.

Co

~1!

~2!

Va T/

Te a C Ad

fre

41 po of


ofC

O2-f

ree

air,

until

solid

phas

epr

ecip

itate

d.T

hesy

stem

sw

ere

stirr

edfo

rse

vera

lday

ssi

nce

equi

libriu

mw

asat

tain

edve

rysl

owly

.Id

entic

alre

sults

wer

eob

tain

edby

stirr

ing

exce

ssso

lids

with

smal

lam

ount

ofw

ater

for

seve

rald

ays.

Sam

ples

,ap

prox

.0.

5g,

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

with

afil

terin

gro

d,an

dan

alyz

edfo

rpo

tass

ium

grav

imet

rical

lyw

ithN

aB~C

6H

5) 4

,fo

rca

lciu

mtit

rimet

rical

lyw

ithE

DTA

,an

dfo

raz

ide

byco

nduc

tom

etric

titra

tion

with

AgN

O 3so

lutio

n.W

etso

lidph

ases

wer

ech

arac

teriz

edby

x-ra

ydi

ffrac

tion.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

3.8.

Str

ontiu

mA

zide

3.8.

1.E

valu

atio

nof

the

Sr„N

3…2–

H2O

Sys

tem

mpo

nent

s:E

valu

ator

:

Str

ontiu

maz

ide;

Sr~N

3) 2

;@1

9465

-89-

5#W

ater

;H 2

O;

@773

2-18

-5#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,Ju

ne20

01.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

Sr~N

3) 2

inw

ater

has

been

repo

rted

intw

odo

cum

ents

.Cur

tius

and

Ris

som

1re

port

eda

sing

leso

lubi

lity

valu

eat

289.

1w

ithou

tsp

ecify

ing

the

com

posi

tion

ofth

eeq

uilib

rium

solid

phas

e,w

hile

Kirs

chne

re

ta

l.2ca

rrie

dou

tan

exte

nsiv

est

udy

ofth

elu

bilit

yof

Sr~N

3) 2

asa

func

tion

ofte

mpe

ratu

re.

The

yal

sono

ted

ast

rong

tend

ency

ofS

r~N

3) 2

hydr

ates

tocr

ysta

llize

asm

etas

tabl

eas

es.

Itap

pear

sth

atth

eso

lubi

lity

repo

rted

inR

ef.

1,i.e

.,m

15

2.67

mol

kg2

1,

alth

ough

inex

celle

ntag

reem

ent

with

the

valu

ere

port

edK

irsch

nere

ta

l.,2

refe

rsin

fact

toth

eso

lubi

lity

ofm

etas

tabl

eS

r~N

3) 2•4

H2O

,an

das

such

shou

ldno

tbe

used

asth

eeq

uilib

rium

lubi

lity

ofS

r~N3) 2

atth

iste

mpe

ratu

re.A

ccor

ding

toK

irsch

ner

et

al.,

2th

eeq

uilib

rium

solid

phas

eat

289.

1K

isS

r~N

3) 2•2

H2O

with

aner

pola

ted

solu

bilit

yof

m15

2.42

mol

kg2

1~e

valu

ator!

.T

heda

taof

Kirs

chne

ret

al.2

can

bere

com

men

ded

aste

ntat

ive

solu

bilit

ylu

es.

fere

nces

:

.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

~198

9!.

.K

irsch

ner,

K.

Tork

ar,

and

H.

E.

Rot

h,Z

.Ano

rg.A

llgem

.C

hem

.40

5,11

9~1

974!

.

2121JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Cal

cium

azid

e;C

a~N3) 2

;@1

9465

-88-

4#~2

!P

otas

sium

azid

e;K

N 3;

@207

62-6

0-1#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

H.

Kirs

chne

ran

dH

.E

.M

aier

,Z

.A

norg

.A

llgem

.C

hem

.46

0,21

7–

20~1

980!

.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

0–

36.2

100

w1

/mas

s%

:0

–37

.2

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eC

a~N3) 2

–K

N3–

H2O

syst

emat

25°C

KN

3

(100

w2

/mas

s%

)K

N3

(m2

/mol

kg2

1)a

Ca~

N3) 2

(100

w1

/mas

s)C

a~N

3) 2

(m1

/mol

kg2

1)a

Sol

idph

aseb

00

37.2

4.77

2A

5.2

1.05

434

.04.

505

A

6.0

1.13

028

.63.

522

B

8.5

1.54

723

.82.

833

B

10.8

1.94

620

.82.

450

B

13.1

2.37

418

.92.

239

B

18.5

3.39

814

.31.

714

B

21.0

3.85

911

.91.

428

B

26.6

4.96

07.

30.

899

B

31.7

5.15

34.

90.

622

B

32.2

5.27

04.

50.

572

B1C

33.0

5.40

53.

50.

444

C

36.2

5.99

10

0C

a Cal

cula

ted

byco

mpi

ler.

b A:

Ca~

N3) 2•1.

5H2O

,@2

2119

-71-

7#;B

:K

2C

a~N

3) 4•4

H2O

,@

#;C

:K

N3

,@2

0762

-60-

1#.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Bot

hsa

ltsw

ere

diss

olve

din

diffe

rent

mol

era

tios

inw

ater

acid

ified

with

HN 3,

and

the

solu

tion

was

slow

lyev

apor

ated

bypa

ssin

gth

roug

hit

ast

ream

Ca~

N3) 2

and

KN 3

wer

epr

epar

edby

pass

ing

ast

ream

ofw

etH

N3

gas

into

asu

spen

sion

ofC

aCO

3,

orin

toa

solu

tion

ofK

OH

,re

spec

tivel

y.A

naly

sis

ofth

epr

oduc

tsw

asno

tre

port

ed.

Co

~1!

~2!

K so ph in so int

va Re

1 T 2 H

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Str

ontiu

maz

ide;

Sr~N

3) 2

;@1

9465

-89-

5#W

ater

;H 2

O;

@773

2-18

-5#H

.K

irsch

ner,

K.

Tork

ar,

and

H.

E.

Rot

h,Z

.A

norg

.A

llgem

.C

hem

.405

,11

9–

28~1

974!

.

riabl

es:

Pre

pare

dB

y:

K:

263.

5–

338

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofS

r~N3) 2

inw

ater

asa

func

tion

ofte

mpe

ratu

re

mpe

ratu

re(t

/°C

)S

r~N3) 2

(100

w1

/mas

s%

)S

r~N3) 2

(m1

/mol

kg2

1)a

Sol

idph

aseb

Tem

pera

ture

(t/°

C)

Sr~N

3) 2

(100

w1

/mas

s%

)S

r~N3) 2

(m1

/mol

kg2

1)a

Sol

idph

aseb

29.

623

.91.

830

Ac2

2.0

25.5

1.94

4Cc

29.

024

.11.

850

Ac10

.028

.12.

277

C

27.

024

.91.

932

Ac15

.029

.22.

403

C

26.

025

.31.

973

Ac17

.029

.62.

449

C

25.

025

.62.

005

Ac20

.030

.22.

521

C

23.

026

.12.

057

Ac21

.030

.42.

545

C

29.

223

.21.

760

B23

.030

.82.

593

C

28.

023

.41.

780

B24

.031

.02.

617

C

26.

023

.91.

830

B26

.031

.52.

679

C

22.

024

.91.

932

B27

.031

.72.

704

C

21.

025

.41.

984

B30

.032

.52.

805

Cc

0.0

25.7

2.01

5B

31.0

32.7

2.83

1C

c

1.0

26.0

2.04

7B

15.5

31.2

2.64

2D

c

3.0

26.7

2.12

2B

19.0

31.5

2.67

9D

c

5.0

27.4

2.19

9Bc

20.0

31.5

2.67

9Dc

7.5

28.5

2.32

2Bc

22.0

31.6

2.69

1Dc

10.0

29.3

2.41

4Bc

24.0

31.6

2.69

1Dc

12.0

29.7

2.46

1Bc

25.0

31.7

2.70

4Dc

13.0

30.2

2.52

1Bc

30.0

32.0

2.74

1D

15.0

30.8

2.59

3Bc

40.0

32.2

2.76

7D

16.0

31.2

2.64

2Bc

50.0

32.1

2.75

4D

17.0

31.6

2.69

1Bc

65.0

32.2

2.76

7D

18.0

32.4

2.79

2Bc

19.0

33.2

2.89

5Bc

a Cal

cula

ted

byco

mpi

ler.

b A:S

r~N

3) 2•6

H2O

,@52

075-

71-5#

;the

hydr

ate

was

form

edea

sily

butw

asm

etas

tabl

esi

nce

the

tem

pera

ture

oftr

ansi

tion

from

hexa

hydr

ate

tote

trah

ydra

tew

asde

duce

dby

the

auth

ors

tobe

at2

79°C

,i.e

.,de

epbe

low

the

eute

ctic

poin

t;B

:S

r~N

3) 2•4

H2O

,@5

2214

-22-

9#,st

able

betw

een2

9.2

and

3°C

,m

etas

tabl

efr

om3

to19

°C;

C:

Sr

~N3) 2•2

H2O

,@5

2075

-72-

6#,st

able

from

3to

28°C

,m

etas

tabl

efr

om22

to3

°C,

and

from

28to

31°C

;D

:S

r~N

3) 2

;@1

9465

-89-

5#,st

able

abov

e28

°C,

met

asta

ble

from

15to

28°C

.c M

etas

tabl

e.

Add

ition

alin

form

atio

n:E

utec

ticpo

int

(ice

–S

r~N

3) 2•4

H2O

)w

asat

29.

2°C

and

23.2

mas

s%

Sr

~N3) 2

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Str

ontiu

maz

ide;

Sr~N

3) 2

;@1

9465

-89-

5#~2

!S

olve

nts

T.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

–30

9~18

98!.

Varia

bles

:P

repa

red

By:

T/K

:28

9J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofS

r~N3) 2

inw

ater

oret

hano

lat

16°Ca

Sol

vent

Sr~N

3) 2

(g/1

00g

solv

ent!

Sr~N

3) 2

(m1

/mol

kg2

1)b

Wat

er;

H 2O

;@7

732-

18-5#

45.8

32.

67

Eth

anol

;C 2

H6O

;@6

4-17

-5#

0.09

50.

005

53

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

salt

was

kept

inco

ntac

tw

ithth

eso

lven

tfo

rse

vera

lwee

ksun

der

occa

sion

alst

irrin

gin

aro

omw

ithco

nsta

ntte

mpe

ratu

re.

Equ

ilibr

ium

tem

pera

ture

was

mea

sure

din

the

satu

rate

dso

lutio

nspr

ior

with

draw

alof

the

sam

ples

.Aw

eigh

edam

ount

ofth

esa

tura

ted

solu

tion

was

then

evap

orat

edin

apl

atin

umdi

sh,

and

drie

din

ade

sicc

ator

until

cons

tant

wei

ght

was

atta

ined

.

Sr~N

3) 2

was

prep

ared

bydi

ssol

ving

Sr

~OH

) 2in

8%aq

ueou

sso

lutio

nof

HN 3

,or

bybo

iling

Sr~O

H) 2

with

NH

4N

3so

lutio

n.E

xces

sS

r~OH

) 2w

asre

mov

edby

prec

ipita

tion

asS

rCO

3w

ithC

O2

gas,

and

the

salt

was

obta

ined

byev

apor

atin

gth

efil

trat

e.A

fter

recr

ysta

lliza

tion

from

wat

erth

epr

oduc

tco

ntai

ned,

inm

ass

%,

50.8

5S

ran

d48

.55

–48

.64

N.

Cal

cula

ted

for

Sr

~N3) 2

:51

.02

Sr,

48.9

8N

.The

HN 3

solu

tion

was

obta

ined

acco

rdin

gto

Cur

tius.1

Pur

ityof

wat

erno

tsp

ecifi

ed.

Abs

olut

eet

hano

lw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 T.C

urtiu

s,B

er.2

4,33

41~1

891!

.

Co

~1!

~2!

Va T/

Te


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Str

ontiu

maz

ide;

Sr~N

3) 2

;@1

9465

-89-

5#P

otas

sium

azid

e;K

N 3;

@207

62-6

0-1#

Wat

er;

H 2O

;@7

732-

18-5#

W.P

aar

and

H.K

irsch

ner,

Z.A

norg

.Allg

em.C

hem

.47

9,21

2–

8~1

981!

.

riabl

es:

Pre

pare

dB

y:

K:

268

0w

2/m

ass

%:

0–

27.5

0w

1/m

ass

%:

0–

25.2

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eS

r~N3) 2

–K

N3–

H2O

syst

emat

25

°C

KN

3

00w

2/m

ass

%)

KN

3

(m2

/mol

kg2

1)a

Sr~N

3) 2

(100

w1

/mas

s)S

r~N3) 2

(m1

/mol

kg2

1)a

Sol

idph

aseb

00

25.2

1.96

2A

3.5

0.59

524

.01.

929

B

5.0

0.86

023

.41.

903

B1C

4.7

0.77

320

.41.

586

D

5.2

0.82

317

.01.

272

D

6.9

1.04

511

.80.

845

D

10.2

1.52

57.

40.

523

D

12.7

1.91

15.

40.

384

D

15.1

2.29

23.

70.

265

D

16.4

2.51

13.

10.

224

D1F

19.5

3.05

81.

90.

140

D1F

27.5

4.69

90.

20.

0151

D1F

27.2

4.60

50

0E

alcu

late

dby

com

pile

r.:S

r~N

3) 2•5

H2O

,@#;

B:S

r~N3) 2•4

H2O

,@52

214-

22-9#

;C:K

1.34

Sr 1

.67(

N3) 4

.69(

H2O

) 6.6

2;

D:s

tabl

em

ixed

crys

tals

with

the

com

posi

tion

aryi

ngfr

omK 2

.08S

r 1.3

0(N

3) 4

.69(

H2O

) 6.6

2to

that

ofth

eco

mpo

und

C;

E:

KN 3,

@207

62-6

0-1#;

F:

K2S

r~N3) 4•4

H2O

,@

#.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Bot

hsa

ltsw

ere

diss

olve

din

fere

ntm

ole

ratio

sin

wat

er,

the

solu

tions

wer

eac

idifi

edw

ithH

N3

gas

top

H6,

plac

edin

jack

eted

ther

mos

tate

dve

ssel

s,an

dis

othe

rmal

lyev

apor

ated

bypa

ssin

gth

roug

hth

ema

stre

amof

CO

2-f

ree

air,

until

solid

phas

espr

ecip

itate

d.T

hesy

stem

sw

ere

stirr

edfo

r6

days

tore

ach

equi

libriu

m.A

ppro

xim

atel

y1

gsa

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

with

draw

nw

itha

filte

ring

rod,

and

anal

yzed

for

pota

ssiu

mgr

avim

etric

ally

with

NaB

~C6H

5) 4

,fo

rst

ront

ium

titrim

etric

ally

with

ED

TA,

and

for

azid

eby

cond

ucto

met

rictit

ratio

nw

ithA

gNO 3so

lutio

n.S

olid

phas

esw

ere

char

acte

rized

byx-

ray

diffr

actio

nus

ing

alo

w-t

empe

ratu

rech

ambe

r.T

heco

mpo

sitio

nsof

mix

edso

lidso

lutio

nsan

dof

the

mix

edsa

ltw

ere

confi

rmed

bych

emic

alan

alys

is.

Sr~N

3) 2

and

KN 3

wer

epr

epar

edby

pass

ing

ast

ream

ofw

etH

N3

gas

into

asu

spen

sion

ofS

rCO

3,

orin

toa

solu

tion

ofK

OH

,re

spec

tivel

y.A

naly

sis

ofth

epr

oduc

tsw

asno

tre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

2323JIRI HALA


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Mix

ture

sof

wat

erw

ithex

cess

ofth

eco

rres

pond

ing

hydr

ate

ofth

esa

ltw

ere

equi

libra

ted

byst

irrin

gfo

rse

vera

lday

sin

ath

erm

osta

ted

vess

el.

Sol

idph

ases

wer

eid

entifi

edby

x-ra

ydi

ffrac

tion

usin

ga

low

-tem

pera

ture

diffr

acto

met

er.

The

syst

emsh

owed

ast

rong

tend

ency

tow

ards

the

form

atio

nof

supe

rsat

urat

edso

lutio

nsan

dm

etas

tabl

eso

lidph

ases

.T

hela

tter

wer

est

able

for

upto

seve

ralw

eeks

.W

hene

ver

doub

tsar

ose

asto

the

true

equi

libriu

mso

lidph

ase,

the

syst

emco

ntai

ning

both

hydr

ates

inqu

estio

nw

aseq

uilib

rate

dfo

rse

vera

lday

s,an

dth

eco

nclu

sion

was

draw

nfr

omth

ech

ange

ofth

eco

nten

tsof

the

hydr

ates

inth

eso

lidph

ase

afte

req

uilib

ratio

n.W

ater

cont

ent

ofth

ehy

drat

esw

asal

sove

rified

byus

ing

ther

mos

tate

dau

tore

cord

ing

scal

eson

whi

chth

ehy

drat

esw

ere

drie

dto

cons

tant

wei

ght

bypa

ssin

gov

erth

ema

stre

amof

gas

with

equi

libriu

mw

ater

pres

sure

corr

espo

ndin

gto

the

tem

pera

ture

used

.

Sr~N

3) 2

was

prep

ared

byre

actin

ga

solu

tion

ofS

r~O

H) 2

with

dilu

teH

N3

gas.

The

solid

salt

was

then

obta

ined

byei

ther

evap

orat

ion

ofby

prec

ipita

tion

with

acet

one.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

Va T/

10 10 (1 a C b A v Me

An

dif

J

ormpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bar

ium

azid

e;B

a~N3) 2

;@1

8810

-58-

7#S

olve

nts~

wat

eran

det

hano

l!

T.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

–30

9~18

98!.

riabl

es:

Pre

pare

dB

y:

K:

273

–29

0J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofB

a~N

3) 2

inw

ater

oret

hano

lat

diffe

rent

tem

pera

ture

sa

Sol

vent

Tem

pera

ture

(t/°

C)

Ba~

N3) 2

(g/1

00g

solv

ent!

Ba~

N3) 2

(m1

/mol

kg2

1)b

ater

;H 2

O;

@773

2-18

-5#0

12.5

0.56

5

10.5

16.2

0.73

2

1516

.70.

754

1717

.30.

782

hano

l;C 2

H6O

;@6

4-17

-5#

160.

0172

7.773

102

4

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

salt

was

kept

innt

act

with

the

solv

ent

for

seve

ralw

eeks

unde

roc

casi

onal

rrin

gin

aro

omw

ithco

nsta

ntte

mpe

ratu

re.

Equ

ilibr

ium

pera

ture

was

mea

sure

din

the

satu

rate

dso

lutio

nspr

ior

thdr

awal

ofth

esa

mpl

es.A

wei

ghed

amou

ntof

the

satu

rate

dlu

tion

was

then

evap

orat

edin

apl

atin

umdi

shan

ddr

ied

ina

sicc

ator

until

cons

tant

wei

ght

was

atta

ined

.

Ba~

N3) 2

was

prep

ared

bydi

ssol

ving

Ba

~OH

) 2in

8%aq

ueou

sso

lutio

nof

HN 3

,or

bybo

iling

Ba~

OH

) 2w

ithN

H4N

3so

lutio

n.E

xces

sB

a~OH

) 2w

asre

mov

edby

prec

ipita

tion

asB

aCO

3w

ithC

O2

gas,

and

the

salt

was

obta

ined

byev

apor

atin

gth

efil

trat

e.A

fter

recr

ysta

lliza

tion

from

wat

erth

epr

oduc

tco

ntai

ned,

inm

ass

%,

37.8

6–

38.3

2N

and

61.5

5–

62.0

3B

a.C

alcu

late

dfo

rB

a~N

3) 2

:38

.04

N,

61.9

6B

a.P

urity

ofw

ater

not

spec

ified

.A

bsol

ute

etha

nolw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.


3.9.

Bar

ium

Azi

de

3.9.

1.E

valu

atio

nof

the

Ba

„N

3…2–

H2O

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Bar

ium

azid

e;B

a~N3) 2

;@1

8810

-58-

7#~2

!W

ater

;H 2

O;

@773

2-18

-5#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,Ju

ne20

01.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

Ba~N

3) 2

inw

ater

has

been

repo

rted

intw

odo

cum

ents

.C

urtiu

san

dR

isso

m1

repo

rted

the

resu

ltsof

four

mea

sure

-m

ents

inth

ete

mpe

ratu

rera

nge

from

273.

1to

291.

1K

with

out

iden

tifyi

ngth

eso

lidph

ases

,w

hile

Tork

are

ta

l.2pe

rfor

med

solu

bilit

ym

easu

rem

ents

over

aw

ide

tem

pera

ture

rang

e,an

did

entifi

edtw

ohy

drat

esof

Ba

~N3) 2

,in

addi

tion

toth

ean

hydr

ous

salt.

The

data

inC

urtiu

san

dR

isso

m1ar

esy

stem

atic

ally

low

erby

2.5%

–4.

4%th

anth

ose

repo

rted

inTo

rkar

et

al.,

2th

ere

ason

ofw

hich

isno

tcl

ear

from

the

publ

ishe

din

form

atio

n.In

view

ofth

eex

iste

nce

ofB

a~N

3) 2

hydr

ates

,th

egr

avim

etric

dete

rmin

atio

nof

bariu

mas

BaS

O4

inth

esa

tura

ted

solu

tions

used

inTo

rkaret

al.2

seem

sto

bem

ore

relia

ble

than

wei

ghin

gth

ere

sidu

esob

tain

edby

evap

orat

ion

ofth

esa

tura

ted

solu

tions

beca

use

the

tem

pera

ture

ofev

apor

atio

nw

asno

tsp

ecifi

ed.

How

ever

,it

isno

tcl

ear

if,or

tow

hat

exte

nt,

this

coul

dac

coun

tf

the

diffe

renc

esin

the

solu

bilit

ies.

Itis

,th

eref

ore,

reco

mm

ende

dto

use

the

data

ofTo

rkar

et

al.2

aste

ntat

ive

solu

bilit

yda

ta.

Ref

eren

ces:

1 T.C

urtiu

san

dJ.

Ris

som

,J.

Pra

kt.

Che

m.

58,

261

~189

8!.

2 K.

Tork

ar,

H.

Kirs

chne

r,an

dK

.H

.R

adl,

Mon

atsh

.C

hem

.97

,31

3~1

966!

.

Co

~1!

~2!

Va T/ W Et

a S b C Me

An

co sti

tem

wi

so de


s:

pass

ing

ast

ream

ofdr

y,C

O 2-fr

eeni

trog

enga

sov

erth

eso

lutio

n.W

hen

suffi

cien

tam

ount

ofth

eso

lidph

ase

prec

ipita

ted,

nitr

ogen

gas

was

disc

onne

cted

,an

dth

em

ixtu

rew

asst

irred

for

seve

ralm

ore

hour

s.S

ampl

esof

the

satu

rate

dso

lutio

nsw

ere

then

with

draw

nw

itha

filte

ring

rod,

and

bariu

mw

asde

term

ined

grav

imet

rical

lyas

BaS

O4

ina

wei

ghed

sam

ple.

Sol

idph

ases

wer

eid

entifi

edby

x-ra

ydi

ffrac

tion

and

optic

alm

icro

scop

y.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

4.T

heS

olub

ility

ofC

yani

des

4.1.

Lith

ium

Cya

nide

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Lith

ium

cyan

ide;

LiC

N;@

2408

-36-

8#Te

trae

thyl

amm

oniu

mpe

rchl

orat

e;C

8H

20C

lNO

4;

567-

83-1#

4-m

ethy

l-1,3

-dio

xala

n-2-

one;

prop

ylen

eca

rbon

ate;

08-3

2-7#

T.N

akam

ura

and

K.

Izut

su,A

nal.

Sci

.7,16

77–

9~19

91!.

riabl

es:

Pre

pare

dB

y:

K:

298

/mol

dm2

3:

0.01

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

prod

uct

ofLi

CN

inpr

opyl

ene

carb

onat

eco

ntai

ning

0.01

mol

dm2

3(C

2H

5) 4

NC

lO4

was

dete

rmin

edasK

sp5

@Li1

#

CN

2#5

102

9.5

mol

2dm

26.

Add

ition

alin

form

atio

n:T

hepr

oced

ure

for

anal

yzin

gex

perim

enta

lre

sults

toob

tain

the

solu

bilit

ypr

oduc

tw

asno

tre

port

ed;

itw

assc

ribed

byth

eau

thor

sin

Nak

amur

ae

ta

l.1

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eso

lubi

lity

prod

uct

ofLi

CN

was

obta

ined

bypo

tent

iom

etric

atio

nof

aso

lutio

nof

(C2H

5) 4

NC

Nw

itha

solu

tion

oflO

4,

both

inpr

opyl

ene

carb

onat

e.A

nio

n-se

lect

ive

ctro

de,

prep

ared

byco

atin

ga

plat

inum

disk

with

aly

acry

lam

ide

mem

bran

eco

uple

dto

the

raam

inop

htha

locy

anin

eC

oco

mpl

ex,

acco

rdin

gto

Nak

amur

aa

l.1w

asus

ed.

(C2H

5) 4

NC

Nw

asa

prod

ucto

fFlu

kaC

o.Lt

d.S

ourc

ean

dpu

rity

ofot

her

chem

ical

sw

ere

desc

ribed

inN

akam

ura

et

al.1

–4

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

typr

oduc

t:pr

ecis

ion

not

repo

rted

.

Ref

eren

ces:

1 T.N

akam

ura,

Y.Ts

ukam

oto,

and

K.I

zuts

u,B

unse

kiK

agak

u39

,68

9~1

990!

.2 T.

Nak

amur

a,H

.H

iguc

hi,

and

K.

Izut

su,

Bul

lC

hem

.S

oc.

Jpn

61,

1988

~198

8!.

3 T.N

akam

ura,

M.K

omai

,S.H

oson

o,an

dK

.Izu

tsu,

Ana

l.C

him

.A

cta

238,

351

~199

0!.

4 T.N

akam

ura,

Y.N

akam

ura,

T.K

ojim

a,an

dK

.Iz

utsu

,B

ull

Che

m.

Soc

.Jp

n.63,

2615

~199

0!.

2525JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Bar

ium

azid

e;B

a~N3) 2

;@1

8810

-58-

7#~2

!W

ater

;H 2

O;

@773

2-18

-5#K

.To

rkar

,H

.K

irsch

ner,

and

K.

H.

Rad

l,M

onat

sh.

Che

m.

97,

313

–21

~196

6!.

Varia

bles

:P

repa

red

By:

T/K

:27

3–

358

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofB

a~N

3) 2

inw

ater

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

Ba~

N3) 2

(g/1

00g

wat

er)

Ba~

N3) 2

(100

w1

/mas

s%

)

Ba~

N3) 2

(m1

/m

olkg

21)b

Tem

pera

ture

(t/°

C)

Ba~

N3) 2

(g/1

00g

wat

er!

Ba~

N3) 2

(100

w1

/m

ass

%)

Ba~

N3) 2

(m1

/mol

kg2

1)b

013

.00

11.5

00.

5873

34.5

22.9

218

.66

1.03

5

1.9

13.2

011

.67

0.59

6339

.524

.85

19.9

01.

123

2.0

13.3

811

.75

0.60

4445

.026

.90

21.2

01.

215

4.5

13.6

712

.03

0.61

7549

.828

.50

22.2

01.

287

6.0

14.0

412

.28

0.63

4252

.129

.42

22.7

31.

329

11.0

16.7

814

.38

0.75

8053

.029

.90

23.0

01.

351

13.6

17.3

514

.80

0.78

3855

.030

.18

23.2

01.

363

15.7

17.6

214

.98

0.79

6062

.531

.70

24.0

81.

432

17.7

17.7

615

.09

0.80

2370

.032

.90

24.7

51.

486

20.0

18.1

315

.36

0.81

9075

.834

.02

25.3

91.

537

25.0

19.3

516

.20

0.87

4185

.035

.90

26.4

21.

622

28.0

20.7

017

.15

0.93

51

a The

auth

ors

com

bine

dth

eso

lubi

lity

data

with

free

zing

poin

tmea

sure

men

tsto

obta

inth

efo

llow

ing

exis

tenc

ere

gion

sof

the

solid

phas

eB

a~N

3) 2•1.

5H2O

,@2

2208

-76-

0#,be

low

116

1°C

;B

a~N

3) 2•H

2O

,@1

2047

-22-

2#,fr

om11

61

°Cto

52.5

°C;

Ba~N

3) 2

,@1

8810

-58-

7#,ab

ove

52.2

°C.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:T

hecr

yohy

drat

icpo

int

was

at22.

6°C

and

11.2

mas

s%

Ba

~N3) 2

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

near

lysa

tura

ted

solu

tion

ofth

esa

ltw

asis

othe

rmal

lyev

apor

ated

ina

ther

mos

tate

dfla

skby

No

deta

ilsre

port

ed.

Co

~1!

~2!

@2 ~3!

@1 Va T/

c 2 3@

de Me

Th

titr

LiC

ele

po tet

et

J

valu

esw

ere

repo

rted

for

the

solu

bilit

yof

NaC

Nin

wat

er,

i.e.,

36.1

6m

ass

%at

298.

1K

,an

d42

.50

mas

s%

at31

3.1

K.

Sin

ceno

deta

ilsw

ere

repo

rted

asto

the

met

hod

used

,th

ese

data

have

not

been

cons

ider

edfo

rco

mpi

latio

nor

eval

uatio

n.

Ref

eren

ces:

1 O.

I.F

rost

,Z

h.O

bsh.

Khi

m.6,

1910

~193

6!.

2 K.

Yaj

ima

and

S.

Oda

naka

,K

ogyo

Kag

aku

Zas

shi

71,

460

~196

8!.

3 G.

D.

Oliv

eran

dS

.E

.J.

John

son,

J.A

m.

Che

m.

Soc

.76

,47

21~1

954!

.4 V.

A.

Kire

evan

dL.

I.Va

gran

skay

a,Z

h.O

bsh.

Khi

m.

5,96

3~1

935!

.5 G

.I.

Voin

ilovi

ch,

L.K

.Akh

rap,

and

L.S

.M

ai,

Zh.

Prik

l.K

him

.8,58

9~1

935!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

Wat

er;

H 2O

;@7

732-

18-5#

O.

I.F

rost

,Z

h.O

bsh.

Khi

m.6,

1910

–2~

1936

!.

riabl

es:

Pre

pare

dB

y:

K:

245

–30

8J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aCN

inw

ater

asa

func

tion

ofte

mpe

ratu

re

mpe

ratu

re(t

/°C

)N

aCN

(100

w1

/mas

s%

)N

aCN

(m1

/mol

kg2

1)a

Tem

pera

ture

(t/°

C)

NaC

N(1

00w

1/m

ass

%)

NaC

N(m

1/m

olkg

21)a

24.

05.

561.

203

218

.125

.90

7.13

2

29.

211

.03

2.53

02

14.8

26.5

7.35

7

212

.513

.90

3.29

42

7.6

27.9

7.89

6

213

.814

.56

3.47

72

4.0

28.9

8.29

4

215

.216

.01

3.90

010

.032

.59.

825

219

.519

.11

4.82

112

.633

.310

.19

223

.421

.23

5.50

015

.034

.210

.61

223

.821

.90

5.72

220

.437

.02

11.9

9

224

.222

.05.

755

25.0c

39.0

13.0

5

225

.422

.65.

958

25.4

39.1

13.1

0

226

.423

.46

6.25

429

.541

.56

14.5

1

227

.8b

23.7

56.

356

34.0

44.8

616

.57

221

.424

.84

6.74

435

.0c45

.016

.70

alcu

late

dby

com

pile

r.ut

ectic

poin

t.T

heau

thor

cons

ider

edN

aCN

•2

H2O

,@2

5178

-25-

0#,to

beth

eeq

uilib

rium

solid

phas

eab

ove

the

tem

pera

ture

ofth

eut

ectic

poin

t.bt

aine

dby

isot

herm

alm

etho

d.

ditio

nali

nfor

mat

ion:

The

poin

tof

tran

sitio

nfr

omN

aCN•2

H2O

toN

aCN

was

repo

rted

tobe

at34

.5°C

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

poly

ther

mal

met

hod

was

used

.S

olut

ions

ofkn

own

mpo

sitio

nw

ere

plac

edin

ate

sttu

beeq

uipp

edw

itha

plat

inum

stirr

eran

da

ther

mom

eter

grad

uate

dto

0.2

°C.

The

syst

emw

asco

oled

ina

Dew

arfla

skin

liqui

dai

run

tilfir

stcr

ysta

lsap

pear

ed.

The

nth

etu

bew

asw

arm

edup

slow

ly,

and

the

tem

pera

ture

ofdi

sapp

eara

nce

ofla

stcr

ysta

lsw

asno

ted.

Toel

imin

ate

erro

rsca

used

byhy

drol

ysis

ofN

aCN

,ea

chm

easu

rem

ent

was

carr

ied

out

with

afr

eshl

ypr

epar

edso

lutio

nof

the

desi

red

conc

entr

atio

n.T

heN

aCN

cont

ent

inth

eso

lutio

nsw

asde

term

ined

bytit

ratio

nw

ithst

anda

rd0.

1m

oldm

23

AgN

O3

solu

tion

agai

nst

KI

asin

dica

tor.

Sol

idph

ases

wer

eno

tin

vest

igat

ed.

Det

ails

ofth

etw

om

easu

rem

ents

perf

orm

edby

isot

herm

alpr

oced

ure

wer

eno

tre

port

ed.

NaC

N,s

ourc

eun

spec

ified

,was

recr

ysta

llize

das

dihy

drat

eun

der

redu

ced

pres

sure

,and

drie

dov

erH

2S

O4

.T

hepr

oduc

tcon

tain

edle

ssth

an0.

5%N

a 2CO

3.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n60.

2K

~the

diffe

renc

ebe

twee

nte

mpe

ratu

res

ofap

pear

ance

and

disa

ppea

ranc

eof

crys

tals

was

repo

rted

tobe

with

in0.

4°C!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.


4.2.

Sod

ium

Cya

nide

4.2.

1.E

valu

atio

nof

the

NaC

N–

H2O

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

Feb

ruar

y20

01.

Crit

ical

Eva

luat

ion

Dat

aon

the

solu

bilit

yof

NaC

Nin

wat

erar

eco

ntai

ned

inse

vera

ldo

cum

ents

.F

rost

1re

port

edso

lubi

lity

inm

ass

%,

obta

ined

inth

ebi

nary

syst

emN

aCN

–H 2O

,fu

rthe

rda

ta,a

lso

inm

ass

%,h

ave

been

repo

rted

inth

est

udie

sof

tern

ary

syst

ems

NaC

N–

NaC

l–H

2O

~Yaj

ima

and

Oda

naka2 !

and

NaC

N–

NaO

H–

H 2O~O

liver

and

John

son3 !.

The

follo

win

gta

ble

sum

mar

izes

data

from

thes

eth

ree

docu

men

tsas

obta

ined

inth

ete

mpe

ratu

rera

nge

of28

8–

308

K.

Tem

pera

ture

(T/K

)N

aCN

(100

w1

/mas

s%

)N

aCN

(m1

/mol

kg2

1)

Met

hod

Tem

pera

ture

erro

r(T

/K)

Ref

eren

ce

288.

134

.210

.61

Pol

ythe

rmal

60.

21

293.

537

.02

11.9

9P

olyt

herm

al6

0.2

1

294.

137

.14

12.0

6Is

othe

rmal

61

2

298.

139

.013

.05

Isot

herm

alno

tre

port

ed1

298.

138

.812

.93

Isot

herm

al6

0.05

3

298.

539

.113

.10

Pol

ythe

rmal

60.

21

302.

541

.56

14.5

1P

olyt

herm

al6

0.2

1

307.

144

.82

16.5

7P

olyt

herm

al6

0.2

1

308.

145

.016

.70

Isot

herm

alno

tre

port

ed1

308.

145

.016

.70

Isot

herm

al6

0.05

3

The

data

from

Fro

st1an

dO

liver

and

John

son

3ag

ree

inth

atth

eso

lubi

lity

ofN

aCN

inw

ater

incr

ease

sw

ithte

mpe

ratu

reup

toth

epo

int

oftr

ansi

tion

ofN

aCN•

2H

2O

toN

aCN

at34

.5°C

,1an

dth

atfu

rthe

ron

the

solu

bilit

yof

anhy

drou

sN

aCN

varie

sve

rylit

tlew

ithte

mpe

ratu

re.

Of

the

data

inth

eta

ble,

thos

eat

298.

1an

d30

8.1

Kfr

omF

rost

1an

dO

liver

and

John

son

3ca

nbe

com

pare

d,an

dve

rygo

odag

reem

ent

isob

serv

ed.

The

eval

uato

rre

com

men

dsth

ese

data

,re

calc

ulat

edto

mol

kg2

1 ,be

used

aste

ntat

ive

valu

es,

i.e.,

m15

13.0

60.

1m

olkg

21

at29

8.1

K,

and

16.76

0.1

mol

kg2

1at

308.

1K

.In

the

tem

pera

ture

rang

eof

288

–30

8K

,th

eso

lubi

lity

ofN

aCN

inw

ater

asa

func

tion

ofte

mpe

ratu

reco

uld

befit

ted

toa

third

orde

rpo

lyno

mia

l

m15

268

58.4

3170

.588

~T/K

!20.

2425

48~T

/K!2

10.

2787

0310

23

~T/K

!3,

whe

rem

1is

the

solu

bilit

yof

NaC

Nin

mol

kg21 ,

and

Tis

tem

pera

ture

inK

elvi

n.K

ireev

and

Vagr

ansk

aya

4re

port

edth

eso

lubi

lity

ofN

aCN

inw

ater

ingr

ams

per

dm3 .S

ince

dens

ities

ofth

esa

tura

ted

solu

tions

wer

eno

tre

port

ed,

com

paris

onof

thei

rda

taw

ithth

ose

ofF

rost1

and

Oliv

eran

dJo

hnso

n3

isno

tpos

sibl

e.In

apa

per

devo

ted

toth

em

easu

rem

ento

fvap

orpr

essu

reov

erN

aCN

–H

2O

solu

tions

,5tw

o

Co

~1!

~2!

Va T/

Te a C b E e c O Ad

Me

A co


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

cyan

ide;@

143-

33-9#

Am

mon

ia;

NH 3

;@7

664-

41-7#

B.

B.

Vasi

liev,

J.L.

Etti

nger

,an

dM

.P.

Gol

ovko

v,Z

.A

norg

.A

llgem

.C

hem

.219

,34

1–

7~1

934!

.

riabl

es:

Pre

pare

dB

y:

K:

283

–32

3J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aCN

inliq

uid

amm

onia

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

tureb

~°C

!N

aCN

(g/k

gN

H3)

NaC

N(m

1/m

olkg

21)c

1040

3.0

8.22

3

2049

4.0

10.0

8

3058

5.0

11.9

4

4067

6.0

13.7

9

5076

7.0

15.6

5

quili

briu

mso

lidph

ase

was

NaC

N,@143

-33-

9#,in

allm

easu

rem

ents

.Am

mon

iate

sof

NaC

Nw

ere

repo

rted

tobe

stab

lebe

low

240

°C.

reez

ing

poin

tte

mpe

ratu

re.

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lyth

erm

alm

etho

dsw

ere

used

.T

heap

para

tus

was

desc

ribed

Akh

umov

and

Vasi

liev,1

and

was

kept

inan

air

ther

mos

tat.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.

I.A

khum

ovan

dB

.B

.Va

silie

v,Z

h.O

bsh.

Khi

m.2,

271

~193

2!.

2727JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

~2!

Sul

fur

diox

ide;

SO 2

;@7

446-

09-5#

G.

Jand

eran

dW

.R

uppo

lt,Z

.P

hys.

Che

m.

179,

43–

50~1

937!

.

Varia

bles

:P

repa

red

By:

T/K

:27

3J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aCN

inliq

uid

sulfu

rdi

oxid

ew

asre

port

edto

be0.

018

gsa

ltin

100

gso

lven

tat0

°C.F

rom

this

valu

eth

eco

mpi

ler

calc

ulat

edm

1/m

olkg

215

0.00

367

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

bout

10g

SO

2,

care

fully

drie

d,w

aseq

uilib

rate

dw

ithex

cess

solid

at0

°Cin

wat

er-ic

eba

thin

ath

ree-

com

part

men

tgl

ass

vess

elin

whi

cheq

uilib

ratin

gan

dsa

mpl

ing

com

part

men

tsw

ere

sepa

rate

dby

aco

mpa

rtm

ent

cont

aini

nggl

ass/

woo

lfilte

r.E

quili

brat

ion

was

perf

orm

edfo

run

spec

ified

,pr

olon

ged

perio

dof

time

unde

rfr

eque

ntsh

akin

g.A

fter

equi

libriu

mha

dbe

enat

tain

ed,

the

vess

elw

astu

rned

upsi

dedo

wn,

and

the

satu

rate

dso

lutio

nw

asfil

tere

din

toth

eem

pty

sam

plin

gco

mpa

rtm

ent,

whi

chw

assu

bseq

uent

lyco

oled

and

seal

edof

f.A

fter

wei

ghin

gth

eco

mpa

rtm

ent

with

the

sam

ple,

SO 2

was

allo

wed

toev

apor

ate,

the

resi

due

was

wei

ghed

,di

ssol

ved

inw

ater

,an

dth

eco

nten

tof

the

salt

was

dete

rmin

ed.

Met

hod

ofan

alys

isw

asno

tsp

ecifi

ed.

NaC

N,

sour

ceno

tsp

ecifi

ed,

was

care

fully

drie

dbe

fore

use.

Com

mer

cial

lyav

aila

ble

SO 2

was

purifi

edby

pass

ing

itth

roug

hco

ncen

trat

edH 2S

O4

and

over

asbe

stos

woo

l,an

ddr

ied

byus

ing

P 2O

5.

Spe

cific

cond

uctiv

ityof

the

prod

uct

was

repo

rted

as4.

53

102

7S

/cm

~Jan

der

and

Wic

kert1 !.

Ref

eren

ces:

1 G.

Jand

eran

dK

.W

icke

rt,

Z.

Phy

s.C

hem

.17

8,57

~193

6!.

Co

~1!

~2!

Va T/

a E b F c C Me

Po

in

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

Met

hano

l;C

H 4O

;@6

7-56

-1#

H.

Hen

stoc

k,J.

Che

m.

Soc

.13

40–

3~1

934!

.

riabl

es:

Pre

pare

dB

y:

K:

287;

340

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aCN

inm

etha

nola

ttw

ote

mpe

ratu

res

a

mpe

ratu

re~°

C!

NaC

N(g

/100

gso

lven

t!bN

aCN

(m1

/mol

kg2

1)c

156.

441.

314

67.4

d4.

100.

837

olid

phas

esw

ere

not

inve

stig

ated

.ve

rage

ofth

ree

dete

rmin

atio

ns,

indi

vidu

alva

lues

not

repo

rted

.al

cula

ted

byco

mpi

ler.

oilin

gpo

int

ofth

esa

tura

ted

solu

tion.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Mea

sure

men

tsat

15°C

wer

err

ied

out

inan

appa

ratu

sde

scrib

edin

Bro

¨ nst

edan

dte

rsen

,1im

mer

sed

ina

ther

mos

tat.

At

boili

ngpo

int,

the

tura

ted

solu

tion

was

prep

ared

unde

rre

flux.

Por

tions

ofth

etu

rate

dso

lutio

nsw

ere

wei

ghed

at15

°Cin

agr

adua

ted

ette

,2us

ing

ath

imbl

eto

sepa

rate

the

solid

.W

here

stal

lizat

ion

occu

rred

onco

olin

g,th

epi

pette

was

rehe

ated

tilth

eso

liddi

ssol

ved,

the

cont

ents

bein

gdi

scha

rged

into

aig

hing

bottl

e,th

epi

pette

was

hed

with

boili

ngso

lven

t,an

dre

sidu

ew

eigh

edaf

ter

evap

orat

ion

ofth

eso

lven

tan

dyi

ngat

50°C

for

2h.

NaC

N,s

ourc

eno

tspe

cifie

d,w

astw

ice

recr

ysta

llize

dan

ddr

ied

4h

at50

°C.

Met

hano

lw

aspu

rified

first

from

acet

one

and

alde

hyde

bytr

eatm

ent

with

iodi

ne.

3It

was

then

dist

illed

with

conc

entr

ated

H 2SO

4to

rem

ove

basi

csu

bsta

nces

,th

enfr

omca

ustic

soda

tore

mov

eac

idic

subs

tanc

es,

and

final

lydi

still

edov

erso

dium

met

al.

The

prod

uct

boile

dat

66°C

at75

8m

mH

gpr

essu

re.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 J.N

.B

rons

ted

and

A.

Pet

erse

n,J.

Am

.C

hem

.S

oc.

43,

2265

~192

1!.

2 F.D

.C

hatta

way

and

W.

J.La

mbe

rt,

J.C

hem

.S

oc.

107,

1766

~191

5!.

3 R.

C.

Men

zies

,J.

Che

m.

Soc

.12

1,27

90~1

922!

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

~2!

Sol

vent

sM

.R

.T

hom

pson

,J.

Res

.N

atl.

Bur

.S

td.

6,10

51–

9~19

31!.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aCN

inm

etha

nola

ndet

hano

lat

25°Ca

Sol

vent

NaC

N~g

dm2

3so

lven

t!N

aCN

(m1

/mol

kg2

1)

Met

hano

l;C

H 3O

H;

@67-

56-1

#78

.02.

02b

Eth

anol

;C 2

H6O

;@6

4-17

-5#

9.7

0.25

2c

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler

usin

gde

nsity

ofm

etha

nolo

f0.

7865

gcm

23

at25

°C.1

c Cal

cula

ted

byco

mpi

ler

usin

gde

nsity

ofet

hano

lof

0.78

52g

cm2

3at

25°C

.1

Add

ition

alin

form

atio

n:T

heso

lubi

lity

ofN

aCN

at25

°Cin

95%

etha

nol

~v/v

;5%

wat

er!w

asre

port

edto

be19

.2g

salt

in1

dm23

solv

ent.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

tech

niqu

eus

edan

deq

uilib

rium

time

appl

ied

wer

eno

tre

port

ed.

The

cyan

ide

cont

ent

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

am

odifi

edLi

ebig

’sm

etho

dof

titra

tion

agai

nst

AgN

O3

solu

tion

inth

epr

esen

ceof

KI

and

NaO

H.

NaC

Nin

99.1

3%pu

rity

was

prep

ared

byre

actin

ga

solu

tion

ofso

dium

etho

xide

inab

solu

teet

hano

lwith

exce

ssof

liqui

dH

CN

.A

bsol

ute

met

hano

land

etha

nolw

ere

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

Alth

ough

the

met

hod

ofC

N2de

term

inat

ion

was

repo

rted

tobe

accu

rate

with

in60.

2%–

0.3%

,th

eso

lubi

lity

valu

esw

ere

repo

rted

asap

prox

imat

e.N

ore

ason

for

this

was

give

n.

Ref

eren

ces:

1 Ha

nd

bo

ok

of

Ch

em

istr

ya

nd

Ph

ysic

s,

38th

ed.~

Che

mic

alR

ubbe

r,C

leve

land

,O

H,

1956!.

Co

~1!

~2!

Va T/ Te a S b A c C d B Me

An

ca Pe

sa sa pip

cry

un we

the

dr


4.2.

2.E

valu

atio

nof

the

NaC

N–

NaO

H–

H2O

Sys

tem

mpo

nent

s:E

valu

ator

:

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

Sod

ium

hydr

oxid

e;N

aOH

;@131

0-73

-2#W

ater

;H 2

O;

@773

2-18

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

Mar

ch20

01.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

NaC

Nin

solu

tions

ofso

dium

hydr

oxid

eha

sbe

enre

port

edin

two

docu

men

ts.

Kire

evan

dVa

gran

skay

a1

repo

rted

irda

tain

gram

spe

rdm3

at27

3,29

8,an

d31

3K

,w

hile

Oliv

eran

dJo

hnso

n2

repo

rted

the

solu

bilit

ies

inm

ass

%at

298,

308,

and

328

Thu

s,co

mpa

rison

has

been

mad

epo

ssib

leon

lyfo

rfo

urso

lubi

lity

valu

esat

298

K,

for

whi

chK

ireev

and

Vagr

ansk

aya

1re

port

edns

ities

ofth

esa

tura

ted

solu

tions

.C

ompa

red

with

the

resp

ectiv

eda

taof

Oliv

eran

dJo

hnso

n,2

the

valu

eof

m15

15.3

6m

olkg

21,

calc

ulat

edby

the

eval

uato

rfr

omth

eda

taof

Kire

evan

dVa

gran

skay

a1

~see

the

com

pila

tion!,

isob

viou

sly

too

high

,whi

leth

eth

ree

othe

rlu

esar

eco

nsid

erab

lylo

wer

.In

addi

tion,

the

data

ofK

ireev

and

Vagr

ansk

aya

1se

emto

bele

ssac

cura

tesi

nce

the

auth

ors

roun

ded

thei

rsu

ltsto

tens

ofgr

ams

per

dm3 ,du

eto

unsp

ecifi

eder

rors

inan

alys

is.

The

refo

re,

the

eval

uato

rsu

gges

tsth

eda

taof

Oliv

eran

dJo

hnso

n2

give

npr

efer

ence

.

fere

nces

:

.A.

Kire

evan

dL.

I.Va

gran

skay

a,Z

h.O

bsh.

Khi

m.

5,96

3~1

935!

.

.D

.O

liver

and

S.

E.

J.Jo

hnso

n,J.

Am

.C

hem

.S

oc.

76,

4721

~195

4!.

2929JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

~2!

2-fu

ranc

arbo

xald

ehyd

e~fur

fura

l!;C

5H

4O

2;

@98-

01-1

#F.

Trim

ble,

Ind.

Eng

.C

hem

.,In

d.E

d.33,

660

–2

~194

1!.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aCN

isre

port

edto

be0.

02m

ass

%at

25°C

.F

rom

this

valu

eth

eco

mpi

ler

calc

ulat

edm

15

0.00

41m

olkg

21.

The

com

posi

tion

ofth

eso

lidph

ase

was

not

inve

stig

ated

. Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

solid

was

agita

ted

with

furf

ural

for

24h

ina

cons

tant

tem

pera

ture

bath

,w

hich

was

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

The

mix

ture

was

filte

red,

and

the

NaC

Nco

nten

tin

the

satu

rate

dso

lutio

nw

asde

term

ined

grav

imet

rical

lyas

Na

2S

O4

.To

this

aim

,10

0m

Lw

ater

was

adde

dto

aw

eigh

edpo

rtio

n~a

bout

40g!

ofth

esa

tura

ted

solu

tion,

and

the

mix

ture

was

evap

orat

edun

tilth

eto

talv

olum

ew

asre

duce

dto

abou

t10

mL.

The

solu

tion

was

tran

sfer

red

toa

wei

ghed

cruc

ible

,an

dev

apor

atio

nco

ntin

ued

todr

ynes

s.T

here

sidu

ew

asm

oist

ened

with

conc

entr

ated

H2S

O4

,an

dig

nite

dto

abou

t70

0°C

.

NaC

Nw

asa

C.P

.pr

oduc

t.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

the

K.

de re va re be Re

1 V 2 G

J

400

054

0c11

.02

100.

2553

010

.81

200.

5052

510

.71

350.

875

505

10.3

090

2.25

460

9.39

110

2.75

445

9.08

164

4.10

400

8.16

235

5.88

330

6.73

260

6.50

325

6.63

290

7.25

305

6.22

340

8.50

280

5.71

370

9.25

255

5.20

700

055

5c,d

11.3

215

0.37

554

011

.02

100

00

560c,

d11

.47

100.

2555

011

.22

a Equ

ilibr

ium

solid

phas

esw

ere

NaC

N•2

H2O

,@2

5178

-25-

0#at

20°C

and

belo

w,

and

NaC

N,@143

-33-

9#,at

25°C

and

abov

e.b C

alcu

late

dby

com

pile

r.c S

olub

ility

ofN

aCN

inw

ater

.O

btai

ned

byth

eau

thor

sby

extr

apol

atin

gto

zero

NaO

Hco

ncen

trat

ion

ofN

aCN

solu

bilit

yin

NaO

Hco

ntai

ning

solu

tions

.T

heau

thor

sus

edth

isap

proa

chin

orde

rto

avoi

dth

ein

terf

erin

gin

fluen

ceof

NaC

Nhy

drol

ysis

inw

ater

.d T

heen

tire

serie

sof

mea

sure

men

tsof

NaC

Nso

lubi

lity

asa

func

tion

ofN

aOH

conc

entr

atio

nw

asno

tre

port

ed.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

tura

ted

solu

tions

wer

epr

epar

edby

slow

isot

herm

alap

orat

ion

ofN

aCN

/NaO

Hso

lutio

nsin

ast

ream

ofdr

yai

r,ed

from

CO 2

,in

ath

erm

osta

ted

bath

unde

rre

duce

des

sure

.W

hen

the

solid

phas

eap

pear

ed,

itw

asfil

tere

dou

gha

glas

ssi

nter

inth

esa

me

ther

mos

tat.

The

satu

rate

dlu

tions

wer

ean

alyz

edfo

rth

eN

aCN

and

NaO

Hco

nten

tim

etric

ally

,us

ing

the

Den

iges

’met

hod,

and

stan

dard

acid

lutio

n,re

spec

tivel

y.T

heso

lidph

ases

wer

ean

alyz

edfo

rth

eC

Nco

nten

tby

the

Den

iges

’met

hod.

NaC

Nw

aspr

epar

edby

addi

ngex

cess

anhy

drou

sH

CN

toa

4%so

lutio

nof

NaO

Hin

abso

lute

etha

nol.

1T

hesa

ltpr

ecip

itate

ddu

eto

itslo

wso

lubi

lity

inet

hano

l.It

was

was

hed

with

etha

nol

and

drie

din

vacu

umov

erP 2O

5.

The

entir

epr

oced

ure

was

carr

ied

out

inan

atm

osph

ere

ofC

O 2-fr

eeai

r.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

The

auth

ors

roun

ded

mos

tof

the

resu

ltsto

tens

ofgr

ams

per

dm3 ,d

ueto

erro

rsin

anal

yses

.The

natu

reof

the

erro

rsw

asno

tsp

ecifi

ed.

Ref

eren

ces:

1 E.W

.Goe

rsne

yan

dM

.S.S

herm

an,J

.Am

.Che

m.S

oc.

48,6

97~1

926!

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

~2!

Sod

ium

hydr

oxid

e;N

aOH

;@131

0-73

-2#~3

!W

ater

;H 2

O;

@773

2-18

-5#

V.A

.K

ireev

and

L.I.

Vagr

ansk

aya,

Zh.

Obs

h.K

him

.5,

963

–6

~193

5!.

Varia

bles

:P

repa

red

By:

T/K

:27

3–

373

Con

cent

ratio

nof

NaO

H~in

gdm

23 !

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aCN

inaq

ueou

sso

lutio

nsof

NaO

Hat

0–

100

°Ca

Tem

pera

ture

~°C

!N

aOH

~gdm

23 !

NaO

H(c

2/m

oldm

23)b

NaC

N~g

dm2

3 !N

aCN

(c1

/mol

dm2

3)b

010

0.25

370

7.55

401.

0035

07.

1440

1.00

347

7.10

140

3.50

300

6.21

160

4.00

280

5.71

50

038

0c,d

7.75

100.

2537

07.

5510

00

395c,

d8.

066

0.15

390

7.96

200

046

5c,d

9.49

60.

1546

09.

3825

00

530c

10.8

145

1.12

549

010

.012

53.

125

430

8.77

130

3.25

425

8.67

140

3.50

417

8.50

160

4.00

400

8.16

178

4.45

388

7.92

210

5.25

365

7.45

230

5.75

330

6.73

288

7.20

300

6.12

290

7.25

305

6.22

420

10.5

220

4.49

520

13.0

160

3.26

300

051

5c,d

10.5

110

0.25

505

10.3

0

Me

Sa

ev fre

pr thr

so titr

so Na


43.7

26.2

614

.77.

210

B

47.3

31.2

814

.98.

043

B

48.2

31.3

813

.47.

120

D

49.0

31.8

212

.56.

625

D

49.6

31.7

111

.35.

897

D

51.6

34.1

210

.65.

722

C

51.8

34.1

710

.35.

545

C

51.5

31.4

87.

53.

791

C

52.5

32.0

16.

53.

234

C

51.6

28.8

63.

71.

689

C

52.3

28.8

62.

41.

081

C

55.0

30.5

50

0C

550

045

.216

.82

B

7.6

8.49

938

.114

.31

B

16.1

7.49

530

.211

.47

B

32.9

17.0

318

.87.

942

B

45.9

31.0

117

.19.

430

B

46.8

32.5

017

.29.

749

B

47.5

32.9

816

.59.

352

D

48.5

38.9

615

.89.

030

D

49.7

35.0

014

.88.

506

D

52.6

37.7

912

.57.

388

D

52.6

37.7

912

.67.

388

D

56.0

41.5

410

.36.

236

D

57.4

43.2

29.

45.

777

D

58.3

44.9

89.

35.

857

D

58.5

45.0

09.

05.

650

D

58.2

43.8

28.

65.

285

C

57.0

40.3

77.

74.

450

C

57.2

39.6

16.

73.

787

C

57.9

37.5

03.

51.

850

C

61.4

39.7

60

0C

alcu

late

dby

com

pile

r.:

NaC

N•2

H2O

,@2

5178

-25-

0#;B

:N

aCN

,@14

3-33

-9#;

C:

NaO

H•H

2O

,@

#;D

:N

aCN•

NaO

H,@

#,in

cong

ruen

tlysa

tura

ting.

The

com

posi

tion

ofin

varia

ntpo

ints

onso

lubi

lity

isot

herm

s~a

utho

rs!:

mpe

ratu

re(t

/°C

)N

aOH

(100

w2

/mas

s%

)N

aCN

(100

w2

/mas

s%

)N

otat

ion

inth

eph

ase

diag

ram

259.

834

.2k

56.0

14.0

j

3547

.515

.0g

51.5

10.5

f

5547

.017

.0h

59.0

9.0

e

te:

See

Fig

.5

and

also

repo

rted

wer

eph

ase

diag

ram

sat

35an

d55

°C.

FIG

.5.

Pha

sedi

agra

mof

the

NaC

N–

NaO

H–

H2O

syst

emat

25°C

.

3131JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

~2!

Sod

ium

hydr

oxid

e;N

aOH

;@131

0-73

-2#~3

!W

ater

;H 2

O;

@773

2-18

-5#

G.D

.Oliv

eran

dS

.E.J

.Joh

nson

,J.A

m.C

hem

.Soc

.76

,472

1–

4~1

954!

.

Varia

bles

:P

repa

red

By:

T/K

:29

8;30

8;32

810

0w

2/m

ass

%:

0–

49.2

at29

8K

;0

–55

at30

8K

;0

–61

.4at

328

K

J.H

ala

Exp

erim

enta

lDat

aC

ompo

sitio

nof

satu

rate

dso

lutio

nsin

the

NaC

N–

NaO

H–

H2O

syst

emat

thre

ete

mpe

ratu

res

Tem

pera

ture

(t/°

C)

NaO

H(1

00w

2/m

ass

%)

NaO

H(m

2/m

olkg

21)a

NaC

N(1

00w

1/m

ass

%)

NaC

N(m

1/m

olkg

21)a

Sol

idph

aseb

250

038

.812

.93

A

2.5

1.04

637

.812

.91

A

6.4

2.75

835

.612

.52

A

8.9

3.93

134

.512

.43

A

9.5

4.31

835

.513

.17

A

10.2

4.54

533

.712

.25

B

11.5

5.15

232

.711

.95

B

23.8

10.8

721

.58.

020

B

38.7

20.4

914

.16.

095

B

45.2

27.6

313

.96.

934

B

46.2

28.4

513

.26.

604

C

46.5

28.5

612

.86.

417

C

46.8

27.7

211

.05.

318

C

48.2

26.7

26.

73.

031

C

49.2

26.1

13.

71.

602

C

350

045

.016

.70

B

0.2

3.75

437

.213

.90

B

16.8

7.65

028

.310

.51

B

25.6

12.0

921

.58.

293

B

26.7

12.5

019

.97.

604

B

37.5

19.9

415

.56.

729

B

a C b A Te No

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

cyan

ide;

NaC

N;@1

43-3

3-9#

Sod

ium

chlo

ride;

NaC

l;@764

7-14

-5#W

ater

;H 2

O;

@773

2-18

-5#

K.

Yaj

ima

and

S.

Oda

naka

,K

ogyo

Kag

aku

Zas

shi

71,

460

–1

~196

8!.

riabl

es:

Pre

pare

dB

y:

K:

294;

313

0w

2/m

ass

%:

0–

24.8

8at

294

K;

0–

26.4

4at

313

K.

H.A

kaiw

aan

dJ.

Ha´ la

Exp

erim

enta

lDat

aC

ompo

sitio

nof

the

satu

rate

dso

lutio

nsin

the

NaC

N–

NaC

l–H

2O

syst

emat

21an

d40

°C

mpe

ratu

re(t

/°C

)N

aCl

(100

w2

/mas

s%

)N

aCl

(m2

/mol

kg2

1)b

NaC

N(1

00w

1/m

ass

%)

NaC

N(m

1/m

olkg

21)b

Sol

idph

asea

2124

.88

5.66

70

0A

24.1

25.

555

1.58

0.43

4A

21.5

44.

929

3.68

1.00

4A

22.4

95.

225

3.86

1.06

9A

18.6

84.

295

6.90

1.89

2A

16.9

93.

993

10.2

12.

862

A

14.7

13.

512

13.6

23.

878

A

12.9

13.

114

16.1

54.

645

A

10.8

52.

670

19.6

15.

754

A

5.14

1.35

429

.90

9.39

2A

3.91

1.04

532

.07

10.2

2A

3.07

0.83

734

.18

11.1

1A

00

37.1

412

.06

B

0.99

0.26

936

.11

11.7

1B

1.46

0.39

935

.93

11.7

1B

2.49

0.68

535

.33

11.5

9B

3.94

1.09

934

.72

11.5

5B

4026

.44

6.15

00

0A

19.8

34.

627

6.84

1.90

3A

14.6

23.

470

13.2

93.

762

A

10.9

62.

687

19.2

55.

628

A

8.21

2.08

824

.52

7.43

8A

5.46

1.44

529

.89

9.43

4A

3.64

1.00

734

.53

11.4

0A

00

43.6

915

.83

c

1.27

0.38

241

.80

14.9

8C

2.49

0.76

241

.61

15.1

9C

2.30

0.67

739

.57

13.8

9C

2.71

0.79

138

.69

13.4

7C

4.77

1.32

133

.44

11.0

4C

6.20

1.65

129

.56

9.38

9C

6.75

1.80

029

.08

9.24

7C

a A:

NaC

l,@7

647-

14-5#

;B

:N

aCN•

2H

2O

,@2

5178

-25-

0#;C

:so

lidso

lutio

nsN

aCl

x(C

N) 1

2x

.b C

alcu

late

dby

com

pile

r~J.H

.!.c C

ompi

ler’s

com

men

t:N

aCls

tate

das

the

solid

phas

e,ob

viou

sly

bym

ista

ke.A

bove

25°C

,the

equi

libriu

mso

lidph

ase

inth

eN

aCN

–H

2O

syst

emw

asre

port

edto

beN

aCN

,@1

43-3

3-9#.

1


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

serie

sof

100

gsa

mpl

esw

ere

prep

ared

byw

eigh

ing~to

the

near

est

0.1

g!th

ere

quire

dam

ount

sof

salt

and

wat

erin

toa

flask

.Afte

rhe

atin

gto

prom

ote

solu

tion,

the

sam

ples

wer

efil

tere

dto

rem

ove

the

carb

onat

e,an

dtr

ansf

erre

dto

200

mL

glas

stu

bes.

Equ

ilibr

ium

was

atta

ined

byag

itatin

gth

etu

bes

for

4–

5h

ina

ther

mos

tate

dba

th.

The

satu

rate

dso

lutio

nsw

ere

anal

yzed

volu

met

rical

lyfo

rC

N2

and

OH2

.E

ach

sam

ple

was

first

titra

ted

with

0.1

NA

gNO

3to

dete

rmin

eC

N2,

and

then

with

0.1

NH 2S

O4

agai

nst

phen

olre

dto

dete

rmin

eN

aOH

.T

heco

mpo

sitio

nof

the

solid

phas

esw

asde

term

ined

byth

em

etho

dof

wet

resi

dues

.

NaC

N,

J.T.

Bak

erre

agen

tgr

ade,

cont

aine

d97

.2%

NaC

N.

NaO

H,

J.T.

Bak

erre

agen

tgr

ade,

cont

aine

d97

.7%

NaO

H.

The

carb

onat

efo

rmed

inst

rong

NaO

Hso

lutio

nsw

asre

mov

edby

filtr

atio

n.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n60.

05K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 Te


4.3.

Pot

assi

umC

yani

de

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#W

ater

;H 2

O;

@773

2-18

-5#G

.N

.Le

wis

and

T.B

.B

right

on,

J.A

m.

Che

m.

Soc

.40

,48

2–

9~1

918!

.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inw

ater

at25

°CT

heso

lubi

lity

ofK

CN

at25

°Cw

asre

port

edto

be71

6g

KC

Npe

r10

00g

wat

er(

m15

10.9

96m

olkg

21;

com

pile

r!.A

lso

repo

rted

refr

eezi

ngpo

intt

empe

ratu

res

for

solu

tions

cont

aini

ng11

3.1

–46

0.1

gK

CN

per

1000

gw

ater

.Cry

ohyd

ric~e

utec

tic!

poin

twas

repo

rted

at2

29.6

1°C

,th

eco

mpo

sitio

nat

eute

ctic

poin

tw

asno

tre

port

ed.T

heeq

uatio

nde

scrib

ing

the

free

zing

poin

tte

mpe

ratu

reas

afu

nctio

nK

CN

conc

entr

atio

nw

asob

tain

edby

the

com

pile

rby

leas

tsq

uare

str

eatm

ent

ofth

eda

taas

t(f

.p.)

/°C

52

5.49

7310

22c1

0.55

5,

ere

cis

the

conc

entr

atio

nof

KC

Nin

gram

spe

r10

00g

wat

er.

Fro

mth

iseq

uatio

n,th

eco

mpo

sitio

nat

the

eute

ctic

poin

tw

asob

tain

edex

trap

olat

ion

as54

8.5

gK

CN

per

1000

gw

ater

,or

8.42

mol

kg2

1at

229

.61

°C.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed,

deta

ilsw

ere

not

repo

rted

.K

CN

,so

urce

not

spec

ified

,co

ntai

ned

smal

ltra

ces

ofca

rbon

ate.

The

salt

was

drie

din

ava

cuum

desi

ccat

or.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

3333JIRI HALA


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

deta

ilsw

ere

not

repo

rted

.A

naly

tical

met

hods

used

wer

eth

eLi

ebig

’sm

etho

dfo

rN

aCN

,an

dVo

lhar

d’s

met

hod

for

NaC

l.N

aClw

asde

term

ined

afte

rde

com

posi

tion

ofN

aCN

.

NaC

Nan

dN

aCl

wer

eco

mm

erci

al,

reag

ent

grad

epr

oduc

ts~s

ourc

eno

trep

orte

d!,an

dw

ere

used

with

outf

urth

erpu

rifica

tion.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n61

Kat

294

K,6

0.5

Kat

313

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1V.

A.

Kire

evan

dL.

I.Va

gran

skay

a,Z

h.O

bsh.

Khi

m.

5,96

3~1

935!

.

Co

~1!

~2!

Va T/

we

to of wh

by Me

An

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#S

olve

nts

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

intw

oso

lven

tsat

25°Ca

Sol

vent

KC

N~g

dm2

3 !K

CN

(c1

/mol

dm2

3)b

Wat

er;

H 2O

;@7

732-

18-5#

845

12.9

8

met

hyl-1

,3-d

ioxa

lan-

2-on

e~pro

pyle

neca

rbon

ate!;C

4H

6O

3;

@108

-32-

7#0.

240.

003

69

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

solv

ent

was

stirr

edor

itate

dw

ithex

cess

solid

ina

seal

ed,

ther

mos

tate

dve

ssel

until

uilib

rium

had

been

atta

ined

.T

his

was

chec

ked

byan

alyz

ing

quot

sta

ken

atin

terv

als.

Imm

edia

tely

afte

rw

ithdr

awal

,m

ples

ofth

esa

tura

ted

solu

tions

wer

eap

prop

riate

lydi

lute

dd

anal

yzed

for

K1an

dC

N2io

ns.

Pot

assi

umw

aste

rmin

edby

flam

eph

otom

etry

agai

nst

stan

dard

K2S

O4

lutio

ns.

Cya

nide

was

titra

ted

agai

nst

stan

dard

AgN

O3

lutio

n.

KC

Nw

asA

nala

R~B

.D.H

.!m

ater

ial,

and

was

used

assu

pplie

d.In

the

cour

seof

the

stud

y,se

vera

lbat

ches

ofK

CN

wer

eus

ed.A

llga

veco

nsis

tent

solu

bilit

yre

sults

.D

eion

ized

wat

erw

asus

ed.

Pro

pyle

neca

rbon

ate~

sour

ceno

tsp

ecifi

ed!w

aspu

rified

acco

rdin

gto

Gor

don

and

For

d.1

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

edS

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,N

ewY

ork,

1972

!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!W

ater

;H 2

O;

@773

2-18

-5#L.

A.

Vasi

levo

y,U

ch.

Zap

.K

azan

sk.

Gos

.U

niv.~S

ci.

Pap

ers

Kaz

ansk

.U

niv.!

85,

81–

2~1

925!

.

Varia

bles

:P

repa

red

By:

T/K

:24

3–

288

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

~°C

!K

CN

(100

w1

/mas

s%

)K

CN

(100

x 1/m

ol%

)K

CN

(m1

/mol

kg2

1)b

229

.833

.64

12.3

07.

785

228

.134

.73

12.8

38.

172

217

.336

.33

13.6

48.

763

214

.137

.06

14.0

19.

043

28.

737

.55

14.2

79.

234

038

.68

14.8

69.

687

9.1

40.1

415

.65

10.3

0

15.3

40.3

715

.75

10.4

0

a Equ

ilibr

ium

solid

phas

esw

ere

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Sol

utio

nsco

ntai

ning

exce

ssK

CN

wer

eeq

uilib

rate

dfo

ran

unsp

ecifi

edpe

riod

oftim

ean

dth

enfil

tere

dqu

ickl

yth

roug

ha

prec

oole

dfu

nnel

.S

atur

ated

solu

tions

wer

ean

alyz

edfo

rpo

tass

ium

grav

imet

rical

lyas

K2S

O4

afte

rev

apor

atin

gso

lutio

nsa

mpl

esin

apl

atin

umcr

ucib

le.

Sol

ubili

ties

abov

e15

°Cco

uld

not

bede

term

ined

beca

use

ofth

ede

com

posi

tion

ofK

CN

.N

ode

com

posi

tion

occu

rred

belo

w0

°C.

KC

N~K

ahlb

aum!

cont

aine

dab

out

3%of

wat

er,

and

trac

esof

sulfa

tes

and

chlo

rides

.D

istil

led

and

boile

dw

ater

was

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

Va T/

4- a S b C Me

An

ag eq ali

sa an de so so


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#H

ydro

gen

cyan

ide;

HC

N;@7

4-90

-8#

K.

Fre

denh

agen

and

J.D

ahm

los,

Z.A

norg

.Allg

em.

Che

m.

179,

77–

88~1

929!

.

riabl

es:

Pre

pare

dB

y:

K:

273

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofK

CN

inliq

uid

HC

Nw

asre

port

edto

bec15

0.10

mol

dm2

3at

0°C

.A

dditi

onal

info

rmat

ion:

Spe

cific

cond

uctiv

ityof

the

satu

rate

dso

lutio

nw

asre

port

edto

be0.

0085

V2

1 .

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

HC

Nw

asdi

still

edon

toso

lidN

ina

spec

ialv

esse

l.T

hesa

ltw

asse

vera

ltim

esw

ashe

dth

fres

hpo

rtio

nsof

HC

Nto

rem

ove

even

tual

impu

ritie

sth

atul

din

crea

seth

eco

nduc

tivity

ofth

eso

lutio

n.T

hesa

ltw

asn

diss

olve

dun

der

agita

tion

until

the

cond

uctiv

ityof

the

lutio

nre

mai

ned

cons

tant

.M

etho

dsof

anal

ysis

ofth

etu

rate

dso

lutio

nsw

ere

not

spec

ified

.S

olid

phas

esw

ere

not

estig

ated

.

KC

Nw

asa

prod

uct

ofK

ahlb

aum~p

uris

s.!an

dw

asdr

ied

befo

reus

e.H

CN

gas

was

prep

ared

from

KC

Nan

dH

2S

O4

~1:2

!.T

hega

sw

asdr

ied

with

CaC

l2

and

P 2O

5,

and

cond

ense

d.T

heliq

uid

was

repe

ated

lydi

still

edto

obta

ina

colo

rless

prod

uct

with

spec

ific

cond

uctiv

ityof

0.63

102

6V

21

at0

°C.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

3535JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!S

ulfu

rdi

oxid

e;S

O 2;

@744

6-09

-5#G

.Ja

nder

and

W.

Rup

polt,

Z.

Phy

s.C

hem

.17

9,43

–50

~193

7!.

Varia

bles

:P

repa

red

By:

T/K

:27

3J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofK

CN

inliq

uid

sulfu

rdi

oxid

ew

asre

port

edto

be0.

017

gsa

ltin

100

gso

lven

tat

0°C

.F

rom

this

valu

eth

eco

mpi

ler

calc

ulat

edm

1/m

olkg

215

0.00

261

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

bout

10g

SO

2,

care

fully

drie

d,w

aseq

uilib

rate

dw

ithex

cess

solid

at0

°Cin

wat

er–

ice

bath

ina

thre

e-co

mpa

rtm

ent

glas

sve

ssel

inw

hich

equi

libra

ting

and

sam

plin

gco

mpa

rtm

ents

wer

ese

para

ted

bya

com

part

men

tco

ntai

ning

glas

s/w

oolfi

lter.

Equ

ilibr

atio

nw

aspe

rfor

med

for

unsp

ecifi

ed,

prol

onge

dpe

riod

oftim

eun

der

freq

uent

shak

ing.

Afte

req

uilib

rium

had

been

atta

ined

,th

eve

ssel

was

turn

edup

side

dow

n,an

dth

esa

tura

ted

solu

tion

was

filte

red

into

the

empt

ysa

mpl

ing

com

part

men

t,w

hich

was

subs

eque

ntly

cool

edan

dse

aled

off.

Afte

rw

eigh

ing

the

com

part

men

tw

ithth

esa

mpl

e,S

O 2w

asal

low

edto

evap

orat

e,th

ere

sidu

ew

asw

eigh

ed,

diss

olve

din

wat

er,

and

the

cont

ent

ofth

esa

ltw

asde

term

ined

.M

etho

dof

anal

ysis

was

not

spec

ified

.

KC

N,

sour

ceno

tsp

ecifi

ed,

was

care

fully

drie

dbe

fore

use.

Com

mer

cial

lyav

aila

ble

SO 2

was

purifi

edby

pass

ing

itth

roug

hco

ncen

trat

edH 2S

O4

and

over

asbe

stos

woo

l,an

ddr

ied

byus

ing

P 2O

5.

Spe

cific

cond

uctiv

ityof

the

prod

uct

was

4.5

310

27

V2

1~J

ande

ran

dW

icke

rt1 !.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 G.

Jand

eran

dK

.W

icke

rt,

Z.

Phy

s.C

hem

.17

8,57

~193

6!.

Co

~1!

~2!

Va T/

Me

An

KC

wi

co the

so sa inv

J

d litympo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#A

mm

onia

;N

H 3;

@766

4-41

-7#W

.C

.Jo

hnso

nan

dO

.F.

Kru

mbo

ltz,

Z.

Phy

s.C

hem

.16

7,24

9–

59~1

933!

.

riabl

es:

Pre

pare

dB

y:

K:

239

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inliq

uid

amm

onia

at2

33.9

°CTw

om

easu

rem

ents

ofth

eso

lubi

lity

ofK

CN

inliq

uid

amm

onia

at233

.9°C

wer

eca

rrie

dou

t,th

eco

mpo

sitio

nof

the

satu

rate

dlu

tions

bein

g0.

0894

gK

CN

in1.

9523

gN

H3

,an

d0.

0618

gK

CN

in1.

3600

gN

H 3.

Fro

mth

ese

valu

esth

eau

thor

sob

tain

edfo

rth

elu

bilit

yof

KC

Nth

eva

lue

of4.

55g

KC

Nin

100

gso

lven

t(

m15

0.69

9m

olkg

21;

com

pile

r!an

d,us

ing

the

dens

ityof

the

satu

rate

dlu

tion

of0.

7048

gcm

23 ,

the

valu

ec15

0.47

1m

oldm

23.

The

auth

ors

assu

med

KC

N,

@151

-50-

8#,to

beth

eeq

uilib

rium

solid

phas

e.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

KC

Nw

asst

irred

with

uid

NH

3fo

r7

hin

aclo

sed

appa

ratu

s,w

hich

mad

eit

ssib

leto

with

draw

sam

ples

ofth

esa

tura

ted

solu

tions

from

solu

bilit

yve

ssel

with

excl

usio

nof

air.

Tem

pera

ture

was

ntro

lled

byke

epin

ga

cons

tant

NH

3pr

essu

reov

erth

elu

tion.

The

ampo

ule

with

the

sam

ple

was

wei

ghed

,N

H3

owed

toev

apor

ate,

and

the

KC

Nco

nten

tw

asde

term

ined

byig

hing

the

resi

due

afte

rdr

ying

itat

100

°C.

KC

N,

sour

ceno

tsp

ecifi

ed,

was

twic

ecr

ysta

llize

dfr

omdi

still

edw

ater

.C

omm

erci

ally

avai

labl

ean

hydr

ous

NH

3w

aske

ptov

erso

dium

met

alin

stee

lcon

tain

ers.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.


4.3.

1.E

valu

atio

nof

the

KC

N–

NH

3S

yste

m

Com

pone

nts:

Eva

luat

or:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!A

mm

onia

;N

H 3;

@766

4-41

-7#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,M

arch

2001

.

Crit

ical

Eva

luat

ion

Sol

ubili

tyof

KC

Nin

liqui

dam

mon

iaha

sbe

enre

port

edin

two

docu

men

ts.

John

son

and

Kru

mbo

ltz1

repo

rted

asi

ngle

valu

eat

239.

3K

,w

hile

Sch

enk

and

Tul

hoff2

repo

rted

the

solu

bilit

yov

erth

ete

mpe

ratu

rera

nge

from

203

to23

8K

.T

here

isan

obvi

ous

disc

repa

ncy

betw

een

the

two

mea

sure

men

ts,a

sse

enfr

omth

eso

lubi

litie

sre

port

edat

239.

3an

d23

8K

,i.e

.,4.

55g

KC

N/1

00g

NH

3or

0.7a

0m

olkg

21

~Joh

nson

and

Kru

mbo

ltz1 !,an

d6.

8g

KC

N/1

00g

NH 3

or1.

044

mol

kg2

1~S

chen

kan

dT

ulho

ff2 !,re

spec

tivel

y.~G

raph

ical

extr

apol

atio

nof

the

data

inS

chen

kan

dT

ulho

ff2

yiel

ded

anap

prox

imat

eK

CN

solu

bilit

yof

1.03

5m

olkg21

at23

9.3

K.!T

heso

urce

ofth

isdi

scre

panc

yis

not

clea

rfr

omth

epu

blis

hed

info

rmat

ion.

Itis

clea

r,ho

wev

er,

from

the

wor

kof

Sch

enk

and

Tul

hoff

2th

atth

esy

stem

need

sth

orou

gheq

uilib

ratio

nto

atta

ineq

uilib

rium

.Alth

ough

the

actu

aleq

uilib

ratio

ntim

ew

asno

trep

orte

din

any

ofth

etw

odo

cum

ents

itca

nbe

assu

me

that

true

equi

libriu

mm

ight

not

have

been

obta

ined

inJo

hnso

nan

dK

rum

boltz

.1

Mor

eove

r,si

nce

the

data

ofS

chen

kan

dT

ulho

ff2

wer

epe

rfor

med

atm

ore

tem

pera

ture

s,an

dal

lthe

data

cons

iste

ntly

fell

ona

stra

ight

line,

itis

sugg

este

dth

atth

eybe

used

aste

ntat

ive

solu

biva

lues

.

Ref

eren

ces:

1 W.

C.

John

son

and

O.

F.K

rum

boltz

,J.

Phy

s.C

hem

.16

7,24

9~1

933!

.2 P.

W.

Sch

enk

and

H.

Tul

hoff,

Ber

.B

unse

nges

.P

hys.

Che

m.

71,

1158

~196

7!.

Co

~1!

~2!

Va T/

so so so Me

An

liq po the

co so all

we


perio

dof

time.

Asm

alle

rror

intr

oduc

edin

this

way

byus

ing

larg

een

ough

amou

ntof

the

solid

.T

heto

tala

mou

ntof

NH

3

cond

ense

dw

asca

lcul

ated

from

the

tem

pera

ture

,vo

lum

eof

the

appa

ratu

s,an

din

itial

and

final

pres

sure

sof

NH

3.

4.3.

2.E

valu

atio

nof

the

KC

N–

Eth

anol

Sys

tem

mpo

nent

s:E

valu

ator

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#E

than

ol;

C 2H

6O

;@6

4-17

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

Mar

ch20

01.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

KC

Nin

etha

nolh

asbe

enre

port

edin

thre

edo

cum

ents

.The

data

are

scar

cean

ddi

fficu

ltto

com

pare

sinc

eth

eyw

ere

tain

edat

diffe

rent

tem

pera

ture

s,an

dre

port

edin

diffe

rent

conc

entr

atio

nun

its.

The

data

are

asfo

llow

s:6.

87g

per

dm3

solv

ent

at29

2.5

~de

Bru

yn1 !

~rec

alcu

late

dby

eval

uato

rfr

omau

thor

’sva

lue

ofg

salt

per

100

gso

lven

t!;

1.9

gpe

rdm

3so

lven

tat

298

K~T

hom

pson

2 !;d

8.4

gpe

rdm

3sa

tura

ted

solu

tion

at29

8K~B

land

amer

et

al.3 !.

Neg

lect

ing

the

diffe

renc

esin

tem

pera

ture

and

units

,the

reco

uld

betw

oas

ons

for

the

disc

repa

ncy

betw

een

the

resu

ltsof

deB

ruyn

1an

dB

land

amere

ta

l.3on

one

hand

,an

dof

Tho

mps

on2on

the

othe

r.Ta

king

oco

nsid

erat

ion

that

the

valu

eof

deB

ruyn1is

rath

ercl

ose

toth

atof

Tho

mps

on2fo

rth

eso

lubi

lity

ofK

CN

in95

%~v

/v!

etha

nol,

i.e.,

gpe

rdm

3so

lven

t,on

em

ight

spec

ulat

eth

atde

Bru

yn1

did

not

use

abso

lute

etha

nol

~pur

ityof

etha

nol

used

was

not

spec

ified!.

wev

er,

itdo

esno

tse

emlik

ely

that

this

has

also

been

the

case

inm

easu

rem

ents

ofB

land

amer

and

Bur

gess

3~s

eeco

mpi

latio

nof

thei

rN

–C

2H

6O

–H

2O

syst

em!,

who

seso

lubi

lity

valu

eis

,ho

wev

er,

clos

erto

that

ofde

Bru

yn.

1T

heot

her

reas

onco

uld

bein

equi

libra

tion

nditi

ons

whi

ch,h

owev

er,h

ave

notb

een

repo

rted

inth

edo

cum

ents

insu

ffici

entd

etai

lto

allo

wfo

ran

estim

ate

ofth

isef

fect

tobe

mad

e.er

efor

e,be

caus

eof

the

unce

rtai

nty

inth

epu

blis

hed

solu

bilit

yva

lues

,no

neof

them

can

bere

com

men

ded.

fere

nces

:

.A.

L.de

Bru

yn,

Z.

Phy

s.C

hem

.10,

782

~189

2!.

.R

.T

hom

pson

,J.

Res

.N

atl.

Bur

.S

td.

6,10

51~1

931!

.

.J.

Bla

ndam

er,

J.B

urge

ss,

and

A.

J.D

uffie

ld,

J.C

hem

.S

oc.,

Dal

ton

Tra

ns.

1~1

980!

.

3737JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!A

mm

onia

;N

H 3;

@766

4-41

-7#P.

W.

Sch

enk

and

H.

Tul

hoff,

Ber

.B

unse

nges

.P

hys.

Che

m.

71,

1155

–8~

1967

!.

Varia

bles

:P

repa

red

By:

T/K

:19

8–

238

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inliq

uid

amm

onia

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

KC

Nb

(g/1

00g

NH 3

)K

CN

(m1

/mol

kg2

1)c

270

10.9

1.67

4

260

9.7

1.49

0

250

8.6

1.32

1

240

7.4

1.13

6

235

6.8

1.04

4

a The

solid

phas

ew

asK

CN

,@151

-50-

8#.T

heau

thor

sst

ated

that

noso

lvat

esw

ere

obse

rved

.b O

btai

ned

byth

eau

thor

sby

inte

rpol

atio

nfr

omth

eir

expe

rimen

tald

ata.

c Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:T

here

sults

ofso

lubi

lity

mea

sure

men

ts(g

KC

Npe

r10

0g

NH

3)

take

nat

15di

ffere

ntte

mpe

ratu

res

wer

epr

e-se

nted

ingr

aphi

calf

orm

.T

heau

thor

sob

tain

edth

eda

tash

own

inth

eta

ble

byin

terp

olat

ion.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

d1w

asus

ed.

Mea

sure

men

tsw

ere

carr

ied

out

ina

vess

elco

nnec

ted

toa

vacu

umlin

e,an

dth

erm

osta

ted

with

met

hano

lcoo

led

ina

cryo

stat

.To

akn

own

amou

ntof

the

solid

salt,

amm

onia

was

grad

ually

cond

ense

dun

tilal

lsol

iddi

ssol

ved.

The

mix

ture

was

inte

nsel

yst

irred

durin

gam

mon

iaco

nden

satio

n.To

war

dth

een

dof

diss

olut

ion,

addi

tions

ofN

H3

wer

em

ade

smal

l,an

dw

ere

adde

dov

ersu

ffici

ently

long

time

inte

rval

sto

allo

wfo

req

uilib

rium

bein

gat

tain

edan

dfo

rke

epin

gth

ete

mpe

ratu

reco

nsta

nt.

The

diss

olut

ion

proc

ess

was

obse

rved

insi

delig

ht.

Toas

cert

ain

that

the

poin

tof

satu

ratio

nw

asno

tex

ceed

ed,

the

diss

olut

ion

was

stop

ped

whe

na

few

very

tiny

crys

tals

rem

aine

dun

diss

olve

dov

era

prol

onge

d

No

deta

ilsw

ere

repo

rted

asfo

rK

CN

.Am

mon

iaga

sw

asdr

ied

bypa

ssin

git

thro

ugh

tow

ers

fille

dw

ithN

aOH

,C

aO,

BaO

,an

dso

dium

met

al.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 P.W

.S

chen

kan

dH

.Tul

hoff,

Ber

.B

unse

nges

.P

hys.

Che

m.

71,

206

~196

7!.

Co

~1!

~2!

ob K an re int

6.1

Ho

KC

co Th

Re

1 C 2 M 3 M

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#S

olve

nts

M.

R.

Tho

mps

on,

J.R

es.

Nat

l.B

ur.

Std

.6,

1051

–9~

1931

!.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inm

etha

nola

ndet

hano

lat

25°Ca

Sol

vent

KC

N~g

dm2

3so

lven

t!K

CN

(m1

/mol

kg2

1)

than

ol;

CH 3

OH

;@6

7-56

-1#

30.0

0.58

6b

than

ol;

C 2H

6O

;@6

4-17

-5#

1.9

0.03

72c

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler

usin

gde

nsity

ofm

etha

nol

1of

0.78

65g

cm2

3at

25°C

.al

cula

ted

byco

mpi

ler

usin

gde

nsity

ofet

hano

l1

of0.

7852

gcm

23

at25

°C.

ditio

nali

nfor

mat

ion:

The

solu

bilit

yof

KC

Nat

25°C

in95

%et

hano

l~v

/v;

5%w

ater!

was

repo

rted

tobe

6.1

gsa

ltin

1dm2

3so

lven

t.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

tech

niqu

eus

edan

dui

libriu

mtim

eap

plie

dw

ere

not

repo

rted

.T

hecy

anid

ent

ent

inth

esa

tura

ted

solu

tions

was

dete

rmin

edby

adi

fied

Lieb

ig’s

met

hod

oftit

ratio

nag

ains

tA

gNO

3so

lutio

nth

epr

esen

ceof

KI

and

NaO

H.

KC

Nw

aspr

epar

edby

reac

ting

aso

lutio

nof

KO

Hin

abso

lute

etha

nolw

itha

10%

exce

ssof

liqui

dH

CN

,dur

ing

whi

chre

actio

nm

ost

ofK

CN

prec

ipita

ted.

The

prod

uct

cont

aine

d99

.74%

–99

.85%

KC

N.A

bsol

ute

met

hano

land

etha

nolw

ere

used

.

Ref

eren

ces:

1 Ha

nd

bo

ok

of

Ch

em

istr

ya

nd

Ph

ysic

s,

38th

ed.~

Che

mic

alR

ubbe

rC

o.,

Cle

vela

nd,

OH

,19

56!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!S

olve

nts

C.A

.L.

deB

ruyn

,Z

.P

hys.

Che

m.10

,78

2–

9~1

892!

.

Varia

bles

:P

repa

red

By:

T/K

:29

2.5

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inm

etha

nola

ndet

hano

lat

19.5

°Ca

Sol

vent

KC

N(g

/100

gso

lven

t!K

CN

(m1

/mol

kg2

1)b

KC

N(1

00w

1/m

ass

%)b

Met

hano

l;C

H 4O

;@6

7-56

-1#

4.91

0.75

44.

68

Eth

anol

;C 2

H6O

;@6

4-17

-5#

0.87

50.

134

0.86

7

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

solid

was

equi

libra

ted

with

the

solv

ent

byfr

eque

ntsh

akin

gin

agl

ass

vess

elcl

osed

with

rubb

erst

oppe

r.E

quili

brat

ion

was

carr

ied

out

inw

ater

bath

for

seve

rald

ays.

The

met

hod

ofK

CN

anal

ysis

was

not

repo

rted

.

100%

met

hano

lwas

used

.N

oot

her

deta

ilsre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

Va T/

Me E

a S b C c C Ad

Me

An

eq co mo

in


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#P

otas

sium

hydr

oxid

e;K

OH

;@131

0-58

-3#W

ater

;H 2

O;

@773

2-18

-5#

H.B

asse

ttan

dA

.S.C

orbe

t,J.

Che

m.S

oc.

125,

1660

–75

~192

4!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0.16

–23

.57

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inaq

ueou

sso

lutio

nsof

KO

Hat

25°Ca

KO

H/1

00g

lutio

n!b

KO

H(g

/100

gso

lutio

n!c

KO

H(1

00w

2/m

ass

%)c

KO

H(c

1/m

oldm

23)c

KC

N(g

/100

gso

lutio

n!K

CN

(100

w1

/mas

s%

)cK

CN

(c1

/mol

dm2

3)c

0.11

0.09

50.

163

0.10

1641

.56

71.2

338

.24

0.69

0.59

1.02

0.67

841

.67

72.1

741

.34

3.30

2.84

4.88

3.07

538

.92

66.8

336

.28

7.39

6.37

10.8

16.

369

34.7

258

.94

29.9

2

8.69

7.72

13.1

57.

908

33.5

857

.21

29.6

4

16.2

914

.04

23.5

713

.08

26.3

944

.30

21.1

7

quili

briu

mso

lidph

ases

wer

eno

tin

vest

igat

ed.

epor

ted

byth

eau

thor

sin

term

sof

gram

sK

CN

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Sol

utio

nsco

ntai

ning

exce

ssN

wer

eeq

uilib

rate

din

ath

erm

osta

ted

bath

.K

CN

was

term

ined

inth

esa

tura

ted

solu

tions

bytit

ratio

nag

ains

tnd

ard

AgN

O 3so

lutio

nin

the

pres

ence

ofam

mon

iaan

dK

I.

KC

Nw

asa

com

mer

cial

prod

uct~s

ourc

eno

tsp

ecifi

ed!co

ntai

ning

asm

uch

as3%

KO

H.

Atte

mpt

sto

neut

raliz

eit

with

HC

Nw

ere

unsu

cces

sful

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

3939JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!1,

2,3-

Pro

pane

trio

l~gly

cero

l!;C

3H

8O

3;

@56-

81-5

#A

.M

.O

ssen

dow

ski,

Zh.

Rus

s.F

iz.

Khi

m.

Obs

h.38,

1071

–2

~190

6!.

Varia

bles

:P

repa

red

By:

T/K

:28

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

ingl

ycer

olat

15°C

.T

heso

lubi

lity

ofK

CN

ingl

ycer

olw

asre

port

edto

be31

.84

gsa

ltin

100

gso

lven

tat

15–

15.6

°C(

m15

4.90

mol

kg2

1;

100

w1

524

.15

mas

s%

;co

mpi

ler

!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.K

CN

,so

urce

and

purit

yno

tsp

ecifi

ed,

was

twic

ere

crys

talli

zed

from

wat

er.

Gly

cero

lw

aspr

epar

edby

sapo

nific

atio

nof

soya

bean

oil.

The

prod

uct

was

dist

illed

with

stea

man

dpu

rified

bydi

still

atio

n.T

hefr

actio

nus

edbo

iled

at28

4°C

,an

dha

dde

nsity

of1.

2561

gcm

23

at15

°C.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed60.

3K

~com

pile

r!.S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 (g so a E b R c C Me

An

KC

de sta

J

1 E.

Col

ton

and

R.

E.

Bro

oker

,J.

Phy

s.C

hem

.62

,15

95~1

958!

.2 A

.J.G

ordo

nan

dR

.A.F

ord,T

he

Ch

em

ist’s

Co

mp

an

ion~W

iley,

New

Yor

k,19

72!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#M

etha

nol;

CH 4

O;

@67-

56-1

#W

ater

;H 2

O;

@773

2-18

-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.,1

–8~1

980!

.

riabl

es:

Pre

pare

dB

y:

K:

298

lum

e%

ofm

etha

nol:

10–

100

100w

2/m

ass

%:

10–

40J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inm

etha

nol–

wat

erm

ixtu

res

at25

°Ca

CH

4O

lum

e%

!K

CN

~gdm

23 !

KC

N(c

1/m

oldm

23)b

CH

4O

(100

w2

/mas

s%

)K

CN

~gdm

23 !

KC

N(c

1/m

oldm

23)b

1081

012

.44

1078

011

.98

2076

011

.67

2072

011

.06

3070

010

.75

3061

09.

37

4060

09.

2140

540

8.29

5045

06.

91

6034

05.

22

7023

03.

53

8011

01.

69

9051

0.78

3

100

210.

323

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

txt

ures

wer

em

ade

upby

volu

me

orby

wei

ght.

The

solv

ent

xtur

esor

the

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dth

exce

ssso

lidin

ase

aled

,th

erm

osta

ted

vess

elun

tilui

libriu

mha

dbe

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gqu

ots

take

nat

inte

rval

s.Im

med

iate

lyaf

ter

with

draw

al,

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

appr

opria

tely

dilu

ted

and

anal

yzed

for

K1an

dC

N2io

ns.

Pot

assi

umw

asde

term

ined

byfla

me

phot

omet

ryag

ains

tst

anda

rdK

2S

O4

solu

tions

.C

yani

dew

astit

rate

dag

ains

tst

anda

rdA

gNO

3

solu

tion.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.M

etha

nol,

sour

ceno

tsp

ecifi

ed,

was

purifi

edac

cord

ing

toG

ordo

nan

dF

ord.

1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,N

ewY

ork,

1972

!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!F

orm

amid

e;C

H 3N

O;

@75-

12-7

#~3

!W

ater

;H 2

O;

@773

2-18

-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

Varia

bles

:P

repa

red

By:

T/K

:29

8Vo

lum

e%

offo

rmam

ide:

20–

100

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

info

rmam

ide

–w

ater

mix

ture

sat

25°Ca

CH

3N

O~v

olum

e%

!K

CN

~gdm

23 !

KC

N(c

1/m

oldm

23)b

2072

011

.06

4054

08.

29

6042

06.

45

8031

04.

76

100

250

3.84

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

ofK

CN

info

rmam

ide

at25

°C,1

46g

KC

Npe

rdm23 ,w

asre

port

edby

Col

ton

and

Bro

oker

.1

Thi

sdo

cum

ent

was

com

pile

din

theSo

lub

ility

Da

taS

erie

s,Vo

l.11

,p.

47,

B.

Scr

osat

iand

C.A

.V

ince

nt,

edito

rs.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

tm

ixtu

res

wer

em

ade

upby

volu

me.

The

solv

ent

mix

ture

sor

the

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dw

ithex

cess

solid

ina

seal

ed,

ther

mos

tate

dve

ssel

until

equi

libriu

mha

dbe

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gal

iquo

tsta

ken

atin

terv

als.

Imm

edia

tely

afte

rw

ithdr

awal

,sa

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

appr

opria

tely

dilu

ted

and

anal

yzed

for

K1

and

CN2

ions

.P

otas

sium

was

dete

rmin

edby

flam

eph

otom

etry

agai

nst

stan

dard

K2S

O4

solu

tions

.C

yani

dew

astit

rate

dag

ains

tst

anda

rdA

gNO

3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.F

orm

amid

e,so

urce

not

spec

ified

,w

aspu

rified

acco

rdin

gto

Gor

don

and

For

d.2

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

Co

~1!

~2!

~3!

Va T/

vo ~vo

a S b C Me

An

mi

mi

wi

eq ali

sa


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#E

than

ol;

C 2H

6O

;@6

4-17

-5#

Wat

er;

H 2O

;@7

732-

18-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

riabl

es:

Pre

pare

dB

y:

K:

298

lum

e%

ofC 2

H6O

:10

–10

0J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inet

hano

l–w

ater

mix

ture

sat

25°Ca

C2H

6O

~vol

ume

%!

KC

N~g

dm2

3 !K

CN

(c1

/mol

dm2

3)b

1074

011

.36

2064

09.

83

3058

08.

91

4046

07.

06

5035

05.

38

6027

34.

19

7018

02.

76

8099

1.52

9024

0.36

9

100

8.4

0.12

9

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

txt

ures

wer

em

ade

upby

volu

me.

The

solv

ent

mix

ture

sor

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dw

ithex

cess

lidin

ase

aled

,th

erm

osta

ted

vess

elun

tileq

uilib

rium

had

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gal

iquo

tsta

ken

ater

vals

.Im

med

iate

lyaf

ter

with

draw

al,

sam

ples

ofth

etu

rate

dso

lutio

nsw

ere

appr

opria

tely

dilu

ted

and

anal

yzed

for

Kan

dC

N2io

ns.

Pot

assi

umw

asde

term

ined

byfla

me

phot

omet

ryag

ains

tst

anda

rdK

2S

O4

solu

tions

.C

yani

dew

astit

rate

dag

ains

tst

anda

rdA

gNO

3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.E

than

ol,

sour

ceno

tsp

ecifi

ed,

was

purifi

edac

cord

ing

toG

ordo

nan

dF

ord.

1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,N

ewY

ork,

1972

!.

4141JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!A

ceto

nitr

ile;

C 2H

3N

;@7

5-05

-8#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.,1

–8~1

980!

.

Varia

bles

:P

repa

red

By:

T/K

:29

8Vo

lum

e%

ofC 2

H3N

:10

–10

0J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inac

eton

itrile

–w

ater

mix

ture

sat

25°Ca

C2H

3N

~vol

ume

%!

KC

N~g

dm2

3 !K

CN

(c1

/mol

dm2

3)b

1081

412

.50

2074

011

.36

3054

08.

29

100

0.15

0.00

230

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:P

hase

sepa

ratio

noc

curr

edin

mix

ture

sco

ntai

ning

40–

80vo

lum

e%

acet

onitr

ilein

the

pres

ence

ofK

CN

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

tm

ixtu

res

wer

em

ade

upby

volu

me.

The

solv

ent

mix

ture

sor

the

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dw

ithex

cess

solid

ina

seal

ed,

ther

mos

tate

dve

ssel

until

equi

libriu

mha

dbe

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gal

iquo

tsta

ken

atin

terv

als.

Imm

edia

tely

afte

rw

ithdr

awal

,sa

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

appr

opria

tely

dilu

ted

and

anal

yzed

for

K1

and

CN2

ions

.P

otas

sium

was

dete

rmin

edby

flam

eph

otom

etry

agai

nst

stan

dard

K2S

O4

solu

tions

.C

yani

dew

astit

rate

dag

ains

tst

anda

rdA

gNO

3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.A

ceto

nitr

ile,

sour

ceno

tsp

ecifi

ed,

was

purifi

edac

cord

ing

toG

ordo

nan

dF

ord.

1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1A

.J.G

ordo

nan

dR

.A.F

ord,T

he

Ch

em

ist’s

Co

mp

an

ion~W

iley,

New

Yor

k,19

72!.

Co

~1!

~2!

~3!

Va T/

Vo a S b C Me

An

mi

the

so be int

sa1

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#S

ulfin

ylbi

s~m

etha

ne!;

dim

ethy

lsul

foxi

de;

C 2H

6O

S;

7-68

-5#

Wat

er;

H 2O

;@7

732-

18-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

riabl

es:

Pre

pare

dB

y:

K:

298

lum

e%

ofC 2

H6O

S:

10–

100

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

indi

met

hyls

ulfo

xide

–w

ater

mix

ture

sat

25°Ca

C2H

6O

S~v

olum

e%

!K

CN

~gdm

23 !

KC

N(c

1/m

oldm

23)b

1092

012

.59

2073

011

.21

3055

08.

45

4040

06.

14

5030

04.

61

6021

03.

23

7011

01.

69

8064

0.98

3

9034

0.52

2

100

7.8

0.12

0

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

txt

ures

wer

em

ade

upby

volu

me.

The

solv

ent

mix

ture

sor

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dw

ithex

cess

lidin

ase

aled

,th

erm

osta

ted

vess

elun

tileq

uilib

rium

had

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gal

iquo

tsta

ken

ater

vals

.Im

med

iate

lyaf

ter

with

draw

al,

sam

ples

ofth

esa

tura

ted

solu

tions

wer

eap

prop

riate

lydi

lute

dan

dan

alyz

edfo

rK

1an

dC

N2io

ns.

Pot

assi

umw

asde

term

ined

byfla

me

phot

omet

ryag

ains

tst

anda

rdK

2S

O4

solu

tions

.C

yani

dew

astit

rate

dag

ains

tst

anda

rdA

gNO

3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.D

imet

hyls

ulfo

xide

,so

urce

not

spec

ified

,w

aspu

rified

acco

rdin

gto

Gor

don

and

For

d.1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,N

ewY

ork,

1972

!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!1,

2-E

than

edio

l~eth

ylen

egly

col!;

C2H

6O

2;

@107

-21-

1#~3

!W

ater

;H 2

O;

@773

2-18

-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

Varia

bles

:P

repa

red

By:

T/K

:29

8Vo

lum

e%

ofC 2

H6O

2:

30–

100

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inet

hyle

negl

ycol

–w

ater

mix

ture

sat

25°Ca

C2H

6O

2

~vol

ume

%!

KC

N~g

dm2

3 !K

CN

(c1

/mol

dm2

3)b

3052

07.

99

5035

05.

38

7023

53.

61

100

180

2.76

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

tm

ixtu

res

wer

em

ade

upby

volu

me.

The

solv

ent

mix

ture

sor

the

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dw

ithex

cess

solid

ina

seal

ed,

ther

mos

tate

dve

ssel

until

equi

libriu

mha

dbe

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gal

iquo

tsta

ken

atin

terv

als.

Imm

edia

tely

afte

rw

ithdr

awal

,sa

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

appr

opria

tely

dilu

ted

and

anal

yzed

for

K1

and

CN2

ions

.P

otas

sium

was

dete

rmin

edby

flam

eph

otom

etry

agai

nst

stan

dard

K2S

O4

solu

tions

.C

yani

dew

astit

rate

dag

ains

tst

anda

rdA

gNO

3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lgav

eco

nsis

tent

solu

bilit

yre

sults

.E

thyl

eneg

lyco

l,so

urce

not

spec

ified

,w

aspu

rified

acco

rdin

gto

Gor

don

and

For

d.1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,N

ewY

ork,

1972

!.

Co

~1!

~2!

@6 ~3!

Va T/

Vo a S b C Me

An

mi

the

so be int


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#A

ceto

ne;

C 3H

6O

;@6

7-64

-1#

Wat

er;

H 2O

;@7

732-

18-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

riabl

es:

Pre

pare

dB

y:

K:

298

lum

e%

ofC 3

H6O

:20

–10

0J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inac

eton

e–

wat

erm

ixtu

res

at25

°Ca

C3H

6O

~vol

ume

%!

KC

N~g

dm2

3 !K

CN

(c1

/mol

dm2

3)b

2070

010

.75

3058

08.

91

5036

05.

53

7010

01.

54

805.

80.

0891

901.

90.

0292

100

0.03

0.00

046

1

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

txt

ures

wer

em

ade

upby

volu

me.

The

solv

ent

mix

ture

sor

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dw

ithex

cess

lidin

ase

aled

,th

erm

osta

ted

vess

elun

tileq

uilib

rium

had

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gal

iquo

tsta

ken

ater

vals

.Im

med

iate

lyaf

ter

with

draw

al,

sam

ples

ofth

etu

rate

dso

lutio

nsw

ere

appr

opria

tely

dilu

ted

and

anal

yzed

for

and

CN2

ions

.P

otas

sium

was

dete

rmin

edby

flam

eot

omet

ryag

ains

tst

anda

rdK

2S

O4

solu

tions

.C

yani

dew

asat

edag

ains

tst

anda

rdA

gNO

3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.A

ceto

ne,

sour

ceno

tsp

ecifi

ed,

was

purifi

edac

cord

ing

toG

ordo

nan

dF

ord.

1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,N

ewY

ork,

1972

!.

4343JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!1,

3-di

oxol

an-2

-one

~eth

ylen

ecar

bona

te!;C

3H

4O

3;

@96-

49-1

#~3

!W

ater

;H 2

O;

@773

2-18

-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

22–

45J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inet

hyle

neca

rbon

ate

–w

ater

mix

ture

sat

25°C

a

C3H

4O

3

(100

w2

/mas

s%

)K

CN

~gdm

23 !

KC

N(c

1/m

oldm

23)b

2244

06.

76

33.5

320

4.91

4530

04.

61

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

tm

ixtu

res

wer

em

ade

upby

wei

ght.

The

solv

ent

mix

ture

sw

ere

stirr

edor

agita

ted

with

exce

ssso

lidin

ase

aled

,th

erm

osta

ted

vess

elun

tileq

uilib

rium

had

been

atta

ined

.T

his

was

chec

ked

byan

alyz

ing

aliq

uots

take

nat

inte

rval

s.Im

med

iate

lyaf

ter

with

draw

al,

sam

ples

ofth

esa

tura

ted

solu

tions

wer

eap

prop

riate

lydi

lute

dan

dan

alyz

edfo

rK

1an

dC

N2io

ns.

Pot

assi

umw

asde

term

ined

byfla

me

phot

omet

ryag

ains

tst

anda

rdK 2

SO

4so

lutio

ns.

Cya

nide

was

titra

ted

agai

nst

stan

dard

AgN

O 3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.E

thyl

enec

arbo

nate

,so

urce

not

spec

ified

,w

aspu

rified

acco

rdin

gto

Gor

don

and

For

d.1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,N

ewY

ork,

1972

!.

Co

~1!

~2!

~3!

Va T/

Vo a S b C Me

An

mi

the

so be int

sa K1

ph titr

J

1 Pro

pe

rtie

sa

nd

Use

so

fD

ime

thyl

form

am

ide

,D

uPon

tIn

form

atio

nB

ookl

et~1

976!

.2 A

.J.G

ordo

nan

dR

.A.F

ord,T

he

Ch

em

ist’s

Co

mp

an

ion~W

iley,

New

Yor

k,19

72!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#1,

2,3-

Pro

pane

trio

l~gly

cero

l!;C

3H

8O

3;

@56-

81-5

#W

ater

;H 2

O;

@773

2-18

-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

20–

80J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

ingl

ycer

ol–

wat

erm

ixtu

res

at25

°Ca

C3H

8O

3

100

w2

/mas

s%

)K

CN

~gdm

23 !

KC

N(c

1/m

oldm

23)b

2068

010

.44

33.3

550

8.45

5042

06.

45

6034

05.

22

8026

03.

99

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

txt

ures

wer

em

ade

upby

wei

ght.

The

solv

ent

mix

ture

sw

ere

rred

orag

itate

dw

ithex

cess

solid

ina

seal

ed,

ther

mos

tate

dss

elun

tileq

uilib

rium

had

been

atta

ined

.T

his

was

chec

ked

anal

yzin

gal

iquo

tsta

ken

atin

terv

als.

Imm

edia

tely

afte

rth

draw

al,

sam

ples

ofth

esa

tura

ted

solu

tions

wer

epr

opria

tely

dilu

ted

and

anal

yzed

for

K1

and

CN2

ions

.ta

ssiu

mw

asde

term

ined

byfla

me

phot

omet

ryag

ains

tnd

ard

K 2S

O4

solu

tions

.C

yani

dew

astit

rate

dag

ains

tnd

ard

AgN

O 3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.G

lyce

rol,

sour

ceno

tsp

ecifi

ed,

was

purifi

edac

cord

ing

toG

ordo

nan

dF

ord.

1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,N

ewY

ork,

1972

!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!N

,N-D

imet

hylfo

rmam

ide;

C 3H

7N

O;

@68-

12-2

#~3

!W

ater

;H 2

O;

@773

2-18

-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

Varia

bles

:P

repa

red

By:

T/K

:29

8Vo

lum

e%

ofC 3

H7N

O:

20–

100

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inN

,N-d

imet

hylfo

rmam

ide

–w

ater

mix

ture

sat

25°Ca

C3H

7N

O~v

olum

e%

!K

CN

~gdm

23 !

KC

N(c

1/m

oldm

23)b

2061

29.

40

4031

04.

76

6018

02.

76

8044

0.67

6

100

4.0

0.06

14

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

ofK

CN

inN

,N-d

imet

hylfo

rmam

ide

was

also

repo

rted

ina

book

let.

1T

his

docu

men

tw

asco

mpi

led

inS

olu

bili

tyD

ata

Se

rie

s,Vo

l.11

,p.

205,

B.

Scr

osat

iand

C.A

.V

ince

nt,

edito

rs.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

tm

ixtu

res

wer

em

ade

upby

volu

me.

The

solv

ent

mix

ture

sor

the

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dw

ithex

cess

solid

ina

seal

ed,

ther

mos

tate

dve

ssel

until

equi

libriu

mha

dbe

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gal

iquo

tsta

ken

atin

terv

als.

Imm

edia

tely

afte

rw

ithdr

awal

,sa

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

appr

opria

tely

dilu

ted

and

anal

yzed

for

K1

and

CN2

ions

.P

otas

sium

was

dete

rmin

edby

flam

eph

otom

etry

agai

nst

stan

dard

K2S

O4

solu

tions

.C

yani

dew

astit

rate

dag

ains

tst

anda

rdA

gNO

3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.N

,N-d

imet

hylfo

rmam

ide,

sour

ceno

tsp

ecifi

ed,

was

purifi

edac

cord

ing

toG

ordo

nan

dF

ord.

2D

e-io

nize

dw

ater

was

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

Co

~1!

~2!

~3!

Va T/

10 (

a S b C Me

An

mi

sti

ve by wi

ap Po

sta

sta


New

Yor

k,19

72!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#2-

Met

hyl-2

-pro

pano

l~ter

t-bu

tano

l!;C

4H

10O

;@7

5-65

-0#

Wat

er;

H 2O

;@7

732-

18-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

riabl

es:

Pre

pare

dB

y:

K:

298

lum

e%

ofC 4

H10

O:

10–

100

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

inte

rt-b

utan

ol–

wat

erm

ixtu

res

at25

°Ca

C4H

10O

~vol

ume

%!

KC

N~g

dm2

3 !K

CN

(c1

/mol

dm2

3)b

579

412

.19

1070

010

.75

9513

0.20

0

100

0.1

0.00

154

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

ditio

nali

nfor

mat

ion:

Pha

sese

para

tion

occu

rred

inm

ixtu

res

cont

aini

ng20

–90

volu

me

%te

rt-b

utan

olin

the

pres

ence

ofK

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

txt

ures

wer

em

ade

upby

volu

me.

The

solv

ent

mix

ture

sor

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dw

ithex

cess

lidin

ase

aled

,th

erm

osta

ted

vess

elun

tileq

uilib

rium

had

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gal

iquo

tsta

ken

ater

vals

.Im

med

iate

lyaf

ter

with

draw

al,

sam

ples

ofth

etu

rate

dso

lutio

nsw

ere

appr

opria

tely

dilu

ted

and

anal

yzed

for

and

CN2

ions

.P

otas

sium

was

dete

rmin

edby

flam

eot

omet

ryag

ains

tst

anda

rdK

2S

O4

solu

tions

.C

yani

dew

asat

edag

ains

tst

anda

rdA

gNO

3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.Te

rt-b

utan

ol,

sour

ceno

tsp

ecifi

ed,

was

purifi

edac

cord

ing

toG

ordo

nan

dF

ord.

1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,N

ewY

ork,

1972

!.

4545JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anid

e;K

CN

;@151

-50-

8#~2

!1,

4-D

ioxa

ne;

C 4H

8O

2;

@123

4-91

-1#~3

!W

ater

;H 2

O;

@773

2-18

-5#

M.

J.B

land

amer

,J.

Bur

gess

,an

dA

.J.

Duf

field

,J.

Che

m.

Soc

.,D

alto

nT

rans

.1

–8~

1980

!.

Varia

bles

:P

repa

red

By:

T/K

:29

8Vo

lum

e%

ofC 4

H8O

2:

10–

100

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

CN

in1,

4-di

oxan

e–

wat

erm

ixtu

res

at25

°Ca

C4H

8O

2

~vol

ume

%!

KC

N~g

dm2

3 !K

CN

(c1

/mol

dm2

3)b

1075

011

.52

3058

08.

91

4049

07.

53

907.

20.

111

100

0.9

0.01

38

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:P

hase

sepa

ratio

noc

curr

edin

mix

ture

sco

ntai

ning

50–

80vo

lum

e%

1,4-

diox

ane

inth

epr

esen

ceof

KC

N.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

bina

ryaq

ueou

s/so

lven

tm

ixtu

res

wer

em

ade

upby

volu

me.

The

solv

ent

mix

ture

sor

the

neat

orga

nic

solv

ent

wer

est

irred

orag

itate

dw

ithex

cess

solid

ina

seal

ed,

ther

mos

tate

dve

ssel

until

equi

libriu

mha

dbe

enat

tain

ed.

Thi

sw

asch

ecke

dby

anal

yzin

gal

iquo

tsta

ken

atin

terv

als.

Imm

edia

tely

afte

rw

ithdr

awal

,sa

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

appr

opria

tely

dilu

ted

and

anal

yzed

for

K1

and

CN2

ions

.P

otas

sium

was

dete

rmin

edby

flam

eph

otom

etry

agai

nst

stan

dard

K2S

O4

solu

tions

.C

yani

dew

astit

rate

dag

ains

tst

anda

rdA

gNO

3so

lutio

n.

KC

Nw

asA

nala

Rm

ater

ial~B

.D.H

.!an

dw

asus

edas

supp

lied.

Inth

eco

urse

ofth

est

udy,

seve

ralb

atch

esof

KC

Nw

ere

used

,an

dal

lga

veco

nsis

tent

solu

bilit

yre

sults

.1,

4-di

oxan

e,so

urce

not

spec

ified

,w

aspu

rified

acco

rdin

gto

Gor

don

and

For

d.1

De-

ioni

zed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.J

.Gor

don

and

R.A

.For

d,Th

eC

he

mis

t’sC

om

pa

nio

n~Wile

y,

Co

~1!

~2!

~3!

Va T/

Vo a S b C Ad

Me

An

mi

the

so be int

sa K1

ph titr

J

he

FIG

.6.

Sol

ubili

tyof

NaO

CN

inliq

uid

NH 3

asa

func

tion

ofte

mpe

ratu

re.

Ref

eren

ces:

1 M.A

riizu

mi,

S,

Kum

oa,

and

R.

Har

a,K

ogyo

Kag

aku

Zas

shi

46,

237

~194

3!.

2 S.A

bean

dT.

Oka

be,

Kog

yoK

agak

uZ

assh

i58

,24

2~1

955!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

cyan

ate;

NaO

CN

;@917

-61-

3#A

mm

onia

;N

H 3;

@766

4-41

-7#M

.Arii

zum

i,S

.K

umoa

,an

dR

.H

ara,

Kog

yoK

agak

uZ

assh

i46

,23

7–

40~1

943!

.

riabl

es:

Pre

pare

dB

y:

K:

253

–28

3H

.Aka

iwa

Exp

erim

enta

lDat

aS

olub

ility

ofN

aOC

Nin

liqui

dam

mon

iaas

afu

nctio

nof

tem

pera

ture

a

Tem

pera

ture

~°C

!N

aOC

N(g

/100

gN

H 3)

NaO

CN

(m1

/mol

kg2

1)b

10.2

1.24

60.

005b

(n5

3)

0.19

1

01.

356

0.03

0b(n

54

)0.

208

210

.11.

506

0.02

5b(n

53

)0.

231

219

.81.

726

0.01

2b(n

53

)0.

265

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Sta

ndar

dde

viat

ions

wer

eca

lcul

ated

for

the

indi

cate

dnu

mbe

rof

mea

sure

men

ts.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Fro

mth

esa

mpl

esof

the

tura

ted

solu

tions

,am

mon

iaw

asal

low

edto

evap

orat

ean

dits

nten

tw

asde

term

ined

from

the

diffe

renc

ein

wei

ght.

NaO

CN

sde

term

ined

from

the

wei

ght

ofth

ere

sidu

e,an

dby

atio

n.T

heso

lubi

lity

was

obta

ined

bydi

ssol

ving

the

resi

due

wat

er,

prec

ipita

ting

AgO

CN

,di

ssol

utio

nof

the

latte

rin

cess

ofst

anda

rdH

NO 3,

and

back

-titr

atin

gex

cess

acid

.

NaO

CN

,sou

rce

nots

peci

fied,

was

of99

.25%

purit

y.It

cont

aine

dtr

ace

amou

nts

ofN

a 2CO

3an

dN

aCl.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

see

abov

e.


5.T

heS

olub

ility

ofC

yana

tes

5.1.

Sod

ium

Cya

nate

5.1.

1.E

valu

atio

nof

the

NaO

CN

–N

H3

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Sod

ium

cyan

ate;

NaO

CN

;@917

-61-

3#~2

!A

mm

onia

;N

H 3;

@766

4-41

-7#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,Apr

il20

01.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

NaO

CN

inliq

uid

amm

onia

has

been

repo

rted

intw

odo

cum

ents

.1,

2In

both

ofth

em,

the

solu

bilit

ies

wer

eob

tain

edby

isot

herm

alm

etho

d,an

dre

port

edas

afu

nctio

nof

tem

pera

ture

.B

oth

sets

ofda

taar

ein

exce

llent

agre

emen

t,as

seen

from

Fig

.6.

Tag

reem

ent

ispa

rtic

ular

lyse

encl

early

from

the

two

resu

ltsat

273.

2K

,i.e

.,0.

208

~Arii

zum

ie

ta

l.1 !an

d0.

212~

Abe

and

Oka

be2 !

mol

kg2

1 .T

hetw

ose

tsof

data

wer

eco

mpu

ter

smoo

thed

bylin

ear

regr

essi

onof

the

data

,an

dfo

und

tofit

the

equa

tion

m1

(mol

kg2

1)5

0.21

222

2.32

1310

23t,

whe

ret

iste

mpe

ratu

rein

°C.

The

stan

dard

devi

atio

nsof

the

cons

tant

sar

e1.

533

102

3an

d6.

713

102

5,

resp

ectiv

ely.

Co

~1!

~2!

Va T/

a S b C Me

An

sa co wa

titr

in ex


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

cyan

ate;

NaO

CN

;@917

-61-

3#E

than

ol;

C 2H

6O

;@6

4-17

-5#

J.A

.C

rans

ton

and

A.

Y.Li

ving

ston

e,J.

Che

m.

Soc

.50

1–

3~1

926!

.

riabl

es:

Pre

pare

dB

y:

K:

273

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aOC

Nw

asre

port

edto

be0.

22g

salt

in10

0g

solv

ent

at0

°C.

Fro

mth

isva

lue

the

com

pile

rca

lcul

ated

m1

0.03

38m

olkg

21.

Add

ition

alin

form

atio

n:T

heau

thor

sal

sore

port

edth

eso

lubi

lity

ofN

aOC

Nin

boili

nget

hano

lto

be0.

52g

salt

in10

0g

solv

ent.

iling

poin

tof

the

satu

rate

dso

lutio

nan

dat

mos

pher

icpr

essu

reat

whi

chth

em

easu

rem

ent

was

take

nw

ere

not

repo

rted

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Det

ails

wer

eno

tre

port

ed.

alys

isof

the

satu

rate

dso

lutio

nsw

asca

rrie

dou

tby

ighi

ngsa

mpl

esof

the

satu

rate

dso

lutio

ns,

and

dete

rmin

ing

cyan

ate

cont

ent

volu

met

rical

lyac

cord

ing

toM

ason

.1

No

info

rmat

ion

onN

aOC

Nre

port

ed.

Eth

anol

used

had

dens

ityof

0.79

9g

cm2

3at

17°C

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 Mas

on,

Che

m.

New

s90,

No.

5,17

~190

6!.

4747JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

cyan

ate;

NaO

CN

;@917

-61-

3#~2

!A

mm

onia

;N

H 3;

@766

4-41

-7#S

.Abe

and

T.O

kabe

,K

ogyo

Kag

aku

Zas

shi

58,

242

–7

~195

5!.

Varia

bles

:P

repa

red

By:

T/K

:27

3–

318

H.A

kaiw

a

Exp

erim

enta

lDat

aS

olub

ility

ofN

aOC

Nin

liqui

dam

mon

iaas

afu

nctio

nof

tem

pera

ture

a

Tem

pera

ture

(t/°

C)

NaO

CN

(g/1

00g

NH 3

)N

aOC

N(m

1/m

olkg

21)b

01.

391.

391.

381.

37

1.38

60.

008b

0.21

2

151.

151.

151.

151.

15

1.15

0.17

7

250.

980.

980.

960.

98

0.98

60.

009b

0.15

1

350.

870.

850.

850.

840.

85

0.85

60.

010b

0.13

1

450.

720.

730.

710.

700.

73

0.72

60.

012b

0.11

1

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Mol

aliti

esan

dst

anda

rdde

viat

ions

calc

ulat

edby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

suffi

cien

tam

ount

ofN

aOC

Nw

aspl

aced

inth

eeq

uilib

ratio

nve

ssel

,an

dliq

uid

amm

onia

was

intr

oduc

ed.

The

vess

elw

asco

nnec

ted

thro

ugh

asi

de-a

rmw

itha

filtr

atio

nse

tup

and

asa

mpl

ing

vess

el.

The

equi

libra

tion

vess

elw

aske

ptin

ath

erm

osta

tfo

r2

–8

hun

der

cons

tant

stirr

ing.

Afte

rsa

tura

tion

had

been

atta

ined

,th

em

ixtu

rew

asfil

tere

din

toth

esa

mpl

ing

vess

el,

and

the

cont

ent

ofN

aOC

Nin

the

satu

rate

dso

lutio

nsw

asde

term

ined

titrim

etric

ally

usin

gVo

lhar

d’s

met

hod.

NaO

CN

was

prep

ared

byex

trac

ting

the

raw

mat

eria

l~s

ourc

eno

tsp

ecifi

ed!

with

liqui

dN

H3

cont

aini

ngN

H 4N

O3

,an

dw

ashi

ngse

vera

ltim

esw

ithm

etha

nol.

Pur

ityof

the

prod

uct

was

assu

med

tobe

100%

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

see

abov

e.

Co

~1!

~2!

Va T/

5 Bo

Me

An

An

we

the

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

cyan

ate;

NaO

CN

;@917

-61-

3#A

mm

oniu

mch

lorid

e;N

H 4C

l;@1

2125

-02-

9#A

mm

onia

;N

H 3;

@766

4-41

-7#

S.A

bean

dT.

Oka

be,

Kog

yoK

agak

uZ

assh

i58

,24

2–

7~1

955!

.

riabl

es:

Pre

pare

dB

y:

K:

273

ncen

trat

ion

of~2

!/g

per

100

gN

H 3:

2.16

–64

.0H

.Aka

iwa

Exp

erim

enta

lDat

aS

olub

ility

at0

°Cof

NaO

CN

inliq

uid

amm

onia

inth

epr

esen

ceof

NH

4C

la

NH

4C

l/1

00g

NH 3

)N

H4C

l(m

2/m

olkg

21)b

NaO

CN

(g/1

00g

NH 3

)N

aOC

N(m

1/m

olkg

21)b

2.16

0.39

643.

200.

4923

4.32

0.79

284.

210.

6476

9.37

1.72

06.

180.

9507

12.7

2.33

17.

161.

101

18.6

3.41

37.

941.

221

28.6

5.24

88.

431.

297

40.2

7.37

78.

421.

295

54.4

9.98

36.

821.

049

64.0

11.7

55.

890.

9061

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.A

suffi

cien

tam

ount

ofth

eo

salts

was

plac

edin

the

equi

libra

tion

vess

el,

and

liqui

dm

onia

was

intr

oduc

ed.

The

vess

elw

asco

nnec

ted

thro

ugh

ae

arm

with

afil

trat

ion

setu

pan

da

sam

plin

gve

ssel

.T

heui

libra

tion

vess

elw

aske

ptin

ath

erm

osta

tfo

r2

–8

hun

der

nsta

ntst

irrin

g.A

fter

satu

ratio

nha

dbe

enat

tain

ed,

the

xtur

ew

asfil

tere

din

toth

esa

mpl

ing

vess

el,

and

the

cont

ent

NaO

CN

inth

esa

tura

ted

solu

tions

was

dete

rmin

edtit

rimet

rical

lyus

ing

Volh

ard’

sm

etho

d.

NaO

CN

was

prep

ared

byex

trac

ting

the

raw

mat

eria

l~s

ourc

eno

tsp

ecifi

ed!

with

liqui

dam

mon

ia,

cont

aini

ngN

H 4NO

3,

and

was

hing

seve

ralt

imes

with

met

hano

l.T

hepr

oduc

tw

asas

sum

edto

be10

0%pu

re.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

cyan

ate;

NaO

CN

;@917

-61-

3#~2

!18

-dib

enzo

-cro

wn-

6;C 20

H24

O6

;@1

4187

-32-

7#;or

18-d

icyc

lohe

xyl-c

row

n-6;

C 20H

36O

6;@

#~3

!N

,N-d

imet

hylfo

rmam

ide;

C 3H7N

O;

@68-

12-2

#;or

o-D

ichl

orob

enze

ne;

C 6H4C

l 2;

@95-

50-1

#

V.A

.Zlo

bin

and

A.K

.Tar

asov

,Izv

.VU

Z,K

him

.Khi

m.T

ekhn

ol.

40,

No.

5,13

4–

5~19

97!

Varia

bles

:P

repa

red

By:

T/K

:29

3;36

3c 2

/mol

dm2

3:

0.04

–0.

10(C

20H

24O

6);

0.02

–0.

10(C

20H

36O

6)

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aOC

Nin

two

solv

ents

inth

epr

esen

ceof

crow

net

hers

at20

and

90°C

Sol

vent

Tem

pera

ture

(t/°

C)

C20

H24

O6

(c2

/mol

dm2

3)

NaO

CN

~gl2

1 !N

aOC

N(1

02c 1

/mol

dm2

3)

C20

H36

O6

(c2

/mol

dm2

3)

NaO

CN

~gl2

1 !N

aOC

N(1

02c 1

/mol

dm2

3)

C3H

7N

O20

—0.

500.

770.

020.

570.

88

0.04

0.55

0.85

0.06

0.78

1.20

0.08

0.68

1.04

0.10

1.09

1.35

0.10

1.09

1.35

90—

0.75

1.15

0.10

1.21

1.86

C6H

4C

l 220

—0.

0157

0.02

5

0.10

0.06

160.

095

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

deta

ilsre

port

edon

lyon

anal

ytic

alm

etho

dsus

ed.

The

conc

entr

atio

nof

OC

N2

inC

3H

7N

Ow

asde

term

ined

chro

noco

n-du

ctom

etric

ally

bytit

ratin

gan

aliq

uot

ofth

esa

tura

ted

solu

tion

agai

nst

0.1

mol

dm2

3A

gNO

3so

lutio

nin

CH 3

CN

,w

hich

was

deliv

ered

into

the

titra

tion

vess

elvi

aa

capi

llary

tube

ata

cons

tant

rate

bya

peris

talti

cpu

mp.

The

appa

ratu

sw

asca

libra

ted

bytit

ratin

ga

0.1

mol

dm2

3H

Cls

olut

ion

inis

oam

ylal

coho

l.In

C 6H4C

l 2,

OC

N2

was

dete

rmin

edch

rono

pote

ntio

met

rical

lyus

ing

Ag/

AgC

lele

ctro

des.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

Co (g a S b C Me

An

tw am sid

eq co mi

of


cons

tant

stirr

ing.

Afte

rsa

tura

tion

had

been

atta

ined

,th

em

ixtu

rew

asfil

tere

din

toth

esa

mpl

ing

vess

el,

and

the

cont

ent

ofN

aOC

Nin

the

satu

rate

dso

lutio

nsw

asde

term

ined

titrim

etric

ally

usin

gVo

lhar

d’s

met

hod.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

cyan

ate;

NaO

CN

;@917

-61-

3#D

ieth

ylet

her;

C 4H

10O

;@6

0-29

-7#

Met

hano

l;C

H 4O

;@6

7-56

-1#

H.

Yas

hio,

J.Ta

kesh

ita,

A.

Oku

wak

i,an

dT.

Oka

be,

Nip

pon

Kag

aku

Kai

shi1

473

–5~1

984!

.

riabl

es:

Pre

pare

dB

y:

K:

298

lum

efr

actio

nof

~2!:

0–

0.5

H.A

kaiw

a

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aOC

N,

ingr

ams

ofsa

ltpe

r10

0g

solv

ent,

inm

ixtu

res

ofdi

ethy

leth

eran

dm

etha

nol

at25

°Cw

asre

port

edin

aphi

calf

orm

~Fig

.7!

.

FIG

.7.

Sol

ubili

tyof

NaO

CN

indi

ethy

leth

er/m

etha

nolm

ixtu

res

at25

°C.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

NaO

CN

was

adde

dto

the

solv

ent

mix

ture

cont

aini

ngth

eso

lven

tsin

the

desi

red

volu

me

ratio

,an

dst

irred

first

at30

°Cfo

r6

h,an

dth

enfo

rat

leas

t6

hat

25°C

ina

seal

edve

ssel

ina

ther

mos

tat.

Asa

mpl

eof

the

satu

rate

dso

lutio

n~30

–50

cm3 !

was

with

draw

n,w

eigh

ed,

the

solv

ents

wer

eev

apor

ated

unde

rre

duce

dpr

essu

re,

and

NaO

CN

was

dete

rmin

edin

the

resi

due

byth

eVo

lhar

d’s

met

hod.

NaO

CN

,sou

rce

nots

peci

fied,

was

diss

olve

din

dist

illed

wat

erat

50°C

,an

dne

utra

lized

bygl

acia

lac

etic

acid

.T

heso

lutio

nw

asfil

tere

d,an

dN

aOC

Nw

asal

low

edto

crys

talli

zein

are

frig

erat

or.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

4949JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

cyan

ate;

NaO

CN

;@917

-61-

3#~2

!A

mm

oniu

mni

trat

e;N

H 4N

O3

;@6

484-

52-2#

~3!

Am

mon

ia;

NH 3

;@7

664-

41-7#

S.A

bean

dT.

Oka

be,

Kog

yoK

agak

uZ

assh

i58

,24

2–

7~1

955!

.

Varia

bles

:P

repa

red

By:

T/K

:27

3C

once

ntra

tion

of~2

!/g

per

100

gN

H 3:

2.35

–66

.6H

.Aka

iwa

Exp

erim

enta

lDat

aS

olub

ility

at0

°Cof

NaO

CN

inliq

uid

amm

onia

inth

epr

esen

ceof

NH

4N

O3a

NH

4N

O3

(g/1

00g

NH 3

)N

H4N

O3

(m2

/mol

kg2

1)b

NaO

CN

(g/1

00g

NH 3

)N

aOC

N(m

1/m

olkg

21)b

2.35

0.29

363.

050.

4692

6.84

0.85

454.

940.

7599

8.70

1.08

75.

390.

8291

11.6

1.44

96.

110.

9400

19.9

2.48

67.

511.

155

28.3

3.53

68.

111.

248

35.4

4.42

38.

471.

303

42.2

5.27

28.

501.

308

45.3

5.65

98.

411.

294

52.2

6.52

18.

111.

248

56.7

7.08

47.

901.

215

66.6

8.32

06.

941.

068

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

suffi

cien

tam

ount

ofth

etw

osa

ltsw

aspl

aced

inth

eeq

uilib

ratio

nve

ssel

,an

dliq

uid

amm

onia

was

intr

oduc

ed.

The

vess

elw

asco

nnec

ted

thro

ugh

asi

de-a

rmw

itha

filtr

atio

nse

tup

and

asa

mpl

ing

vess

el.

The

equi

libra

tion

vess

elw

aske

ptin

ath

erm

osta

tfo

r2

–8

hun

der

NaO

CN

was

prep

ared

byex

trac

ting

the

raw

mat

eria

l~s

ourc

eno

tsp

ecifi

ed!

with

liqui

dam

mon

ia,

cont

aini

ngN

H 4NO

3,

and

was

hing

seve

ralt

imes

with

met

hano

l.T

hepr

oduc

tw

asas

sum

edto

be10

0%pu

re.

Co

~1!

~2!

~3!

Va T/

Vo gr

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anat

e;K

OC

N;@590

-28-

3#A

mm

onia

;N

H 3;

@766

4-41

-7#H

.H

unt,

J.A

m.

Che

m.

Soc

.54,

3509

–12

~193

2!.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofK

OC

Nw

asre

port

edto

be1.

70g

in10

0g

solv

enta

t25

°C,o

r,us

ing

the

dens

ityof

liqui

dam

mon

iaof

0.60

4g

cm2

3

25°C

,1.

02g

KO

CN

in10

0cm3

solv

ent.

Com

pile

rca

lcul

atedm

15

0.20

96m

olkg

21 .

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.A

mm

onia~10

–25

g!w

asui

libra

ted

with

the

salt

inth

ebo

ttom

part

ofa

seal

ed,

o/co

mpa

rtm

ent

Pyr

extu

be.

The

com

part

men

tsw

ere

para

ted

from

each

othe

rw

itha

narr

owne

ck.

The

salt

was

rodu

ced

into

the

tube

befo

rese

alin

git

off

ina

smal

lcup

sed

with

ave

rycl

osel

yw

oven

cotto

ncl

oth.

The

latte

rrm

itted

the

salt

todi

ssol

veth

esa

ltho

ldin

gba

ckth

eso

lidat

sam

etim

e.T

hesy

stem

was

equi

libra

ted

for

1–

3w

eeks

thoc

casi

onal

shak

ing.

The

nth

etu

bew

asin

vert

edin

the

than

dal

lthe

solu

tion

drai

ned

into

the

empt

yco

mpa

rtm

ent,

ich

was

cool

edan

dse

aled

off.

Whe

nit

reac

hed

room

pera

ture

itw

asdr

ied

and

wei

ghed

,th

eam

mon

iaal

low

edto

ilof

f,th

etu

bew

ithth

esa

ltw

arm

edun

tilal

lodo

rof

NH

3

sgo

ne,

and

the

salt

was

wei

ghed

.

KO

CN

,B

aker

C.

P.pr

oduc

t,w

asre

crys

talli

zed

and

care

fully

drie

d.C

omm

erci

ally

avai

labl

ean

hydr

ous

NH

3w

asal

low

edto

stan

dov

erm

etal

licso

dium

for

seve

ralw

eeks

befo

reus

e.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.02

5K

~aut

hor!.

Sol

ubili

ty:

5%~a

utho

r!.


5.2.

Pot

assi

umC

yana

te

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anat

e;K

OC

N;@590

-28-

3#~2

!W

ater

;H 2

O;

@773

2-18

-5#G

.N

.Le

wis

and

T.B

.B

right

on,

J.A

m.

Che

m.

Soc

.40

,48

2–

9~1

918!

.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofK

OC

Nin

wat

erat

25°C

was

repo

rted

tobe

750

gK

OC

Npe

r10

00g

wat

er(

m15

9.24

6m

olkg

21;

com

pile

r!.A

dditi

onal

info

rmat

ion:

Als

ore

port

edw

ere

free

zing

poin

tte

mpe

ratu

res

for

solu

tions

cont

aini

ng98

.4–

320

gK

OC

N/1

000

gw

ater

.T

hecr

yohy

dric

poin

twas

repo

rted

tobe

at218

.14

°C.T

heco

mpo

sitio

nat

the

cryo

hydr

icpo

intw

asno

trep

orte

d.C

ompi

ler

smoo

ther

the

free

zing

poin

tda

taby

linea

rre

gres

sion

ofth

eda

tato

afif

thor

der

poly

nom

ial,

from

whi

chth

eco

mpo

sitio

nat

the

cryo

hydr

icpo

int

was

obta

ined

byex

trap

olat

ion

as35

2.3

gK

OC

N/1

000

gw

ater

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Due

tora

pid

deco

mpo

sitio

nof

KO

CN

inth

eso

lutio

ns,

repr

oduc

ible

resu

ltsw

ere

obta

ined

byvi

olen

tsh

akin

gin

ath

erm

osta

tfo

ra

shor

ttim

e.

KO

CN

,sou

rce

notr

epor

ted,

cont

aine

dun

spec

ified

smal

ltra

ceof

carb

onat

e.It

was

drie

din

ava

cuum

desi

ccat

or.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

0.3%

~aut

hors

,fr

omfo

urde

term

inat

ions!.

Co

~1!

~2!

Va T/

at Me

An

eq tw se int

clo

pe the

wi

ba wh

tem

bo wa


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umcy

anat

e;K

OC

N;@590

-28-

3#E

than

ol;

C 2H

6O

;@6

4-17

-5#

Wat

er;

H 2O

;@7

732-

18-5#

J.A

.C

rans

ton

and

A.

Y.Li

ving

ston

e,J.

Che

m.

Soc

.50

1–

3~1

926!

.

riabl

es:

Pre

pare

dB

y:

K:

273

anol

conc

entr

atio

n:80

%an

d10

0%~v/

v!J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

OC

Nat

0°C

inet

hano

land

one

etha

nol—

wat

ersy

stem

a

Eth

anol

~%,

v/v!

KO

CN

(g/1

00g

solv

ent!

KO

CN

(m1

/mol

kg2

1)b

801.

9

100

0.16

0.02

0

olid

phas

esw

ere

not

inve

stig

ated

.al

ueca

lcul

ated

byco

mpi

ler.

ditio

nali

nfor

mat

ion:

Als

ore

port

edw

ere

the

solu

bilit

ies

ofK

OC

Nat

boili

ngpo

ints

ofth

esa

tura

ted

solu

tions

as6.

2an

d0.

53g

KO

CN

r10

0g

solv

ent

for

80%

and

100%~

v/v!

etha

nol,

resp

ectiv

ely.

The

boili

ngpo

ints

tem

pera

ture

san

dat

mos

pher

icpr

essu

reat

whi

chth

eas

urem

ents

wer

epe

rfor

med

wer

eno

tre

port

ed.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

atio

ntim

ew

asno

tec

ified

.T

hesa

tura

ted

solu

tions

wer

ean

alyz

edby

wei

ghin

gfin

itevo

lum

eof

the

solu

tion,

and

dete

rmin

ing

the

cyan

ate

nten

tvo

lum

etric

ally

.1

Sou

rce

and

purit

yof

KO

CN

use

wer

eno

tspe

cifie

d.E

than

olus

edha

dde

nsity

of0.

799

gcm2

3at

17°C

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 Mas

son,

Che

m.

New

s.90,

5,17

~190

6!.

5151JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umcy

anat

e;K

OC

N;@590

-28-

3#~2

!18

-dib

enzo

-cro

wn-

6;C 20

H24

O6

;@1

4187

-32-

7#;or

18-d

icyc

lohe

xyl-c

row

n-6;

C 20H

36O

6;

@#

~3!

N,N

-dim

ethy

lform

amid

e;C 3H

7N

O;

@68-

12-2

#

V.A

.Zlo

bin

and

A.K

.Tar

asov

,Izv

.VU

Z,K

him

.Khi

m.T

ekhn

ol.

40,

No.

5,13

4–

5~19

97!.

Varia

bles

:P

repa

red

By:

T/K

:29

3;36

3c 2

/mol

dm2

3:

0.02

–0.

10(C

20H

24O

6);

0.02

–0.

10(C

20H

36O

6)

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

OC

Nin

N,N

-dim

ethy

lform

amid

ein

the

pres

ence

ofcr

own

ethe

rsat

20an

d90

°C

Tem

pera

ture

(t/°

C)

C20

H24

O6

(c2

/mol

dm2

3)

KO

CN

~gl2

1 !K

OC

N(1

02c 1

/mol

dm2

3)

C20

H36

O6

(c2

/mol

dm2

3)

KO

CN

~gl2

1 !K

OC

N(1

02c 1

/mol

dm2

3)

20—

0.87

1.08

0.02

1.03

1.27

0.02

0.94

1.16

0.04

1.10

1.36

0.04

1.13

1.39

0.08

1.59

1.97

0.08

1.59

1.97

0.10

1.62

2.00

0.10

2.96

3.65

90—

0.79

0.97

0.10

2.83

3.50

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

deta

ilsre

port

edon

lyon

anal

ytic

alm

etho

dsus

ed.

The

conc

entr

atio

nof

OC

N2

inC

3H

7N

Ow

asde

term

ined

chro

noco

nduc

tom

etric

ally

bytit

ratin

gan

aliq

uot

ofth

esa

tura

ted

solu

tion

agai

nst

0.1

mol

dm2

3A

gNO

3so

lutio

nin

CH 3

CN

,w

hich

was

deliv

ered

into

the

titra

tion

vess

elvi

aa

capi

llary

tube

ata

cons

tant

rate

bya

peris

talti

cpu

mp.

The

appa

ratu

sw

asca

libra

ted

bytit

ratin

ga

0.1

mol

dm2

3H

Cls

olut

ion

inis

oam

ylal

coho

l.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

eth

a S b V Ad

pe me

Me

An

sp de co

J

re,

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#W

ater

;H 2

O;

@773

2-18

-5#E

.Iw

ase,

Bul

l.In

st.P

hys.

Che

m.R

es.

~Tok

yo!

9,54

1–

3~19

30!.

riabl

es:

Pre

pare

dB

y:

K:

293

–31

3H

.Aka

iwa

and

J.H

a´ l

a

Exp

erim

enta

lDat

aS

olub

ility

ofLi

SC

Nin

wat

eras

afu

nctio

nof

tem

pera

ture

a

mpe

ratu

re(t

/°C

)Li

SC

N(1

00w

1/m

ass

%)

LiS

CN

(m1

/mol

kg2

1)

2053

.16

53.1

153

.25

53.26

0.06

17.4

8

2554

.75

54.2

454

.560.

318

.42

3055

.97

56.7

556

.65

56.66

0.3

20.1

4

3558

.99

58.4

958

.76

58.76

0.2

21.9

5

4060

.54

60.2

060

.43

60.46

0.1

23.4

6

vera

geva

lues

,st

anda

rdde

viat

ions

,an

dm

olal

ities

calc

ulat

edby

the

com

pile

r~J

.H.!.

The

resu

ltsw

ere

repo

rted

also

ingr

aphi

cal

form

ig.

8!sh

owin

gth

eeq

uilib

rium

solid

phas

es.

FIG

.8.

Sol

ubili

tycu

rves

oflit

hium

thio

cyan

ate

hydr

ates

inw

ater

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Mea

sure

men

tsw

ere

perf

orm

edac

cord

ing

toF

indl

ay.

1Li

SC

Nw

aspr

epar

edby

doub

lede

com

posi

tion

from

Ba

~SC

N) 2

and

Li2S

O4

,an

dcr

ysta

llize

das

LiS

CN•2

H2O

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

see

the

tabl

eab

ove.

Ref

eren

ces:

1 A.

Fin

dlay

,Pra

ctic

alP

hys

ica

lC

he

mis

try~1

923!

,p.

269.


6.T

heS

olub

ility

ofT

hioc

yana

tes

6.1.

Lith

ium

Thi

ocya

nate

6.1.

1.E

valu

atio

nof

the

LiS

CN

–H

2O

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#~2

!W

ater

;H 2

O;

@773

2-18

-5#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,Apr

il20

01.

Crit

ical

Eva

luat

ion

The

data

onth

eLi

SC

N–

wat

ersy

stem

have

been

repo

rted

inth

ree

docu

men

ts.

Iwas

e1

repo

rted

the

solu

bilit

ies

ofLi

SC

Nob

tain

edby

isot

herm

alm

etho

din

the

tem

pera

ture

rang

efr

om29

3to

313

K,

whi

lein

the

othe

rtw

odo

cum

ents

,2,

3th

esy

stem

was

stud

ied

bypo

lyth

erm

alm

etho

d.E

xcep

tfo

rth

eva

lue

at30

5.6

K,

whi

chse

ems

tobe

too

low

,th

epo

lyth

erm

alda

taof

Sch

imm

el3

are

ingo

odag

reem

ent

with

thos

eof

Iwas

e1

at29

3–

313

K,

whi

leth

eda

taof

Nik

olae

v2

are

cons

ider

ably

high

erin

the

sam

ete

mpe

ratu

rera

nge.

Thi

sm

ayha

vebe

enca

used

byth

ete

nden

cyof

LiS

CN

solu

tions

tosu

pers

atur

atio

n,th

ough

expl

icitl

yth

isha

sbe

enre

port

ed2

only

for

high

lyco

ncen

trat

edLi

SC

Nso

lutio

ns.

Alth

ough

Iwas

e1di

dno

trep

ortt

heer

ror

ofte

mpe

ratu

rem

easu

rem

ent,

here

port

edth

ree

cons

iste

ntm

easu

rem

ents

atea

chte

mpe

ratu

and

his

data

can

besu

gges

ted

aste

ntat

ive

valu

esin

the

tem

pera

ture

rang

eof

293

–31

3K

.T

here

isso

me

inco

nsis

tenc

yin

the

publ

ishe

dda

taas

for

the

exis

tenc

ere

gion

san

dth

eco

mpo

sitio

nof

the

solid

phas

es.I

was

e1

repo

rted

the

eute

ctic

poin

tat

233

°Cas

that

ofth

eic

e/Li

SC

N•2

H2O

pair,

whi

leS

chim

mel3

repo

rted

the

eute

ctic

poin

tat2

92°C

for

the

ice/

LiS

CN•

5H

2O

pair.

Inad

ditio

n,Iw

ase1an

dN

ikol

aev2

repo

rted

the

tran

sitio

nof

LiS

CN•2

H2O

toLi

SC

NH 2

Oto

occu

rat

34–

35°C

,w

hile

Sch

imm

el3de

scrib

edth

edi

hydr

ate

asth

eeq

uilib

rium

solid

phas

eup

to43

.3°C

.Con

trar

yto

Iwas

e1

and

Nik

olae

v,2he

also

obse

rved

the

trih

ydra

tean

dpe

ntah

ydra

te,

but

not

the

mon

ohyd

rate

.

Ref

eren

ces:

1 E.

Iwas

e,B

ull.

Inst

.P

hys.

Che

m.

Res

earc

h~T

okyo

!9,

541

~193

0!.

2 V.I.

Nik

olae

v,Z

h.R

uss.

Fiz

.-K

him

.O

bsh.6

1,93

9~1

929!

.3 F.

A.

Sch

imm

el,

J.C

hem

.E

ng.

Dat

a5,51

9~1

960!

.

Co

~1!

~2!

Va T/

Te a A ~F


Add

ition

alin

form

atio

n:O

neis

othe

rmal

mea

sure

men

tw

aspe

rfor

med

at17

°C,

yiel

ding

100

w15

63.3

mas

s%

(m15

26.3

5m

olkg

21;

com

pile

r!.In

syst

ems

cont

aini

ng12

–21

mol

%Li

SC

N,

glas

ses

with

nodi

stin

ctm

eltin

gpo

ints

wer

efo

rmed

.S

olut

ions

with

the

LiS

CN

/H2O

ratio

grea

ter

than

2sh

owed

stro

ngte

nden

cyto

supe

rsat

urat

ion.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Apo

lyth

erm

alm

etho

dw

asus

ed.

The

syst

ems

wer

epr

epar

edfr

omLi

SC

N•2

H2O

byei

ther

addi

ngw

ater

toth

esa

lt~for

LiS

CN

/H2O

ratio

s,2!

,or

bydr

ying

the

salt

over

H 2SO

4of

vary

ing

conc

entr

atio

nin

ade

sicc

ator~for

LiS

CN

/H2O

ratio

s.

2!.

Sam

ples

ofLi

SC

Nhy

drat

edto

the

desi

red

degr

eew

ere

seal

edin

thin

-wal

led

glas

stu

bes,

solid

ified

byco

olin

g,an

dth

eso

lidus

tem

pera

ture

sw

ere

dete

rmin

edby

the

capi

llary

met

hod.

Sam

ples

with

LiS

CN

/H 2O

ratio

s.2

wer

est

rong

lyhy

gros

copi

can

dha

dto

bepr

epar

edas

quic

kly

aspo

ssib

le.

The

com

posi

tion

ofth

esa

mpl

esw

asde

term

ined

afte

rth

ede

term

inat

ion

ofso

lidus

tem

pera

ture

.T

hetu

bes

wer

ew

eigh

ed,

brok

en,

and

the

cont

ents

anal

yzed

for

SC

N2

.C

ondi

tions

used

for

the

sing

leis

othe

rmal

mea

sure

men

t,an

dth

em

etho

dof

iden

tifica

tion

ofth

eso

lidph

ases

wer

eno

tre

port

ed.

LiS

CN•2

H2O

was

prep

ared

bydo

uble

deco

mpo

sitio

nfr

omLi

2S

O4

and

Ba~S

CN

) 2.

Sou

rce

and

purit

yof

thes

em

ater

ials

wer

eno

tsp

ecifi

ed.

Sin

ceso

lutio

nsof

LiS

CN

tend

tofo

rmsu

pers

atur

ated

solu

tions

,cr

ysta

lliza

tion

ofth

edi

hydr

ate

had

tobe

indu

ced

byse

edin

g.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#W

ater

;H 2

O;

@773

2-18

-5#F.

A.

Sch

imm

el,

J.C

hem

.E

ng.

Dat

a5,51

9–

20~1

950!

.

riabl

es:

Pre

pare

dB

y:

K:

181

–31

6J.

Ha´ la

Exp

erim

enta

lDat

aC

ompo

sitio

nof

the

satu

rate

dso

lutio

nsin

the

LiS

CN

–H

2O

syst

em

iqui

dus

pera

ture

(t/°

C)

LiS

CN

(100

w1

/mas

s%

)Li

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

Liqu

idus

tem

pera

ture

(t/°

C)

LiS

CN

(100

w1

/mas

s%

)Li

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

216

.547

.313

.80

C

27.

510

.19

1.74

5A

212

.547

.914

.14

C

217

.918

.00

3.37

6A

25.

048

.914

.72

C

225

.021

.34

4.17

2A

050

.015

.38

C

233

.024

.75.

045

A1

50.2

15.5

0C1D

262

.533

.07.

575

A3.

050

.315

.56

D

265

.533

.75

7.83

5A

6.0

50.9

615

.98

D

292

38.2

9.50

6A1

B12

.051

.68

16.4

5D

277

39.9

10.2

1B

16.5

52.5

217

.01

D

268

.540

.910

.64

B24

.554

.118

.13

D

259

.042

.311

.27

B27

.055

.419

.10

D

256

.043

.011

.60

B1C

28.0

55.5

19.1

8D

249

.043

.611

.89

C32

.556

.319

.81

D

242

.044

.412

.28

C40

.360

.523

.56

D

235

.045

.112

.63

C43

.063

.827

.10

D

228

.045

.813

.00

C43

.364

.327

.70

D

alcu

late

dby

com

pile

r.:

Ice,

H2O

@773

2-18

-5#;

B:

LiS

CN•5

H2O

@#;

C:

LiS

CN•3

H2O

@#;

D:

LiS

CN•2

H2O

@843

72-5

8-7#.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

poly

ther

mal

met

hod

was

used

.T

heso

lubi

lity

was

foun

dby

dete

rmin

ing

the

tem

pera

ture

atw

hich

the

solid

phas

edi

sapp

eare

d.E

ach

solu

tion

was

first

allo

wed

tocr

ysta

llize

quic

kly

byco

olin

git

tolo

wte

mpe

ratu

res.

See

ding

with

the

prop

erhy

drat

ew

asne

cess

ary

beca

use

othe

rwis

eth

een

tire

syst

emtu

rned

into

ahi

ghly

visc

ous

orso

lid,

glas

s-lik

esu

bsta

nce

whi

chco

uld

not

becr

ysta

llize

d.Ve

ryfin

ecr

ysta

lsw

ere

obta

ined

.Te

mpe

ratu

rew

asth

enra

ised

slow

ly.

The

rate

of1

°Cpe

r15

min

was

suffi

cien

tlylo

wto

obta

inre

prod

ucib

leva

lues

.M

etho

dsof

anal

ysis

ofth

esa

tura

ted

solu

tions

and

ofth

eso

lidph

ases

wer

eno

tre

port

ed.

LiS

CN

was

prep

ared

byre

actin

ga

LiO

Hso

lutio

nw

ithso

lidN

H4S

CN

.T

heso

lutio

nw

asbo

iled

until

noam

mon

iaco

uld

bede

tect

ed.

The

solu

tion

was

filte

red

and

conc

entr

ated

unde

rva

cuum

.T

hesa

ltob

tain

edw

asre

crys

talli

zed

from

wat

er.

The

prod

uct

was

free

from

Fe,

Ca,

and

sulfa

tes.

Afte

rdr

ying

over

H2S

O4

,it

cont

aine

d6.

81%

Lian

d57

.40%

SC

N.

Cal

cula

ted

for

the

dihy

drat

e:6.

87%

Li,

57.4

7%S

CN

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.25

and6

0.5

°Cin

the

rang

esof

med

ium

and

very

low

tem

pera

ture

s,re

spec

tivel

y~aut

hor!.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

5353JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#~2

!W

ater

;H 2

O;

@773

2-18

-5#V.

I.N

ikol

aev,

Zh.

Rus

s.F

iz-K

him

.O

bsh.6

1,93

9–

45~1

929!

.

Varia

bles

:P

repa

red

By:

T/K

:24

0–

533

J.H

a´ la

Exp

erim

enta

lDat

aF

reez

ing

poin

tsan

dso

lubi

lity

inth

eLi

SC

N–

H2O

syst

em

Sol

idus

tem

pera

ture

(t/°

C)

LiS

CN

(100

x 1/m

ol%

)Li

SC

N(1

00w

1/m

ass

%)a

LiS

CN

(m1

/mol

kg2

1)a

Sol

idph

aseb

00

00

A2

4.0

3.09

10.3

21.

770

A2

10.8

4.86

15.5

72.

836

A2

13.7

5.50

17.3

63.

231

A2

18.0

7.04

21.4

74.

205

A2

33.0

11.9

132

.80

7.50

7A1

B0

21.1

549

.19

14.8

9B

5.0

22.5

351

.21

16.1

4B

10.0

23.8

153

.01

17.3

5B

11.5

24.3

253

.70

17.8

4B

17.6

24.8

054

.34

18.3

0B

18.5

25.0

054

.61

18.5

0B

19.5

25.1

354

.78

18.6

3B

27.5

29.5

760

.24

23.3

0B

34.0

33.3

464

.35

27.7

6B

38.5

35.0

966

.12

30.0

1C

44.5

37.3

168

.23

33.0

3C

55.5

45.2

574

.89

C58

47.4

076

.48

C60

.550

.00

78.3

0C

102

51.5

579

.34

D14

453

.19

80.4

0D

201.

558

.13

83.3

6D

260c

83.3

494

.75

D

a Cal

cula

ted

byco

mpi

ler.

b A:

Ice,

H2O

@773

2-18

-5#;

B:

LiS

CN•2

H2O

@843

72-5

8-7#;

C:

LiS

CN•H

2O

@970

34-6

9-8#;

D:

LiS

CN

@556

-65-

0#.c M

eltin

gun

der

deco

mpo

sitio

n.

Co

~1!

~2!

Va T/ L

tem

a C b A Me

A

J

gel-l

ike.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#N

,N-d

imet

hyla

ceta

mid

e;C 4H

9N

O;

@127

-19-

5#A

.A.F

edor

ov,L

.B.S

okol

ov,V

.M.S

avin

ov,M

.A.S

hlio

nska

ya,

and

N.

I.F

ilato

va,

Zh.

Prik

l.K

him

.44,

2361

–2~

1971

!.

riabl

es:

Pre

pare

dB

y:

K:

295

–29

8J.

Ha´ la

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofLi

SC

Nin

N,N

-dim

ethy

lace

tam

ide

isre

port

edto

bec 15

1.80

mol

dm2

3at

22–

25°C

.The

natu

reof

the

equi

libriu

mlid

phas

ew

asno

tin

vest

igat

ed.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eso

lven

tw

assa

tura

ted

with

anhy

drou

ssa

lt.T

hen

apa

rtof

solv

ent

was

dist

illed

off

tore

mov

ew

ater

,an

dth

esa

tura

ted

lutio

nw

ithex

cess

solid

was

kept

for

3da

ysin

ade

ssic

ator

apa

raffi

n-co

ated

flask

.T

heco

nten

tof

wat

erin

the

satu

rate

dlu

tion

was

,0.

1%.

The

satu

rate

dso

lutio

nw

asan

alyz

edfo

rco

nten

tof

sulfu

rby

anun

spec

ified

met

hod.

Anh

ydro

usLi

SC

Nw

aspr

epar

edac

cord

ing

toLe

e.1

N,N

-dim

ethy

lace

tam

ide,

sour

ceno

tsp

ecifi

ed,

was

fres

hly

dist

illed

befo

reus

e.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 D.A

.Le

e,In

org.

Che

m.3,

289

~196

4!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#~2

!A

mm

onia

;N

H 3;

@766

4-41

-7#G

.C

.B

lyta

s,D

.J.

Ker

tesz

,an

dF.

Dan

iels

,J.

Am

.C

hem

.S

oc.

84,

1083

–5~

1962

!.

Varia

bles

:P

repa

red

By:

T/K

:19

1–

293

J.H

a´ la

Exp

erim

enta

lDat

aC

ompo

sitio

nof

the

satu

rate

dso

lutio

nsin

the

LiS

CN

–N

H3

syst

ema

Liqu

idus

tem

pera

ture

(t/°

C)

NH

3

(100

w2

/mas

s%

)M

oles

NH 3

/mol

eLi

SC

NLi

SC

Nb

(100

w1

/mas

s%

)Li

SC

Nb

(m1

/mol

kg2

1)

275

96.5

510

6.8

3.45

0.54

95

282

79.7

515

.04

20.2

53.

905

264

50.8

95.

0449

.11

14.8

4

1644

.11

2.95

55.8

919

.49

2033

.91

1.96

66.0

929

.97

a Com

posi

tion

ofth

eeq

uilib

rium

solid

phas

esno

tre

port

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Apo

lyth

erm

alm

etho

d1w

asus

ed.

The

salt

was

quic

kly

intr

oduc

edin

toa

glas

stu

be,

whi

chw

asth

ense

aled

aton

een

d,he

ated

and

evac

uate

dfo

r24

h,an

dw

eigh

ed.

The

nth

evo

lum

eof

purifi

edN

H 3ne

cess

ary

togi

veth

ede

sire

dsa

ltco

ncen

trat

ion

was

dist

illed

in,

the

tube

was

seal

edof

f,an

dw

eigh

edag

ain.

Equ

ilibr

atin

gan

dth

erm

osta

ting

wer

eca

rrie

dou

tin

diffe

rent

bath

sde

pend

ing

onth

ete

mpe

ratu

rera

nge.

Cal

ibra

ted

ther

mom

eter

sw

ere

used

.Li

quid

uste

mpe

ratu

res

wer

ere

cord

edas

thos

eat

whi

chth

ela

stcr

ysta

lsdi

sapp

eare

dw

ithsl

owhe

atin

g.T

his

was

pref

erre

dto

obse

rvin

gte

mpe

ratu

res

ofap

pear

ance

offir

stcr

ysta

lsbe

caus

eof

the

tend

ency

ofth

esy

stem

tofo

rmsu

pers

atur

ated

solu

tions

onco

olin

g.T

heso

lutio

nsw

ere

visc

ous,

and

wer

edi

fficu

ltto

wor

kw

ith.A

thi

gher

LiS

CN

conc

entr

atio

ns,

the

solu

tions

wer

e

NH

3us

edw

asst

ored

over

sodi

umm

etal

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 G.C

.Bly

tas

and

F.D

anie

ls,J

.Am

.Che

m.S

oc.

84,1

075~

1926

!.

Co

~1!

~2!

Va T/

so Me

Th

the

so in so the


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#T

ri-n-

buty

l~pho

spha

te!;C

12H

27O

4P

;@1

26-7

3-8#

J.H

alaan

dD

.G

.T

uck,

Can

ad.

J.C

hem

.48

,28

43–

6~19

70!.

riabl

es:

Pre

pare

dB

y:

K:

295

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofLi

SC

Nin

tri-n

-but

yl~ph

osph

ate!

isre

port

edto

be12

.0g

salt

in10

0g

solv

ent

at22

°C(

m15

1.84

6m

olkg

21).

Add

ition

alin

form

atio

n:S

atur

ated

solu

tions

ofLi

SC

Nin

the

solv

entw

ere

very

visc

ous.

The

solv

ent/L

iSC

Nm

ole

ratio

inth

esa

tura

ted

lutio

nsw

asfo

und

tobe

2.03

,in

dica

ting

the

exis

tenc

eof

the

diso

lvat

e,Li

SC

N•2

C12

H27

O4P

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.A

nex

cess

ofth

esa

ltw

asak

enov

erni

ght

with

5m

Ldr

yso

lven

t.P

relim

inar

ype

rimen

tssh

owed

that

this

was

suffi

cien

tfo

req

uilib

rium

tore

ache

d.S

ampl

esof

the

satu

rate

dso

lutio

nsw

ere

with

draw

nou

gha

sint

er,

dilu

ted

with

acet

one,

and

anal

yzed

for

the

ocya

nate

cont

ent

bytit

ratio

nag

ains

tA

gNO

3st

anda

rdlu

tion.

Bla

nktit

ratio

nssh

owed

that

asm

allc

orre

ctio

nw

asqu

ired

beca

use

ofth

epr

esen

ceof

tri-n

-but

yl~p

hosp

hate!.

LiS

CN

was

prep

ared

from

lithi

umca

rbon

ate

and

aso

lutio

nof

thio

cyan

icac

id.

The

latte

rw

asob

tain

edby

ion/

exch

ange

ona

colu

mn

ofD

owex

50W

-X8

resi

nin

the

Hfo

rm.

The

solu

tion

ofLi

SC

Nw

asev

apor

ated

todr

ynes

san

dth

enhe

ated

at70

–80

°Cin

ast

ream

ofdr

yni

trog

enga

s.1T

hefin

alpr

oduc

tco

ntai

ned

appr

oxim

atel

y85

%Li

SC

N,

the

rem

aind

erof

wat

erco

uld

not

bere

mov

eddu

eto

the

deco

mpo

sitio

nof

LiS

CN

abov

e80

°C.

Tri-

n-bu

tyl~p

hosp

hate!

~Fis

her

Sci

entifi

cC

o.!w

aspu

rified

byre

fluxi

ngit

with

0.5%

caus

ticso

daso

lutio

n,fo

llow

edby

stea

mdi

still

atio

n.T

hepr

oduc

twas

drie

dfir

stw

ithan

hydr

ous

MgS

O4

,an

dfin

ally

vacu

umdr

ied

at50

°Cin

ast

ream

ofdr

yni

trog

enga

s.2

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

0.1

gsa

lt/10

0g

solv

ent~a

utho

rs!.

Ref

eren

ces:

1 J.E

.C

oate

san

dE

.J.

Tayl

or,

J.C

hem

.S

oc.

1245

~193

6!.

2 D.

G.

Tuc

k,J.

Che

m.

Soc

.27

83~19

58!.

5555JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#~2

!N

,N-d

imet

hyla

ceta

mid

e;C 4H

9N

O;

@127

-19-

5#N

.A

.B

asan

ova,

I.L.

Kru

patk

in,

and

A.

N.

Bas

anov

,F

azo

vye

Ra

vno

vesi

ya~P

hase

Equ

ilibr

ia!~K

alin

in.

Gos

ud.

Uni

v.,

1974!

,pp

.8

–12

.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofLi

SC

Nin

N,N

-dim

ethy

lace

tam

ide

isre

port

edto

be10

0x 1

528

.4m

ol%

at25

°C~c

ompi

ler:

m1

54.

55m

olkg

21).

The

natu

reof

the

equi

libriu

mso

lidph

ase

was

not

repo

rted

.A

dditi

onal

info

rmat

ion:

Als

ore

port

edw

asth

eph

ase

diag

ram

ofth

eLi

SC

N–

N,N

-dim

ethy

lace

tam

ide

–n-

deca

nesy

stem

at25

°C.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

No

deta

ilsre

port

ed.

Anh

ydro

usLi

SC

Nw

aspr

epar

edac

cord

ing

toLe

e.1

Sou

rce

and

purit

y,in

part

icul

arth

eco

nten

tof

wat

er,

ofN

,N-d

imet

hyla

ceta

mid

e,w

asno

tre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 D.A

.Le

e,In

org.

Che

m.3,

289

~196

4!.

Co

~1!

~2!

Va T/

so Me

An

sh ex be thr

thi

so re

J

s

titra

tions

with

stan

dard

AgN

O 3so

lutio

n.T

heso

lidph

ases

wer

eal

soch

arac

teriz

edby

Sch

rein

emak

ers’

met

hod.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

the

erro

rof

the

titrim

etric

met

hod

was

repo

rted

as6

1.5%

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#B

oric

acid

;H 3

BO

3;

@100

43-3

5-3#

Wat

er;

H 2O

;@7

732-

18-5#

V.G

.Skv

orts

ov,R

.S.T

sekh

ansk

ii,S

h.V.

Sad

etdi

nov,

and

A.K

.M

olod

kin,

Zh.

Neo

rg.

Khi

m.2

8,26

77–

9~19

83!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

5.6

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofLi

SC

Nat

25°C

inaq

ueou

sso

lutio

nsof

boric

acid

H3B

O3

00w

2/m

ass

%)

H3B

O3

(m2

/mol

kg2

1)a

LiS

CN

(100

w1

/mas

s%

)Li

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

52.9

417

.30

A

1.97

0.70

152

.58

17.7

9A

1.96

0.69

752

.55

17.7

7A1

B

alcu

late

dby

com

pile

r.:

LiS

CN•2

H2O

@843

72-5

8-7#;

B:

H3B

O3

@100

43-3

5-3#.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofsi

xsa

tura

ted

solu

tions

ntai

ning

1.98

–5.

6m

ass

%H

3B

O3

and

52.5

6–

0m

ass

%Li

SC

N,

whe

reH

3B

O3

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tow

nhe

resi

nce

they

repr

esen

tth

eso

lubi

lity

ofH

3B

O3

inso

lutio

nsof

LiS

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Sol

utio

nsw

ithex

cess

solid

rest

irred

for

20h,

whi

chw

assu

ffici

ent

for

equi

libriu

mto

reac

hed.

Bor

ate

and

SC

N2

wer

ede

term

ined

inth

etu

rate

dso

lutio

nstit

rimet

rical

ly~met

hods

not

spec

ified!,

solid

ases

wer

ech

arac

teriz

edby

Sch

rein

emak

ers’

met

hod.

lubi

lity

isot

herm

sw

ere

also

confi

rmed

byre

frac

tom

etric

asur

emen

ts.

LiS

CN

and

H 3B

O3

wer

ech

emic

ally

pure

prod

ucts

,an

dw

ere

recr

ysta

llize

dbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#~2

!Li

thiu

mch

lorid

e;Li

Cl;

@744

7-41

-8#~3

!W

ater

;H 2

O;

@773

2-18

-5#

M.

K.

Khr

ipun

,A.Y

u.E

fimov

,L.

S.

Lilis

,an

dM

.L.

Kut

uzov

a,Z

h.N

eorg

.K

him

.31,

2659

–65

~198

6!.

Varia

bles

:P

repa

red

By:

T/K

:29

8m

2/m

olkg

21:

0–

20.0

5J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofLi

SC

Nat

25°C

inaq

ueou

sso

lutio

nsof

LiC

l

LiC

l(m

2/m

olkg

21)

LiC

l(1

00w

2/m

ass

%)a

LiS

CN

(m1

/mol

kg2

1)

LiS

CN

(100

w1

/mas

s%

)aS

olid

phas

eb

00

19.7

056

.16

A

1.58

2.95

18.5

053

.00

A

3.65

6.80

17.2

549

.27

A

4.26

8.03

16.4

547

.53

A

6.50

12.0

315

.60

44.3

0A

7.00

13.0

215

.10

43.0

9A

8.80

16.2

014

.30

40.3

8A1

B

8.80

16.2

514

.20

40.2

1A1

B

8.70

16.0

914

.20

40.2

8A1

B

8.60

15.9

314

.20

40.3

6A1

B

8.55

16.1

313

.60

39.3

6A1

B

a Cal

cula

ted

byco

mpi

ler.

b A:

LiS

CN•2

H2O

,@8

4372

-58-

7#;B

:Li

Cl•

H2O

,@1

6712

-20-

2#.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sre

port

edal

soth

eco

mpo

sitio

nsof

11sa

tura

ted

solu

tion

cont

aini

ng10

.40

–20

.05

mol

kg21

LiC

land

11.9

0–

0m

olkg2

1Li

SC

N,

whe

reLi

Cl•H

2O

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tsh

own

here

sinc

eth

eyre

pres

ent

the

solu

bilit

yof

LiC

lin

solu

tions

ofLi

SC

N.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

naly

sis

ofth

eso

lidan

dliq

uid

phas

esw

asca

rrie

dou

tby

diffe

rent

ialp

oten

tiom

etric

No

deta

ilsre

port

ed.

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co sh Me

An

we

be sa ph So

me


smpo

nent

s:O

rigin

alM

easu

rem

ents

:

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#Li

thiu

mte

trab

orat

e;Li 2

B4O

7;

@120

07-6

0-2#

Wat

er;

H 2O

;@7

732-

18-5#

V.G

.S

kvor

tsov

,A

.K

.M

olod

kin,

Sh.

V.S

adet

dino

v,an

dR

.S

.Ts

ekha

nski

i,Z

h.N

eorg

.K

him

.26,

3164

–6~

1981

!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

2.42

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofLi

SC

Nat

25°C

inaq

ueou

sso

lutio

nsof

sodi

umte

trab

orat

e

Li2B

4O

7

00w

2/m

ass

%)

Li2B

4O

7

(m2

/mol

kg2

1)a

LiS

CN

(100

w1

/mas

s%

)Li

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

52.9

417

.30

A

0.35

0.04

3552

.10

16.8

5A1B

alcu

late

dby

com

pile

r.:

LiS

CN•2

H2O

@843

72-5

8-7#;

B:

Li2B

4O

7•3

H2O

@371

95-6

2-3#.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofsi

xsa

tura

ted

solu

tions

ntai

ning

0.37

–2.

92m

ass

%Li 2B

4O

7an

d52

.07

–0

mas

s%

LiS

CN

,w

here

Li2B

4O

7•3

H2O

was

the

equi

libriu

mso

lidph

ase.

The

seda

tae

not

show

nhe

resi

nce

they

repr

esen

tth

eso

lubi

lity

ofLi

2B

4O

7in

solu

tions

ofLi

SC

N.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

ium

was

reac

hed

thin

20h,

whi

chw

asch

ecke

dby

chem

ical

anal

ysis

and

frac

tion

inde

xof

the

satu

rate

dso

lutio

ns.

Bor

ate

and

SC

N2

rede

term

ined

inth

esa

tura

ted

solu

tions

titrim

etric

ally

etho

dsno

tsp

ecifi

ed!,so

lidph

ases

wer

ech

arac

teriz

edby

hrei

nem

aker

s’m

etho

d.

LiS

CN

and

Li2B

4O

7w

ere

chem

ical

lypu

repr

oduc

ts,

and

wer

ere

crys

talli

zed

befo

reus

e.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

5757JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#~2

!Li

thiu

mbo

rate

;Li

BO 2

;@1

3453

-69-

5#~3

!W

ater

;H 2

O;

@773

2-18

-5#

V.G

.Skv

orts

ov,S

h.V.

Sad

etdi

nov,

R.S

.Tse

khan

skii,

and

A.K

.M

olod

kin,

Zh.

Neo

rg.

Khi

m.2

4,20

9–

12~1

979!

.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

0–

3.04

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofLi

SC

Nat

25°C

inaq

ueou

sso

lutio

nsof

lithi

umbo

rate

LiB

O2

(100

w2

/mas

s%

)Li

BO

2

(m2

/mol

kg2

1)a

LiS

CN

(100

w1

/mas

s%

)Li

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

52.9

417

.30

A

1.07

0.46

152

.24

17.2

1A

1.08

0.46

552

.20

17.1

8A1

B

1.05

0.45

252

.23

17.1

9B

1.10

0.41

745

.89

13.1

3B

1.27

0.41

136

.60

9.06

0B

1.38

0.39

428

.18

6.15

3B

a Cal

cula

ted

byco

mpi

ler.

b A:

LiS

CN•2

H2O

@843

72-5

8-7#;

B:

(LiB

O2) m•(L

iSC

N) n

,so

lidso

lutio

nsof

varia

ble

com

posi

tion

(m

.n

).

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sal

sore

port

edth

eco

mpo

sitio

nsof

six

satu

rate

dso

lutio

nco

ntai

ning

1.60

–3.

04m

ass

%Li

BO

2an

d23

.05

–0

mas

s%

LiS

CN

,w

here

LiB

O2•8

H2O

orLi

BO

2•2

H2O

wer

eth

eeq

uilib

rium

solid

phas

es.

The

seda

taar

eno

tsh

own

here

sinc

eth

eyre

pres

ent

the

solu

bilit

yof

LiB

O2

inso

lutio

nsof

LiS

CN

.Als

ore

port

edw

ere

dens

ities

,vi

scos

ities

,an

dre

frac

tion

inde

xes

ofth

esa

tura

ted

solu

tions

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

ium

was

reac

hed

with

in24

hun

der

cons

tant

shak

ing

ina

ther

mos

tat.

Bor

ate

and

SC

N2w

ere

dete

rmin

edin

the

satu

rate

dso

lutio

nstit

rimet

rical

ly~m

etho

dsno

tsp

ecifi

ed!,so

lidph

ases

wer

ech

arac

teriz

edby

Sch

rein

emak

ers’

met

hod

and

chem

ical

anal

ysis

.

LiS

CN

and

LiB

O 2w

ere

chem

ical

lypu

repr

oduc

ts,

and

wer

ere

crys

talli

zed

befo

reus

e.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co ar Me

An

wi

re we

~m Sc

J

49.0

022

.38

00

C

300

056

.70

26.6

0A

3.78

2.01

56.6

127

.78

A

7.09

3.92

56.5

328

.89

A

9.88

5.65

56.0

529

.52

A

10.0

15.

8057

.02

30.4

9A1

D

10.3

75.

9455

.72

29.4

1D

13.7

98.

0654

.24

29.3

5D

17.0

910

.21

52.2

528

.80

D

25.6

517

.06

51.0

031

.25

D

26.2

517

.28

49.8

030

.22

D1B

24.8

815

.95

49.4

429

.21

B

33.8

731

.55

40.2

423

.61

B

46.2

331

.15

31.9

419

.84

B

57.7

241

.94

25.3

116

.96

B

64.0

949

.54

22.5

716

.09

B

71.9

462

.38

20.8

116

.65

B

72.5

061

.07

18.8

614

.66

C

68.9

650

.68

15.0

910

.23

C

68.1

246

.92

12.1

37.

77C

60.5

533

.53

4.76

2.43

C

57.5

028

.87

00

C

4520

.47

13.4

355

.26

33.4

6D

26.0

417

.28

50.5

830

.98

D

28.9

619

.61

48.9

630

.57

D

31.8

821

.88

47.0

129

.79

D

31.8

121

.98

47.4

730

.28

B

39.5

427

.23

39.7

825

.29

B

46.2

232

.03

33.7

021

.55

B

50.6

636

.05

30.9

720

.33

B

56.1

041

.54

27.9

619

.10

B

62.1

048

.59

25.1

318

.12

B

65.1

052

.42

23.7

417

.63

B

70.8

361

.19

21.7

017

.31

B

74.5

267

.65

20.4

417

.10

B1C

73.0

661

.33

18.1

314

.05

C

69.8

450

.74

13.5

99.

11C

67.8

545

.90

11.2

77.

02C

66.3

942

.19

8.72

5.11

C

61.0

034

.79

00

C

:Li

SC

N•2

H2O

@843

72-5

8-7#;

B:

LiS

CN•2

CO

~NH

2) 2

@415

14-7

3-2#;

C:

CO

~NH

2) 2

@57-

13-6

#;D

:Li

SC

N•C

O~N

H2) 2

@415

14-7

4-3#.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.N

othi

ngsp

ecifi

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#~2

!U

rea;

CH 4

N2O

;@5

7-13

-6#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

R.T

urgu

nbek

ova,

K.N

ogoe

v,an

dK

.Sul

aim

anku

lov,

Zh.

Neo

rg.

Khi

m.

18,

1119

–22

~197

3!.

Varia

bles

:P

repa

red

By:

T/K

:28

8,30

3,an

d31

810

0w

2/m

ass

%:

0–

66.4

8at

288

K,

0–

72.5

0at

303

K,

0–

74.5

2at

318

K

J.H

ala

Exp

erim

enta

lDat

aC

ompo

sitio

nof

the

satu

rate

dso

lutio

nsin

the

LiS

CN

–ur

ea–

H2O

syst

emat

thre

ete

mpe

ratu

res

Tem

pera

ture

(t/°

C)

Ure

a(1

00w

2/m

ass

%)

Ure

a(1

00x 2

/mol

%)

LiS

CN

(100

w1

/mas

s%

)Li

SC

N(1

00x 2

/mol

%)

Sol

idph

asea

150

052

.00

23.0

7A

3.32

1.64

51.5

123

.32

A

7.34

3.79

51.0

424

.40

A

9.88

5.26

50.8

625

.03

A

15.3

88.

7750

.72

26.7

4A

20.1

912

.43

50.4

129

.25

A1B

20.7

512

.49

49.3

327

.44

B

23.3

213

.59

44.5

523

.99

B

25.4

914

.41

40.7

021

.39

B

29.0

916

.49

36.9

919

.38

B

38.6

923

.14

31.4

817

.39

B

49.4

131

.33

25.0

414

.67

B

58.4

540

.60

22.0

014

.12

B

65.9

250

.78

20.6

314

.68

B

66.4

851

.87

20.7

714

.97

B1C

66.4

951

.97

20.8

615

.06

C

61.5

540

.41

15.5

39.

42C

59.9

237

.21

13.4

97.

74C

57.9

434

.17

11.8

76.

47C

56.0

631

.28

6.69

4.99

C

53.8

727

.92

6.12

2.93

C

a A Me

An


Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

6.2.

Sod

ium

Thi

ocya

nate

6.2.

1.E

valu

atio

nof

the

NaS

CN

–H

2O

Sys

tem

mpo

nent

s:E

valu

ator

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#W

ater

;H 2

O;

@773

2-18

-5#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,Ju

ne20

01.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

NaS

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

reha

sbe

enre

port

edin

Hug

hes

and

Mea

d,1

Zhu

ravl

evan

dB

ychk

ova,2

dT

itova

and

Bat

ura.3

Par

tingt

on4

repo

rted

asi

ngle

valu

eat

298

K,

and

furt

her

data

coul

dbe

extr

acte

dfr

omth

est

udie

sof

vario

usna

rysy

stem

sN

aSC

N–

salt

–H

2O

.5–

13A

llav

aila

ble

data

have

been

sum

mar

ized

inth

efo

llow

ing

tabl

ean

dF

ig.

9.T

heso

lubi

lity

curv

eha

stw

obr

anch

es.B

elow

303

K,t

heeq

uilib

rium

solid

phas

eis

the

dihy

drat

e,2,

5,7,

12,1

3 NaS

CN•

2H

2O

whi

leab

ove

3K

itis

the

anhy

drou

ssa

lt.2,5,

7T

hedi

hydr

ate

was

confi

rmed

asth

eso

lidph

ase

byth

em

etho

dof

wet

resi

dues

and

care

ful

chem

ical

alys

is,2an

dit

seem

sth

atth

eco

nclu

sion

sab

out

NaS

CN

•H

2O

~Hug

hes

and

Mea

d1 !or

anhy

drou

sN

aSC

N~ref

erto

four

stud

ies8–

11!

asso

lidph

ases

belo

w30

3K

wer

ein

erro

r.T

hetr

ansi

tion

poin

tfr

omN

aSC

N•2

H2O

toN

aSC

Nha

sbe

enre

port

edto

beat

30.3

–30

.5°C

03.5

–30

3.7

K!1or

at27

.7°C

~300

.9K!

.2T

hetr

ansi

tion

poin

ttem

pera

ture

ofab

out3

0°C

can

also

bees

timat

edfr

omth

eph

ase

diag

ram

the

NaS

CN

–H 2

Osy

stem

,re

port

edby

Dar

rin.

16F

rom

this

diag

ram

,th

eic

e–

NaS

CN

•2

H2O

eute

ctic

poin

tw

ases

timat

edby

the

alua

tor

toap

pear

atap

prox

imat

ely

236

°Can

d38

.5m

ass

%N

aSC

N.

Sum

mar

yof

the

solu

bilit

yof

NaS

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

re

mpe

ratu

re(t

/°C

)Te

mpe

ratu

re~K

!N

aSC

N(m

1/m

olkg

21)

Ref

.Te

mpe

ratu

re(t

/°C

)Te

mpe

ratu

re~K

!N

aSC

N(m

1/m

olkg

21)

Ref

.

027

3.2

11.5

22

29.2

302.

420

.66

1

5.0

278.

212

.84

230

.030

3.2

36.5

314

10.0

283.

213

.36

533

.030

6.2

21.4

62

10.7

283.

913

.90

121

.50

3

15.5

288.

715

.70

233

.830

7.0

21.2

71

17.3

290.

515

.73

140

.031

3.2

21.0

07

20.0

293.

217

.39

652

.58

14

20.4

314

40.5

313.

721

.59

3

21.3

294.

517

.18

146

.131

9.3

21.9

61

24.0

297.

218

.12

250

.032

3.2

22.4

12

25.0

298.

215

.21

453

.032

6.2

22.7

12

18.5

02

22.2

13

17.3

97

65.0

338.

223

.45

3

15.8

38

65.8

339.

023

.37

1

17.5

89

–11

73.8

347.

024

.20

1

17.3

812

74.7

347.

924

.04

3

17.8

95

81.8

355.

024

.92

1

17.5

813

85.2

358.

425

.44

3

The

grap

hica

lco

mpa

rison

ofth

eso

lubi

lity

data~n

umbe

rsin

the

grap

hre

fer

toth

eco

rres

pond

ing

refe

renc

es!

show

sa

reas

onab

leag

reem

entb

etw

een

the

poly

ther

mal

1an

dan

alyt

ical2

met

hods

belo

w30

3K

,and

amon

gth

ree

sets

ofda

taab

ove

303

K.

1–

3T

heda

tabe

low

303

Kfr

omR

efs.

1an

d2,

toge

ther

with

thos

efr

omth

est

udie

sof

tern

ary

syst

ems,

5–

7,9

–13

have

been

com

pute

rsm

ooth

edby

alin

ear

regr

essi

onof

the

data

toa

fifth

orde

rpo

lyno

mia

lto

obta

inth

eso

lubi

lity

ofN

aSC

Nin

wat

erov

erth

ete

mpe

ratu

rera

nge

of27

3–

303

Kas

m1

~mol

kg2

1!5

0.15

4699

310

62

0.12

911

0310

4T

20.

784

735T

21

0.36

7702

310

21

T32

0.12

320

4310

23

T4

10.

126

9263

102

6T

5.

The

solu

bilit

yda

taof

Par

tingt

onan

dS

ophe

r,4

and

God

ean

dK

lyav

ina8at

298

Kar

eob

viou

sly

too

low

and

wer

eno

tco

nsid

ered

for

the

smoo

thin

gpr

oced

ure.

Like

wis

e,no

tcon

side

red

was

the

solu

bilit

yat

293.

2K

repo

rted

inLa

vrov

ae

ta

l.14It

isto

ohi

gh,a

ndob

viou

sly

corr

espo

nds

toth

eso

lubi

lity

ofan

hydr

ous

NaS

CN

,w

hich

ism

etas

tabl

eat

this

tem

pera

ture

.S

imila

rly,

the

data

from

Hug

hes

and

Mea

d,1

Zhu

ravl

evan

dB

ychk

ova,2

Tito

vaan

dB

atur

a,3an

dG

olya

ndan

dLu

dkov

skay

a7

have

been

smoo

thed

toob

tain

the

solu

bilit

yof

NaS

CN

asa

func

tion

ofte

mpe

ratu

rein

the

rang

eof

305

–34

9K

as

5959JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Lith

ium

thio

cyan

ate;

LiS

CN

;@556

-65-

0#~2

!A

min

es~3

!D

ichl

orom

etha

ne;

CH 2C

l 2;

@75-

09-2

#

G.

Sou

la,

Eur

.P

at.A

ppl.

0166

73,

1979

;F

r.A

ppl.

7905

438.

Varia

bles

:P

repa

red

By:

T/K

:un

spec

ified

ambi

ent

tem

pera

ture

c 2/m

oldm

23:

0.1

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofLi

SC

Nin

0.1

mol

dm2

3so

lutio

nsof

two

amin

esin

dich

loro

met

hanea

Am

ine

LiS

CN

~mg

dm2

3 !Li

SC

N(c

1/m

oldm

23)b

2-~2

-met

hoxy

etho

xy!-N

,N-b

is2-

~2-m

etho

xyet

hoxy!

ethy

let

hana

min

e;~tr

is~d

ioxa

-3,6

-hep

tyl!a

min

e!;

C15

H33

NO

6;

@703

84-5

1-9#

694

0.01

06

2-m

etho

xy-N

,N-b

is~m

etho

xyet

hyl!e

than

amin

e;~t

ris~o

xa-3

-but

yl!am

ine!

;C

9H

21N

O3

;@3

235-

51-6#

690

0.01

06

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

ofLi

SC

Nin

neat

CH 2C

l 2w

asre

port

edto

bele

ssth

an1

mg

dm23 .

The

solu

biliz

atio

nef

fect

oftr

is~d

ioxa

-3,6

-hep

tyl!a

min

ew

asex

plai

ned

byth

eau

thor

byth

efo

rmat

ion

ofa

1:1

addu

ctof

LiS

CN

with

the

amin

ein

the

satu

rate

dso

lutio

n.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

salt,

0.00

1m

ole,

was

equi

libra

ted

byst

irrin

gw

ith0.

001

mol

eof

the

amin

ein

10m

LC

H2C

l 2fo

r10

min

.T

heco

nten

tof

the

salt

inth

esa

tura

ted

solu

tion

was

dete

rmin

edby

flam

eph

otom

etry

.

No

deta

ilsre

port

edfo

rLi

SC

N.T

ris~dio

xa-3

,6-h

epty

l!am

ine

was

prep

ared

byre

fluxi

ngso

dium

met

hoxy

-2-e

than

olat

ein

met

hoxy

-2-e

than

olfo

r12

hat

125

°C.

The

exce

ssso

lven

tw

asth

endi

still

edof

f,ex

cess

sodi

umm

etho

xy-2

-eth

anol

ate

deco

mpo

sed

with

conc

entr

ated

HC

l,an

dth

eam

ine

dist

illed

at16

5–

180

°Cat

0.5

mm

Hg

pres

sure

.Tris~oxa

-3-b

utyl!

amin

ew

asob

tain

edby

asi

mila

rpr

oced

ure

usin

gso

dium

met

hano

late

,an

dm

etha

nola

sth

eso

lven

t.A

fter

trea

tmen

toft

hem

ixtu

rew

ithH

Cl,

the

amin

ew

asex

trac

ted

into

CH

2C

l 2an

ddi

still

ed.

Dic

hlor

omet

hane

was

dehy

drat

edan

dpu

rified

from

stab

ilize

rs.

Co

~1!

~2!

an ter

30 an the

~3 of ev Te

J

the

rd

V.A

.T

itova

and

Z.

E.

Bat

ura,

Zh.

Neo

rg.

Khi

m.10,

1711

~196

5!.

4 J.R

.P

artin

gton

and

W.

E.

Sop

er,

Phi

los.

Mag

.7,

209

~192

9!.

5 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.6 E

.S

paca

mel

laM

arch

etti,

Atti

.Aca

d.S

ci.

Torin

o,C

lase

.F

is.

Mat

.N

at.

94,

353

~196

0!.

7 S.

M.

Gol

yand

and

B.

G.

Ludk

ovsk

aya,

Zh.

Neo

rg.

Khi

m.

11,

1433

~196

6!.

8 G.

K.

God

ean

dL.

A.

Kly

avin

a,Z

h.N

eorg

.K

him

.15,

1147

~197

0!.

9 V.G

.S

kvor

tsov

,R

.S

.Ts

ekha

nski

i,S

h.V.

Sad

etdi

nov,

and

A.

K.

Mol

odki

n,Z

h.N

eorg

.K

him

.28

,26

77~1

983!

.10

V.G

.S

kvor

tsov

,S

h.V.

Sad

etdi

nov,

R.

S.

Tsek

hans

kii,

and

A.

K.

Mol

odki

n,Z

h.N

eorg

.K

him

.24

,20

9~1

979!

.11

V.G

.S

kvor

tsov

,A.

K.

Mol

odki

n,S

h.V.

Sad

etdi

nov,

R.

S.

Tsek

hans

kii,

and

V.M

.F

edor

ov,

Zh.

Neo

rg.

Khi

m.

26,

3164

~198

1!.

12Z

.G

.K

arov

,I.

N.

Lepe

shko

v,an

dE

.I.

Kuk

ulie

va,

Zh.

Neo

rg.

Khi

m.

17,

509

~197

2!.

13A

.K

.M

cK

erro

w,

V.J.

Occ

lesh

aw,

and

F.D

rabb

le,

J.C

hem

.S

oc.

1~1

946!

.14

O.A

.La

vrov

a,N

.N

.M

okos

ina,

and

O.

S.

Kar

chm

arch

ik,

Zh.

Neo

rg.

Khi

m.

29,

1312

~198

4!.

15C

.K

.B

ump,

J.P

hys.

Che

m.36

,18

51~1

932!

.16

M.

Dar

rin,

U.S

.P

aten

t1,

570

047~1

925!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#W

ater

;H 2

O;

@773

2-18

-5#O

.L.

Hug

hes

and

T.H

.M

ead,

J.C

hem

.S

oc.

2282

–4

~192

9!.

riabl

es:

Pre

pare

dB

y:

K:

283

–37

4J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

wat

eras

afu

nctio

nof

tem

pera

ture

a

mpe

ratu

re(t

/°C

)N

aSC

N(g

/100

gH 2

O)

NaS

CN

(100

w1

/mas

s%

)bN

aSC

N(m

1/m

olkg

21)b

10.7

112.

752

.99

13.9

0

17.3

127.

556

.04

15.7

3

21.3

139.

358

.21

17.1

8

29.2

167.

562

.62

20.6

6

33.8

172.

462

.30

21.2

7

46.1

178.

064

.03

21.9

6

65.8

189.

565

.46

23.3

7

73.8

196.

266

.24

24.2

0

81.8

202.

066

.89

24.9

2

101.

422

5.6

69.2

927

.83

heeq

uilib

rium

solid

phas

esw

ere

repo

rted

tobe

NaS

CN

•H

2O

and

NaS

CN

atte

mpe

ratu

res

belo

wan

dab

ove

30.3

–30

.5°C

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lyth

erm

alm

etho

dus

ed.

Sol

idN

aSC

Nw

ashe

ated

with

ter

ina

seal

edtu

beun

tilon

eor

two

smal

lcry

stal

sm

aine

d.Tw

ote

mpe

ratu

res

wer

eth

enre

cord

ed,

one

atw

hich

shar

pnes

sof

the

crys

tale

dges

indi

cate

dth

atth

eyw

ere

owin

g,an

dth

eot

her

whe

reth

ero

undn

ess

ofth

ecr

ysta

lsow

edth

eyw

ere

diss

olvi

ng.

Sin

ceth

ese

tem

pera

ture

sne

ver

fere

dby

mor

eth

an0.

5°C

,th

eir

mea

nw

asta

ken

asth

epe

ratu

reof

satu

ratio

n.O

win

gto

the

deliq

uesc

ence

ofN

aSC

N,

the

salt

was

intr

oduc

edin

toth

ew

eigh

edtu

bes

inan

oven

at13

0°C

.T

hetu

bew

asal

low

edto

cool

ina

dess

icat

or,

wei

ghed

with

aru

bber

cap,

the

solv

ent

quic

kly

intr

oduc

ed,

the

tube

seal

edan

dw

eigh

edag

ain.

The

ther

mom

eter

,gr

adua

ted

in0.

2°C

,w

asst

anda

rdiz

edat

the

mel

ting

poin

tof

ice,

tem

pera

ture

ofth

eN

a 2SO

4•10

H2O

/Na 2

SO

4tr

ansi

tion,

and

the

boili

ngpo

int

ofw

ater

.T

heco

mpo

sitio

nof

the

hydr

ated

salt

was

dete

rmin

edby

chem

ical

anal

ysis

:ca

lcul

ated

/foun

dfo

rth

em

onoh

ydra

te,

20.4

/20.

0an

d20

.6%

H2O

.

NaS

CN

was

prep

ared

byhe

atin

gA

.R.

NH

4S

CN

with

equi

mol

aram

ount

ofca

ustic

soda

inaq

ueou

sso

lutio

nun

tilno

mor

eam

mon

iaw

asev

olve

d.T

heso

lutio

nw

asev

apor

ated

,an

dN

aSC

Nre

crys

talli

zed

from

alco

hol,

acet

one,

and

agai

nfr

omal

coho

l.C

ondu

ctiv

itygr

ade

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.5

K~c

ompi

ler!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.


m1

~mol

kg2

1!5

20.

103

4443

1071

0.15

754

5310

5T

20.

958

9193

102

T21

0.29

157

8T32

0.44

291

4310

23

T4

10.

268

8873

102

6T

5.

The

data

ofLa

vrov

aet

al.14

are

obvi

ousl

yun

real

istic

ally

high

,an

dw

ere

not

incl

uded

for

the

smoo

thin

gpr

oced

ure.

The

reis

not

stra

ight

forw

ard

expl

anat

ion

for

thes

etw

om

easu

rem

ents

.The

two

equa

tions

can

besu

gges

ted

asyi

eldi

ngte

ntat

ive

solu

bilit

yva

lues

inre

spec

tive

tem

pera

ture

rang

es.

Itis

note

wor

thy

that

solu

tions

ofN

aSC

Nsa

tura

ted

atab

out6

0°C

and

cool

edto

room

tem

pera

ture

show

ave

ryhi

ghte

nden

cyto

wa

supe

rsat

urat

ion.15

The

data

repo

rted

byB

ump

15ar

esh

own

inF

ig.

9.

FIG

.9.

Sol

ubili

tyof

NaS

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

re.

Ref

eren

ces:

1 O.

L.H

ughe

san

dT.

H.

Mea

d,J.

Che

m.

Soc

.22

82~192

9!.

2 E.

F.Z

hura

vlev

and

M.

N.

Byc

hkov

a,Z

h.N

eorg

.K

him

.4,

2367

~195

9!.

3

Co

~1!

~2!

Va T/

Te a T b C Me

Po

wa

re the

gr sh dif

tem


dmpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#W

ater

;H 2

O;

@773

2-18

-5#E

.F.

Zhu

ravl

evan

dM

.N

.B

ychk

ova,

Zh.

Neo

rg.

Khi

m.4,

2367

–75

~195

9!.

riabl

es:

Pre

pare

dB

y:

K:

273

–32

6J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

wat

eras

afu

nctio

nof

tem

pera

ture

mpe

ratu

re(t

/°C

)N

aSC

N(1

00w

1/m

ass

%)

NaS

CN

(m1

/mol

kg2

1)a

Sol

idph

aseb

048

.311

.52

A

5.0

51.0

12.8

4A

15.5

56.0

15.7

0A

24.0

59.5

18.1

2A

33.0

63.5

21.4

6B

53.0

64.8

22.7

1B

alcu

late

dby

com

pile

r.:

NaS

CN•

2H

2O

@170

32-4

0-5#;

B:

NaS

CN

@540

-72-

7#.

ditio

nali

nfor

mat

ion:

The

poin

tof

tran

sitio

nfr

omN

aSC

N•2

H2O

toN

aSC

Nw

asre

port

edto

beat

27.7

°C.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eso

lubi

litie

sw

ere

obta

ined

bygr

aphi

cala

naly

tical

thod

.1,2

Ase

ries

ofm

ixtu

res

ofth

esa

ltan

dw

ater

cove

ring

field

sof

unsa

tura

ted

and

satu

rate

dso

lutio

nsw

ere

prep

ared

wei

ghin

g.A

fter

equi

libriu

mha

dbe

enat

tain

ed,

refr

activ

eex

esof

the

solu

tions

wer

em

easu

red.

The

tran

sitio

nfr

omsa

tura

ted

tosa

tura

ted

solu

tions

,i.e

.,th

eco

rres

pond

ing

lubi

lity

valu

e,w

asob

tain

edas

abr

eak

onth

ere

frac

tive

exve

rsus

com

posi

tion

plot

.T

heco

mpo

sitio

nof

NaS

CN

H2O

asth

eso

lidph

ase

was

confi

rmed

grav

imet

rical

lyby

ying

the

solid

prod

uct,

whi

chw

asob

tain

edby

cool

ing

the

ritec

ticso

lutio

ns.

Cal

cula

ted/

foun

d~mas

s%!

for

the

ydra

te:

30.7

6/32

.49.

NaS

CN

,sou

rce

nots

peci

fied,

was

recr

ysta

llize

das

dihy

drat

ean

dth

ende

hydr

ated

at12

0–

130

°Cto

obta

inth

ean

hydr

ous

salt.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

2 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.

6161JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!S

olve

nts

J.R

.Par

tingt

onan

dW

.E.S

oper

,Phi

los.

Mag

.7,

209

–47

~192

9!.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

wat

eran

det

hano

lat

25°Ca

Sol

vent

NaS

CN

NaS

CN

(m1

/mol

kg2

1)b

Wat

er;

H 2O

;@7

732-

18-5#

14.6

649

gsa

ltin

11.8

907

gso

lven

t15

.21

Eth

anol

;C 2

H6O

;@6

4-17

-5#

2.68

32g

salt

in12

.729

2g

solv

ent

2.60

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.N

aSC

N,a

naly

tical

grad

e,so

urce

nots

peci

fied,

was

recr

ysta

llize

befo

reus

e.A

bsol

ute

etha

nol

was

prep

ared

from

a96

%pr

oduc

tin

the

follo

win

gw

ay.I

twas

first

kept

over

fres

hly

burn

tlim

efo

rso

me

days

with

perio

dica

lsha

king

.It

was

then

frac

tiona

ted,

the

first

and

last

runn

ings

bein

gre

ject

ed.

Itw

asth

enal

low

edto

stan

dov

erfr

eshl

ycl

eane

dan

dtu

rned

met

allic

calc

ium

,an

dw

asre

frac

tiona

ted,

the

first

and

last

runn

ings

bein

gag

ain

reje

cted

.T

hepr

oduc

tw

asfr

eefr

omal

dehy

de,

and

was

stor

edin

ave

ssel

with

asi

phon

atta

chm

ent

and

agu

ard

tube

with

P2O

5.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

only

one

solu

bilit

ym

easu

rem

ent

repo

rted

for

each

solv

ent.

Co

~1!

~2!

Va T/

Te a C b A Ad

Me

Th

me

the

by ind

un so ind

•2 dr pe dih

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate:

NaS

CN

;@540

-72-

7#W

ater

;H 2

O;

@773

2-18

-5#O

.A

.La

vrov

a,N

.N

.M

okos

ina,

and

O.

S.

Kar

chm

arch

ik,

Zh.

Neo

rg.

Khi

m.2

9,13

12–

6~19

84!.

riabl

es:

Pre

pare

dB

y:

K:

293

–31

3J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

wat

erat

thre

ete

mpe

ratu

res

a

mpe

ratu

re(t

/°C

)N

aSC

N(1

00w

1/m

ass

%)

NaS

CN

(100

x 1/m

ol%

)N

aSC

N(m

1/m

olkg

21)b

2062

.426

.920

.43

3077

.042

.636

.53

4081

.048

.652

.58

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

d1w

asus

ed.

Exc

ess

solid

was

stirr

edth

wat

erin

ath

erm

osta

ted

vess

elun

tileq

uilib

rium

was

ache

d.T

heco

nten

tof

NaS

CN

inth

esa

tura

ted

solu

tions

was

term

ined

bytit

ratio

nag

ains

ta

stan

dard

AgN

O3

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

rs!.

Sol

ubili

ty:6

0.2

–0.

5m

ol%

~aut

hors!

.

Ref

eren

ces:

1 T.M

.Le

stev

aan

dV.

I.C

hern

aya,

Zh.

Neo

rg.

Khi

m.

23,

2556

~197

8!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!W

ater

;H 2

O;

@773

2-18

-5#V.

A.

Tito

vaan

dZ

.E

.B

atur

a,Z

h.N

eorg

.K

him

.10,

1711

–2

~196

5!.

Varia

bles

:P

repa

red

By:

T/K

:30

6–

425

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

wat

eras

afu

nctio

nof

tem

pera

ture

a

Tem

pera

ture

(t/°

C)

NaS

CN

(g/1

00g

H 2O

)N

aSC

N(1

00w

1/m

ass

%)b

NaS

CN

(m1

/mol

kg2

1)b

33.0

174.

363

.54

21.5

0

40.5

175.

063

.64

21.5

9

53.0

180.

064

.29

22.2

1

65.0

190.

165

.53

23.4

5

74.7

194.

966

.09

24.0

4

85.2

206.

367

.35

25.4

4

99.3

226.

169

.34

27.9

0

122.

125

2.9

71.6

631

.19

139.

928

2.2

73.8

334

.82

152.

030

1.1

75.0

737

.14

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpl

ier.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

bym

eans

ofsp

ecia

lfiltr

atio

neq

uipm

ent.

Car

ew

asta

ken

toav

oid

cond

ensa

tion

ofw

ater

vapo

rin

the

filtr

atio

nap

para

tus

from

the

satu

rate

dso

lutio

ns.

The

solu

tions

wer

ean

alyz

edfo

rth

eS

CN

2co

nten

tby

pote

ntio

met

rictit

ratio

nw

ithA

gNO 3

solu

tion.

NaS

CN

,ch

emic

ally

pure

grad

e,w

asre

crys

talli

zed

from

wat

er.

Dis

tille

dw

ater

was

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

Va T/

Te a S b C Me

An

wi

re de


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#A

mm

onia

;N

H 3;

@766

4-41

-7#H

.H

unt,

J.A

m.

Che

m.

Soc

.54,

3509

–12

~193

2!.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aSC

Nw

asre

port

edto

be20

5.50

gin

100

gso

lven

tat

25°C

,or

,us

ing

the

dens

ityof

liqui

dam

mon

iaof

0.60

4cm

23

at25

°C,

124.

12g

NaS

CN

in10

0cm3

solv

ent.

Com

pile

rca

lcul

atedm

15

25.3

5m

olkg

21.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.A

mm

onia~10

–25

g!w

asui

libra

ted

with

the

salt

inth

ebo

ttom

part

ofa

seal

ed,

o/co

mpa

rtm

ent

Pyr

extu

be.

The

com

part

men

tsw

ere

para

ted

from

each

othe

rw

itha

narr

owne

ck.

The

salt

was

rodu

ced

into

the

tube

befo

rese

alin

git

off

ina

smal

lcup

sed

with

ave

rycl

osel

yw

oven

cotto

ncl

oth.

The

latte

rrm

itted

the

salt

todi

ssol

veth

esa

ltho

ldin

gba

ckth

eso

lidat

sam

etim

e.T

hesy

stem

was

equi

libra

ted

for

1–

3w

eeks

thoc

casi

onal

shak

ing.

The

nth

etu

bew

asin

vert

edin

the

than

dal

lthe

solu

tion

drai

ned

into

the

empt

yco

mpa

rtm

ent,

ich

was

cool

edan

dse

aled

off.

Whe

nit

reac

hed

room

pera

ture

itw

asdr

ied

and

wei

ghed

,th

eam

mon

iaal

low

edto

ilof

f,th

etu

bew

ithth

esa

ltw

arm

edun

tilal

lodo

rof

NH

3

sgo

ne,

and

the

salt

was

wei

ghed

.

NaS

CN

,B

aker

C.

P.pr

oduc

t,w

asre

crys

talli

zed

and

care

fully

drie

d.C

omm

erci

ally

avai

labl

ean

hydr

ous

NH

3w

asal

low

edto

stan

dov

erm

etal

licso

dium

for

seve

ralw

eeks

befo

reus

e.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.02

5K

~aut

hor!.

Sol

ubili

ty:

5%~a

utho

r!.

6363JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!S

ulfu

rdi

oxid

e;S

O 2;

@744

6-09

-5#G

.Ja

nder

and

W.

Rup

polt,

Z.

Phy

s.C

hem

.17

9,43

–50

~193

7!.

Varia

bles

:P

repa

red

By:

T/K

:27

3J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aSC

Nin

liqui

dsu

lfur

diox

ide

was

repo

rted

tobe

0.65

2g

salt

in10

0g

solv

enta

t0°C

.Fro

mth

isva

lue

the

com

pile

rca

lcul

ated

m1

/mol

kg2

15

0.08

04.

Add

ition

alin

form

atio

n:A

brig

ht-y

ello

weq

uilib

rium

solid

phas

e,N

aSC

N•2

SO 2

,w

asre

port

edin

Foo

tean

dF

leis

cher

.2

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

bout

10g

SO

2,

care

fully

drie

d,w

aseq

uilib

rate

dw

ithex

cess

NaS

CN

at0

°Cin

wat

er–

ice

bath

ina

thre

e-co

mpa

rtm

ent

glas

sve

ssel

inw

hich

equi

libra

ting

and

sam

plin

gco

mpa

rtm

ents

wer

ese

para

ted

bya

com

part

men

tco

ntai

ning

agl

ass/

woo

lfilte

r.E

quili

brat

ion

was

perf

orm

edfo

run

spec

ified

,pr

olon

ged

perio

dof

time

unde

rfr

eque

ntsh

akin

g.A

fter

equi

libriu

mha

dbe

enat

tain

ed,

the

vess

elw

astu

rned

upsi

dedo

wn,

and

the

satu

rate

dso

lutio

nw

asfil

tere

din

toth

eem

pty

sam

plin

gco

mpa

rtm

ent,

whi

chw

assu

bseq

uent

lyco

oled

and

seal

edof

f.A

fter

wei

ghin

gth

eco

mpa

rtm

ent

with

the

sam

ple,

SO

2w

asal

low

edto

evap

orat

e,th

ere

sidu

ew

asw

eigh

ed,

diss

olve

din

wat

er,

and

the

cont

ent

ofth

esa

ltw

asde

term

ined

.M

etho

dof

anal

ysis

was

not

spec

ified

.

NaS

CN

,so

urce

not

spec

ified

,w

asca

refu

llydr

ied

befo

reus

e.C

omm

erci

ally

avai

labl

eS

O 2w

aspu

rified

bypa

ssin

git

thro

ugh

conc

entr

ated

H 2SO

4an

dov

eras

best

osw

ool,

and

drie

dby

usin

gP 2

O5

.S

peci

ficco

nduc

tivity

ofth

epr

oduc

tw

as4.

53

102

7V

21

~Jan

der

and

Wic

kert1 !.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 G.

Jand

eran

dK

.W

icke

rt,

Z.

Phy

s.C

hem

.17

8,57

~193

6!.

2 H.

W.

Foo

tean

dJ.

Fle

isch

er,

J.A

m.

Che

m.

Soc

.54

,39

03~1

932!

.

Co

~1!

~2!

Va T/

g Me

An

eq tw se int

clo

pe the

wi

ba wh

tem

bo wa

J

FIG

.10

.P

hase

diag

ram

ofth

eN

aSC

N–

NH

3sy

stem

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

poly

ther

mal

met

hod1

was

used

.T

hesa

ltw

asqu

ickl

yro

duce

din

toa

glas

stu

be,

whi

chw

asth

ense

aled

aton

een

d,at

edan

dev

acua

ted

for

24h,

and

wei

ghed

.T

hen

the

volu

me

purifi

edN

H 3ne

cess

ary

togi

veth

ede

sire

dsa

ltnc

entr

atio

nw

asdi

still

edin

,th

etu

bew

asse

aled

off,

and

ighe

dag

ain.

Equ

ilibr

atin

gan

dth

erm

osta

ting

wer

eca

rrie

dt

indi

ffere

ntba

ths

depe

ndin

gon

the

tem

pera

ture

rang

e.lib

rate

dth

erm

omet

ers

wer

eus

ed.

Liqu

idus

tem

pera

ture

sre

reco

rded

asth

ose

atw

hich

the

last

crys

tals

disa

ppea

red

thsl

owhe

atin

g.T

his

was

pref

erre

dto

obse

rvin

gpe

ratu

res

ofap

pear

ance

offir

stcr

ysta

lsbe

caus

eof

the

denc

yof

the

syst

emto

form

supe

rsat

urat

edso

lutio

nson

olin

g.

NaS

CN

,che

mic

ally

pure

,was

heat

edan

dev

acua

ted,

pulv

eriz

ed,

rehe

ated

,an

dre

-eva

cuat

ed.

NH

3us

edw

asst

ored

over

sodi

umm

etal

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

0.01

mas

s%

~aut

hors!

.

Ref

eren

ces:

1 G.C

.Bly

tas

and

F.D

anie

ls,J

.Am

.Che

m.S

oc.

84,1

075~

1962

!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!A

mm

onia

;N

H 3;

@766

4-41

-7#G

.C

.B

lyta

san

dF.

Dan

iels

,J.

Am

.C

hem

.S

oc.

84,

1075

–83

~196

2!.

Varia

bles

:P

repa

red

By:

T/K

:19

2–

578

J.H

a´ la

Exp

erim

enta

lDat

aC

ompo

sitio

nsat

eute

ctic

poin

tsan

dth

eph

ase

diag

ram

ofth

eN

aSC

N–

NH

3sy

stem

~see

Fig

.10

!

Tem

pera

ture

(t/°

C)

NH

3

(100

w2

/mas

s%

)N

aSC

N(1

00w

1/m

ass

%)b

NaS

CN

(m1

/mol

kg2

1)a

218

.536

6421

.93

281

73.5

26.5

4.44

7

a Cal

cula

ted

byco

mpi

ler.

Me

A int

he of co we

ou Ca

we

wi

tem

ten

co


boili

ngpo

int

ofw

ater

.

6.2.

2.E

valu

atio

nof

the

NaS

CN

–E

than

olS

yste

m

mpo

nent

s:E

valu

ator

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#E

than

ol;

C 2H

6O

;@6

4-17

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

June

2001

.

Crit

ical

Eva

luat

ion

Ava

ilabl

eso

lubi

lity

data

for

NaS

CN

inet

hano

lare

the

isot

herm

ally

obta

ined

valu

esof

Par

tingt

onan

dco

-wor

kers

1–

3at

298

K,a

ndth

ely

ther

mal

data

ofH

ughe

san

dM

ead.

4T

heso

lubi

lity

at29

8K

repo

rted

orig

inal

lyby

Par

tingt

on,

i.e.,

2.59~K

ing

and

Par

tingt

on1 !an

d0

~Par

tingt

onan

dS

oper2 !

mol

kg2

1 ,w

ere

late

rre

fined

byth

eau

thor

s3

toob

tain

m15

2.54

8m

olkg

21.

The

auth

ors

expl

aine

dth

isfe

renc

eby

mor

eth

orou

ghdr

ying

ofth

em

ater

ials

used

inP

artin

gton

and

Win

tert

on.

3A

valu

eof

2.29

mol

kg2

1ca

nbe

obta

ined

for

the

lubi

lity

ofN

aSC

Nin

etha

nol

at29

8K

byin

terp

olat

ion

ofth

eda

taof

Hug

hes

and

Mea

d.4

Par

tingt

onan

dW

inte

rton3

anal

yzed

the

ason

sfo

rth

isdi

scre

panc

yan

dca

me

toth

eco

nclu

sion

that

the

solu

tions

ofH

ughe

san

dM

ead

4w

ere

prob

ably

not

satu

rate

d.T

hey

peat

edth

epo

lyth

erm

alm

easu

rem

ents

,and

thei

rre

sults

wer

e,ho

wev

er,i

ncon

sist

ent,

and

alw

ays

low

erth

anth

ose

obta

ined

byis

othe

rmal

asur

emen

ts.

Rec

omm

ende

dva

lue

for

the

solu

bilit

yof

NaS

CN

inet

hano

lat

298

K:

2.54

8m

olkg

21

or17

.12

mas

s%

.

fere

nces

:

.E

.K

ing

and

J.R

.P

artin

gton

,T

rans

.F

arad

ayS

oc.

23,

522

~192

7!.

.R

.P

artin

gton

and

W.

E.

Sop

er,

Phi

los.

Mag

.7,

209

~192

9!.

.R

.P

artin

gton

and

R.

J.W

inte

rton

,T

rans

.F

arad

ayS

oc.

30,

1104

~193

4!.

.L.

Hug

hes

and

T.H

.M

ead,

J.C

hem

.S

oc.

2282~192

9!.

6565JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!M

etha

nol;

CH 4

O;

@67-

56-1

#O

.L.

Hug

hes

and

T.H

.M

ead,

J.C

hem

.S

oc.

2282

–4

~192

9!.

Varia

bles

:P

repa

red

By:

T/K

:28

9–

325

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

met

hano

las

afu

nctio

nof

tem

pera

ture

a

Tem

pera

ture

(t/°

C)

NaS

CN

(g/1

00g

CH 4

O)

NaS

CN

(100

w1

/mas

s%

)bN

aSC

N(m

1/m

olkg

21)b

15.8

35.0

025

.93

4.31

7

24.7

40.0

428

.59

4.93

9

34.6

45.1

431

.10

5.56

8

48.0

50.9

833

.77

6.28

8

48.9

51.5

033

.99

6.35

2

52.3

53.5

434

.87

6.60

4

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Apo

lyth

erm

alm

etho

dw

asus

ed.

Sol

idN

aSC

Nw

ashe

ated

with

met

hano

lin

ase

aled

tube

until

one

ortw

osm

allc

ryst

als

rem

aine

d.Tw

ote

mpe

ratu

res

wer

eth

enre

cord

ed,

one

atw

hich

the

shar

pnes

sof

the

crys

tale

dges

indi

cate

dth

atth

eyw

ere

grow

ing,

and

the

othe

rw

here

the

roun

dnes

sof

the

crys

tals

show

edth

eyw

ere

diss

olvi

ng.

Sin

ceth

ese

tem

pera

ture

sne

ver

diffe

red

bym

ore

than

0.5

°C,

thei

rm

ean

was

take

nas

the

tem

pera

ture

ofsa

tura

tion.

Ow

ing

toth

ede

lique

scen

ceof

NaS

CN

,th

esa

ltw

asin

trod

uced

into

the

wei

ghed

tube

sin

anov

enat

130

°C.

The

tube

was

allo

wed

toco

olin

ade

ssic

ator

,w

eigh

edw

itha

rubb

erca

p,th

eso

lven

tqu

ickl

yin

trod

uced

,th

etu

bese

aled

and

wei

ghed

agai

n.T

heth

erm

omet

er,

grad

uate

din

0.2

°C,

was

stan

dard

ized

atth

em

eltin

gpo

int

ofic

e,te

mpe

ratu

reof

the

Na 2S

O4•10

H2O

/Na 2

SO

4tr

ansi

tion,

and

the

NaS

CN

was

prep

ared

byhe

atin

gA

.R.

NH

4S

CN

with

equi

mol

aram

ount

ofca

ustic

soda

inaq

ueou

sso

lutio

nun

tilno

mor

eam

mon

iaw

asev

olve

d.T

heso

lutio

nw

asev

apor

ated

,an

dN

aSC

Nre

crys

talli

zed

from

alco

hol,

acet

one,

and

agai

nfr

omal

coho

l.C

ondu

ctiv

itygr

ade

met

hano

lwas

prep

ared

acco

rdin

gto

Har

tley

and

Rai

kes1an

dW

oolc

ock

and

Har

tley.2

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.5

K~c

ompi

ler!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 H.

Har

tley

and

H.

R.

Rai

kes,

J.C

hem

.S

oc.

127,

524

~192

5!.

2 J.W

.W

oolc

ock

and

H.

Har

tley,

Phi

los.

Mag

.5,

1133

~192

8!.

Co

~1!

~2!

po 2.6

dif

so re re me

Re

1 F 2 J 3 J 4 O

J

tem

pera

ture

ofth

eN

a 2SO

4•10

H2O

/Na 2

SO

4tr

ansi

tion,

and

the

boili

ngpo

int

ofw

ater

.

2 J.W

.W

oolc

ock

and

H.

Har

tley,

Phi

los.

Mag

.5,

1133

~192

8!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#A

lcoh

ols

A:

F.E

.K

ing

and

J.R

.P

artin

gton

,T

rans

.F

arad

ayS

oc.

23,

522

–31

~192

7!.

B:

J.R

.P

artin

gton

and

R.

J.W

inte

rton

,T

rans

.F

arad

ayS

oc.

30,

1104

–5~

1934

!.C

:J.

R.

Par

tingt

onan

dR

.J.

Win

tert

on,

Tra

ns.

Far

aday

Soc

.30

,61

9–

26~1

934!

.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

two

alco

hols

at25

°Ca

Alc

ohol

NaS

CN

~gsa

lt/10

0g

solv

ent!

NaS

CN

(m1

/mol

kg2

1)b

dc

~gcm

23 !

Eth

anol

;C 2

H6O

;@6

4-17

-5#

~sou

rce

A!20

.99

2.58

90.

882

502

Eth

anol

;C 2

H6O

;@6

4-17

-5#

~sou

rce

B!20

.66

2.54

8

prop

en-1

-ol~a

llyla

lcoh

ol!;

C3H

6O

;@1

07-1

8-6#

~sou

rce

C!12

.40

1.53

00.

904

65

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

ensi

tyof

the

satu

rate

dso

lutio

n.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

d1w

asus

ed.

The

salt

was

equi

libra

ted

thth

eso

lven

tin

anat

mos

pher

eof

hydr

ogen

gas,

first

inan

ther

mos

tat

at256

0.05

°Cun

tileq

uilib

rium

was

reac

hed,

dth

enle

ftfo

r12

hin

wat

erth

erm

osta

tat

2560.

015

°C.

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

take

nin

toan

apor

atin

gbo

ttle,

whi

chw

asm

ade

tofit

the

equi

libriu

mss

elth

roug

ha

grou

ndjo

int.

Ana

lysi

sw

asca

rrie

dou

tbo

thdi

rect

evap

orat

ion

ofth

eso

lutio

n,an

dgr

avim

etric

ally

asC

N.

NaS

CN

was

prep

ared

byde

com

posi

tion

ofpu

reN

H4S

CN

with

caus

ticso

da,

whi

ch,

intu

rn,

was

prep

ared

from

sodi

umm

etal

.N

aSC

Nw

asre

crys

talli

zed

from

dist

illed

wat

eran

d96

%et

hano

l,an

ddr

ied

at12

0°C

over

P 2O5

.A

naly

sis

ofth

epr

oduc

tas

AgS

CN

yiel

ded

the

theo

retic

alpe

rcen

tage

ofS

CN

,i.e

.,71

.64%

.E

than

olw

aspr

epar

edfr

oma

96%

prod

uct.

The

latte

rw

asre

fluxe

dfor

6h

over

fres

hly

burn

tC

aO,

dist

illed

,an

dag

ain

reflu

xed

with

CaO

.It

was

then

dist

illed

ont

o5

gdr

iedA

gNO

3,

reflu

xed,

and

redi

still

ed,

agai

nre

fluxe

dw

ithC

atu

rnin

gsan

ddi

still

ed.

The

prod

uct~d

ensi

tyof

0.78

51g

cm2

3at

25°C

!w

asst

ored

ina

bottl

ew

itha

guar

dtu

bew

ithP

2O

5.

Ally

lalc

ohol

~Kah

lbau

m!w

asfr

actio

nate

dth

rough

a5

ftco

lumn.

The

frac

tion

boili

ngat

96°C

was

allo

wed

tost

and

over

CuS

O4

for

24h

and

agai

nfr

actio

nate

d.T

hefin

alpr

oduc

tbo

iled

at97

.1°C

at76

0m

mH

gpr

essu

re~de

nsity

of0.

8457

2g

cm23 !

was

stor

edin

the

dark

with

hydr

ogen

abov

eit

inor

der

toav

oid

the

form

atio

nof

alde

hyde

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.01

5K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 F.S

.Haw

kins

and

J.R

.Par

tingt

on,T

rans

.Far

aday

Soc

.24

,518

~192

8!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!E

than

ol;

C 2H

6O

;@6

4-17

-5#

O.

L.H

ughe

san

dT.

H.

Mea

d,J.

Che

m.

Soc

.22

82–

4~1

929!

.

Varia

bles

:P

repa

red

By:

T/K

:29

2–

344

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

etha

nola

sa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

NaS

CN

(g/1

00g

C 2H

6O

)N

aSC

N(1

00w

1/m

ass

%)b

NaS

CN

(m1

/mol

kg2

1)b

18.8

18.3

715

.52

2.26

6

35.8

19.0

516

.00

2.35

0

39.6

19.3

416

.21

2.38

6

52.8

21.0

517

.39

2.59

6

59.6

22.2

018

.17

2.73

8

61.8

22.6

018

.43

2.78

8

70.9

24.4

319

.63

3.01

3

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Apo

lyth

erm

alm

etho

dw

asus

ed.

Sol

idN

aSC

Nw

ashe

ated

with

etha

noli

na

seal

edtu

beun

tilon

eor

two

smal

lcry

stal

sre

mai

ned.

Two

tem

pera

ture

sw

ere

then

reco

rded

,on

eat

whi

chth

esh

arpn

ess

ofth

ecr

ysta

ledg

esin

dica

ted

that

they

wer

egr

owin

g,an

dth

eot

her

whe

reth

ero

undn

ess

ofth

ecr

ysta

lssh

owed

they

wer

edi

ssol

ving

.S

ince

thes

ete

mpe

ratu

res

neve

rdi

ffere

dby

mor

eth

an0.

5°C

,th

eir

mea

nw

asta

ken

asth

ete

mpe

ratu

reof

satu

ratio

n.O

win

gto

the

deliq

uesc

ence

ofN

aSC

N,

the

salt

was

intr

oduc

edin

toth

ew

eigh

edtu

bes

inan

oven

at13

0°C

.T

hetu

bew

asal

low

edto

cool

ina

dess

icat

or,

wei

ghed

with

aru

bber

cap,

the

solv

ent

quic

kly

intr

oduc

ed,

the

tube

seal

edan

dw

eigh

edag

ain.

The

ther

mom

eter

,gr

adua

ted

in0.

2°C

,w

asst

anda

rdiz

edat

the

mel

ting

poin

tof

ice,

NaS

CN

was

prep

ared

byhe

atin

gA

.R.

NH

4S

CN

with

equi

mol

aram

ount

ofca

ustic

soda

inaq

ueou

sso

lutio

nun

tilno

mor

eam

mon

iaw

asev

olve

d.T

heso

lutio

nw

asev

apor

ated

,an

dN

aSC

Nre

crys

talli

zed

from

alco

hol,

acet

one,

and

agai

nfr

omal

coho

l.C

ondu

ctiv

itygr

ade

etha

nol

was

prep

ared

acco

rdin

gto

Har

tley

and

Rai

kes1an

dW

oolc

ock

and

Har

tley.2

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.5

K~c

ompi

ler!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 H.

Har

tley

and

H.

R.

Rai

kes,

J.C

hem

.S

oc.

127,

524

~192

5!.

Co

~1!

~2!

Va T/

2- a S b C c D Me

An

wi

air

an Sa

ev ve by Ag


ture

ing

FIG

.11

.S

olub

ility

ofN

aSC

Nin

acet

one

asa

func

tion

ofte

mpe

ratu

re.

The

sing

leva

lue

ofD

erni

niet

al.3

for

the

solu

bilit

yof

NaS

CN

atth

ebo

iling

poin

tof

the

satu

rate

dso

lutio

nis

also

show

nin

the

grap

h.S

ince

the

boili

ngpo

int

tem

pera

ture

was

not

repo

rted

byth

eau

thor

sth

isso

lubi

lity

valu

ew

asno

tco

nsid

ered

for

the

com

pute

rsm

ooth

ing

proc

edur

e.T

here

appe

ars

tobe

adi

sagr

eem

ent

asfo

rth

eco

mpo

sitio

nof

the

equi

libriu

mso

lidph

ase.

Whi

leK

rum

galz

et

al.2

repo

rted

the

solid

phas

eto

beth

ean

hydr

ous

salt,

Hug

hes

and

Mea

d1

isol

ated

the

NaS

CN•O

C~C

H3) 2

addu

ctfr

omth

esa

tura

ted

solu

tion.

Ref

eren

ces:

1 O.

L.H

ughe

san

dT.

H.

Mea

d,J.

Che

m.

Soc

.22

82~192

9!.

2 B.

S.

Kru

mga

lz,

V.A

.S

mirn

ova,

and

Yu.

I.G

erzh

berg

,Z

h.N

eorg

.K

him

.17

,17

78~1

972!

.3 S

.D

erni

ni,

R.

DeS

antis

,an

dL.

Mar

relli

,J.

Che

m.

Eng

.D

ata

21,

170

~197

6!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#2-

Pro

pano

ne~a

ceto

ne!;

C3H

6O

;@6

7-64

-1#

O.

L.H

ughe

san

dT.

H.

Mea

d,J.

Che

m.

Soc

.22

82–

4~1

929!

.

riabl

es:

Pre

pare

dB

y:

K:

292

–32

9J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

acet

one

asa

func

tion

ofte

mpe

ratu

rea

mpe

ratu

re(t

/°C

)N

aSC

N(g

/100

gC 3

H6O

)N

aSC

N(1

00w

1/m

ass

%)b

NaS

CN

(m1

/mol

kg2

1)b

18.8

6.85

6.41

0.84

50

29.2

9.50

8.68

1.17

2

41.9

14.0

812

.34

1.73

7

51.0

18.6

115

.69

2.29

6

56.0

21.4

017

.63

2.64

0

heeq

uilib

rium

solid

phas

ew

asN

aSC

N•O

C~C

H3) 2

@#

atal

ltem

pera

ture

s.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

poly

ther

mal

met

hod

was

used

.S

olid

NaS

CN

was

heat

edth

acet

one

ina

seal

edtu

beun

tilon

eor

two

smal

lcry

stal

sm

aine

d.Tw

ote

mpe

ratu

res

wer

eth

enre

cord

ed,

one

atw

hich

shar

pnes

sof

the

crys

tale

dges

indi

cate

dth

atth

eyw

ere

owin

g,an

dth

eot

her

whe

reth

ero

undn

ess

ofth

ecr

ysta

lsow

edth

eyw

ere

diss

olvi

ng.

Sin

ceth

ese

tem

pera

ture

sne

ver

fere

dby

mor

eth

an0.

5°C

,th

eir

mea

nw

asta

ken

asth

epe

ratu

reof

satu

ratio

n.O

win

gto

the

deliq

uesc

ence

ofS

CN

,th

esa

ltw

asin

trod

uced

into

the

wei

ghed

tube

sin

anen

at13

0°C

.T

hetu

bew

asal

low

edto

cool

ina

dess

icat

or,

ighe

dw

itha

rubb

erca

p,th

eso

lven

tqu

ickl

yin

trod

uced

,th

ee

seal

edan

dw

eigh

edag

ain.

The

ther

mom

eter

,gr

adua

ted

in°C

,w

asst

anda

rdiz

edat

the

mel

ting

poin

tof

ice,

pera

ture

ofth

eN

a 2SO

4•10

H2O

/Na 2

SO

4tr

ansi

tion,

and

the

iling

poin

tof

wat

er.

The

solid

phas

esob

tain

edfr

omth

esa

tura

ted

solu

tions

wer

eke

ptin

ade

sicc

ator

over

anhy

drou

sN

aSC

Nfo

r1

day

tore

mov

ean

yex

cess

ofac

eton

e.A

naly

sis

foun

d45

.3–

45.8

mas

s%

acet

one;

calc

ulat

edfo

rN

aSC

N•O

C~C

H3) 2

,45

.0m

ass

%.

NaS

CN

was

prep

ared

byhe

atin

gA

.R.

NH

4S

CN

with

equi

mol

aram

ount

ofca

ustic

soda

inaq

ueou

sso

lutio

nun

tilno

mor

eam

mon

iaw

asev

olve

d.T

heso

lutio

nw

asev

apor

ated

,an

dN

aSC

Nre

crys

talli

zed

from

alco

hol,

acet

one,

and

agai

nfr

omal

coho

l.A

ceto

ne~P

oule

nc!

was

drie

dov

eran

hydr

ous

K 2CO

3,

frac

tiona

ted

twic

e,an

ddi

still

edin

acu

rren

tof

dry

air.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.5

K~c

ompi

ler!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

6767JIRI HALA


6.2.

3.E

valu

atio

nof

the

NaS

CN

–A

ceto

neS

yste

m

Com

pone

nts:

Eva

luat

or:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!2-

prop

anon

e~ac

eton

e!;C

3H

6O

;@6

7-64

-1#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

June

2001

.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

NaS

CN

inac

eton

eas

afu

nctio

nof

tem

pera

ture

has

been

repo

rted

intw

odo

cum

ents

.1,

2A

lthou

ghth

epo

lyth

erm

alda

ta1su

ffer

from

ate

mpe

ratu

reer

ror

of60.

25K

,F

ig.

11sh

ows

afa

irly

good

agre

emen

tbe

twee

nis

othe

rmal

2an

dpo

lyth

erm

al1re

sults

.T

hetw

ose

tsof

data

have

been

com

pute

rsm

ooth

edby

alin

ear

regr

essi

onto

ase

cond

orde

rpo

lyno

mia

l.T

heeq

uatio

nfo

rth

ete

mpe

rade

pend

ence

ofN

aSC

Nso

lubi

lity

inac

eton

ew

asob

tain

edas

m1

/mol

kg2

15

49.1

572

0.35

507

(T/K

)10.

000

649

(T/K

)2,

with

stan

dard

devi

atio

nsof

the

cons

tant

sof

2.28

5,0.

0149

,an

d0.

000

024,

resp

ectiv

ely.

The

equa

tion

can

besu

gges

ted

asyi

eld

tent

ativ

eda

tafo

rth

eso

lubi

lity

ofN

aSC

Nin

acet

one

over

the

tem

pera

ture

rang

eof

280

–34

0K

.

Co

~1!

~2!

Va T/

Te a T b C Me

A wi

re the

gr sh dif

tem

Na

ov we

tub

0.2

tem

bo

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#S

olve

nts

S.D

erni

ni,R

.DeS

antis

,and

L.M

arre

lli,J

.Che

m.E

ng.D

ata

21,

170

–3

~197

6!.

riabl

es:

Pre

pare

dB

y:

asur

emen

tsat

boili

ngpo

ints

ofth

esa

tura

ted

solu

tions

.J.

Ha

´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

two

solv

ents

atbo

iling

poin

tsat

760

mm

Hg

pres

sure

a

Sol

vent

NaS

CN

(g/1

00g

solv

ent!

NaS

CN

(m1

/mol

kg2

1)b

Boi

ling

poin

tof

the

satu

rate

dso

lutio

nc

(t/°

C)

eton

e;C 3

H6O

;@6

7-64

-1#

26.5

3.27

61.7

than

ol;

CH 4

O;

@67-

56-1

#63

.97.

8870

.8

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

alcu

late

dby

com

pile

rus

ing

ebul

iosc

opic

cons

tant

sof

1.7

and

0.8,

and

norm

albo

iling

poin

ts1

of56

.15

and

64.5

1°C

for

acet

one

and

etha

nol,

resp

ectiv

ely,

and

assu

min

gun

diss

ocia

ted

NaS

CN

inth

esa

tura

ted

solu

tions

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Det

erm

inat

ion

ofth

elu

bilit

ies

was

perf

orm

edby

sam

plin

g10

mL

ofth

ebo

iling

uid,

and

wei

ghin

gfir

stth

esa

mpl

e,an

dth

enth

ere

sidu

eer

thor

ough

evap

orat

ion

ofth

eso

lven

t.

NaS

CN

was

of98

.5m

ass

%pu

rity.

Ace

tone

and

met

hano

l,so

urce

not

spec

ified

,w

ere

both

of99

.9m

ass

%pu

rity.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 E.

Hal

aan

dA

.R

eise

r,P

hys

ica

lC

he

mis

try

~Cze

ched

.!~A

cade

mia

,P

ragu

e,19

71!,Vo

l.1,

p.27

8.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!2-

Pro

pano

ne~a

ceto

ne!;

C3H

6O

;@6

7-64

-1#

B.

S.

Kru

mga

lz,

V.A

.S

mirn

ova,

and

Yu.

I.G

erzh

berg

,Z

h.N

eorg

.K

him

.17,

1778

–80

~197

2!.

Varia

bles

:P

repa

red

By:

T/K

:28

3–

323

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

acet

one

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

NaS

CN

(m1

/mol

kg2

1)

100.

680

200.

860

251.

000

301.

210

401.

644

502.

190

a The

equi

libriu

mso

lidph

ase

was

NaS

CN@540

-72-

7#at

allt

empe

ratu

res.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

d1w

asus

ed.

Exc

ess

solid

was

equi

libra

ted

with

acet

one

byst

irrin

gin

acl

osed

,th

erm

osta

ted

vess

el.A

ttain

men

tof

equi

libriu

mw

asch

ecke

dby

mea

surin

gel

ectr

ical

cond

uctiv

ityof

the

solu

tion.

Toth

isai

m,

anel

ectr

olyt

icce

llcl

osed

with

agl

ass

sint

erw

asim

mer

sed

inth

eso

lutio

nth

roug

hout

the

mea

sure

men

t.A

tch

osen

time

inte

rval

s,th

em

easu

red

solu

tion

was

suck

edin

betw

een

two

plat

inum

elec

trod

es,

the

cond

uctiv

ityw

asm

easu

red,

and

the

solu

tion

was

tran

sfer

red

back

from

the

cell

toth

eso

lubi

lity

vess

elby

appl

ying

over

pres

sure

ofdr

yai

r.T

hepr

oced

ure

was

repe

ated

until

stea

dyco

nduc

tivity

ofth

eso

lutio

nw

asob

tain

ed.

The

equi

libriu

mco

nduc

tivity

valu

ew

asth

enus

edto

read

the

conc

entr

atio

nof

NaS

CN

inth

esa

tura

ted

solu

tion

from

aca

libra

tion

grap

hof

cond

uctiv

itypl

otte

dag

ains

tN

aSC

Nco

ncen

trat

ion

inac

eton

e.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

60.

2%~e

rror

ofco

nduc

tivity

mea

sure

men

ts;

auth

ors!.

Ref

eren

ces:

1 B.

S.

Kru

mga

lz,

Yu.

I.G

erzh

berg

,I.

P.N

ikiti

na,

V.I.

Der

evsk

aya,

G.

F.F

edot

ova,

and

D.

G.

Tra

ber,

Zh.

Prik

l.K

him

.42

,14

14~1

969!

.

Co

~1!

~2!

Va Me

Ac

Me

a S b C c C m Me

An

so liq aft


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#S

olve

nts

I.L.

Kru

patk

in,

L.D

.Vo

robe

va,

V.P.

Mas

khul

ia,

and

M.

E.

Vese

lova

,Z

h.O

bsh.

Khi

m.45

,98

5–

90~1

975!

.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

furf

ural

and

met

hyle

thyl

keto

neat

25°Ca

Sol

vent

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(m

1/m

olkg

21)b

fura

ncar

boxa

ldeh

yde~fur

fura

l!;C

5H

4O

2;

@98-

01-1

#14

.60

2.10

9

-but

anon

e~m

ethy

leth

ylke

tone!

;C

4H

8O

;@7

8-93

-3#

11.4

01.

587

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.N

aSC

N,

sour

cean

dpu

rity

not

spec

ified

,w

asdr

ied

at10

0°C

toco

nsta

ntw

eigh

tbe

fore

use.

The

solv

ents

wer

epu

rified

byst

anda

rdm

etho

ds,

1an

dth

eir

purit

yw

asch

ecke

dth

roug

hph

ysic

alco

nsta

nts.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.W

eisb

erge

r,E

.Pro

skan

zer,

J.R

iddi

ck,a

ndE

.Too

ps,

Org

an

icS

olv

en

ts~R

ussi

antr

ansl

atio

nof

Eng

lish

ed.

!~I

LP

ubl.

Hou

se,

Mos

cow

,19

58!,

pp.

351,

361.

6969JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!2-

But

anon

e~m

ethy

leth

ylke

tone!

;C

4H

8O

;@7

8-93

-3#

B.

S.

Kru

mga

lz,

V.A

.S

mirn

ova,

and

Yu.

I.G

erzh

berg

,Z

h.N

eorg

.K

him

.17,

1778

–80

~197

2!.

Varia

bles

:P

repa

red

By:

T/K

:28

3–

323

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

2-bu

tano

neas

afu

nctio

nof

tem

pera

ture

a

Tem

pera

ture

(t/°

C)

NaS

CN

(m1

/mol

kg2

1)

102.

361

202.

179

252.

094

302.

013

401.

868

501.

740

a The

equi

libriu

mso

lidph

ase

was

NaS

CN@540

-72-

7#at

allt

empe

ratu

res.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

d1w

asus

ed.

Exc

ess

solid

was

equi

libra

ted

with

2-bu

tano

neby

stirr

ing

ina

clos

ed,

ther

mos

tate

dve

ssel

.Atta

inm

ent

ofeq

uilib

rium

was

chec

ked

bym

easu

ring

elec

tric

alco

nduc

tivity

ofth

eso

lutio

n.To

this

aim

,an

elec

trol

ytic

cell

clos

edw

itha

glas

ssi

nter

was

imm

erse

din

the

solu

tion

thro

ugho

utth

em

easu

rem

ent.

At

chos

entim

ein

terv

als,

the

mea

sure

dso

lutio

nw

assu

cked

inbe

twee

ntw

opl

atin

umel

ectr

odes

,th

eco

nduc

tivity

was

mea

sure

d,an

dth

eso

lutio

nw

astr

ansf

erre

dba

ckfr

omth

ece

llto

the

solu

bilit

yve

ssel

byap

plyi

ngov

erpr

essu

reof

dry

air.

The

proc

edur

ew

asre

peat

edun

tilst

eady

cond

uctiv

ityof

the

solu

tion

was

obta

ined

.T

heeq

uilib

rium

cond

uctiv

ityva

lue

was

then

used

tore

adth

eco

ncen

trat

ion

ofN

aSC

Nin

the

satu

rate

dso

lutio

nfr

oma

calib

ratio

ngr

aph

ofco

nduc

tivity

plot

ted

agai

nst

NaS

CN

conc

entr

atio

nin

2-bu

tano

ne.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

60.

2%~e

rror

ofco

nduc

tivity

mea

sure

men

ts;

auth

ors!.

Ref

eren

ces:

1 B.

S.

Kru

mga

lz,

Yu.

I.G

erzh

berg

,I.

P.N

ikiti

na,

V.I.

Der

evsk

aya,

G.

F.F

edot

ova,

and

D.

G.

Tra

ber,

Zh.

Prik

l.K

him

.42

,14

14~1

969!

.

Co

~1!

~2!

Va T/

2- 2

a S b C Me

An

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#1,

2-et

hane

diam

ine~e

thyl

ened

iam

ine!;

C2H

8N

2;

@107

-15-

3#H

.S

.Is

bin

and

K.

A.

Kob

e,J.

Am

.C

hem

.S

oc.

67,

464

–5

~194

5!.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

ethy

lene

diam

ine

at25

°CT

heso

lubi

lity

ofN

aSC

Nis

repo

rted

tobe

93.5

gin

100

gso

lven

t~c

ompi

ler:

m15

11.5

3m

olkg

21).

The

com

posi

tion

ofth

eso

lidas

ew

asno

tin

vest

igat

ed.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

solv

ent

and

exce

ssso

lidre

seal

edin

agl

ass

test

tube

and

rota

ted

for

atle

ast

1w

eek

aw

ater

ther

mos

tat,

whi

chw

asfo

und

suffi

cien

tfo

rui

libriu

mto

bere

ache

d.S

ampl

esof

the

satu

rate

dso

lutio

nre

with

draw

nw

itha

wei

ghin

gpi

pette

,an

dan

alyz

edfo

rN2

cont

ent

bytit

ratio

nag

ains

ta

stan

dard

AgN

O3

solu

tion.

NaS

CN

,an

alyt

ical

grad

e,w

asdr

ied

at15

0°C

befo

reus

e.E

thyl

ened

iam

ine,

sour

ceno

tsp

ecifi

ed,

was

dehy

drat

edan

dpu

rified

acco

rdin

gto

Put

nam

and

Kob

e.1

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.08

K~a

utho

rs!.

Sol

ubili

ty:6

0.5%

~aut

hors!

.

Ref

eren

ces:

1 G.L

.Put

nam

and

K.A

.Kob

e,T

rans

.Ele

ctro

chem

.Soc

.74

,609

~193

8!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!M

ethy

lace

tate

;C 3H

6O

2;

@79-

20-9

#J.

Sch

roed

eran

dM

.S

tein

er,

J.P

rakt

.C

hem

.79

,49

–65

~190

9!.

Varia

bles

:P

repa

red

By:

One

mea

sure

men

tat

boili

ngpo

int

tem

pera

ture

.J.

Ha

´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

boili

ngm

ethy

lace

tate

The

solu

bilit

yof

NaS

CN

isre

port

edto

be10

0w15

12.0

0m

ass

%at

boili

ngpo

int

ofth

esa

tura

ted

solu

tion

~com

pile

r:m

1

51.

682

mol

kg2

1).

The

boili

ngpo

int

tem

pera

ture

was

not

repo

rted

.T

heso

lidph

ase

was

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Exc

ess

salt

was

boile

dw

ithm

ethy

lace

tate

for

apr

olon

ged

perio

dof

time

ina

flask

clos

edw

itha

stop

per

thro

ugh

whi

cha

shor

tgl

ass

tube

was

prot

rudi

ng.

The

latte

rco

ntai

ned

glas

sw

oola

sa

filte

rat

the

botto

men

d,an

dw

asm

ade

into

ash

ort

capi

llary

atth

eup

per

end.

By

turn

ing

the

flask

upsi

dedo

wn,

apo

rtio

nof

the

satu

rate

dso

lutio

nw

asal

low

edto

pour

out

into

aw

eigh

ing

flask

.Afte

rm

ore

boili

ng,

anot

her

two

sam

ples

wer

eta

ken

inth

esa

me

way

.T

hesa

mpl

esw

ere

then

evap

orat

ed,

and

the

resi

due

wei

ghed

.

NaS

CN

,so

urce

and

purit

yno

tsp

ecifi

ed,

was

drie

dat

110

°Cbe

fore

use.

Met

hyla

ceta

tew

aske

ptov

eran

hydr

ous

CuS

O4

for

apr

olon

ged

perio

dof

time,

and

dist

illed

.T

hefr

actio

nbo

iling

at56

.2–

56.7

°Cw

asco

llect

edan

dst

ored

inth

eda

rk.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

Va T/

ph Me

An

we

in eq we

SC


Vin

cent

~Per

gam

onP

ress

,O

xfor

d!,

Vol.

11,

pp.

181

–18

5.3 T.

M.

Lest

eva

and

V.I.

Che

rnay

a,Z

h.N

eorg

.K

him

.23

,25

56~1

978!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#N

,N-d

imet

hyla

ceta

mid

e;C 4H

9N

O;

@127

-19-

5#A

.A.F

edor

ov,L

.B.S

okol

ov,V

.M.S

avin

ov,M

.A.S

hlio

nska

ya,

and

N.

I.F

ilato

va,

Zh.

Prik

l.K

him

.44,

2361

–2~

1971

!.

riabl

es:

Pre

pare

dB

y:

K:

295

–29

8J.

Ha´ la

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aSC

Nin

N,N

-dim

ethy

lace

tam

ide

isre

port

edto

bec 15

1.78

mol

dm2

3at

22–

25°C

.The

natu

reof

the

equi

libriu

mlid

phas

ew

asno

tin

vest

igat

ed.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eso

lven

tw

assa

tura

ted

with

anhy

drou

ssa

lt.T

hen

apa

rtof

solv

ent

was

dist

illed

off

tore

mov

ew

ater

,an

dth

esa

tura

ted

lutio

nw

ithex

cess

solid

was

kept

for

3da

ysin

ade

sicc

ator

apa

raffi

n-co

ated

flask

.T

heco

nten

tof

wat

erin

the

satu

rate

dlu

tion

was

,0.

1%.

The

satu

rate

dso

lutio

nw

asan

alyz

edfo

rco

nten

tof

sulfu

rby

anun

spec

ified

met

hod.

NaS

CN

was

ach

emic

ally

pure

prod

uct,

sour

cew

asno

tspe

cifie

dN

,N-d

imet

hyla

ceta

mid

e,so

urce

not

spec

ified

,w

asfr

eshl

ydi

still

edbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

7171JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!S

olve

nts

O.

A.

Lavr

ova,

N.

N.

Mok

osin

a,an

dO

.S

.K

arch

mar

chik

,Z

h.N

eorg

.K

him

.29,

1312

–6~

1984

!.

Varia

bles

:P

repa

red

By:

T/K

:29

3,31

3,33

3J.

Ha

´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

thre

eso

lven

tsat

two

orth

ree

tem

pera

ture

sa

Sol

vent

Tem

pera

ture

(t/°

C)

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(1

00x 1

/mol

%)

NaS

CN

(m1

/mol

kg2

1)b

N,N

-dim

ethy

lform

amid

e;C 3H

7N

O;

@68-

12-2

#40

26.3

24.3

4.40

6032

.430

.25.

91

N,N

-dim

ethy

lace

tam

ide;

C 4H9N

O;

@127

-19-

5#20

17.8

18.9

2.67

4022

.323

.53.

54

6030

.431

.95.

39

N-m

ethy

l-2-p

yrro

lidon

e;C 5

H9N

O;

@872

-50-

4#40

22.3

25.9

3.54

6026

.730

.94.

49

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:E

arlie

rda

taon

the

solu

bilit

yof

NaS

CN

inN

,N-d

imet

hylfo

rmam

ide

1ha

vebe

enco

mpi

led

inLe

stev

aan

dC

hern

aya.2

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

d3w

asus

ed.

Exc

ess

solid

was

stirr

edw

ithth

eso

lven

tin

ath

erm

osta

ted

vess

elun

tileq

uilib

rium

was

reac

hed.

The

cont

ent

ofN

aSC

Nin

the

satu

rate

dso

lutio

nsw

asde

term

ined

bytit

ratio

nag

ains

ta

stan

dard

AgN

O3

solu

tion.

No

deta

ilsre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

rs!.

Sol

ubili

ty:6

0.2

–0.

5m

ol%

~aut

hors!

.

Ref

eren

ces:

1 R.

C.

Pau

l,J.

P.S

ingh

,M

.S

.La

mba

,D

.S

.G

ill,

and

S.

P.N

arul

a,In

dian

J.C

hem

.11,

1024

~197

3!.

2 IUPA

CS

olu

bili

tyD

ata

Se

rie

s,ed

ited

byB

.S

cros

ati

and

C.

A.

Co

~1!

~2!

Va T/

so Me

Th

the

so in so the

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#N

,N-d

imet

hyla

ceta

mid

e;C 4H

9N

O;

@127

-19-

5#W

ater

;H 2

O;

@773

2-18

-5#

O.

A.

Lavr

ova,

N.

N.

Mok

osin

a,an

dO

.S

.K

arch

mar

cik,

Zh.

Neo

rg.

Khi

m.2

9,13

12–

6~19

84!.

riabl

es:

Pre

pare

dB

y:

K:

293

0x 2

/mol

%:

0–

0.81

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

wat

er–

N,N

-dim

ethy

lace

tam

ide

solu

tions

at20

°C

C4H

9N

O00

x 2/m

ol%

)N

aSC

N(1

00x 1

/mol

%)

Sol

idph

asea

C4H

9N

O(1

00x 2

/mol

%)

NaS

CN

(100

x 1/m

ol%

)S

olid

phas

ea

026

.9A

43.2

19.9

D

15.4

26.9

A44

.818

.1D

23.6

26.9

A47

.718

.8E

27.0

24.2

B58

.716

.5E

31.2

26.0

B60

.216

.8E

36.1

23.3

C71

.018

.9E

43.8

20.8

C81

.118

.9no

tre

port

ed

:N

aSC

N,@

540-

72-7#

;B

:N

aSC

N•C

4H

9N

O,

@#;

C:

3N

aSC

N•4

C4H

9N

O,

@#;

:N

aSC

N•2

C4H

9N

O,

@#;

E:

2N

aSC

N•5

C4H

9N

O,

@#. Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

d1w

asus

ed.

Exc

ess

solid

was

stirr

edth

the

solv

ent

ina

ther

mos

tate

dve

ssel

until

equi

libriu

mw

asac

hed.

The

cont

ent

ofN

aSC

Nin

the

satu

rate

dso

lutio

nsw

aste

rmin

edby

titra

tion

agai

nst

stan

dard

AgN

O3

solu

tion.

Sol

idas

esw

ere

char

acte

rized

byth

em

etho

dof

wet

resi

dues

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

rs!.

Sol

ubili

ty:6

0.2

–0.

5m

ol%

~aut

hors!

.

Ref

eren

ces:

1 T.M

.Le

stev

aan

dV.

I.C

hern

aya,

Zh.

Neo

rg.

Khi

m.

23,

2556

~197

8!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!T

ri-n-

buty

l~pho

spha

te!;C

12H

27O

4P

;@1

26-7

3-8#

J.H

alaan

dD

.G

.T

uck,

Can

.J.

Che

m.

48,

2843

–6~

1970

!.

Varia

bles

:P

repa

red

By:

T/K

:29

5J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

aSC

Nin

tri-n

-but

yl~pho

spha

te!is

repo

rted

tobe

12.5

gsa

ltin

100

gso

lven

tat

22°C

(m

15

1.54

2m

olkg

21;

com

pile

r!.A

dditi

onal

info

rmat

ion:

The

solv

ent/N

aSC

Nm

ole

ratio

inth

esa

tura

ted

solu

tions

was

foun

dto

be2.

44,i

ndic

atin

gth

eex

iste

nce

ofth

edi

solv

ate,

NaS

CN•

2C

12H

27O

4P

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

nex

cess

ofth

esa

ltw

assh

aken

over

nigh

tw

ith5

mL

dry

solv

ent.

Pre

limin

ary

expe

rimen

tssh

owed

that

this

was

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

thro

ugh

asi

nter

,di

lute

dw

ithac

eton

e,an

dan

alyz

edfo

rth

eth

iocy

anat

eco

nten

tby

titra

tion

agai

nst

AgN

O3

stan

dard

solu

tion.

Bla

nktit

ratio

nssh

owed

that

asm

allc

orre

ctio

nw

asre

quire

dbe

caus

eof

the

pres

ence

oftr

i-n-b

utyl

~pho

spha

te!.

NaS

CN

,F

ishe

rS

cien

tific

Co.

,w

asus

edw

ithou

tfu

rthe

rpu

rifica

tion.

Tri-

n-bu

tyl~p

hosp

hate!

~Fis

her

Sci

entifi

cC

o.!w

aspu

rified

byre

fluxi

ngit

with

0.5%

caus

ticso

daso

lutio

n,fo

llow

edby

stea

mdi

still

atio

n.T

hepr

oduc

twas

drie

dfir

stw

ithan

hydr

ous

MgS

O4

,an

dfin

ally

vacu

um/d

ried

at50

°Cin

ast

ream

ofdr

yni

trog

enga

s.1

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

0.4

gsa

lt/10

0g

solv

ent~a

utho

rs!.

Ref

eren

ces:

1 D.

G.

Tuc

k,J.

Che

m.

Soc

.27

83~19

58!.

Co

~1!

~2!

~3!

Va T/

10 (1 a A D Me

An

wi

re de ph


s g Cl

anal

ytic

alm

etho

dsus

ed.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

efir

stdr

ied

toco

nsta

ntw

eigh

tan

dth

enan

alyz

edfo

rC

l2

and

SC

N2co

nten

tby

pote

ntio

met

rictit

ratio

nw

ithA

gNO 3

solu

tion.

Two

titra

tions

wer

epe

rfor

med

.In

one,

the

sum

ofS

CN2

and

Cl2

was

dete

rmin

ed,

inth

eot

her

Cl

2w

astit

rate

daf

ter

deco

mpo

sitio

nof

SC

N2w

ithH

2O

2in

alka

line

med

ium

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#S

odiu

mch

lorid

e;N

aCl;@7

647-

14-5#

Wat

er;

H 2O

;@7

732-

18-5#

E.

F.Z

hura

vlev

and

M.

N.

Byc

hkov

a,Z

h.N

eorg

.K

him

.4,23

67–

75~1

959!

.

riabl

es:

Pre

pare

dB

y:

K:

278,

298,

and

323

0w

2/m

ass

%:

0–

26.2

at27

8K

;0

–26

.5at

298

K;

0–

26.9

323

K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

aSC

N–

NaC

l–H 2O

syst

emat

thre

ete

mpe

ratu

res

mpe

ratu

re(t

/°C

)N

aCl

(100

w2

/mas

s%

)N

aCl

(m2

/mol

kg2

1)a

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(m

1/m

olkg

21)a

Sol

idph

aseb

50

051

.012

.88

B

2.1

0.74

049

.412

.56

B1A

4.4

1.35

440

.08.

873

A

11.3

3.01

624

.64.

733

A

19.7

4.87

811

.21.

999

A

26.2

6.07

40

0B

250

060

.018

.50

B1A

1.9

0.82

058

.518

.22

A

2.5

0.97

253

.514

.99

A

4.8

1.49

239

.88.

861

A

11.5

3.07

924

.64.

748

A

19.9

4.94

111

.22.

005

A

26.5

6.16

90

0C

00

64.5

22.4

1C1

A

502.

01.

118

62.5

21.9

0A

3.3

1.24

051

.213

.88

A

5.2

1.61

439

.78.

887

A

11.7

3.14

224

.64.

763

A

20.1

5.00

511

.22.

010

A

26.9

6.29

60

0A

alcu

late

dby

com

pile

r.b A

:N

aCl,

@764

7-14

-5#;

B:

NaS

CN

.2

H 2O

,@1

7032

-40-

5#;C

:N

aSC

N,@

540-

72-7#

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ies

wer

eob

tain

edby

grap

hica

lana

lytic

alm

etho

d.1,2

Ase

ries

ofm

ixtu

res

ofth

esa

ltsan

dw

ater

corr

espo

ndin

gto

ach

osen

sect

ion

inth

etr

iang

ular

diag

ram

,ru

nnin

gfr

omon

epu

resa

ltto

the

oppo

site

leg

ofth

etr

iang

le,

thus

cove

ring

the

field

sof

unsa

tura

ted

and

satu

rate

dso

lutio

nsw

ere

prep

ared

byw

eigh

ing.

Afte

req

uilib

rium

had

been

atta

ined

,re

frac

tive

inde

xes

ofth

eso

lutio

nsw

ere

mea

sure

d.T

hetr

ansi

tion

from

unsa

tura

ted

tosa

tura

ted

solu

tions

,i.e

.,th

eco

rres

pond

ing

solu

bilit

yva

lue,

was

obta

ined

asa

brea

kon

the

refr

activ

ein

dex

vers

usco

mpo

sitio

npl

ot.

The

met

hod

ofid

entifi

catio

nof

the

solid

phas

esw

asno

tre

port

ed.

NaS

CN

,sou

rce

nots

peci

fied,

was

recr

ysta

llize

das

dihy

drat

ean

dth

ende

hydr

ated

at12

0–

130

°Cto

obta

inth

ean

hydr

ous

salt.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

2 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.

7373JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!S

odiu

mch

lorid

e;N

aCl;@7

647-

14-5#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

V.A

.T

itova

and

Z.

E.

Bat

ura,

Zh.

Neo

rg.

Khi

m.10

,17

11–

2~1

965!

.

Varia

bles

:P

repa

red

By:

100

w2

/mas

s%

inth

edr

yre

sidu

e:0

–10

0J.

Ha

´ la

Exp

erim

enta

lDat

aC

ompo

sitio

nof

solu

tions

satu

rate

dat

boili

ngpo

ints

a

NaC

l(1

00w

2/m

ass

%)b

H2O

(gpe

r10

0g

dry

resi

due!

Tem

pera

ture

(t/°

C)c

NaC

ld

(100

w2

/mas

s%

)N

aCld

(m2

/mol

kg2

1)

NaS

CNd

(100

w1

/mas

s%

)N

aSC

Nd

(m1

/mol

kg2

1)

033

.215

2.0

00

75.0

837

.15

f

1.5

33.0

152.

51.

130.

7793

74.0

636

.82

f

1.7e

32.3

153.

01.

290.

9043

74.3

037

.55

g

a Atm

osph

eric

pres

sure

of74

56

5m

mH

g.b In

the

dry

resi

due.

c Boi

ling

poin

tof

the

satu

rate

dso

lutio

n.d C

ompo

sitio

nof

the

satu

rate

dso

lutio

ns~cal

cula

ted

byco

mpi

ler!.

e Eut

onic

poin

t.f S

olid

phas

e:N

aSC

N,@5

40-7

2-7#.

g Sol

idph

ases

:N

aSC

N1N

aCl,

@764

7-14

-5#.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

inth

eta

ble,

the

auth

ors

repo

rted

also

the

resu

ltsfo

ran

othe

r11

satu

rate

dso

lutio

nco

ntai

ning

1.55

–28

.69

mas

s%

NaC

lan

d69

.07

–0

mas

s%

NaS

CN

,w

ithN

aCl

asth

eeq

uilib

rium

solid

phas

e.T

here

spec

tive

boili

npo

ints

ofth

ese

solu

tions

decr

ease

dfr

om14

0.5

to10

9.0

°C.

The

seda

taw

ere

not

incl

uded

here

sinc

eth

eyre

fer

toth

eso

lubi

lity

ofN

ain

solu

tions

ofN

aSC

N.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Det

erm

inat

ions

wer

epe

rfor

med

ina

four

-nec

kfla

skeq

uipp

edw

ithst

irrer

,co

nden

ser,

ther

mom

eter

,an

da

sam

plin

gde

vice

.T

hefla

skw

asth

erm

osta

ted

inan

oilb

ath.

Atm

osph

eric

pres

sure

was

with

in74

565

mm

Hg

thro

ugho

utth

em

easu

rem

ents

,an

dva

riatio

nsin

solu

bilit

yin

duce

dby

thes

eva

riatio

nsof

pres

sure

wer

efo

und

tobe

with

inth

eer

rors

ofth

e

NaS

CN

and

NaC

lw

ere

chem

ical

lypu

repr

oduc

ts,

and

wer

ere

crys

talli

zed

befo

reus

e.D

istil

led

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

rs!.

Sol

ubili

ty:6

0.01

5m

ass

%~au

thor

s!.

Co

~1!

~2!

~3!

Va T/

10 at Te a C

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#A

mm

oniu

mch

lorid

e;N

H 4C

l;@1

2125

-02-

9#W

ater

;H 2

O;

@773

2-18

-5#

E.

F.Z

hura

vlev

and

M.

N.

Byc

hkov

a,Z

h.N

eorg

.K

him

.4,23

67–

75~1

959!

.

riabl

es:

Pre

pare

dB

y:

K:

278,

298,

and

323

0w

2/m

ass

%:

0–

23.8

at27

8K

;0

–28

.6at

298

K;

0–

33.5

323

K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

aSC

N–

NH 4

Cl–

H2O

syst

emat

thre

ete

mpe

ratu

res

mpe

ratu

re(t

/°C

)N

H4C

l(1

00w

2/m

ass

%)

NH

4C

l(m

2/m

olkg

21)a

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(m

1/m

olkg

21)a

Sol

idph

aseb

50

051

.012

.83

A2.

10.

797

49.6

12.6

6A1

B2.

20.

818

48.5

12.1

3B

6.6

2.15

537

.28.

164

B10

.13.

195

31.9

6.78

4B

15.7

4.82

624

.65.

082

B1C

19.1

5.34

315

.32.

876

C21

.35.

505

7.7

1.33

7C

23.8

5.73

10

0C

250

060

.018

.50

A1.

90.

884

58.7

18.3

7A1

B2.

60.

979

48.7

12.3

3B

7.0

2.30

237

.28.

223

B17

.25.

386

24.2

5.09

3B

20.1

6.25

120

.94.

369

B1C

22.5

6.60

615

.02.

960

C25

.06.

796

7.5

1.37

0C

28.5

7.35

00

0C

500

064

.522

.41

D2.

31.

219

63.1

22.4

9D1

B3.

01.

135

48.5

12.3

3B

7.8

2.58

836

.98.

230

B18

.76.

031

24.4

5.28

9B

26.1

8.37

316

.73.

601

B1C

26.8

8.29

214

.63.

073

C29

.78.

610

7.0

1.36

4C

33.5

9.24

40

0C

a Cal

cula

ted

byco

mpi

ler.

b A:

NaS

CN•

2H

2O

,@1

7032

-40-

5#;B

:N

aCl,

@764

7-14

-5#;

C:

NH

4C

l;@1

2125

-02-

9#;D

:N

aSC

N,@

540-

72-7#

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ies

wer

eob

tain

edby

grap

hica

lana

lytic

alm

etho

d.1,2

Ase

ries

ofm

ixtu

res

ofth

esa

ltsan

dw

ater

corr

espo

ndin

gto

ach

osen

sect

ion

inth

etr

iang

ular

diag

ram

,ru

nnin

gfr

omon

epu

resa

ltto

the

oppo

site

leg

ofth

etr

iang

le,

thus

cove

ring

the

field

sof

unsa

tura

ted

and

satu

rate

dso

lutio

nsw

ere

prep

ared

byw

eigh

ing.

Afte

req

uilib

rium

had

been

atta

ined

,re

frac

tive

inde

xes

ofth

eso

lutio

nsw

ere

mea

sure

d.T

hetr

ansi

tion

from

unsa

tura

ted

tosa

tura

ted

solu

tions

,i.e

.,th

eco

rres

pond

ing

solu

bilit

yva

lue,

was

obta

ined

asa

brea

kon

the

refr

activ

ein

dex

vers

usco

mpo

sitio

npl

ot.

The

met

hod

ofid

entifi

catio

nof

the

solid

phas

esw

asno

tre

port

ed.

NaS

CN

,sou

rce

nots

peci

fied,

was

recr

ysta

llize

das

dihy

drat

ean

dth

ende

hydr

ated

at12

0–

130

°Cto

obta

inth

ean

hydr

ous

salt.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

2 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!S

odiu

mch

lorid

e;N

aCl;@7

647-

14-5#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

S.

M.

Gol

yand

and

B.

G.

Ludk

ovsk

aya,

Zh.

Neo

rg.

Khi

m.

11,

1433

–5~

1966

!.

Varia

bles

:P

repa

red

By:

T/K

:29

8an

d31

310

0w

2/m

ass

%:

0an

d0.

72at

298

K;

0an

d0.

51at

313

KJ.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

wat

er,

and

com

posi

tions

ofeu

toni

cpo

ints

inth

ete

rnar

yN

aSC

N–

NaC

l–H

2O

syst

emat

25an

d40

°C

Tem

pera

ture

(t/°

C)

NaC

l(1

00w

2/m

ass

%)

NaC

l(m

2/m

olkg

21)b

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(m

1/m

olkg

21)b

Sol

idph

asea

250

058

.517

.39

A

0.72

0.29

457

.416

.91

A1B

400

063

.021

.00

C

0.51

0.23

562

.320

.66

D1B

a A:

NaS

CN•

2H

2O

,@1

7032

-40-

5#;B

:N

aCl,

@764

7-14

-5#;

C:

NaS

CN

,@540

-72-

7#;D

:so

lidso

lutio

nof

NaC

land

NaS

CN~o

f1.

85m

ass

%N

aCli

nth

eso

lidph

ase,

0.7

mas

s%

was

inth

efo

rmof

NaC

l,an

dth

ere

stin

the

form

ofth

eso

lidso

lutio

n!.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Sat

urat

edso

lutio

nsw

itheq

uilib

rium

solid

phas

esw

ere

prep

ared

eith

erby

cool

ing

satu

rate

dso

lutio

nspr

epar

edat

80°C

,or

byw

arm

ing

from

20°C

solu

tions

cont

aini

ngex

cess

ofso

lidsa

lts.

Inte

nse

stirr

ing

and

seed

ing

was

appl

ied.

Bot

hm

etho

dsyi

elde

did

entic

alre

sults

.S

atur

ated

solu

tions

and

the

solid

phas

esw

ere

anal

yzed

titrim

etric

ally

for

SC

N2,

Cl2

~afte

rde

com

posi

tion

ofS

CN2

byH

2O

2in

alka

line

med

ium!

,an

dth

esu

mof

both

ions

.S

olid

phas

esw

ere

also

inve

stig

ated

byx-

ray

diffr

actio

n.It

was

poss

ible

toid

entif

yas

low

as0.

5m

ass

%N

aCli

nm

ixtu

res

ofN

aSC

N•2

H2O

and

NaC

l.X

-ray

patte

rns

ofN

aSC

N•2

H2O

wer

ere

cord

edin

dry

atm

osph

ere

toav

oid

deliq

uesc

ence

ofth

esa

lt.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

Va T/

10 at Te


corr

espo

ndin

gto

ach

osen

sect

ion

inth

etr

iang

ular

diag

ram

,ru

nnin

gfr

omon

epu

resa

ltto

the

oppo

site

leg

ofth

etr

iang

le,

thus

cove

ring

the

field

sof

unsa

tura

ted

and

satu

rate

dso

lutio

nsw

ere

prep

ared

byw

eigh

ing.

Afte

req

uilib

rium

had

been

atta

ined

,re

frac

tive

inde

xes

ofth

eso

lutio

nsw

ere

mea

sure

d.T

hetr

ansi

tion

from

unsa

tura

ted

tosa

tura

ted

solu

tions

,i.e

.,th

eco

rres

pond

ing

solu

bilit

yva

lue,

was

obta

ined

asa

brea

kon

the

refr

activ

ein

dex

vers

usco

mpo

sitio

npl

ot.

The

met

hod

ofid

entifi

catio

nof

the

solid

phas

esw

asno

tre

port

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

2 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#P

otas

sium

thic

yana

te;

KS

CN

;@333

-20-

0#W

ater

;H 2

O;

@773

2-18

-5#

E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9–

52~1

968!

.

riabl

es:

Pre

pare

dB

y:

K:

273

–32

30

w1

/mas

s%

:0

–48

.3at

273

K;

0–

52at

283

K;

0–

59.2

at8

K;

0–

65at

323

K0

w2

/mas

s%

:0

–64

at27

3K

;0

–67

.2at

283

K;

0–

70.9

at8

K;

0–

76.4

at32

3K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

aSC

N–

KS

CN

–H 2O

syst

emat

four

tem

pera

ture

s

mpe

ratu

re(t

/°C

)N

aSC

N(1

00w

2/m

ass

%)

NaS

CN

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

064

.018

.29

A9.

03.

066

54.8

15.5

7A

23.6

8.22

341

.011

.91

A33

.412

.33

33.2

10.2

2A1

B35

.213

.56

32.8

10.5

4B

37.5

12.5

325

.67.

138

B40

.612

.03

17.8

4.40

3B

45.2

12.3

09.

52.

157

B48

.311

.52

00

B10

00

67.2

21.0

8A

8.3

3.01

258

.718

.30

A21

.78.

235

45.8

14.5

0A

31.2

12.3

337

.612

.40

A38

.316

.17

32.5

11.4

5A1

B41

.315

.16

25.1

7.68

7B

44.5

14.1

416

.74.

429

B48

.813

.05

5.1

1.13

8B

52.0

13.3

60

0B

250

070

.925

.07

A7.

23.

041

68.5

22.4

1A

19.0

8.25

252

.619

.05

A27

.512

.33

45.0

16.8

3A

36.5

18.5

239

.216

.59

A38

.720

.66

38.2

17.0

1A1

C46

.221

.18

26.9

10.2

9C

49.6

25.8

126

.711

.59

C54

.821

.39

13.6

4.42

8B1

C57

.418

.48

4.3

1.15

5B

59.2

17.8

90

0B

500

076

.433

.31

5.5

2.96

271

.632

.17

14.6

8.18

563

.429

.65

21.5

12.3

357

.027

.28

29.3

18.5

351

.227

.01

33.2

23.0

049

.028

.32

36.5

23.6

944

.524

.10

48.5

23.2

725

.810

.33

51.8

22.4

919

.87.

174

56.5

22.9

213

.14.

434

62.0

22.3

63.

81.

143

65.0

22.9

00

0

a Cal

cula

ted

byco

mpi

ler.

b A:

KS

CN

,@33

3-20

-0#;

B:

NaS

CN•

2H

2O

,@1

7032

-40-

5#;C

:N

aSC

N,@

540-

72-7#

.

7575JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!S

odiu

msu

lfate

;N

a 2SO

4;

@775

7-82

-6#~3

!W

ater

;H 2

O;

@773

2-18

-5#

E.

F.Z

hura

vlev

and

M.

N.

Byc

hkov

a,Z

h.N

eorg

.K

him

.4,23

67–

75~1

959!

.

Varia

bles

:P

repa

red

By:

T/K

:30

6an

d32

610

0w

2/m

ass

%:

0–

33.0

at30

6K

;0

–31

.6at

326

KJ.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

aSC

N–

Na 2S

O4–

H2O

syst

emat

two

tem

pera

ture

s

Tem

pera

ture

(t/°

C)

Na 2

SO

4

(100

w2

/mas

s%

)N

a 2S

O4

(m2

/mol

kg2

1)a

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(m

1/m

olkg

21)a

Sol

idph

aseb

330

068

.521

.45

A

0.4

0.07

7763

.421

.60

A1B

1.0

0.11

839

.68.

223

B

5.5

0.58

528

.45.

299

B

13.3

1.34

917

.33.

074

B

33.7

2.42

87.

61.

364

B

333.

467

00

B

530

064

.822

.70

A

0.8

0.16

264

.422

.82

A1B

1.0

0.11

839

.68.

223

B

5.0

0.52

928

.55.

286

B

12.7

1.28

017

.53.

092

B

22.3

2.24

67.

81.

376

B

31.6

3.25

20

0B

a Cal

cula

ted

byco

mpi

ler.

b A:

NaS

CN

,@54

0-72

-7#;

B:

Na 2

SO

4;

@775

7-82

-6#.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ies

wer

eob

tain

edby

grap

hica

lana

lytic

alm

etho

d.1,2

Ase

ries

ofm

ixtu

res

ofth

esa

ltsan

dw

ater

NaS

CN

,sou

rce

nots

peci

fied,

was

recr

ysta

llize

das

dihy

drat

ean

dth

ende

hydr

ated

at12

0–

130

°Cto

obta

inth

ean

hydr

ous

salt.

Co

~1!

~2!

~3!

Va T/

10 29 10 29 Te

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#A

mm

oniu

mth

icya

nate

;N

H 4SC

N;@

1762

-95-

4#W

ater

;H 2

O;

@773

2-18

-5#

E.

F.Z

hura

vlev

and

M.

N.

Byc

hkov

a,Z

h.N

eorg

.K

him

.4,23

67–

75~1

959!

.

riabl

es:

Pre

pare

dB

y:

K:

278,

298,

and

323

0w

1/m

ass

%:

0–

51at

278

K;

0–

60at

298

K;

0–

64.5

at3

K0

w2

/mas

s%

:0

–56

.2at

278

K;

0–

64.4

at29

8K

;0

–73

.832

3K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

aSC

N–

NH 4

SC

N–

H 2O

syst

emat

four

tem

pera

ture

s

mpe

ratu

re(t

/°C

)N

aSC

N(1

00w

1/m

ass

%)

NaS

CN

(m1

/mol

kg2

1)a

NH

4S

CN

(100

w2

/mas

s%

)N

H4S

CN

(m2

/mol

kg2

1)a

Sol

idph

aseb

50

056

.216

.58

A

7.7

2.19

349

.014

.86

A

17.9

5.26

940

.212

.60

A

26.8

8.22

333

.010

.78

A

38.0

12.3

324

.08.

297

A

39.4

12.9

523

.18.

092

A1B

40.3

12.5

820

.26.

718

B

45.0

12.3

310

.02.

919

B

47.5

12.4

46.

01.

684

B

51.0

12.8

30

0B

250

064

.423

.76

A

6.2

2.17

258

.621

.87

A

14.6

5.29

651

.419

.86

A

22.0

8.22

345

.017

.91

A

31.2

12.2

937

.515

.73

A

45.0

19.5

426

.612

.30

A1C

48.3

19.2

120

.78.

772

C

49.5

19.0

818

.57.

594

C1B

53.3

18.1

610

.53.

810

B

56.3

17.9

45.

01.

697

B

58.0

18.2

52.

80.

938

B

60.0

18.5

00

0B

500

073

.837

.00

A

4.6

2.18

269

.435

.06

A

10.9

5.27

263

.632

.76

A

16.6

8.25

658

.631

.04

A

23.7

12.2

852

.528

.97

A

35.1

19.6

742

.925

.61

A

40.3

23.6

738

.724

.20

A1C

43.0

23.2

634

.219

.70

C

48.0

22.7

726

.013

.13

C

53.8

22.1

216

.27.

094

C

59.8

21.5

66.

02.

304

C

64.5

22.4

10

0C

a Cal

cula

ted

byco

mpi

ler.

b A:

NH

4S

CN

,@17

62-9

5-4#;

B:

NaS

CN•

2H

2O

,@1

7032

-40-

5#;C

:N

aSC

N,@

540-

72-7#

.


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ies

wer

eob

tain

edby

grap

hica

lana

lytic

alm

etho

d.1

Ase

ries

ofm

ixtu

res

ofth

esa

ltsan

dw

ater

corr

espo

ndin

gto

ach

osen

sect

ion

inth

etr

iang

ular

diag

ram

,ru

nnin

gfr

omon

epu

resa

ltto

the

oppo

site

leg

ofth

etr

iang

le,

thus

cove

ring

the

field

sof

unsa

tura

ted

and

satu

rate

dso

lutio

nsw

ere

prep

ared

byw

eigh

ing.

Afte

req

uilib

rium

had

been

atta

ined

,re

frac

tive

inde

xes

ofth

eso

lutio

nsw

ere

mea

sure

d.T

hetr

ansi

tion

from

unsa

tura

ted

tosa

tura

ted

solu

tions

,i.e

.,th

eco

rres

pond

ing

solu

bilit

yva

lue,

was

obta

ined

asa

brea

kon

the

refr

activ

ein

dex

vers

usco

mpo

sitio

npl

ot.

The

met

hod

ofid

entifi

catio

nof

the

solid

phas

esw

asno

tre

port

ed.

NaS

CN

and

KS

CN~

sour

ceno

tsp

ecifi

ed!w

ere

chem

ical

lypu

repr

oduc

ts,

and

wer

edr

ied

over

anhy

drou

sC

aCl

2.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

Co

~1!

~2!

~3!

Va T/

10 32 10 at Te


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#B

oric

acid

;H 3

BO

3;

@100

43-3

5-3#

Wat

er;

H 2O

;@7

732-

18-5#

G.

K.

God

ean

dL.

A.

Kly

avin

a,Z

h.N

eorg

.K

him

.15,

1147

~197

0!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

5.46

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nat

25°C

inaq

ueou

sso

lutio

nsof

boric

acid

H3B

O3

00w

2/m

ass

%)

H3B

O3

(m2

/mol

kg2

1)a

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

56.2

015

.83

A

4.32

1.70

154

.60

16.3

9A1

B

alcu

late

dby

com

pile

r.:

NaS

CN

,@54

0-72

-7#;

B:

H3B

O3

,@1

0043

-35-

3#.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofni

nesa

tura

ted

solu

tions

ntai

ning

4.35

–5.

46m

ass

%H

3B

O3

,an

d49

.75

–0

mas

s%

NaS

CN

,w

here

H3B

O3

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tow

nhe

resi

nce

they

repr

esen

tth

eso

lubi

lity

ofH

3B

O3

inso

lutio

nsof

NaS

CN

.Als

ore

port

edw

ere

dens

ities

ofth

esa

tura

ted

solu

tions

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Sol

utio

nsw

ithex

cess

solid

rest

irred

at80

0rp

mfo

r1

–2

days

ina

ther

mos

tate

dve

ssel

.tu

rate

dso

lutio

nsw

ere

anal

yzed

for

H3B

O3

alka

limet

rical

lyai

nst

naph

thol

phth

alei

neas

the

indi

cato

r,an

dfo

rS

CN

2by

lhar

d’s

met

hod.

The

met

hod

used

for

iden

tifica

tion

ofth

elid

phas

esw

asno

tsp

ecifi

ed.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

7777JIRI HALA


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ies

wer

eob

tain

edby

grap

hica

lana

lytic

alm

etho

d.1,2

Ase

ries

ofm

ixtu

res

ofth

esa

ltsan

dw

ater

corr

espo

ndin

gto

ach

osen

sect

ion

inth

etr

iang

ular

diag

ram

,ru

nnin

gfr

omon

epu

resa

ltto

the

oppo

site

leg

ofth

etr

iang

le,

thus

cove

ring

the

field

sof

unsa

tura

ted

and

satu

rate

dso

lutio

nsw

ere

prep

ared

byw

eigh

ing.

Afte

req

uilib

rium

had

been

atta

ined

,re

frac

tive

inde

xes

ofth

eso

lutio

nsw

ere

mea

sure

d.T

hetr

ansi

tion

from

unsa

tura

ted

tosa

tura

ted

solu

tions

,i.e

.,th

eco

rres

pond

ing

solu

bilit

yva

lue,

was

obta

ined

asa

brea

kon

the

refr

activ

ein

dex

vers

usco

mpo

sitio

npl

ot.

The

met

hod

ofid

entifi

catio

nof

the

solid

phas

esw

asno

tre

port

ed.

NaS

CN

and

NH 4

SC

N~s

ourc

eno

tsp

ecifi

ed!w

ere

chem

ical

lypu

repr

oduc

ts,

and

wer

edr

ied

over

anhy

drou

sC

aCl

2.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

2 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co sh Me

An

we

Sa

ag Vo so

J

smpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#S

odiu

mbo

rate

;N

aBO 2

;@7

775-

19-1#

Wat

er;

H 2O

;@7

732-

18-5#

V.G

.Skv

orts

ov,S

h.V.

Sad

etdi

nov,

R.S

.Tse

khan

skii,

and

A.K

.M

olod

kin,

Zh.

Neo

rg.

Khi

m.2

4,20

9–

12~1

979!

.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

22J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nat

25°C

inaq

ueou

sso

lutio

nsof

sodi

umbo

rate

NaB

O2

00w

2/m

ass

%)

NaB

O2

(m2

/mol

kg2

1)a

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

58.7

717

.58

A

2.85

1.09

257

.48

17.8

7A

2.84

c1.

088

57.5

017

.88

A1B

alcu

late

dby

com

pile

r.:

NaS

CN

,@54

0-72

-7#;

B:

NaB

O2•4

H2O

,@1

0555

-76-

7#.ut

onic

poin

t.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofni

nesa

tura

ted

solu

tions

ntai

ning

2.87

–21

.99

mas

s%

NaB

O2

,an

d57

.46

–0

mas

s%

NaS

CN

,whe

reN

aBO

2•4

H2O

was

the

equi

libriu

mso

lidph

ase.

The

seda

tae

not

show

nhe

resi

nce

they

repr

esen

tth

eso

lubi

lity

ofN

aBO

2in

solu

tions

ofN

aSC

N.

Als

ore

port

edw

ere

dens

ities

,vi

scos

ities

,an

dfr

actio

nin

dexe

sof

the

satu

rate

dso

lutio

ns.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

ium

was

reac

hed

thin

24h

unde

rco

nsta

ntsh

akin

gin

ath

erm

osta

t.B

orat

ean

dN2

wer

ede

term

ined

inth

esa

tura

ted

solu

tions

imet

rical

ly~m

etho

dsno

tsp

ecifi

ed!,so

lidph

ases

wer

ear

acte

rized

byS

chre

inem

aker

s’m

etho

dan

dch

emic

alal

ysis

.

NaS

CN

and

NaB

O 2w

ere

chem

ical

lypu

repr

oduc

ts.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!B

oric

acid

;H 3

BO

3;

@100

43-3

5-3#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

V.G

.Skv

orts

ov,R

.S.T

sekh

ansk

ii,S

h.V.

Sad

etdi

nov,

and

A.K

.M

olod

kin,

Zh.

Neo

rg.

Khi

m.2

8,26

77–

9~19

83!.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

0–

5.6

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nat

25°C

inaq

ueou

sso

lutio

nsof

boric

acid

H3B

O3

(100

w2

/mas

s%

)H

3B

O3

(m2

/mol

kg2

1)a

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

58.7

717

.58

A

3.40

1.42

558

.01

18.5

4A

3.41

1.42

957

.99

18.5

3A1

B

a Cal

cula

ted

byco

mpi

ler.

b A:

NaS

CN

,@54

0-72

-7#;

B:

H3B

O3

,@1

0043

-35-

3#.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sal

sore

port

edth

eco

mpo

sitio

nsof

six

satu

rate

dso

lutio

nco

ntai

ning

3.41

–5.

60m

ass

%H

3B

O3

,an

d57

.98

–0

mas

s%

NaS

CN

,w

here

H3B

O3

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tsh

own

here

sinc

eth

eyre

pres

ent

the

solu

bilit

yof

H3B

O3

inso

lutio

nsof

NaS

CN

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Sol

utio

nsw

ithex

cess

solid

wer

est

irred

for

20h,

whi

chw

assu

ffici

ent

for

equi

libriu

mto

bere

ache

d.B

orat

ean

dS

CN

2w

ere

dete

rmin

edin

the

satu

rate

dso

lutio

nstit

rimet

rical

ly~met

hods

not

spec

ified!,

solid

phas

esw

ere

char

acte

rized

byS

chre

inem

aker

s’m

etho

d.S

olub

ility

isot

herm

sw

ere

also

confi

rmed

byre

frac

tom

etric

mea

sure

men

ts.

NaS

CN

and

H 3B

O3

wer

ech

emic

ally

pure

prod

ucts

,an

dw

ere

recr

ysta

llize

dbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A c E Ad

co ar re Me

An

wi

SC

titr

ch an


smpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#S

odiu

mm

olyb

date

;N

a 2MoO

4;

@763

1-95

-0#W

ater

;H 2

O;

@773

2-18

-5#

Z.

G.

Kar

ov,

I.N

.Le

pesh

kov,

and

E.

I.K

ukul

ieva

,Z

h.N

eorg

.K

him

.17

,50

9–

13~1

972!

.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

40J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

aSC

N–

Na 2M

oO4–

H2O

syst

emat

25°C

.T

heph

ase

diag

ram

ofth

eN

aSC

N–

Na

2M

oO4–

H2O

syst

emat

25°C

was

repo

rted

ingr

aphi

calf

orm

.The

only

num

eric

alda

tare

port

edre

thos

eof

the

solu

bilit

yof

NaS

CN

inw

ater

as10

0w

1/m

ass

%558

.63

(m15

17.3

8m

olkg

21),

and

the

com

posi

tion

ofth

eeu

toni

clu

tion:

100w

1/m

ass

%558

.41

and

100w

2/m

ass

%50.

38(m

15

17.4

8m

olkg

21;

m25

0.04

48m

olkg

21;

com

pile

r!.T

hesy

stem

isa

ple

euto

nic

one

with

equi

libriu

mso

lidph

ases

NaS

CN

•2

H2O

,@17

032-

40-5#

at10

0w

2/m

ass

%,0.

38,a

ndN

a 2MoO

4•2

H2O

,@10

102-

-6#

at10

0w

2/m

ass

%.0.

38.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

ium

was

atta

ined

thin

5–

6h,

sam

ples

for

anal

ysis

wer

ew

ithdr

awn

afte

r2

–3

ys.

Inth

esa

tura

ted

solu

tions

and

the

wet

resi

dues

,M

oO42

2

sde

term

ined

titrim

etric

ally

byan

unsp

ecifi

edre

duct

omet

ricth

odaf

ter

deco

mpo

sitio

nof

SC

N2

inac

idic

solu

tion

ofO

2,

and

SC

N2w

asde

term

ined

byth

eVo

lhar

d’s

met

hod.

lidph

ases

wer

ech

arac

teriz

edby

the

met

hod

ofw

etsi

dues

.

NaS

CN

was

ach

emic

ally

pure

prod

uct,

and

was

recr

ysta

llize

dtw

ice

befo

reus

e.T

hepr

oduc

tw

as99

.92%

pure

.N

a2M

oO4

was

prep

ared

bym

eltin

gst

oich

iom

etric

amou

nts

ofM

oO 3an

dN

aOH

.The

prod

uctw

asre

crys

talli

zed

thre

etim

es,i

tspu

rity

was

99.9

6%.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

7979JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!S

odiu

mte

trab

orat

e;N

a2B

4O

7;

@610

88-2

4-8#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

V.G

.S

kvor

tsov

,A

.K

.M

olod

kin,

Sh.

V.S

adet

dino

v,an

dR

.S

.Ts

ekha

nski

i,Z

h.N

eorg

.K

him

.26,

3164

–6~

1981

!.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

0–

2.42

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nat

25°C

inaq

ueou

sso

lutio

nsof

sodi

umte

trab

orat

e

Na 2

B4O

7

(100

w2

/mas

s%

)N

a 2B

4O

7

(m2

/mol

kg2

1)a

NaS

CN

(100

w1

/mas

s%

)N

aSC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

58.7

717

.58

A

0.16

0.01

9158

.10

17.1

7A1B

a Cal

cula

ted

byco

mpi

ler.

b A:

NaS

CN

,@54

0-72

-7#;

B:

Na 2

B4O

7•10

H2O

,@1

303-

96-4#

.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sal

sore

port

edth

eco

mpo

sitio

nsof

seve

nsa

tura

ted

solu

tion

cont

aini

ng0.

14–

2.42

mas

s%

Na

2B

4O

7,

and

58.0

4–

0m

ass

%N

aSC

N,

whe

reN

a2B

4O

7•10

H2O

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tsh

own

here

sinc

eth

eyre

pres

ent

the

solu

bilit

yof

Na

2B

4O

7in

solu

tions

ofN

aSC

N.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

ium

was

reac

hed

with

in20

h,w

hich

was

chec

ked

bych

emic

alan

alys

isan

dre

frac

tion

inde

xof

the

satu

rate

dso

lutio

ns.

Bor

ate

and

SC

N2

wer

ede

term

ined

inth

esa

tura

ted

solu

tions

titrim

etric

ally

~met

hods

not

spec

ified!,

solid

phas

esw

ere

char

acte

rized

byS

chre

inem

aker

s’m

etho

d.

NaS

CN

and

Na 2B

4O

7•10

H2O

wer

ech

emic

ally

pure

prod

ucts

,an

dw

ere

recr

ysta

llize

dbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 we

so sim

40 Me

An

wi

da wa

me

H2

So

re

J

Num

eric

alva

lues

wer

ere

port

edfo

rth

eso

lubi

lity

ofN

aSC

Nin

wat

er-r

ich

and

CH

3C

NS

-ric

hC

H 3C

NS

–H 2

Om

ixtu

res~

curv

esR

Pan

dQ

Sin

the

phas

edi

agra

m,

resp

ectiv

ely

!.

H2O

-ric

hre

gion

CH 3

CN

S-r

ich

regi

on

H2O

(100

w3

/mas

s%

)N

aSC

N(1

00w

1/m

ass

%)

CH

3C

NS

(100

w2

/mas

s%

)H

2O

(100

w3

/mas

s%

)N

aSC

N(1

00w

1/m

ass

%)

CH

3C

NS

(100

w2

/mas

s%

)

41.5

58.5a

013

.916

.369

.8

39.3

55.8

4.9

8.0

9.2

82.8

38.4

54.5

7.1

4.9

4.9

90.2

37.7

52.9

9.4

01.

9b98

.1

37.9

50.0

13.1

36.7

47.3

16.0

36.5

44.2

19.3

a Sol

ubili

tyof

NaS

CN

inw

ater

,m15

17.3

9m

olkg

21

~com

pile

r!.b S

olub

ility

ofN

aSC

Nin

CH 3

CN

S,m

15

0.23

9m

olkg

21

~com

pile

r!.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lubi

lity

curv

esw

ere

obta

ined

bytit

ratio

nof

am

ixtu

reof

oco

mpo

nent

sw

ithth

eth

irdon

ein

ath

erm

osta

ted

bath

.re

ttes

grad

uate

dby

0.01

cm3w

ere

used

for

titra

tions

.S

ome

thes

em

easu

rem

ents

wer

eve

rified

bypr

epar

ing

the

tern

ary

stem

,an

dob

serv

ing

the

tem

pera

ture

ofho

mog

eniz

atio

n.T

helu

bilit

yva

lue

corr

espo

ndin

gto

20°C

was

then

obta

ined

byer

pola

tion.

NaS

CN

was

drie

dat

110

°Cbe

fore

use.

Sou

rce

and

purit

yof

CH

3C

NS

not

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!M

ethy

lthio

cyan

ate;

C 2H3N

S;

@556

-64-

9#~3

!W

ater

;H 2

O;

@773

2-18

-5#

E.S

pacc

amel

aM

arch

etti,

Atti

.Aca

d.S

ci.T

orin

o,C

lase

Fis

.Mat

.N

at.9

4,35

3–

70~1

960!

.

Varia

bles

:P

repa

red

By:

T/K

:29

3R

atio

ofH 2

O/C

H3C

NS

conc

entr

atio

ns.

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

aSC

N–

CH 3C

NS

–H 2

Osy

stem

at20

°CT

heph

ase

diag

ram

ofth

eN

aSC

N–

CH

3C

NS

–H 2

Osy

stem

at20

°Cw

asre

port

edin

Fig

.12

.

FIG

.12

.F

ield

sin

the

diag

ram

:I

and

II—on

eliq

uid

phas

e,III

—tw

oliq

uid

phas

es,

IVan

dV

I—on

eliq

uid

phas

ein

equi

libriu

mw

ithso

lidN

aSC

N,

and

V—

two

liqui

dph

ases

ineq

uilib

rium

with

solid

NaS

CN

.

Me

So

tw Bu

of sy so int


Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#A

cetic

acid

;C 2

H4O

2;

@64-

19-7

#N

,N-d

ieth

ylet

hana

min

e~trie

thyl

amin

e!;C

6H

15N

;21

-44-

8#;or

N,N

-dim

ethy

lben

zene

amin

e;~dim

ethy

l-Ani

line!

;H

11N

;@1

21-6

9-7#

Sol

vent

s

T.Ja

sins

kian

dR

.K

orew

a,R

ocz.

Che

m.

~War

saw!

39,

963

–8

~196

5!.

riabl

es:

Pre

pare

dB

y:

K:

293

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nat

20°C

inso

lven

tsin

the

pres

ence

ofam

ines

and

acet

icac

ida

Sol

vent

C2H

4O

2

(c2

/mol

dm2

3)

C6H

15N

(c3

/mol

dm2

3)

C8H

11N

(c3

/mol

dm2

3)

NaS

CN

(c1

/mol

dm2

3)

thyl

acet

ate;

C 4H8O

2;

@141

-78-

6#0.

050

00.

0110

00.

050

0.00

48

0.05

0.05

00.

0122b

00

0.05

0.00

20

0.05

00.

050.

0050b

chlo

rom

etha

ne;

CH 2C

l 2;

@75-

09-2

#0.

050

00.

0016

00.

050

0.00

02

0.05

0.05

00.

0030b

00

0.05

0.00

02

0.05

00.

050.

0012b

Ben

zene

;C 6

H6

;@7

1-43

-2#

0.05

0.05

00.

0108b

hlor

oben

zene

;C 6H

5C

l;@1

08-9

0-7#

0.05

0.05

00.

0120b

0.05

00.

050.

0095b

Die

thyl

ethe

r;C 4

H10

O;

@60-

29-7

#0.

050.

050

0.01

28b

olid

phas

esw

ere

not

inve

stig

ated

.ol

ubili

tyof

NaS

CN

inth

epr

esen

ceof

the

corr

espo

ndin

gam

mon

ium

acet

ate.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

salt

was

equi

libra

ted

incl

osed

flask

sfo

r5

days

with

20cm3

port

ions

ofth

eso

lutio

nsof

the

amin

e,ac

etic

acid

,or

thei

rm

ixtu

re,

asm

aybe

the

case

,in

the

desi

red

solv

ent.

The

na

10cm3

sam

ple

was

with

draw

n,ad

ded

tow

ater

,an

dth

esa

ltw

asex

trac

ted

into

wat

erby

shak

ing.

The

SC

N2co

nten

tw

asde

term

ined

inth

eaq

ueou

sla

yer

bypo

tent

iom

etric

titra

tion

with

0.01

mol

dm23

AgN

O3

solu

tion.

NaS

CN

,re

agen

tgr

ade,

was

twic

ere

crys

talli

zed

from

wat

er,

and

drie

din

anov

ento

cons

tant

wei

ght.

Ace

ticac

id,

sour

ceno

tsp

ecifi

ed,

was

purifi

edby

crys

talli

zatio

nan

ddi

still

atio

n.T

heam

ines

,so

urce

unsp

ecifi

ed,

wer

edr

ied

over

KO

Han

ddi

still

edov

erzi

ncpo

wde

r.C

H 2Cl 2

,ch

loro

benz

ene,

and

ethy

lace

tate

wer

edr

ied

over

P 2O5

,an

ddi

still

edov

eran

hydr

ous

Na

2C

O3

.B

enze

nean

ddi

ethy

leth

erw

ere

drie

dw

ithso

dium

met

al,

and

dist

illed

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.5

K~a

utho

rs!.

Sol

ubili

ty:6

2%~a

utho

rs!.

8181JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Sod

ium

thio

cyan

ate;

NaS

CN

;@540

-72-

7#~2

!2-

~2-m

etho

xyet

hoxy!

-N,N

-bis

-2-~2

-met

hoxy

etho

xy!et

hyl

etha

nam

ine$

tris

~dio

xa-3

,6-h

epty

l!am

ine%

;C

15H

33N

O3

;@7

0384

-51-

9#;or

2-m

etho

xy-N

,N-b

is~met

hoxy

ethy

l!eth

anam

ine;

$tris

~oxa

-3-b

utyl!

amin

e%;

C9H

21N

O3

;@3

235-

51-6#

~3!

Dic

hlor

omet

hane

;C

H 2Cl 2

;@7

5-09

-2#

G.

Sou

la,

Eur

.P

at.A

ppl.

0166

73,

1979

;F

renc

hA

ppl.

7905

438.

Varia

bles

:P

repa

red

By:

T/K

:un

spec

ified

c 2/m

oldm

23:

0.1

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

aSC

Nin

CH 2

Cl 2

inth

epr

esen

ceof

amin

esa

Am

ine

NaS

CN

~mg

dm2

3 !N

aSC

N(c

1/m

oldm

23)b

C15

H33

NO

323

000.

0284

C9H

21N

O3

2150

0.02

65

a Mea

sure

men

tspe

rfor

med

atan

unsp

ecifi

ed,

ambi

ent

tem

pera

ture

.S

olid

phas

esw

ere

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

r.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

ofN

aSC

Nin

neat

CH

2C

l 2w

asre

port

edto

bele

ssth

an1

mg

dm23 .

The

solu

biliz

atio

nef

fect

ofC

15H

33N

O3

was

expl

aine

dby

the

auth

ors

inte

rms

ofth

efo

rmat

ion

ofa

1:1

addu

ctof

NaS

CN

with

the

amin

ein

the

solu

tion.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

salt

~0.0

01m

ole!

was

equi

libra

ted

with

0.00

1m

ole

amin

ein

10m

LC

H2C

l 2by

stirr

ing.

The

cont

ent

ofth

esa

ltin

the

satu

rate

dso

lutio

nw

asde

term

ined

byfla

me

phot

omet

ry.

C15

H33

NO

3w

aspr

epar

edby

reflu

xing

sodi

umm

etho

xy-2

-eth

anoa

tew

ithch

loro

hydr

ate

oftr

is~c

hlor

o-2-

ethy

l!am

ine

inm

etho

xy-2

-eth

anol

for

12h

at12

5°C

.T

heex

cess

ofso

lven

tw

asth

endi

still

edof

f,ex

cess

ofso

dium

met

hoxy

-2-e

than

oate

deco

mpo

sed

with

conc

entr

ated

HC

l,an

dth

eam

ine

was

dist

illed

at16

5–

180

°Cat

0.5

mm

Hg.

C9H

21N

O3

was

obta

ined

bya

sim

ilar

proc

edur

eus

ing

sodi

umm

etha

noat

ean

dm

etha

nola

sth

eso

lven

t.A

fter

trea

tmen

tof

the

mix

ture

with

HC

l,th

eam

ine

was

extr

acte

din

toC

H2C

l 2,

and

dist

illed

.A

nhyd

rous

CH 2

Cl 2

was

purifi

edfr

omst

abili

zers

.

Co

~1!

~2!

~3!

@1 C8

~4!

Va T/ E

Di C a S b S Me

J

r lso

FIG

.13

.S

urve

yof

the

data

onth

eso

lubi

lity

ofK

SC

Nin

wat

er.

Sol

ubili

tyof

KS

CN

asa

func

tion

ofte

mpe

ratu

re

mpe

ratu

re(t

/°C

)Te

mpe

ratu

re~K

!K

SC

N(m

1/m

olkg

21)

Ref

.Te

mpe

ratu

re(t

/°C

)Te

mpe

ratu

re~K

!K

SC

N(m

1/m

olkg

21)

Ref

.

230

243.

211

.15a

6–

825

298.

225

.32f

12,1

3

220

253.

212

.83a

6–

824

.98g

14

210

263.

215

.24a

6–

824

.83g

15–

17

22.

227

1.0

17.7

7b2

25.0

7c9

027

3.2

18.2

9a6

–8

24.5

9g18

–20

18.6

2c9

25.0

8g21

1028

3.2

20.4

3a6

–8

25.0

6e26

12.9

286.

120

.97b

230

303.

226

.46a

6–

8

1528

8.2

22.1

8d10

24.0

1d10

2029

3.2

22.9

0a6

–8

32.6

305.

827

.28b

1

22.2

7a7,

1140

313.

229

.87f,g

13,1

6

20.5

293.

722

.38b

228

.75d

22

2529

8.2

24.4

5,24

.81e

345

318.

230

.22d

10

23.9

6d4

47.3

320.

532

.63b

1

24.6

7,24

.63,

24.5

6,24

.58

e5

5032

3.2

33.3

1c9

5733

0.2

36.9

0b1

perim

enta

lmet

hod

used

:

erna

rysy

stem

stud

ied

byvi

sual

poly

ther

mal

met

hod,

isot

herm

alda

taob

tain

edgr

aphi

cally

.is

ualp

olyt

herm

al.

raph

ical

met

hod

usin

gre

frac

tive

inde

xof

the

solu

tions

.ot

herm

al,

anal

ysis

ofth

esa

tura

ted

solu

tions

not

repo

rted

.ot

herm

al,

grav

imet

rican

alys

isof

the

satu

rate

dso

lutio

ns.

othe

rmal

,sa

tura

ted

solu

tions

anal

yzed

bypo

tent

iom

etric

titra

tions

.ot

herm

al,

satu

rate

dso

lutio

nsan

alyz

edby

Volh

ard’

sm

etho

d.

Irre

spec

tive

ofth

eva

riety

ofex

perim

enta

lm

etho

dsus

ed,

the

data

show

are

mar

kabl

eco

nsis

tenc

yex

cept

,pe

rhap

s,fo

rth

eda

taof

rgun

beko

vae

ta

l.10ta

ken

from

thei

rte

rnar

ysy

stem

KS

CN

–ur

ea–

H2O

,an

dw

ere

com

pute

rsm

ooth

edby

alin

ear

regr

essi

onof

the

data

afif

thor

der

poly

nom

ial.

The

solu

bilit

yva

lue

at30

3.2

K~Ref

.10

!w

asno

tco

nsid

ered

for

the

smoo

thin

gpr

oced

ure.

The

follo

win

gua

tion

has

been

obta

ined

for

the

KS

CN

solu

bilit

yas

afu

nctio

nof

tem

pera

ture

:(m

olkg

21)5

0.14

002

1310

42

0.10

319

2310

2T

20.

335

2593

102

1T

21

0.50

546

9310

23

T32

0.15

823

7310

25

T41

0.16

018

14

310

28

T5,

dca

nbe

reco

mm

ende

dfo

rob

tain

ing

tent

ativ

eva

lues

ofK

SC

Nso

lubi

litie

sin

wat

erov

erth

ete

mpe

ratu

rera

nge

from

243

to33

0K

.O

fnum

erou

sda

tare

port

edat

298.

2K

,tho

seof

Foo

te3

and

Cha

ng5ha

vebe

enob

tain

edby

care

fulg

ravi

met

rican

alys

isof

the

satu

rate

dso

lutio

ns,a

ndca

nbe

cons

ider

edas

bein

gsu

perio

rin

prec

isio

nto

the

data

obta

ined

byot

her

met

hods

.The

data

ofF

oote

3an

dC

hang5

have

been

take

nto

obta

inth

eso

lubi

lity

ofK

SC

Nin

wat

erat

298.

2K

as24

.66

0.1

mol

kg2

1~o

r70

.56

0.1

mas

s%!

,w

hich

issu

gges

ted

asth

ere

com

men

ded

valu

e.11

The

follo

win

gta

ble

sum

mar

izes

the

repo

rted

tem

pera

ture

san

dco

mpo

sitio

nsof

the

eute

ctic

~cry

ohyd

ric!

poin

tin

the

KS

CN

–H 2

Osy

stem

:

Tem

pera

ture

(t/°

C)

KS

CN

conc

entr

atio

nat

the

eute

ctic

poin

t

Ref

eren

ce(1

00w

1/m

ass

%)

(m1

/mol

kg2

1)

(100

x 1/m

ol%

)

229

.551

.210

.80a

23

231

.253

.60a

11.8

9a17

.64

1

231

24

231

.250

.23

10.3

9a25

a Cal

cula

ted

byev

alua

tor.

Ref

eren

ces:

1 F.C

.K

racz

ek,

J.W

ashi

ngto

nA

cad.

Sci

.26

,30

7~1

936!

.2 F.

Rud

orff,

Ann

.P

hys.

Che

m.13

6,27

6~1

869!

.3 H

.W

.F

oote

,Z

.P

hys.

Che

m.46

,79

~190

3!.


6.3.

Pot

assi

umT

hioc

yana

te

6.3.

1.E

valu

atio

nof

the

KS

CN

–H

2O

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!W

ater

;H 2

O;

@773

2-18

-5#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,Ju

ne20

01.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

KS

CN

inw

ater

has

been

repo

rted

ina

num

ber

ofpa

pers

.Mea

sure

men

tsin

the

bina

ryK

SC

N–

H2O

syst

emha

vebe

enca

rrie

dou

tby

Kra

czek1

bya

poly

ther

mal

met

hod

over

aw

ide

tem

pera

ture

rang

eof

305.

7–

450

K,

and

byR

u¨ d

orff2

who

repo

rted

isot

herm

alm

easu

rem

ents

atth

ree

tem

pera

ture

s.In

thre

edo

cum

ents

,3

–5

the

solu

bilit

yha

sbe

enob

tain

edis

othe

rmal

lyat

298.

2K

.In

addi

tion,

data

onth

eK

SC

N–

H 2Osy

stem

coul

dbe

extr

acte

dfr

omth

em

easu

rem

ents

onva

rious

tern

ary

syst

ems.

All

the

data

avai

labl

efo

the

tem

pera

ture

rang

efr

om24

3to

330

Kha

vebe

ensu

mm

ariz

edin

the

follo

win

gta

ble

and,

inor

der

tote

stho

wco

nsis

tent

they

have

abe

enpl

otte

din

the

grap

h~Fig

.13

!.F

ourt

een

data

avai

labl

efo

r29

8.2

Kar

ere

pres

ente

din

the

grap

has

the

bar,

show

ing

the

rang

ein

tow

hich

thes

eda

tafa

ll.

Te Ex

a T b V c G d Is e Is f Is g Is Tu

to eq m1

an


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#W

ater

;H 2

O;

@773

2-18

-5#F.

Rud

orff,

Ann

.P

hys.

Che

m.13

6,27

6–

84~1

869!

.

riabl

es:

Pre

pare

dB

y:

K:

271

–29

3J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

wat

eras

afu

nctio

nof

tem

pera

ture

a

empe

ratu

re(t

/°C

)K

SC

N(g

/100

gH 2

O)

KS

CN

(m1

/mol

kg2

1)c

22.

217

2.7

17.7

7

0b17

7.2

18.2

3

12.9

203.

820

.97

20b

217.

022

.33

20.5

217.

522

.38

olid

phas

esw

ere

not

inve

stig

ated

.te

rpol

ated

valu

esob

tain

edby

the

auth

or;

repo

rted

also

inR

u¨ d

orff.

1

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

salt

was

first

shak

enw

ithte

rto

obta

ina

solu

tion

satu

rate

dat

ate

mpe

ratu

resl

ight

lyov

eth

ede

sire

don

e.T

hen

the

solu

tion

was

allo

wed

toco

olw

n,an

dst

and

atth

ede

sire

dte

mpe

ratu

refo

r12

h.T

heC

Nco

nten

tw

asde

term

ined

ina

wei

ghed

port

ion

ofth

etu

rate

dso

lutio

nby

titra

tion

with

stan

dard

AgN

O3

solu

tion

ains

tK 2

CrO

4as

the

indi

cato

r.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 F.R

udor

ff,B

er.

Deu

tsch

.C

hem

.G

es.

2,68

–70

~186

9!.

8383JIRI HALA


4 J.R

.P

artin

gton

and

W.

E.

Sop

er,

Phi

los.

Mag

.7,

209

~192

9!.

5 T.L.

Cha

ngan

dY.

Y.H

sieh

,J.

Chi

nese

Che

m.

Soc

.16

,65

~194

9!.

6 A.

M.

Bab

enko

and

A.

M.A

ndria

nov,

Ukr

ain.

Khi

m.

Zh.4

5,93

1~1

979!

.7 A

.M

.B

aben

koan

dA

.M

.And

riano

v,Z

h.N

eorg

.K

him

.23,

2826

~197

8!.

8 A.

M.

Bab

enko

and

A.

M.A

ndria

nov,

Zh.

Neo

rg.

Khi

m.23,

1344

~197

8!.

9 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.10

R.

Tur

gunb

ekov

a,K

.N

ogoe

v,an

dK

.S

ulai

man

kulo

v,Z

h.N

eorg

.K

him

.17

,14

55~1

972!

.11

A.

M.

Bab

enko

and

A.

M.A

ndria

nov,

Zh.

Neo

rg.

Khi

m.23,

3123

~197

8!.

12P.

S.

Bog

oyav

lens

kiia

ndK

.M

.S

yui,

Zh.

Str

ukt.

Khi

m.

1,42

5~1

960!

.13

P.S

.B

ogoy

avle

nski

iand

K.

M.

Syu

i,Z

h.N

eorg

.K

him

.6,

469

~196

1!.

14P.

S.

Bog

oyav

lens

kiia

ndL.

Van,

Zh.

Str

ukt.

Khi

m.

1,43

1~1

960!

.15

P.S

.B

ogoy

avle

nski

i,D

okl.

Aka

d.N

auk

SS

SR10

1,86

5~1

955!

.16

P.S

.B

ogoy

avle

nski

iand

E.

D.

Gha

spar

,Z

h.N

eorg

.K

him

.17

,30

55~1

972!

.17

P.S

.B

ogoy

avle

nski

iand

G.

V.S

ukm

ansk

aya,

Zh.

Obs

h.K

him

.23

,10

92~1

953!

.18

V.G

.S

kvor

tsov

,R

.S

.Ts

ekha

nski

i,S

h.V.

Sad

etdi

nov,

and

A.

K.

Mol

odki

n,Z

h.N

eorg

.K

him

.28

,26

77~1

983!

.19

V.G

.S

kvor

tsov

,S

h.V.

Sad

etdi

nov,

R.

S.

Tsek

hans

kii,

and

A.

K.

Mol

odki

n,Z

h.N

eorg

.K

him

.24

,20

9~1

979!

.20

V.G

.S

kvor

tsov

,A.

K.

Mol

odki

n,S

h.V.

Sad

etdi

nov,

R.

S.

Tsek

hans

kii,

and

V.M

.F

edor

ov,

Zh.

Neo

rg.

Khi

m.

26,

3164

~198

1!.

21Z

.G

.K

arov

,I.

N.

Lepe

shko

v,an

dS

.B

.S

emen

ova,

Zh.

Neo

rg.

Khi

m.

16,

2273

~197

1!.

22M

.I.

Bak

eev

and

I.P.

Aki

mov

a,D

ep.

Doc

.V

INIT

I,N

o.11

48-7

6~197

6!.

23A

.C

hret

ien

and

O.

Hof

fer,

Com

pt.

Ren

d.201

,11

31~1

935!

.24

E.

Kor

des,

Z.A

norg

.Allg

em.

Che

m.16

7,97

~192

7!.

25A

.M

.Va

ssili

ev,

Zh.

Rus

s.F

iz.

Khi

m.

Obs

h.42,

423

~191

0!.

26V.

J.O

ccle

shaw

,J.

Che

m.

Soc

.55~1

931!

.

Co

~1!

~2!

Va T/ T

a S b In c C Me

An

wa

ab do KS

sa ag

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#W

ater

;H 2

O;

@773

2-18

-5#J.

R.P

artin

gton

and

W.E

.Sop

er,P

hilo

s.M

ag.

7,20

9–

47~1

929!

.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofK

SC

Nin

wat

eris

repo

rted

tobe

23.9

1g

KS

CN

in10

.27

gso

lven

tat

25°C

(m

15

23.9

6m

olkg

21;

com

pile

r!.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

KS

CN

,so

urce

not

spec

ified

,w

asan

anal

ytic

algr

ade

prod

uct,

and

was

recr

ysta

llize

dbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!W

ater

;H 2

O;

@773

2-18

-5#H

.W

.F

oote

,Z

.P

hys.

Che

m.46

,79

–86

~190

3!.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aTw

om

easu

rem

ents

ofth

eso

lubi

lity

ofK

SC

Nin

wat

erat

25°C

wer

ere

port

ed,i

.e.,

100

w15

70.3

8an

d70

.68

mas

s%

(m

15

24.4

5an

d24

.805

mol

kg2

1 ,re

spec

tivel

y;co

mpi

ler!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Toan

accu

rate

lyw

eigh

edqu

antit

yof

KS

CN

,a

know

nam

ount

ofw

ater

was

adde

din

agl

ass

tube

soth

atth

esa

ltw

asin

exce

ss.

The

mix

ture

was

first

heat

edtil

lthe

salt

diss

olve

d,an

dth

eneq

uilib

rate

dat

25°C

.Afte

req

uilib

ratio

n,a

smal

lpor

tion

ofth

esa

tura

ted

solu

tion

was

with

draw

n,an

dth

eS

CN

2

cont

ent

was

dete

rmin

edgr

avim

etric

ally

asA

gSC

N.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

Va T/

Me

An


FIG

.14

.P

hase

diag

ram

ofth

eK

SC

N–

H2O

syst

em.

Num

eric

alda

taw

ere

give

nfo

rth

efo

llow

ing

sign

ifica

ntpo

ints

:

mpe

ratu

re(t

/°C

)K

SC

N(1

00w

1/m

ass

%)

KS

CN

(m1

/mol

kg2

1)a

Sig

nific

ant

poin

t

229

.551

.210

.80

eute

ctic~F

!

233

.254

.412

.28

eute

ctic

–m

etas

tabl

e~E

!

230

.05

51.8

11.0

6eu

tect

ic–

met

asta

ble

~G!

16.

8tr

ansi

tion

~C!

217

.75

59.7

15.2

4tr

ansi

tion

–m

etas

tabl

e~H

!

alcu

late

dby

com

pile

r.

ditio

nali

nfor

mat

ion:

Anh

ydro

usK

SC

N,@3

33-2

0-0#,

isth

eeq

uilib

rium

solid

phas

eov

erth

ete

mpe

ratu

rein

terv

alfr

om6.

8to

177.

2°C

eltin

gpo

into

fKS

CN!

.At1

42.3

°C~p

oint

Din

the

diag

ram!,

tran

sitio

nbe

twee

ntw

ofo

rms

ofK

SC

Noc

curs

.Bel

ow6.

8°C

,anh

ydro

usC

Nis

met

asta

ble~s

ectio

nC

E!.In

the

tem

pera

ture

inte

rval

from

229

.5to

16.

8°C

,th

eeq

uilib

rium

solid

phas

eis

KS

CN

•0.

5H2O

ctio

nC

F!.A

tte

mpe

ratu

res

from

230

.1to

217

.75

°C,

am

etas

tabl

eph

ase

KS

CN

•0.

8H2O

was

obse

rved

~sec

tion

GH!

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

poly

ther

mal

met

hod

was

used

,no

deta

ilsre

port

ed.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

8585JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!W

ater

;H 2

O;

@773

2-18

-5#A

.C

hret

ien

and

O.

Hof

fer,

Com

pt.

Ren

d.201

,11

31–

3~19

35!.

Varia

bles

:P

repa

red

By:

Tem

pera

ture

J.H

a´ l

a

Exp

erim

enta

lDat

aP

hase

diag

ram

ofth

eK

SC

N–

H2O

syst

emT

heda

taw

ere

pres

ente

din

grap

hica

lfor

m~see

Fig

.14

!.

Te a C Ad

~m KS

~se

Me

A

J

e

Apo

lyth

erm

alm

etho

dw

asus

ed.

Wei

ghed

quan

titie

sof

KS

CN

and

wat

erw

ere

seal

edin

Pyr

extu

bes.

The

tube

sw

ere

rota

ted

ina

ther

mos

tat

until

allt

hecr

ysta

lsdi

ssol

ved,

asju

dged

byvi

sual

obse

rvat

ion.

Ow

ing

toth

ede

stru

ctio

nof

nucl

eion

com

plet

edi

ssol

utio

n,th

eeq

uilib

rium

coul

dno

tbe

appr

oach

edfr

omab

ove.

Sol

ubili

tyde

term

inat

ions

cons

iste

din

esta

blis

hing

the

tem

pera

ture

atw

hich

the

last

crys

tald

isap

pear

ed.

The

ther

mos

tat

was

aco

pper

-line

dm

uffle

furn

ace

ofre

ctan

gula

rcr

oss

sect

ion,

open

atbo

then

ds,

and

prov

ided

with

anai

rpr

opel

ler,

and

with

asl

owly

revo

lvin

gtu

beho

lder

.

KS

CN

,rea

gent

grad

e,w

asre

crys

talli

zed,

and

drie

din

vacu

umat

ate

mpe

ratu

reab

ove

the

tran

sitio

npo

int,

but

belo

wth

em

eltin

gpo

int.

No

deco

mpo

sitio

nw

asno

ticed

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.01

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#W

ater

-d2

;H

2O

-d2

;@7

789-

20-0#

A.

Sel

ecki

,B

.Ty

min

ski,

and

B.

Mar

iano

wsk

a,J.

Che

m.

Eng

.D

ata

15,

130

–4

~197

0!.

riabl

es:

Pre

pare

dB

y:

K:

298

–36

3J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

heav

yw

ater

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

KS

CN

(100

x 1/m

ole

%)

KS

CN

(m1

/mol

kg2

1)b

2530

.021

.40

3532

.624

.15

4535

.227

.12

6039

.833

.01

75.5

44.4

39.8

7

9148

.747

.39

ompo

sitio

nof

equi

libriu

mso

lidph

ases

was

not

repo

rted

.al

cula

ted

byco

mpi

ler

usin

gMr5

20.0

28fo

rH 2

O-d

2.

ditio

nali

nfor

mat

ion:

Ref

ract

ive

indi

ces

for

solu

tions

ofK

SC

Nat

vario

usco

ncen

trat

ions

inhe

avy

wat

erw

ere

repo

rted

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.A

curv

ew

aspl

otte

dof

frac

tive

indi

ces

ofK

SC

Nso

lutio

nsag

ains

tco

ncen

trat

ion,

atco

nsta

ntte

mpe

ratu

re.A

tth

esa

tura

tion

poin

tth

ecu

rve

isok

en,

and

runs

horiz

onta

llyab

ove

the

satu

ratio

npo

int.

The

tura

tion

poin

tw

asob

tain

edgr

aphi

cally

asth

epo

int

ofer

sect

ion

ofth

etw

obr

anch

esof

the

curv

e.T

hete

chni

que

sch

ecke

dby

dete

rmin

ing

the

solu

bilit

ycu

rve

ofN

aBr

indi

nary

wat

erw

ithgo

odag

reem

ent

with

publ

ishe

dda

ta.

frac

tive

indi

ces

wer

em

easu

red

byus

ing

aR

Lre

frac

tom

eter

,O

,W

arsa

w,

equi

pped

with

Am

icip

rism

s.P

reci

sion

ofth

efr

acto

met

erw

as0.

0002

.

KS

CN

,so

urce

not

spec

ified

,w

asof

anal

ytic

alpu

rity.

H2O

-d2

,pr

oduc

tof

the

US

SR

.B

efor

eso

lubi

lity

dete

rmin

atio

ns,

the

isot

opic

com

posi

tion

ofox

ygen

was

norm

aliz

edby

elec

trol

ytic

deco

mpo

sitio

nof

wat

er.

The

conc

entr

atio

nof

deut

eriu

min

the

final

prod

uct

was

dete

rmin

edby

the

picn

omet

ricm

etho

dto

be99

.8m

ole

%.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

60.

1m

ole

%~m

axim

umde

viat

ion

from

arith

met

icm

ean;

auth

ors!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

2#~2

!W

ater

;H 2

O;

@773

2-18

-5#F.

C.

Kra

czek

,J.

Was

hing

ton

Aca

d.S

ci.

26,

307

–13

~193

6!.

Varia

bles

:P

repa

red

By:

T/K

:30

5.7

–41

3.9

J.H

a´ l

a

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

wat

eras

afu

nctio

nof

tem

pera

ture

a

Tem

pera

ture

(t/°

C)

KS

CN

(g/1

00g

H 2O

)K

SC

N(1

00x 1

/mol

e%

)K

SC

N(m

1/m

olkg

21)b

Tem

pera

ture

(t/°

C)

KS

CN

(g/1

00g

H 2O

)K

SC

N(1

00x 1

/mol

e%

)

32.6

265.

1032

.95

27.2

814

0.6

1825

.677

.19

47.3

317.

0537

.02

32.6

314

2.7

1957

.778

.40

57.0

358.

6039

.93

36.9

014

6.1

2188

.280

.23

66.7

408.

4543

.09

42.0

314

9.4

2471

.182

.08

74.5

455.

9045

.81

46.9

115

5.0

3116

.285

.25

84.2

526.

949

.42

54.2

215

7.4

3599

.686

.97

99.0

673.

655

.53

69.3

116

0.0

4185

.888

.59

108.

480

2.9

59.8

282

.62

164.

557

7391

.46

116.

895

6.6

63.9

498

.44

169.

293

4294

.55

124.

611

50.2

68.0

817

0.7

1196

195

.69

130.

713

46.2

71.4

017

6.8

c—

—

133.

914

76.1

73.2

4

a Sol

idph

ases

wer

eth

etw

opo

lym

orph

icfo

rms

ofK

SC

N,

labe

led

byth

eau

thor

sas

KS

CN

Ian

dK

SC

NII.

The

yex

iste

dbe

low

and

abov

140.

6°C

,w

hich

was

the

poin

tof

tran

sitio

nbe

twee

nth

etw

ofo

rms.

b Cal

cula

ted

byco

mpi

ler.

c Mel

ting

poin

tof

KS

CN

.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

ofK

SC

Nin

wat

eras

afu

nctio

nof

tem

pera

ture

was

expr

esse

dby

the

auth

oras

lg(1

00x 1

)5a

1b

(T/K

)1c

lg(T

/K)1

d(T

/K),

whe

reth

eco

effic

ient

sa,b,

c,an

dd

are

220

.719

04,

892.

459,

7.81

532,

and

0,re

spec

tivel

y,fo

rth

ete

mpe

ratu

rera

nge

whe

reK

SC

NI

was

the

equi

libriu

mso

lidph

ase,

and

31.8

5576

,2

957.

918,

212

.278

25,

and

0.01

082

07fo

rth

eK

SC

NII

regi

on.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Co

~1!

~2!

Va T/

a C b C Ad

Me

An

re a br sa int

wa

or Re

PZ

re


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#S

ulfu

rdi

oxid

e;S

O 2;

@744

6-09

-5#G

.Ja

nder

and

W.

Rup

polt,

Z.

Phy

s.C

hem

.17

9,43

–50

~193

7!.

riabl

es:

Pre

pare

dB

y:

K:

273

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofK

SC

Nin

liqui

dsu

lfur

diox

ide

was

repo

rted

tobe

4.87

gsa

ltin

100

gso

lven

tat

0°C

(m

1/m

olkg

215

0.50

1;m

pile

r!.S

olid

phas

esw

ere

not

inve

stig

ated

.H

owev

er,

the

auth

ors

quot

edth

eex

iste

nce

ofth

ead

duct

sK

SC

N•S

O2

~Wal

den

and

ntne

rszw

er1an

dE

phra

iman

dK

ornb

lum2 !

and

KS

CN•

0.5S

O 2~E

phra

iman

dK

ornb

lum2 !.

Add

ition

alin

form

atio

n:H

igh

solu

bilit

yof

KS

CN

inliq

uid

amm

onia

,tho

ugh

notp

rope

rlysp

ecifi

ed,w

asre

port

edin

Sha

tens

htei

nan

dto

rov4

and

Foo

tean

dF

leis

cher

.5

Sat

urat

edso

lutio

nsw

ere

yello

win

colo

r,an

dth

eso

lidph

ase

was

red

–or

ange

.In

Foo

tean

dis

cher

,5th

eco

mpo

sitio

nof

the

solid

phas

ew

asre

port

edto

beK

SC

N•2

SO 2

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.A

bout

10g

SO

2,

care

fully

ied,

was

equi

libra

ted

with

exce

ssso

lidat

0°C

inw

ater

–ic

eth

ina

thre

e-co

mpa

rtm

ent

glas

sve

ssel

inw

hich

equi

libra

ting

dsa

mpl

ing

com

part

men

tsw

ere

sepa

rate

dby

aco

mpa

rtm

ent

ntai

ning

glas

s/w

oolfi

lter.

Equ

ilibr

atio

nw

aspe

rfor

med

for

spec

ified

,pr

olon

ged

perio

dof

time

unde

rfr

eque

ntsh

akin

g.te

req

uilib

rium

had

been

atta

ined

,th

eve

ssel

was

turn

edsi

dedo

wn,

and

the

satu

rate

dso

lutio

nw

asfil

tere

din

toth

ept

ysa

mpl

ing

com

part

men

t,w

hich

was

subs

eque

ntly

cool

edd

seal

edof

f.A

fter

wei

ghin

gth

eco

mpa

rtm

ent

with

the

mpl

e,S

O 2w

asal

low

edto

evap

orat

e,th

ere

sidu

ew

asig

hed,

diss

olve

din

wat

er,

and

the

cont

ent

ofth

esa

ltw

aste

rmin

ed.

The

met

hod

ofan

alys

isw

asno

tsp

ecifi

ed.

KS

CN

,so

urce

not

spec

ified

,bu

tw

asca

refu

llydr

ied

befo

reus

e.C

omm

erci

ally

avai

labl

eS

O 2w

aspu

rified

bypa

ssin

git

thro

ugh

conc

entr

ated

H 2SO

4an

dov

eras

best

osw

ool,

and

drie

dby

usin

gP 2

O5

.T

hesp

ecifi

cco

nduc

tivity

ofth

epr

oduc

tw

as4.

53

102

7V

21

~Jan

der

and

Wic

kert3 !.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 P.W

alde

nan

dM

.C

entn

ersz

wer

,Z

.P

hys.

Che

m.

42,

432

~190

3!.

2 F.E

phra

iman

dI.

Kor

nblu

m,

Ber

.49,

2007

~191

6!.

3 G.

Jand

eran

dK

.W

icke

rt,

Z.

Phy

s.C

hem

.17

8,57

~193

6!.

4 A.

IS

hate

nsht

ein

and

M.

M.

Vik

toro

v,A

cta

Phy

sico

khim

.U

SS

R7,

883

~193

7!.

5 H.

W.

Foo

tean

dJ.

Fle

isch

er,

J.A

m.

Che

m.

Soc

.54

,39

03~1

932!

.

8787JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!W

ater

;H 2

O;

@773

2-18

-5#;

orW

ater

-d2

;H

2O

-d2

;@7

789-

20-0#

T.L.

Cha

ngan

dY.

Y.H

sieh

,J.

Chi

n.C

hem

.S

oc.

16,

65–

71~1

949!

.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

at25

°Cof

KS

CN

inw

ater

and

heav

yw

ater

Sol

ubili

tyof

KS

CN

inH 2

O:

The

solu

bilit

yw

asre

port

edto

bem15

24.6

mol

kg2

1at

25°C

.T

his

valu

eis

the

mea

nof

four

inde

pend

ent

mea

sure

men

ts,

i.e.,

24.6

7,24

.63,

24.5

6,an

d24

.58.

Sol

ubili

tyof

KS

CN

inH 2

O-d

2:

Dup

licat

ean

alys

isof

one

satu

rate

dso

lutio

nat

25°C

yiel

ded

the

follo

win

gco

mpo

sitio

nsof

the

satu

rate

dso

lutio

n:0.

4469

gK

SC

Nin

0.21

35g

solv

ent,

and

0.48

05g

KS

CN

in0.

2298

gso

lven

t(

m1

/mol

kg2

15

21.5

4an

d21

.52,

resp

ectiv

ely;

com

pile

r!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Sat

urat

edso

lutio

nsw

ere

prep

ared

byth

em

etho

dof

supe

rsat

urat

ion.

1T

hesu

pers

atur

ated

solu

tions

,m

ade

byag

itatin

gex

cess

salt

with

the

solv

ent

at60

°Cfo

r1

h,w

ere

agita

ted

at25

°Cfo

r2

–3

hin

aw

ater

bath

.Asa

mpl

eof

the

clea

rso

lutio

nw

asde

liver

edin

toa

wei

ghin

gbo

ttle,

the

solv

ent

was

allo

wed

toev

apor

ate,

and

the

resi

dual

salt

was

drie

din

vacu

umat

100

°Can

dw

eigh

ed.

KS

CN

was

aco

olin

gpo

int

prod

uct

ofM

erck

.H

2O

-d2

~Nor

skH

ydro

-Ele

ctris

kK

vals

tofa

ktie

sels

kab,

Osl

o!

cont

aine

d99

.7m

ole

%de

uter

ium

oxid

e.T

heH 2O

-d2

cont

enti

nth

eso

lven

twas

dete

rmin

edby

dens

itym

easu

rem

ent

befo

rean

daf

ter

the

mea

sure

men

t.T

hem

ole

%da

taw

ere

calc

ulat

edfr

omth

ede

nsity

acco

rdin

gto

Sw

ift.2

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

stan

dard

devi

atio

nof

m15

60.

05m

olkg

21

~com

pile

r!.

Ref

eren

ces:

1 T.L.

Cha

ngan

dY.

Y.H

sieh

,J.

Chi

nese

Che

m.

Soc

.16

,10

~194

9!.

2 E.

Sw

ift,

J.A

m.

Che

m.

Soc

.61,

198

~193

9!.

Co

~1!

~2!

Va T/

co Ce

Vik

Fle

Me

An

dr ba an co un Af

up em an sa we

de

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#A

mm

onia

;N

H 3;

@766

4-41

-7#P.

W.

Sch

enk

and

H.

Tul

hoff,

Ber

.B

unse

nges

.P

hys.

Che

m.

71,

1155

–8~

1967

!.

riabl

es:

Pre

pare

dB

y:

K:

198

–25

9J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

liqui

dam

mon

iaas

afu

nctio

nof

tem

pera

ture

The

solu

bilit

ym

easu

rem

ents

wer

epr

esen

ted

ingr

aphi

calf

orm

~equ

ilibr

ium

solid

phas

esar

ein

dica

ted

inF

ig.

15!.

FIG

.15

.S

olub

ility

ofK

SC

Nin

liqui

dam

mon

iaas

afu

nctio

nof

tem

pera

ture

.F

rom

the

grap

h,th

eau

thor

sob

tain

edth

efo

llow

ing

num

eric

alda

taby

inte

rpol

atio

n:

mpe

ratu

re(t

/°C

)K

SC

Na

(g/1

00g

NH 3

)K

SC

N(m

1/m

olkg

21)b

Tem

pera

ture

(t/°

C)

KS

CN

a

(g/1

00g

NH 3

)K

SC

N(m

1/m

olkg

21)b

275

75.0

7.71

82

6014

9c15

.33

270

81.2

8.35

62

5015

3c15

.74

265

88.1

9.06

62

4015

716

.16

260

96.5

9.93

02

3016

216

.67

255

110

11.3

22

2016

817

.29

250

144

14.8

2

a Exp

ress

edas

unso

lvat

edsa

lt.b C

alcu

late

dby

com

pile

r.c K

SC

Nas

met

asta

ble

solid

phas

e.S

ince

the

amm

onia

tes

crys

talli

zed

with

diffi

culty

itw

aspo

ssib

leto

dete

rmin

eth

eso

lubi

lity

ofK

SC

Nin

the

met

asta

ble

rang

efr

om249

to2

62°C

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!A

mm

onia

;N

H 3;

@766

4-41

-7#G

.C

.B

lyta

san

dF.

Dan

iels

,J.

Am

.C

hem

.S

oc.

84,

1075

–83

~196

2!.

Varia

bles

:P

repa

red

By:

T/K

:21

4J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

liqui

dN

H 3at

one

tem

pera

ture

The

solu

tion

satu

rate

dat2

59°C

~liqu

idus

tem

pera

ture!

was

repo

rted

toco

ntai

n51

.38

mas

s%

NH

3.

Fro

mth

is,

the

com

pile

rca

lcul

ated

the

solu

bilit

yof

KS

CN

at259

°Cto

be10

0w15

48.6

2m

ass

%,

orm15

9.73

7m

olkg

21.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Apo

lyth

erm

alm

etho

d1w

asus

ed.

The

salt

was

quic

kly

intr

oduc

edin

toa

glas

stu

be,

whi

chw

asth

ense

aled

aton

een

d,he

ated

and

evac

uate

dfo

r24

h,an

dw

eigh

ed.

The

nth

evo

lum

eof

purifi

edN

H 3ne

cess

ary

togi

veth

ede

sire

dsa

ltco

ncen

trat

ion

was

dist

illed

in,

the

tube

was

seal

edof

f,an

dw

eigh

edag

ain.

Equ

ilibr

atin

gan

dth

erm

osta

ting

wer

eca

rrie

dou

tin

diffe

rent

bath

sde

pend

ing

onth

ete

mpe

ratu

rera

nge.

Cal

ibra

ted

ther

mom

eter

sw

ere

used

.Li

quid

uste

mpe

ratu

res

wer

ere

cord

edas

thos

eat

whi

chth

ela

stcr

ysta

lsdi

sapp

eare

dw

ithsl

owhe

atin

g.T

his

was

pref

erre

dto

obse

rvin

gte

mpe

ratu

res

ofap

pear

ance

offir

stcr

ysta

lsbe

caus

eof

the

tend

ency

ofth

esy

stem

tofo

rmsu

pers

atur

ated

solu

tions

onco

olin

g.

NH

3us

edw

asst

ored

over

sodi

umm

etal

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

0.01

mas

s%

~aut

hors!

.

Ref

eren

ces:

1 G.C

.Bly

tas

and

F.D

anie

ls,J

.Am

.Che

m.S

oc.

84,1

075~

1962

!.

Co

~1!

~2!

Va T/

Te


he mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#A

ceto

nitr

ile;

C 2H

3N

;@7

5-05

-8#

A.

Nau

man

n,B

er.4

7,24

7–

56~1

914!

.

riabl

es:

Pre

pare

dB

y:

K:

291

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

acet

onitr

ileat

one

tem

pera

ture

The

solu

bilit

yof

KS

CN

was

repo

rted

tobe

0.11

31g

salt

in

1g

solv

ent

at18

°C.

Fro

mth

isva

lue,

the

com

pile

rca

lcul

ated

100

w1

10.1

6m

ass

%,

orm15

1.16

4m

olkg

21.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

solid

was

shak

enw

ithso

lven

tin

aw

ater

ther

mos

tat

for

2–

6h.

Atta

inm

ent

ofui

libriu

mw

asch

ecke

dby

occa

sion

alan

alys

isof

the

liqui

das

e.T

hesa

tura

ted

solu

tions

wer

era

pidl

yfil

tere

din

toig

hing

vess

els

kept

at18

°C,

and

the

cont

ent

ofS

CN

2w

aste

rmin

edtit

rimet

rical

ly~pr

esum

ably

byth

eVo

lhar

d’s

thod

!.

KS

CN

,so

urce

and

purit

yno

tsp

ecifi

ed,

was

drie

din

ava

cuum

dess

icat

orbe

fore

use.

Ace

toni

trile~K

ahlb

aum!

was

purifi

edfr

omac

etam

ide

byal

low

ing

the

solv

ent

tost

and

for

3–

4w

eeks

over

P 2O

5,

and

dist

illed

.T

hepr

oduc

tus

edbo

iling

poin

tat

81.6

°C.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.T

heso

lubi

lity

valu

ere

port

edis

the

mea

nof

two

dete

rmin

atio

ns~in

divi

dual

resu

ltsno

tre

port

ed!.

8989JIRI HALA


Tens

imet

ricm

easu

rem

ents

ofth

eso

lidre

sidu

esob

tain

edfr

omth

esa

tura

ted

solu

tions

afte

rev

apor

atio

nof

the

solv

ent

yiel

ded

tex

iste

nce

regi

ons

ofth

efo

llow

ing

amm

onia

tes:

Tem

pera

ture

rang

e,t/°C

Sol

idph

ase

,2

69.7

KS

CN•5

NH

3

269

.7–2

67.9

KS

CN•5

NH

31

a-K

SC

N•4

NH

3

267

.9–2

60.4

a-K

SC

N•4

NH

3

260

.4–2

56.1

a-K

SC

N•4

NH

31

b-K

SC

N•4

NH

3

256

.1–2

53.1

b-K

SC

N•4

NH

3

253

.1–2

52.0

b-K

SC

N•4

NH

31

g-K

SC

N•4

NH

3

252

.0–2

49.1

g-K

SC

N•4

NH

3

.2

49.1

KS

CN

,@33

3-20

-2#

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

d1w

asus

ed.

Mea

sure

men

tsw

ere

carr

ied

out

ina

vess

elco

nnec

ted

toa

vacu

umlin

e,an

dth

erm

osta

ted

with

met

hano

lcoo

led

ina

cryo

stat

.To

akn

own

amou

ntof

the

solid

salt,

amm

onia

was

grad

ually

cond

ense

dun

tilal

lsol

iddi

ssol

ved.

The

mix

ture

was

inte

nsel

yst

irred

durin

gam

mon

iaco

nden

satio

n.To

war

dth

een

dof

diss

olut

ion,

addi

tions

ofN

H3

wer

em

ade

smal

l,an

dw

ere

adde

dov

ersu

ffici

ently

long

time

inte

rval

sto

allo

wfo

req

uilib

rium

bein

gat

tain

edan

dfo

rke

epin

gth

ete

mpe

ratu

reco

nsta

nt.

The

diss

olut

ion

proc

ess

was

obse

rved

insi

delig

ht.

Toas

cert

ain

that

the

poin

tof

satu

ratio

nw

asno

tex

ceed

ed,

the

diss

olut

ion

was

stop

ped

whe

na

few

very

tiny

crys

tals

rem

aine

dun

diss

olve

dov

era

prol

onge

dpe

riod

oftim

e.A

smal

lerr

orin

trod

uced

inth

isw

ayby

usin

gla

rge

enou

gham

ount

ofth

eso

lid.

The

tota

lam

ount

ofN

H3

cond

ense

dw

asca

lcul

ated

from

the

tem

pera

ture

,vo

lum

eof

the

appa

ratu

s,an

din

itial

and

final

pres

sure

sof

NH

3.

No

deta

ilsw

ere

repo

rted

asfo

rK

SC

N.A

mm

onia

gas

was

drie

dby

pass

ing

itth

roug

hto

wer

sfil

led

with

NaO

H,

CaO

,B

aO,

and

sodi

umm

etal

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 P.W

.S

chen

kan

dH

.Tul

hoff,

Ber

.B

unse

nges

.P

hys.

Che

m.

71,

206

~196

7!.

Co

~1!

~2!

Va T/

5 Me

An

the

eq ph we

de me

J

6.3.

2.E

valu

atio

nof

the

KS

CN

–E

than

olS

yste

m

mpo

nent

s:E

valu

ator

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#E

than

ol;

C 2H

6O

;@6

4-17

-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

July

2001

.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

KS

CN

inet

hano

lha

sbe

enre

port

edin

thre

edo

cum

ents

.N

ikiti

nae

ta

l.1re

port

edth

eso

lubi

lity

asa

func

tion

ofpe

ratu

reov

erth

era

nge

from

283

to32

3K

whi

leS

tepi

nan

dco

-wor

kers

2re

port

eda

sing

leva

lue

at29

8K

.T

heot

her

docu

men

t3

has

tbee

nav

aila

ble

toth

eev

alua

tor.

Nik

itinaet

al.1

did

nots

peci

fyth

eco

ncen

trat

ion

unit

inw

hich

they

expr

esse

dth

eso

lubi

lity.

Ass

umin

gy

used

mol

ality

,as

they

did

inth

eir

late

rw

ork,

4th

eir

solu

bilit

yva

lue

at29

8K

can

beco

mpa

red

toth

atof

Ste

pin

et

al.,

2th

ere

spec

tive

lues

bein

gm1

/mol

kg2

15

0.24

1~N

ikiti

nae

ta

l.1 !an

d0.

530~

Ste

pin

et

al.2 !.

Thi

sdi

ffere

nce

can

pres

umab

lybe

ascr

ibed

toth

epu

rity

etha

nol

sinc

efo

rth

eso

lubi

lity

ofK

SC

Nin

orga

nic

solv

ents

,w

ater

cont

ent

inth

ela

tter

isof

cruc

ial

impo

rtan

cedu

eto

the

high

lubi

lity

ofK

SC

Nin

wat

er.H

owev

er,i

thas

notb

een

poss

ible

todr

awan

yde

finite

conc

lusi

onas

for

the

purit

yof

etha

nolu

sed

inth

etw

ocu

men

ts.N

ikiti

nae

ta

l.1di

dno

trep

orta

nyin

form

atio

non

purit

yof

the

solv

ent,

whi

leth

ede

nsity

ofet

hano

lof0

.798

7g

cm2

3re

port

edS

tepi

ne

ta

l.2se

ems

toco

rres

pond

toap

prox

imat

ely

98%

purit

yof

etha

nol.

Due

tosc

arci

tyof

info

rmat

ion

prov

ided

inth

etw

ocu

men

ts,

noda

taca

nbe

reco

mm

ende

d.5

fere

nces

:

P.N

ikiti

na,

B.

S.

Kru

mga

lz,

D.

G.

Tra

ber,

and

G.

F.F

edot

ova,

Zh.

Neo

rg.

Khi

m.

14,

2593

~196

9!.

.D

.S

tepi

n,V.

E.

Ply

ushc

hev,

and

Yu.A

.Iv

anov

a,K

him

.P

rom

.~C

hem

.In

dust

ry!40

4~1

962!

.

.S

.K

rum

galz

,Te

oria

Ras

tvor

ov~T

heor

yof

Sol

utio

ns!24

2~1

971!

;C

hem

.Abs

tr.77

,ab

stra

ctno

.15

7018~

1972

!.

.S

.K

rum

galz

,V.

A.

Sm

irnov

a,an

dYu

.I.

Ger

zber

g,Z

h.N

eorg

.K

him

.17

,17

78~1

972!

.

hys

ico

-Ch

em

ica

lTa

ble

s~Pub

l.H

ouse

Tech

.Li

t,P

ragu

e,19

53!,Vo

l.1,

p.32

0.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!1,

2-et

hane

diam

ine~e

thyl

ened

iam

ine!;

C2H

8N

2;

@107

-15-

3#H

.S

.Is

bin

and

K.

A.

Kob

e,J.

Am

.C

hem

.S

oc.

67,

464

–5

~194

5!.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

ethy

lene

diam

ine

at25

°CT

heso

lubi

lity

ofK

SC

Nis

repo

rted

tobe

83.0

gin

100

gso

lven

t~c

ompi

ler:

m15

8.54

mol

kg2

1).

The

com

posi

tion

ofth

eso

lidph

ase

was

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

solv

ent

and

exce

ssso

lidw

ere

seal

edin

agl

ass

test

tube

and

rota

ted

for

atle

ast

1w

eek

ina

wat

erth

erm

osta

t,w

hich

was

foun

dsu

ffici

ent

for

equi

libriu

mto

bere

ache

d.S

ampl

esof

the

satu

rate

dso

lutio

nw

ere

with

draw

nw

itha

wei

ghin

gpi

pette

,an

dan

alyz

edfo

rS

CN2

cont

ent

bytit

ratio

nag

ains

ta

stan

dard

AgN

O3

solu

tion.

KS

CN

,an

alyt

ical

grad

e,w

asdr

ied

at15

0°C

befo

reus

e.E

thyl

ened

iam

ine,

sour

ceno

tsp

ecifi

ed,

was

dehy

drat

edan

dpu

rified

acco

rdin

gto

Put

nam

and

Kob

e.1

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.08

K~a

utho

rs!.

Sol

ubili

ty:6

0.5%

~aut

hors!

.

Ref

eren

ces:

1 G.L

.Put

nam

and

K.A

.Kob

e,T

rans

.Ele

ctro

chem

.Soc

.74

,609

~193

8!.

Co

~1!

~2!

tem

no the

va of so do by do Re

1 I. 2 B 3 B 4 B 5 P


until

stea

dyco

nduc

tivity

ofth

eso

lutio

nw

asob

tain

ed.

The

equi

libriu

mco

nduc

tivity

valu

ew

asth

enus

edto

read

the

conc

entr

atio

nof

KS

CN

inth

esa

tura

ted

solu

tion

from

aca

libra

tion

grap

hof

cond

uctiv

itypl

otte

dag

ains

tK

SC

Nco

ncen

trat

ion

inac

eton

e.

B.

S.

Kru

mga

lz,

Yu.

I.G

erzh

berg

,I.

P.N

ikiti

na,

V.I.

Der

evsk

aya,

G.

F.F

edot

ova,

and

D.

G.

Tra

ber,

Zh.

Prik

l.K

him

.42

,14

14~1

969!

.

6.3.

3.E

valu

atio

nof

the

KS

CN

–A

ceto

neS

yste

m

mpo

nent

s:E

valu

ator

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#2-

prop

anon

e~ac

eton

e!;C

3H

6O

;@6

7-64

-1#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

July

2001

.

Crit

ical

Eva

luat

ion

Two

inve

stig

atio

nsof

the

solu

bilit

yof

KS

CN

inac

eton

eha

vebe

enre

port

ed.L

aszc

zyns

ki1

repo

rted

the

solu

bilit

ies

at29

5an

d33

1K

,d

Der

nini

et

al.2

repo

rted

the

solu

bilit

yat

the

boili

ngpo

int

ofth

esa

tura

ted

solu

tion,

but

did

not

repo

rtth

ebo

iling

poin

tte

mpe

ratu

re.

ela

tter

has

been

calc

ulat

edby

the

eval

uato

rto

be33

1.8

K,

usin

geb

ulio

scop

icco

nsta

ntan

dno

rmal

boili

ngpo

int

ofac

eton

e.A

lthou

ghs

tem

pera

ture

isve

rycl

ose

toth

atof

331

Kus

edin

Lasz

czyn

ski,

1th

etw

ore

spec

tive

solu

bilit

yva

lues

diffe

rco

nsid

erab

ly,

i.e.,

/mol

kg2

15

2.10

~Las

zczy

nski1 !

and

1.41

~Der

nini

et

al.2 !.

The

reas

onfo

rth

isdi

scre

panc

yis

not

clea

r.E

ven

thou

ghth

eso

lubi

lity

port

edby

Lasz

czyn

ski

1at

295

Kco

inci

des

wel

lwith

that

for

293

Kgi

ven

grap

hica

llyby

Wei

tzan

dG

rohr

ock

3no

neof

the

solu

bilit

yta

can

bere

com

men

ded.

fere

nces

:

.vo

nLa

szcz

ynsk

i,B

er.27

,22

85~1

894!

.

.D

erni

ni,

R.

DeS

antis

,an

dL.

Mar

relli

,J.

Che

m.

Eng

.D

ata

21,

170

~197

6!.

.W

eitz

and

E.

Gro

hroc

k67,

1085

~193

4!.

9191JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!E

than

ol;

C 2H

6O

;@6

4-17

-5#

I.P.

Nik

itina

,B.S

.Kru

mga

lz,D

.G.T

rabe

r,an

dG

.F.F

edot

ova,

Zh.

Neo

rg.

Khi

m.1

4,25

93–

4~19

69!.

Varia

bles

:P

repa

red

By:

T/K

:28

3–

323

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

etha

nola

sa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

KS

CN

(m1

/mol

kg2

1)b

100.

188

150.

205

200.

222

250.

241

300.

260

350.

281

400.

301

450.

322

500.

342

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Con

cent

ratio

nun

itno

tsp

ecifi

edin

the

orig

inal

docu

men

t.T

heco

mpi

ler

assu

med

this

tobe

mol

ality

,as

inth

eau

thor

s’ot

her

wor

k.1

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

d2w

asus

ed.

Exc

ess

solid

was

equi

libra

ted

with

etha

nolb

yst

irrin

gin

acl

osed

,th

erm

osta

ted

vess

el.A

ttain

men

tof

equi

libriu

mw

asch

ecke

dby

mea

surin

gel

ectr

ical

cond

uctiv

ityof

the

solu

tion.

Toth

isai

m,

anel

ectr

olyt

icce

llcl

osed

with

agl

ass

sint

erw

asim

mer

sed

inth

eso

lutio

nth

roug

hout

the

mea

sure

men

t.A

tch

osen

time

inte

rval

s,th

em

easu

red

solu

tion

was

suck

edin

betw

een

two

plat

inum

elec

trod

es,

the

cond

uctiv

ityw

asm

easu

red,

and

the

solu

tion

was

tran

sfer

red

back

from

the

cell

toth

eso

lubi

lity

vess

elby

appl

ying

over

pres

sure

ofdr

yai

r.T

hepr

oced

ure

was

repe

ated

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

60.

2%~e

rror

ofco

nduc

tivity

mea

sure

men

ts;

auth

ors!.

Ref

eren

ces:

1 B.

S.

Kru

mga

lz,

V.A

.S

mirn

ova,

and

Yu.

I.G

erzb

erg,

Zh.

Neo

rg.

Khi

m.1

7,17

78~1

972!

.2

Co

~1!

~2!

an Th

thi

m1

re da Re

1 S 2 S 3 E

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;N

aSC

N;

@333

-20-

0#M

ethy

lace

tate

;C 3H

6O

2;

@79-

20-9

#J.

Sch

roed

eran

dM

.S

tein

er,

J.P

rakt

.C

hem

.79

,49

–65

~190

9!.

riabl

es:

Pre

pare

dB

y:

em

easu

rem

ent

atbo

iling

poin

tte

mpe

ratu

re.

J.H

a´ l

a

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

boili

ngm

ethy

lace

tate

The

solu

bilit

yof

KS

CN

isre

port

edto

be10

0w15

0.85

mas

s%

atbo

iling

poin

tof

the

satu

rate

dso

lutio

n~c

ompi

ler:

m1

0.08

82m

olkg

21).

The

boili

ngpo

int

tem

pera

ture

was

not

repo

rted

.T

heso

lidph

ase

was

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

cess

salt

was

boile

dw

ithm

ethy

lace

tate

for

apr

olon

ged

riod

oftim

ein

afla

skcl

osed

with

ast

oppe

rth

roug

hw

hich

aor

tgl

ass

tube

was

prot

rudi

ng.

The

latte

rco

ntai

ned

glas

sol

asa

filte

rat

the

botto

men

d,an

dw

asm

ade

into

ash

ort

pilla

ryat

the

uppe

ren

d.B

ytu

rnin

gth

efla

skup

side

dow

n,a

rtio

nof

the

satu

rate

dso

lutio

nw

asal

low

edto

pour

out

into

wei

ghin

gfla

sk.A

fter

mor

ebo

iling

,an

othe

rtw

osa

mpl

esre

take

nin

the

sam

ew

ay.

The

sam

ples

wer

eth

enap

orat

ed,

and

the

resi

due

wei

ghed

.

KS

CN

,so

urce

and

purit

yno

tsp

ecifi

ed,

was

drie

dat

110

°Cbe

fore

use.

Met

hyla

ceta

tew

aske

ptov

eran

hydr

ous

CuS

O4

for

apr

olon

ged

perio

dof

time,

and

dist

illed

.T

hefr

actio

nbo

iling

at56

.2–

56.7

°Cw

asco

llect

edan

dst

ored

inth

eda

rk.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!2-

Pro

pano

ne~a

ceto

ne!;

C3H

6O

;@6

7-64

-1#

S.

von

Lasz

czyn

ski,

Ber

.27,

2285

–8~

1894

!.

Varia

bles

:P

repa

red

By:

T/K

:29

5,33

1J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

acet

one

attw

ote

mpe

ratu

res

a

Tem

pera

ture

(t/°

C)

KS

CN

(g/1

00g

solv

ent!b

KS

CN

(m1

/mol

kg2

1)c

KS

CN

(100

w1

/mas

s%

)c

2220

.75

2.13

517

.2

5820

.40

2.09

916

.9

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Mea

nof

atle

ast

two

mea

sure

men

ts,

indi

vidu

alre

sults

not

repo

rted

.c C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

solid

was

equi

libra

ted

with

the

solv

ent

for

apr

olon

ged

perio

dof

time

ina

flask

equi

pped

with

are

flux

cond

ense

r.T

hefla

skw

aske

ptin

aw

ater

bath

atth

ede

sire

dte

mpe

ratu

re.

Sam

ples

ofcl

ear

satu

rate

dso

lutio

nsw

ere

with

draw

nin

tosm

allfl

asks

,w

eigh

ed,

the

solv

ent

was

allo

wed

toev

apor

ate,

and

the

resi

due

was

wei

ghed

agai

n.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

Va On

5 Me

Ex

pe sh wo

ca po a we

ev


es,

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#E

thyl

acet

ate;

C 4H8O

2;

@141

-78-

6#S

.vo

nLa

szcz

ynsk

i,B

er.27

,22

85–

8~18

94!.

riabl

es:

Pre

pare

dB

y:

K:

273,

287,

352

J.H

a´ l

a

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

ethy

lace

tate

atth

ree

tem

pera

ture

sa

empe

ratu

re(t

/°C

)K

SC

N(g

/100

gso

lven

t!bK

SC

N(m

1/m

olkg

21)c

00.

440.

0453

140.

400.

0412

790.

200.

0206

olid

phas

esw

ere

not

inve

stig

ated

.ea

nof

atle

ast

two

mea

sure

men

ts,

indi

vidu

alre

sults

not

repo

rted

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

solid

was

equi

libra

ted

thth

eso

lven

tfo

ra

prol

onge

dpe

riod

oftim

ein

afla

skui

pped

with

are

flux

cond

ense

r.T

hefla

skw

aske

ptin

ate

rba

that

the

desi

red

tem

pera

ture

.S

ampl

esof

clea

rtu

rate

dso

lutio

nsw

ere

with

draw

nin

tosm

allfl

asks

,w

eigh

ed,

solv

ent

was

allo

wed

toev

apor

ate,

and

the

resi

due

was

ighe

dag

ain.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

9393JIRI HALA


6.3.

4.E

valu

atio

nof

the

KS

CN

–2-

But

anon

eS

yste

m

Com

pone

nts:

Eva

luat

or:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!2-

But

anon

e;C 4

H8O

;@7

8-93

-3#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

July

2001

.

Crit

ical

Eva

luat

ion

Two

mea

sure

men

tsof

the

solu

bilit

yof

KS

CN

in2-

buta

none~m

ethy

leth

ylke

tone!

at29

8K

have

been

repo

rted

.1,

2T

heso

lubi

litie

sw

ere

obta

ined

byis

othe

rmal

met

hod

asm1

/mol

kg2

15

0.18

0~S

tepi

ne

ta

l.1 !an

d0.

141~

Kru

patk

ine

ta

l.2 !,as

calc

ulat

edfr

omth

eau

thor

s’m

ass

%da

ta.

Sin

cein

both

docu

men

tsth

eso

lven

tw

aspu

rified

befo

reus

e,it

isre

com

men

ded

tous

eth

em

ean

ofth

etw

ova

lu0.

166

0.02

mol

kg2

1 ,as

the

tent

ativ

eso

lubi

lity

at29

8K

.

Ref

eren

ces:

1 B.

D.

Ste

pin,

V.E

.P

lyus

hche

v,an

dYu

.A.

Ivan

ova,

Khi

m.

Pro

m.

~Che

m.

Indu

stry!

404

~196

2!.

2 I.L.

Kru

patk

in,

L.D

.Vo

robe

va,

V.P.

Mak

hulia

,an

dM

.E

.Ve

selo

va,

Zh.

Obs

h.K

him

.45

,98

5~1

975!

.

Co

~1!

~2!

Va T/ T a S b M c C Me

An

wi

eq wa

sa the

we

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#1-

But

anol

;C 4

H10

O;

@71-

36-3

#M

.V.

Ioni

n,Z

.B

.K

uzne

tsov

a,an

dT.

I.M

olev

a,Z

h.N

eorg

.K

him

.14

,28

50–

3~19

69!.

riabl

es:

Pre

pare

dB

y:

K:

273

–33

8J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

1-bu

tano

las

afu

nctio

nof

tem

pera

ture

a

Tem

pera

ture

(t/°

C)

KS

CN

(m1

/mol

kg2

1)

00.

050

100.

047

150.

070

200.

077

250.

090

350.

114

450.

146

550.

173

650.

219

olid

phas

esw

ere

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

No

deta

ilsre

port

edex

cept

tth

eco

ncen

trat

ion

ofS

CN2

inth

esa

tura

ted

solu

tions

was

term

ined

bytit

ratio

nw

itha

stan

dard

Hg

~NO

3) 2

solu

tion

ains

tF

e~III!

salt

asan

indi

cato

r.

KS

CN

,ch

emic

ally

pure

,w

asre

crys

talli

zed

from

wat

er.

1-B

utan

olw

asdr

ied

and

dist

illed

ona

colu

mn.

The

frac

tion

boili

ngpo

int

at11

7.5

°Cw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.


6.3.

5.E

valu

atio

nof

the

KS

CN

–1-

But

anol

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!1-

But

anol

;C 4

H10

O;

@71-

36-3

#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,Ju

ly20

01.

Crit

ical

Eva

luat

ion

Two

mea

sure

men

tsof

the

solu

bilit

yof

KS

CN

in1-

buta

nol

have

been

repo

rted

.1,

2In

both

docu

men

ts,

isot

herm

alm

etho

dw

asus

ed,

and

the

solv

ent

was

drie

dan

ddi

still

edbe

fore

use.

Ioni

ne

ta

l.1re

port

edth

eso

lubi

lity

ofK

SC

Nas

afu

nctio

nof

tem

pera

ture

over

the

rang

efr

om27

3to

338

K,

whi

leB

akee

van

dA

kim

ova

2re

port

eda

sing

leva

lue

at31

3K

asm15

0.14

8m

olkg

21.

The

solu

bilit

yva

lue

obta

ined

byin

terp

olat

ion

to31

3K

from

the

data

inIo

nin

et

al.1

isap

prox

imat

ely

0.13

mol

kg21 .

Sin

ceth

etw

ova

lues

agre

ere

ason

ably

,an

dth

eda

taof

Ioni

net

al.1

cove

ra

wid

erte

mpe

ratu

rera

nge,

itis

reco

mm

ende

dto

use

the

latte

rda

taas

tent

ativ

eva

lues

.

Ref

eren

ces:

1 M.

V.Io

nin,

Z.

B.

Kuz

nets

ova,

and

T.I.

Mol

eva,

Zh.

Neo

rg.

Khi

m.

14,

2850

~196

9!.

2 M.

I.B

akee

van

dI.

P.A

kim

ova,

Dep

.D

oc.

VIN

ITI

No.

1148

–76~1

976!

.

Co

~1!

~2!

Va T/

a S Me

An

tha

de ag


6.3.

6E

valu

atio

nof

the

KS

CN

–P

yrid

ine

Sys

tem

mpo

nent

s:E

valu

ator

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

yrid

ine;

C 5H

5N

;@1

10-8

6-1#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,

July

2001

.

Crit

ical

Eva

luat

ion

Two

inve

stig

atio

ns1,2

ofth

eso

lubi

lity

ofK

SC

Nin

pyrid

ine

have

been

repo

rted

.Bot

hse

tsof

data

agre

ein

that

the

solu

bilit

yde

crea

ses

thin

crea

sing

tem

pera

ture

.H

owev

er,

the

solu

bilit

yda

tadi

ffer

cons

ider

ably

,th

eda

tafr

omth

epo

lyth

erm

alm

easu

rem

ents

2be

ing

3–

4es

low

erth

anth

ose

obta

ined

byth

eis

othe

rmal

met

hod.

1It

isno

tcl

ear

from

the

publ

ishe

din

form

atio

nw

heth

erth

isis

caus

edby

viat

ions

from

the

true

equi

libriu

min

the

poly

ther

mal

mea

sure

men

ts,

2or

byin

suffi

cien

tdr

ying

ofth

eso

lven

tus

edin

the

isot

herm

aldy

1si

nce

node

tails

wer

ere

port

edab

out

mat

eria

lsus

ed.

Due

toth

ehi

ghso

lubi

lity

ofK

SC

Nin

wat

er,

the

purit

yof

the

solv

ent

with

spec

tto

wat

erco

nten

tco

uld

affe

ctth

eso

lubi

lity

ofth

esa

ltin

pyrid

ine

cons

ider

ably

.F

orth

ese

reas

ons,

none

ofth

etw

ose

tsof

data

can

reco

mm

ende

d,an

dth

eK

SC

N–

pyrid

ine

syst

emw

ould

need

are

inve

stig

atio

n.

fere

nces

:

.vo

nLa

szcz

ynsk

i,B

er.27

,22

85~1

894!

.

.L.

Wag

ner

and

E.

Zer

ner,

Mon

atsh

.C

hem

.31

,83

3~1

910!

.

9595JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!Te

trah

ydro

-1,1

-thi

ophe

nedi

oxid

e~sul

fola

ne!;

C4H

8O

2S

;@1

26-3

3-0#

P.S

rivas

tava

,M

.M

.H

usai

n,an

dR

.G

opal

,J.

Che

m.

Eng

.D

ata

30,

144

–5

~198

5!.

Varia

bles

:P

repa

red

By:

T/K

:31

3–

328

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

sulfo

lane

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

KS

CN

(g/1

00g

solv

ent!

KS

CN

(m1

/mol

kg2

1)b

4018

.59

1.91

3

4520

.59

2.11

9

5021

.44

2.20

6

5522

.38

2.30

3

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

sam

ple

ofth

esa

tura

ted

solu

tion

ina

Pet

ridi

shw

ashe

ated

care

fully

inan

oven

,an

dfin

ally

onan

elec

tric

alhe

ater

toex

pelt

heso

lven

tco

mpl

etel

y.To

ora

pid

heat

ing

was

avoi

ded

toch

eck

spur

ting

ofth

eso

lutio

nan

dch

arrin

gof

sulfo

lane

.T

hedi

shw

asth

enco

oled

indr

yni

trog

enbo

xan

dw

eigh

ed.

The

proc

edur

ew

asre

peat

edun

tilco

nsta

ntw

eigh

tof

the

resi

due

was

obta

ined

.

KS

CN

,so

urce

and

purit

yno

tsp

ecifi

ed,

was

recr

ysta

llize

dtw

ice

from

cond

uctiv

ityw

ater

,an

ddr

ied

unde

rva

cuum

befo

reus

e.S

ulfo

lane

,F

luka

puris

s.,

was

purifi

edac

cord

ing

toP

anka

jan

dG

opal

.1M

eltin

gpo

into

fthe

purifi

edpr

oduc

twas

clos

eto

27°C

,de

nsity

at40

°Cw

as1.

2515

gcm2

3 .

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

1%~a

utho

rs!.

Ref

eren

ces:

1 Pan

kaja

ndR

.G

opal

,In

dian

J.C

hem

.21

A,

404

~198

2!.

Co

~1!

~2!

wi

tim de stu

re be Re

1 S 2 K

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

yrid

ine;

C 5H

5N

;@1

10-8

6-1#

K.

L.W

agne

ran

dE

.Z

erne

r,M

onat

sh.

Che

m.

31,

833

–41

~191

0!.

riabl

es:

Pre

pare

dB

y:

K:

230

–39

0J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

inth

eK

SC

N–

pyrid

ine

syst

em

uidu

ste

mpe

ratu

re(t

/°C

)K

SC

N(1

00w

1/m

ass

%)

KS

CN

(m1

/mol

kg2

1)a

Sol

idph

asee

116

–11

70.

890.

0924

A

70–

711.

230.

128

A

10b

2.2

0.23

1A

243

.3c

3.1

0.32

9A1

B

242

.82.

40.

253

B

242

.41.

330.

139

B

242

.10.

50.

0517

B

242

d0

alcu

late

dby

com

pile

r.ea

nof

seve

ralr

eadi

ngs

take

nbe

twee

n8

and

12°C

.er

ycl

ose

toeu

tect

icpo

int.

eltin

gpo

int

ofpy

ridin

e.:

KS

CN

;@33

3-20

-0#;

B:

C5H

5N

;@1

10-8

6-1#.

ditio

nal

info

rmat

ion:

At

172.

8°C

,th

eho

mog

eneo

usso

lutio

nse

para

ted

into

two

liqui

dph

ases

cont

aini

ngap

prox

imat

ely

0.6

mas

s%

CN

,an

dat

leas

t92

.7m

ass

%K

SC

N.

The

pyrid

ine

rich

phas

eco

ntai

ned

0.4

mas

s%

KS

CN

at18

8.5

°C.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

thet

icpo

lyth

erm

alm

etho

dus

ed.

Mea

sure

men

tsw

ere

carr

ied

tin

seal

edgl

ass

ampo

ules

with

volu

mes

of0.

5–

1.0

cm3 .

st,

KS

CN

was

intr

oduc

ed,

drie

dat

100

°C,

and

wei

ghed

.en

pyrid

ine

was

adde

dfr

oma

capi

llary

pipe

tte,

the

ampo

ule

sse

aled

and

wei

ghed

agai

n.T

heam

poul

esw

ere

rota

ted

ina

rmos

tate

dba

thof

conc

entr

ated

H2S

O4

.Li

quid

uste

mpe

ratu

res

wer

eob

tain

edas

the

mea

nof

read

ings

ofdi

sapp

eara

nce

ofla

stcr

ysta

ls,

and

appe

aran

ceof

first

crys

tals

.

KS

CN

,M

erck

,p.

a.,

was

twic

ere

crys

talli

zed

from

wat

er,

then

prec

ipita

ted

byet

hano

l,an

ddr

ied

inva

cuum

over

P2O

5.

Pyr

idin

ew

asre

fluxe

dfo

r3

hw

ithC

aO,

and

frac

tiona

ted.

The

mid

dle

frac

tion

was

then

thre

etim

esfr

actio

nate

d,an

dth

efr

actio

nbo

iling

at11

5.37

°Cw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

2K

arou

nd10

°C,

60.

5K

athi

gher

tem

pera

ture

s~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

yrid

ine;

C 5H

5N

;@1

10-8

6-1#

S.

von

Lasz

czyn

ski,

Ber

.27,

2285

–8~

1984

!.

Varia

bles

:P

repa

red

By:

T/K

:27

3–

388

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

pyrid

ine

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

KS

CN

(g/1

00g

solv

ent!b

KS

CN

(m1

/mol

kg2

1)c

KS

CN

(100

w1

/mas

s%

)c

06.

750.

695

6.32

206.

150.

633

5.96

584.

970.

511

4.73

953.

880.

399

3.74

115

3.21

0.33

03.

11

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Mea

nof

atle

ast

two

mea

sure

men

ts,

indi

vidu

alre

sults

not

repo

rted

.c C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

solid

was

equi

libra

ted

with

the

solv

ent

for

apr

olon

ged

perio

dof

time

ina

flask

equi

pped

with

are

flux

cond

ense

r.T

hefla

skw

aske

ptin

aw

ater

bath

atth

ede

sire

dte

mpe

ratu

re.

Sam

ples

ofcl

ear

satu

rate

dso

lutio

nsw

ere

with

draw

nin

tosm

allfl

asks

,w

eigh

ed,

the

solv

ent

was

allo

wed

toev

apor

ate,

and

the

resi

due

was

wei

ghed

agai

n.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

Va T/

Liq

a C b M c V d M e A Ad

KS

Me

Sy

ou Fir

Th

wa

the


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#1-

Pen

tano

l;C 5

H12

O;

@71-

41-0

#S

.vo

nLa

szcz

ynsk

i,B

er.27

,22

85–

8~18

94!.

riabl

es:

Pre

pare

dB

y:

K:

284

–40

6J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

1-pe

ntan

olas

afu

nctio

nof

tem

pera

ture

a

mpe

ratu

re(t

/°C

)K

SC

N(g

/100

gso

lven

t!bK

SC

N(m

1/m

olkg

21)c

KS

CN

(100

w1

/mas

s%

)c

130.

180.

0185

0.18

651.

340.

138

1.32

100

2.14

0.22

02.

10

133.

53.

150.

324

3.05

olid

phas

esw

ere

not

inve

stig

ated

.ea

nof

atle

ast

two

mea

sure

men

ts,

indi

vidu

alre

sults

not

repo

rted

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

solid

was

equi

libra

ted

thth

eso

lven

tfo

ra

prol

onge

dpe

riod

oftim

ein

afla

skui

pped

with

are

flux

cond

ense

r.T

hefla

skw

aske

ptin

ate

rba

that

the

desi

red

tem

pera

ture

.S

ampl

esof

clea

rtu

rate

dso

lutio

nsw

ere

with

draw

nin

tosm

allfl

asks

,w

eigh

ed,

solv

ent

was

allo

wed

toev

apor

ate,

and

the

resi

due

was

ighe

dag

ain.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

9797JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!N

,N-D

imet

hyla

ceta

mid

e;C 4H

9N

O;

@127

-19-

5#A

.A.F

edor

ov,L

.B.S

okol

ov,V

.M.S

avin

ov,M

.A.S

hlio

nska

ya,

and

N.

I.F

ilato

va,

Zh.

Prik

l.K

him

.44,

2361

–2~

1971

!.

Varia

bles

:P

repa

red

By:

T/K

:29

5–

298

J.H

a´ la

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofK

SC

Nin

N,N

-dim

ethy

lace

tam

ide

isre

port

edtoc 1

51.

10m

oldm

23

at22

–25

°C.

The

natu

reof

the

equi

libriu

mso

lidph

ase

was

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solv

ent

was

satu

rate

dw

ithan

hydr

ous

salt.

The

na

part

ofth

eso

lven

tw

asdi

still

edof

fto

rem

ove

wat

er,

and

the

satu

rate

dso

lutio

nw

ithex

cess

solid

was

kept

for

3da

ysin

ade

sicc

ator

ina

para

ffine

-coa

ted

flask

.T

heco

nten

tof

wat

erin

the

satu

rate

dso

lutio

nw

asle

ssth

an0.

1%.

The

satu

rate

dso

lutio

nw

asan

alyz

edfo

rth

eco

nten

tof

sulfu

rby

anun

spec

ified

met

hod.

Anh

ydro

usK

SC

N,

sour

ceno

tsp

ecifi

ed,

was

drie

dat

120

°Cfo

r6

hN

,N-d

imet

hyla

ceta

mid

e,so

urce

not

spec

ified

,w

asfr

eshl

ydi

still

edbe

fore

use.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

Va T/

Te a S b M c C Me

An

wi

eq wa

sa the

we

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#S

olve

nts

S.D

erni

ni,R

.DeS

antis

,and

L.M

arre

lli,J

.Che

m.E

ng.D

ata

21,

170

–3

~197

6!.

riabl

es:

Pre

pare

dB

y:

asur

emen

tsat

boili

ngpo

ints

ofth

esa

tura

ted

solu

tions

.J.

Ha

´ la

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

two

solv

ents

atbo

iling

poin

tsat

760

mm

Hg

pres

sure

a

Sol

vent

KS

CN

(g/1

00g

solv

ent!

KS

CN

(m1

/mol

kg2

1)b

Boi

ling

poin

tof

the

satu

rate

dso

lutio

nc

(t/°

C)

eton

e;C 3

H6O

;@6

7-64

-1#

13.7

1.41

58.6

than

ol;

CH 4

O;

@67-

56-1

#50

.15.

1668

.6

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

alcu

late

dby

com

pile

rus

ing

ebul

iosc

opic

cons

tant

sof

1.7

and

0.8,

and

norm

albo

iling

poin

ts1

of56

.15

and

64.5

1°C

for

acet

one

and

etha

nol,

resp

ectiv

ely,

and

assu

min

gun

diss

ocia

ted

KS

CN

inth

esa

tura

ted

solu

tions

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Det

erm

inat

ion

ofth

elu

bilit

ies

was

perf

orm

edby

sam

plin

g10

mL

ofth

ebo

iling

uid,

and

wei

ghin

gfir

stth

esa

mpl

e,an

dth

enth

ere

sidu

eer

thor

ough

evap

orat

ion

ofth

eso

lven

t.

KS

CN

was

of99

.5m

ass

%pu

rity.

Ace

tone

and

met

hano

l,so

urce

not

spec

ified

,w

ere

both

of99

.9m

ass

%pu

rity.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 E.

Hal

aan

dA

.R

eise

r,Ph

ysic

al

Ch

em

istr

y~C

zech

Edi

tion!

~Aca

dem

ia,

Pra

gue,

1971!,

Vol.

1,p.

278.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!T

ri-n-

buty

l~pho

spha

te!;C

12H

27O

4P

;@1

26-7

3-8#

J.H

alaan

dD

.G

.T

uck,

Can

.J.

Che

m.

48,

2843

–6~

1970

!.

Varia

bles

:P

repa

red

By:

T/K

:29

5J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofK

SC

Nin

tri-n

-but

yl~ph

osph

ate!

isre

port

edto

be6.

96g

salt

in10

0g

solv

ent

at22

°C(

m15

0.71

6m

olkg

21;

com

pile

r!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.A

nex

cess

ofth

esa

ltw

assh

aken

over

nigh

tw

ith5

mL

dry

solv

ent.

Pre

limin

ary

expe

rimen

tssh

owed

that

this

was

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

thro

ugh

asi

nter

,di

lute

dw

ithac

eton

e,an

dan

alyz

edfo

rth

eth

iocy

anat

eco

nten

tby

titra

tion

agai

nst

AgN

O3

stan

dard

solu

tion.

Bla

nktit

ratio

nssh

owed

that

asm

allc

orre

ctio

nw

asre

quire

dbe

caus

eof

the

pres

ence

oftr

i-n-b

utyl

~pho

spha

te!.

KS

CN

,F

ishe

rS

cien

tific

Co.

,w

asus

edw

ithou

tfu

rthe

rpu

rifica

tion.

Tri-

n-bu

tyl~p

hosp

hate!

~Fis

her

Sci

entifi

cC

o.!w

aspu

rified

byre

fluxi

ngit

with

0.5%

caus

ticso

daso

lutio

n,fo

llow

edby

stea

mdi

still

atio

n.T

hepr

oduc

twas

drie

dfir

stw

ithan

hydr

ous

MgS

O4

,an

dfin

ally

vacu

um/d

ried

at50

°Cin

ast

ream

ofdr

yni

trog

enga

s.1

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

0.1

gsa

lt/10

0g

solv

ent~a

utho

rs!.

Ref

eren

ces:

1 D.

G.

Tuc

k,J.

Che

m.

Soc

.27

83~19

58!.

Co

~1!

~2!

Va Me

Ac

Me

a S b C c C m Me

An

so liq aft


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#S

olve

nts

B.D

.Ste

pin,

V.E

.Ply

ushc

hev,

and

Yu.A

.Iva

nova

,Khi

m.P

rom

.~C

hem

.In

dust

ry!40

4–

7~1

962!

.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25°C

infiv

eso

lven

tsa

Sol

vent

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)b

Met

hano

l;C

H 4O

;@6

7-56

-1#

22.4

02.

970

Eth

anol

;C 2

H6O

;@6

4-17

-5#

4.90

0.53

0

2-B

utan

one;

C 4H

8O

;@7

8-93

-3#

1.72

0.18

0

cloh

exan

one;

C 6H10

O;

@108

-94-

1#3.

700.

395

Phe

nyle

than

one;

C 8H8O

;@9

8-86

-2#

1.10

0.11

5

olid

phas

esno

tin

vest

igat

ed.

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.R

efra

ctiv

ein

dice

san

dde

nsiti

es,

resp

ectiv

ely,

both

at20

°C,

ofth

eso

lven

tsus

edw

ere

asfo

llow

s:m

etha

nol,

1.32

89,

0.79

08;

etha

nol,

1.36

09,

0.79

87;

2-bu

tano

ne,

1.37

80,

0.80

41;

cycl

ohex

anon

e,1.

4500

,0.

9453

;1-

phen

ylet

hano

ne~a

ceto

phen

one!,

1.53

28,

1.02

70.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

9999JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!S

olve

nts

I.L.

Kru

patk

in,

L.D

.Vo

robe

va,

V.P.

Mas

khul

ia,

and

M.

E.

Vese

lova

,Z

h.O

bsh.

Khi

m.45

,98

5–

90~1

975!

.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

furf

ural

and

met

hyle

thyl

keto

neat

25°Ca

Sol

vent

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)b

2-fu

ranc

arbo

xald

ehyd

e~fur

fura

l!;C

5H

4O

2;

@98-

01-1

#16

.30

2.00

4

2-bu

tano

ne~m

ethy

leth

ylke

tone!

;C

4H

8O

;@7

8-93

-3#

1.35

0.14

1

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.K

SC

N,

sour

cean

dpu

rity

not

spec

ified

,w

asdr

ied

at10

0°C

toco

nsta

ntw

eigh

tbe

fore

use.

The

solv

ents

wer

epu

rified

byst

anda

rdm

etho

ds,

1an

dth

eir

purit

yw

asch

ecke

dth

roug

hph

ysic

alco

nsta

nts.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.W

eisb

erge

r,E

.Pro

skan

zer,

J.R

iddi

ck,a

ndE

.Too

ps,

Org

an

icS

olv

en

ts,R

ussi

aned

.~IL

Pub

l.H

ouse

,M

osco

w,

1958!,

pp.

351

and

361.

Co

~3!

~4!

Va T/ Cy

1- a S b C Me

An

J

l,mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

otas

sium

chlo

ride;

KC

l;@744

7-40

-7#W

ater

;H 2

O;

@773

2-18

-5#

P.S

.Bog

oyav

lens

kii,

and

K.M

.Syu

i,Z

h.S

truk

t.K

him

.1,

425

–30

~196

0!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

25.5

6J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25°C

inw

ater

and

one

aque

ous

solu

tions

ofK

Cl

KC

l00

w2

/mas

s%

)K

Cl

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

71.1

025

.32

A

1.62

0.75

569

.59

24.8

7A1

B

alcu

late

dby

com

pile

r.:

KS

CN

,@33

3-20

-2#;

B:

KC

l,@7

447-

40-7#

.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

of18

satu

rate

dso

lutio

nsnt

aini

ng2.

00–

26.5

6m

ass

%K

Cl,

whe

reK

Clw

asth

eeq

uilib

rium

solid

phas

e.T

hese

data

are

not

show

nhe

resi

nce

they

refe

rto

the

lubi

lity

ofK

Cli

nso

lutio

nsof

KS

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

No

deta

ilsre

port

edex

cept

tth

eso

lidan

dliq

uid

phas

esw

ere

anal

yzed

for

the

cont

ent

Cl2

and

SC

N2io

nsby

pote

ntio

met

rictit

ratio

nag

ains

tnd

ard

AgN

O 3so

lutio

n.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!W

ater

;H 2

O;

@773

2-18

-5#~3

!1-

But

anol

;C 4

H10

O;

@71-

36-3

#

M.

I.B

akee

van

dI.

P.A

kim

ova,

Dep

.D

oc.

VIN

ITI,

No.

1148

–76

~197

6!.

Varia

bles

:P

repa

red

By:

T/K

:31

310

0w

2/m

ass

%:

0–

26.4

8J.

Hala

Exp

erim

enta

lDat

aC

ompo

sitio

nof

solu

tions

satu

rate

dat

40°C

a

H2O

(100

w2

/mas

s%

)H

2O

(m2

/mol

kg2

1)b

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)b

00

1.42

0.14

8

0.96

0.55

22.

560.

273

1.42

0.82

63.

150.

340

26.4

873

.52c

28.7

5

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

c Sol

ubili

tyof

KS

CN

inw

ater

.

Add

ition

alin

form

atio

n:T

heph

ase

diag

ram

ofth

eK

SC

N–

C4H

10O

–H

2O

syst

emat

20°C

was

also

repo

rted

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.K

SC

N,

reag

ent

grad

e,w

asre

crys

talli

zed

befo

reus

e.B

utan

ore

agen

tgr

ade,

was

drie

dan

ddi

still

edbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co so Me

An

tha

of sta


1.76

0.70

5964

.819

.94

C

200

069

.022

.90

C

1.63

0.70

5967

.422

.39

C

3.48

1.49

065

.221

.42

C

300

072

.026

.46

C

0.86

40.

4148

71.2

26.2

3C

3.2

1.49

068

.024

.30

C

3.5

1.62

267

.55

24.0

1C

a A:

Ice,

H2O

,@7

732-

18-5#

;B

:K

Cl,

@744

7-40

-7#;

C:

KS

CN

;@33

3-20

-2#;

D:

KS

CN•

0.5H

2O

,@

#.b S

olub

ility

isot

herm

sw

ere

obta

ined

byth

eau

thor

sfr

ompo

lyth

erm

alm

easu

rem

ents

.O

fnu

mer

ous

data

repo

rted

,on

lyth

ose

refe

rrin

gto

the

solu

bilit

yof

KS

CN

wer

ein

clud

edhe

re.I

nsy

stem

sco

ntai

ning

high

erK

Clc

once

ntra

tions

,the

equi

libriu

mso

lidph

ases

wer

eei

ther

ice

orK

Cl.

c Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ualp

olyt

herm

alm

etho

dus

ed.

Into

tal,

12se

ctio

nsof

the

CN

–K

Cl–

H 2O

syst

emw

ere

inve

stig

ated

,of

whi

chni

nerr

espo

nded

to10

,20

,30

,40

,48

,55

,60

,67

,an

d70

mas

s%

CN

,an

dth

ree

to3,

5,an

d10

mas

s%

KC

l.M

easu

rem

ents

reca

rrie

dou

tin

anap

para

tus

desc

ribed

inE

raiz

eran

dga

nski

i.1T

heso

lubi

lity

vess

el,

equi

pped

with

arm

omet

er,

was

coat

edw

itha

tran

spar

ent

sem

icon

duct

orer

tow

hich

two

heat

ing

silv

erel

ectr

odes

wer

eso

lder

ed.

eve

ssel

was

plac

edin

side

aD

ewar

flask

with

tran

spar

ent

llsw

hich

,in

mea

sure

men

tspe

rfor

med

belo

wro

ompe

ratu

re,

was

fille

dto

1/5

ofits

volu

me

with

liqui

dro

gen

orso

lidC

O 2.

With

the

solu

bilit

yve

ssel

kept

abov

eco

olan

t,it

was

poss

ible

toco

ntro

lthe

rate

ofco

olin

gor

atin

gby

mov

ing

the

Dew

arfla

sk.

The

mix

ture

inth

elu

bilit

yve

ssel

was

stirr

edby

usin

gtw

oex

tern

alct

rom

agne

ts,

and

illum

inat

edto

obse

rve

disa

ppea

ranc

eor

pear

ance

ofcr

ysta

ls.

KS

CN

and

KC

lw

ere

chem

ical

lypu

repr

oduc

ts.

The

yw

ere

recr

ysta

llize

dtw

ice

befo

reus

e,an

ddr

ied

at40

–50

°C.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 L.N

.E

raiz

eran

dI.

M.

Kag

ansk

ii,Z

avod

skay

aLa

b.33,

119

~196

7!.

101101JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

otas

sium

chlo

ride;

KC

l;@744

7-40

-7#~3

!W

ater

;H 2

O;

@773

2-18

-5#

A.

M.

Bab

enko

and

A.

M.

And

riano

v,U

krai

n.K

him

.Z

h.45,

931

–4

~197

9!.

Varia

bles

:P

repa

red

By:

T/K

:24

2–

299

100

w2

/mas

s%

:0

–19

.9J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eK

SC

N–

KC

l–H 2

Osy

stem

asm

easu

red

bypo

lyth

erm

alm

etho

d

KC

l(1

00w

2/m

ass

%)

KS

CN

(100

w1

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

KC

l(1

00w

2/m

ass

%)

KS

CN

(100

w1

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

19.9

02

10.8

A1B

1.66

244

.42

21.6

A1B

1D

16.0

8.4

210

.0A1

B3.

053

.35

221

.0B1

D

12.0

17.6

213

.0A1

B2.

558

.52

14.0

B1D

8.0

27.6

215

.6A1

B0

63.9

0C1

D

6.8

32.0

217

.6A1

B1.

155

62.5

211

.5B1

C1

D

4.0

38.5

62

19.6

A1B

3.3

64.7

891

15.0

B1C

2.0

47.0

42

24.2

A1B

3.1

64.9

231

26.0

B1C

1.56

48.0

226

.5A1

B1

C3.

862

.00

B1C

050

.22

31.2

A1B

1D

Sol

ubili

tyis

othe

rms

inth

eK

SC

N–

KC

l–H 2O

syst

emb

Tem

pera

ture

(t/°

C)

KC

l(1

00w

2/m

ass

%)

KC

l(m

2/m

olkg

21)c

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)c

Sol

idph

asea

220

00

55.5

12.8

3D

210

00

59.7

15.2

4D

3.4

1.04

953

.13

12.5

8D

00

064

.018

.29

D

1.09

20.

4148

63.6

18.5

4D

100

066

.520

.43

C

1.08

10.

4431

66.2

20.8

2C

Me

Vis

KS

co KS

we

Ka

the

lay

Th

wa

tem

nit

the

he so ele

ap

J

sempo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

otas

sium

iodi

de;

KI;@

7681

-11-

0#W

ater

;H 2

O;

@773

2-18

-5#

P.S

.B

ogoy

avle

nski

iand

K.

M.

Syu

i,Z

h.S

truk

t.K

him

.1,

425

–30

~196

0!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

59.4

2J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25°C

inw

ater

and

aque

ous

solu

tions

ofK

I

KI

00w

2/m

ass

%)

KI

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

71.1

025

.32

A

4.72

1.00

867

.06

24.4

5A

6.72

1.46

365

.61

24.4

0A

9.38

2.08

063

.45

24.0

3A

12.8

72.

907

60.4

623

.33

A

15.5

53.

592

58.3

723

.03

A1B

alcu

late

dby

com

pile

r.:

KS

CN

,@33

3-20

-2#;

B:

KI,

@768

1-11

-0#.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofte

nsa

tura

ted

solu

tions

ntai

ning

16.9

7–

59.4

2m

ass

%K

I,w

here

KI

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tsh

own

here

sinc

eth

eyre

fer

toth

elu

bilit

yof

KI

inso

lutio

nsof

KS

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

No

deta

ilsre

port

edex

cept

tth

eso

lidan

dliq

uid

phas

esw

ere

anal

yzed

for

the

cont

ent

I2an

dS

CN2

ions

bypo

tent

iom

etric

titra

tion

agai

nst

ndar

dA

gNO 3

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

otas

sium

brom

ide;

KB

r;@775

8-02

-3#~3

!W

ater

;H 2

O;

@773

2-18

-5#

P.S

.B

ogoy

avle

nski

iand

K.

M.

Syu

i,Z

h.N

eorg

.K

him

.6,

469

–73

~196

1!.

Varia

bles

:P

repa

red

By:

T/K

:29

8,31

310

0w

2/m

ass

%:

0–

40.8

7at

298

K0

–43

.17

at31

3K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25an

d40

°Cin

wat

eran

daq

ueou

sso

lutio

nsof

KB

r

Tem

pera

ture

(t/°

C)

KB

r(1

00w

2/m

ass

%)

KB

r(m

2/m

olkg

21)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

250

071

.10

25.3

2A

4.00

1.17

167

.30

24.1

3A1

B

400

074

.38

29.8

7A

1.98

0.64

772

.32

28.9

6A

4.29

1.44

570

.76

29.1

8A1

B

a Cal

cula

ted

byco

mpi

ler.

b A:

KS

CN

,@33

3-20

-2#;

B:

KB

r,@7

758-

02-3#

.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sal

sore

port

edth

eco

mpo

sitio

nsof

12~a

t25

°C!

and

20~a

t40

°C!

satu

rate

dso

lutio

nsco

ntai

ning

5.60

–40

.87

and

4.79

–43

.17

mas

s%

KB

r,re

spec

tivel

y,w

here

KB

rw

asth

eeq

uilib

rium

solid

phas

e.T

heda

taar

eno

tsh

own

here

sinc

eth

eyre

fer

toth

eso

lubi

lity

ofK

Br

inso

lutio

nsof

KS

CN

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

No

deta

ilsre

port

edex

cept

that

the

solid

and

liqui

dph

ases

wer

ean

alyz

edfo

rth

eco

nten

tof

Br2

and

SC

N2io

nsby

pote

ntio

met

rictit

ratio

nag

ains

tst

anda

rdA

gNO 3

solu

tion

acco

rdin

gto

Mah

ran

dO

tterb

ein.

1In

one

sam

ple,

the

sum

ofbo

than

ions

was

dete

rmin

ed,

inan

othe

rsa

mpl

e,th

eS

CN

2w

asde

com

pose

dby

actio

nof

H2O

2,

and

Br2

was

titra

ted.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 C.

Mah

ran

dH

.O

tterb

ein,

Ang

ew.

Che

m.

66,

636

~195

4!.

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co so Me

An

tha

of sta


s

32

4

resp

ectiv

ely.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

otas

sium

nitr

ate;

KN

O 3;

@775

7-79

-1#W

ater

;H 2

O;

@773

2-18

-5#

P.S

.B

ogoy

avle

nski

i,D

okl.

Aka

d.N

auk

SS

SR10

1,86

5–

8~1

955!

;Z

h.F

iz.

Khi

m.3

2,20

35–

41~1

958!

.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

27.1

6J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25°C

inw

ater

and

aque

ous

solu

tions

ofK

NO

3

KN

O3

00w

2/m

ass

%)

KN

O3

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

70.7

24.8

3A

6.35

2.32

566

.64

25.3

9A

9.45

3.68

765

.226

.47

A1B

alcu

late

dby

com

pile

r.:

KS

CN

,@33

3-20

-0#;

B:

KN

O3

,@7

757-

79-1#

.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofni

nesa

tura

ted

solu

tions

ntai

ning

9.94

–27

.16

mas

s%

KN

O3

,w

here

KN

O 3w

asth

eeq

uilib

rium

solid

phas

e.T

hese

data

are

not

show

nhe

resi

nce

they

refe

rto

solu

bilit

yof

KN

O 3in

solu

tions

ofK

SC

N.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

deta

ilsre

port

edbu

tth

eco

mpi

ler

assu

mes

that

the

sam

eoc

edur

ew

asad

opte

das

inth

eau

thor

spr

evio

usw

ork,

1i.e

.,th

erm

alm

etho

dan

dch

emic

alan

alys

isof

the

equi

libriu

mlid

phas

es,

and

iden

tifica

tion

ofso

lidph

ases

byop

tical

cros

copy

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 P.S

.B

ogoy

avle

nski

iand

G.V

.S

ukm

ansk

aya,

Zh.

Obs

h.K

him

.23

,10

92~1

953!

.

103103JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

otas

sium

nitr

ite;

KN

O 2;

@775

8-09

-0#~3

!W

ater

;H 2

O;

@773

2-18

-5#

P.S

.Bog

oyav

lens

kiia

ndL.

Kh.

Van,

Zh.

Str

ukt.

Khi

m.

1,43

1–

6~1

960!

.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

0–

76.1

6J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25°C

inw

ater

and

aque

ous

solu

tions

ofK

NO

2

KN

O2

(100

w2

/mas

s%

)K

NO

2

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

70.8

324

.90

A

3.68

1.53

168

.08

24.8

0A

8.41

3.72

365

.05

25.2

2A

13.2

26.

319

62.2

026

.03

A

18.1

29.

197

58.7

326

.10

A

22.4

411

.86

55.3

425

.62

A

27.8

516

.09

51.8

226

.22

A

32.4

620

.49

48.9

327

.95

A

40.1

729

.87

43.8

728

.28

A

45.2

137

.22

40.5

229

.21

A1B

a Cal

cula

ted

byco

mpi

ler.

b A:

KS

CN

,@33

3-20

-2#;

B:

KN

O2

,@7

758-

09-0#

.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sal

sore

port

edth

eco

mpo

sitio

nsof

seve

nsa

tura

ted

solu

tion

cont

aini

ng50

.82

–76

.16

mas

s%

KN

O2

,w

here

KN

O 2w

asth

eeq

uilib

rium

solid

phas

e.T

hese

data

are

not

show

nhe

resi

nce

they

refe

rto

the

solu

bilit

yof

KN

O 2in

solu

tions

ofK

SC

N.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

No

deta

ilsre

port

edex

cept

that

the

solid

and

liqui

dph

ases

wer

ean

alyz

edfo

rth

eco

nten

tof

SC

N2an

dK1

ions

bypo

tent

iom

etric

titra

tion

agai

nst

stan

dard

AgN

Oso

lutio

n,an

dgr

avim

etric

ally

asKS

O,

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co the

Me

No

pr iso

so mi

J

100

066

.520

.43

D

1.02

0.30

666

.020

.59

D

2.88

0.86

064

.019

.88

D

200

068

.422

.27

D

0.93

0.30

669

.023

.61

D

2.72

0.86

066

.021

.71

D

300

072

.026

.46

D

0.85

0.30

471

.526

.61

D

2.48

0.86

069

.024

.90

D

a A:

Ice,

H2O

,@7

732-

18-5#

;B

:K

NO

3,

@775

7-79

-1#;

C:

KS

CN•

0.5H

2O

,@

#;D

:K

SC

N;@

333-

20-2#

.b S

olub

ility

isot

herm

sw

ere

obta

ined

byth

eau

thor

sfr

ompo

lyth

erm

alm

easu

rem

ents

.O

fnu

mer

ous

data

repo

rted

,on

lyth

ose

refe

rrin

gto

the

solu

bilit

yof

KS

CN

wer

ein

clud

edhe

re.

Insy

stem

sco

ntai

ning

high

erK

NO

3co

ncen

trat

ions

,th

eeq

uilib

rium

solid

phas

esw

ere

eith

eric

eor

KN

O3

.c C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ualp

olyt

herm

alm

etho

dus

ed.

Into

tal,

12se

ctio

nsof

the

CN

–K

NO

3–

H2O

syst

emw

ere

inve

stig

ated

,of

whi

chte

nrr

espo

nded

to10

,20

,30

,40

,50

,55

,60

,62

,66

,an

d70

ss%

KS

CN

,an

dtw

oto

cons

tant

KN

O3

cont

ent~

only

one

ennu

mer

ical

ly,

i.e.,

3.86

mas

s%

KN

O3).

Mea

sure

men

tsre

carr

ied

out

inan

appa

ratu

sde

scrib

edin

Ref

.1.

The

lubi

lity

vess

el,

equi

pped

with

ath

erm

omet

er,

was

coat

edth

atr

ansp

aren

tse

mic

ondu

ctor

laye

rto

whi

chtw

ohe

atin

gve

rel

ectr

odes

wer

eso

lder

ed.

The

vess

elw

aspl

aced

insi

dea

war

flask

with

tran

spar

ent

wal

lsw

hich

,in

mea

sure

men

tsrf

orm

edbe

low

room

tem

pera

ture

,w

asfil

led

to1/

5of

itslu

me

with

liqui

dni

trog

enor

solid

CO 2

.W

ithth

eso

lubi

lity

ssel

kept

abov

eth

eco

olan

t,it

was

poss

ible

toco

ntro

lthe

teof

cool

ing

orhe

atin

gby

mov

ing

the

Dew

arfla

sk.

The

xtur

ein

the

solu

bilit

yve

ssel

was

stirr

edby

usin

gtw

ote

rnal

elec

trom

agne

ts,

and

illum

inat

edto

obse

rve

appe

aran

ceor

appe

aran

ceof

crys

tals

.

KS

CN

and

KN

O 3w

ere

chem

ical

lypu

repr

oduc

ts.

The

yw

ere

recr

ysta

llize

dtw

ice

befo

reus

e,an

ddr

ied

at40

°C.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 L.N

.E

raiz

eran

dI.

M.

Kag

ansk

ii,Z

avod

skay

aLa

b.33,

119

~196

7!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

otas

sium

nitr

ate;

KN

O 3;

@775

7-79

-1#~3

!W

ater

;H 2

O;

@773

2-18

-5#

A.

M.

Bab

enko

and

A.

M.

And

riano

v,Z

h.N

eorg

.K

him

.23,

3123

–6~

1978

!.

Varia

bles

:P

repa

red

By:

T/K

:24

3–

292

100

w2

/mas

s%

:0

–10

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eK

SC

N–

KN

O 3–

H2O

syst

emas

mea

sure

dby

poly

ther

mal

met

hod

KN

O3

(100

w2

/mas

s%

)K

SC

N(1

00w

1/m

ass

%)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

KN

O3

(100

w2

/mas

s%

)K

SC

N(1

00w

1/m

ass

%)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

10.0

02

2.9

A1

B3.

253

.24

223

.0B1

C

7.36

8.0

22.

0A

1B

2.0

60.7

62

10.0

B1C

6.0

9.4

24.

8A

1B

4.0

59.5

22

10.2

B1D

4.0

19.2

28.

2A

1B

4.0

57.6

214

.2B1

D

4.0

28.8

213

.4A1

B6.

062

.04

14.

0B1

D

3.2

38.7

22

19.2

A1B

8.0

64.4

119

.0B1

D

3.0

48.5

225

.2A1

B1

C3.

556

.02

21.0

B1C

1D

052

.02

30.0

A1C

1.2

60.0

216

.0C1

D

1.44

52.0

228

.0A1

C0

64.0

20.

8C1

D

Sol

ubili

tyis

othe

rms

inth

eK

SC

N–

KN

O 3–H

2O

syst

emb

Tem

pera

ture

(t/°

C)

KN

O3

(100

w2

/mas

s%

)K

NO

3

(m2

/mol

kg2

1)c

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)c

Sol

idph

asea

220

1.26

0.30

658

.014

.65

C

3.64

0.86

054

.513

.40

C

210

00

59.7

15.2

4C

1.17

0.30

661

.016

.59

C

00

064

.018

.29

D

1.08

0.30

664

.018

.86

D

3.08

0.86

061

.517

.87

D

Me

Vis

KS

co ma

giv

we

so wi

sil

De

pe vo ve ra mi

ex dis


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

otas

sium

hydr

ogen

carb

onat

e;K

HC

O3

;@2

98-1

4-6#

Wat

er;

H 2O

;@7

732-

18-5#

A.

M.

Bab

enko

and

A.

M.

And

riano

v,Z

h.N

eorg

.K

him

.23,

2826

–32

~197

8!.

riabl

es:

Pre

pare

dB

y:

K:

243

–30

50

w2

/mas

s%

:0

–16

.2J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eK

SC

N–

KH

CO 3

–H

2O

syst

emas

mea

sure

dby

poly

ther

mal

met

hod

KH

CO

3

00w

2/m

ass

%)

KS

CN

(100

w1

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

KH

CO

3

(100

w2

/mas

s%

)K

SC

N(1

00w

1/m

ass

%)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

16.2

02

5.2

A1

B1.

048

.52

27.0

A1B

14.2

55.

02

7.2

A1

B0.

751

.32

29.2

A1B

1C

12.0

8.8

27.

8A

1B

1.5

53.1

92

24.6

B1C

8.38

16.2

210

.0A1

B1.

057

.42

221

.0B1

C

8.0

18.4

210

.4A1

B0.

561

.69

29.

0B1

C

4.0

28.8

213

.6A1

B0.

363

.52

4.8

B1C

1D

4.0

33.6

216

.8A1

B0

52.0

230

.0A1

D

3.30

34.0

215

.6A1

B0

64.0

20.

8C1

D

2.0

39.2

219

.3A1

B1.

864

.01

31.6

B1D

1.5

44.3

22

23.6

A1B

Sol

ubili

tyis

othe

rms

inth

eK

SC

N–

KH

CO 3–

H2O

syst

emb

mpe

ratu

ret/

°CK

HC

O3

(100

w2

/mas

s%

)K

HC

O3

(m2

/mol

kg2

1)c

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)c

Sol

idph

asea

210

00

59.7

15.2

4C

00

064

.018

.29

D

100

066

.520

.43

D

200

069

.022

.90

D

:Ic

e,H

2O

,@7

732-

18-5#

;B

:K

HC

O3

,@2

98-1

4-6#;

C:

KS

CN•

0.5H

2O

,@

#;D

:K

SC

N;@

333-

20-0#

.S

olub

ility

isot

herm

sw

ere

obta

ined

byth

eau

thor

sfr

ompo

lyth

erm

alm

easu

rem

ents

.O

fnu

mer

ous

data

repo

rted

,on

lyth

ose

refe

rrin

gto

the

solu

bilit

yof

KS

CN

wer

ein

clud

edhe

re.

Inot

her

syst

ems,

the

equi

libriu

mso

lidph

ases

wer

eei

ther

ice

orK

HC

O3

.c C

alcu

late

dby

com

pile

r.

105105JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

otas

sium

hydr

ogen

carb

onat

e;K

HC

O3

;@2

98-1

4-6#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

P.S

.B

ogoy

avle

nski

ian

dE

.D

.G

ashp

ar,

Zh.

Neo

rg.

Khi

m.

17,

3055

–8~

1972

!.

Varia

bles

:P

repa

red

By:

T/K

:29

8,31

310

0w

2/m

ass

%:

0–

26.7

2at

298

K0

–31

.98

at31

3K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25an

d40

°Cin

wat

eran

daq

ueou

sso

lutio

nsof

KH

CO

3

Tem

pera

ture

(t/°

C)

KH

CO

3

(100

w2

/mas

s%

)K

HC

O3

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

250

070

.70

24.8

3A

1.03

0.34

6469

.27

24.0

0A1B

400

074

.38

29.8

7A

1.32

0.49

471

.99

27.7

6A1

B

a Cal

cula

ted

byco

mpi

ler.

b A:

KS

CN

,@33

3-20

-2#;

B:

KH

CO

3,

@289

-14-

6#.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sal

sore

port

edth

eco

mpo

sitio

nsof

ten

~at2

5°C

!an

d11

~at4

0°C

!

satu

rate

dso

lutio

nsco

ntai

ning

1.07

–26

.72

and

1.36

–31

.98

mas

s%

KH

CO

3,

resp

ectiv

ely,

whe

reK

HC

O 3w

asth

eeq

uilib

rium

solid

phas

e.T

hese

data

are

not

show

nhe

resi

nce

they

refe

rto

the

solu

bilit

yof

KH

CO

3in

solu

tions

ofK

SC

N.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

idph

ases

wer

ech

arac

teriz

edby

Sch

rein

emak

er’s

met

hod.

The

satu

rate

dso

lutio

nsan

dw

etre

sidu

esw

ere

anal

yzed

for

SC

N2

ions

bypo

tent

iom

etric

titra

tion

agai

nst

stan

dard

AgN

O 3,

and

for

HC

O 32by

titra

tion

agai

nst

stan

dard

acid

solu

tion.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 (1 Te a A b

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

otas

sium

carb

onat

e;K

2C

O3

;@5

84-0

8-7#

Wat

er;

H 2O

;@7

732-

18-5#

A.

M.

Bab

enko

and

A.

M.

And

riano

v,Z

h.N

eorg

.K

him

.23,

2826

–32

~197

8!.

riabl

es:

Pre

pare

dB

y:

K:

238

–36

10

w2

/mas

s%

:0

–51

.5J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eK

SC

N–

K 2C

O3–

H2O

syst

emas

mea

sure

dby

poly

ther

mal

met

hod

K2C

O3

00w

2/m

ass

%)

KS

CN

(100

w1

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

K2C

O3

(100

w2

/mas

s%

)K

SC

N(1

00w

1/m

ass

%)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

41.4

02

31.0

A1B

44.0

11.2

065

.0B1

E

22.4

7.76

213

.0A1

B40

.018

.076

.5B1

E

16.0

16.8

214

.6A1

B36

.025

.680

.0B1

E

11.6

26.5

22

18.3

A1B

36.0

28.8

54.6

B1E

5.4

37.8

42

22.2

A1B

32.0

37.4

56.4

B1E

7.0

41.8

52

28.6

A1B

28.0

43.2

54.5

B1E

15.8

820

.62

17.0

A1B

20.5

52.4

749

.4B1

E

28.8

4.0

213

.0A1

B16

.058

.852

.2B1

E

052

.02

30.0

A1C

19.3

656

.088

.0B1

E

2.88

52.0

234

.0A1

C8.

064

.433

.0B1

D

5.2

48.0

234

.5A1

B1

C6.

468

.046

.0B1

D

6.0

51.7

226

.0B1

C9.

668

.064

.0B1

D

4.0

57.6

214

.0B1

C13

.30

65.0

75.0

B1D

6.0

62.0

416

.0B1

C1

D0

64.0

0.8

C1D

51.5

02

4.0

B1E

21.6

64.0

8.0

C1D

48.0

5.2

63.0

B1E

3.6

64.0

13.0

C1D

Sol

ubili

tyis

othe

rms

inth

eK

SC

N–

K 2CO

3–

H2O

syst

emb,

c

mpe

ratu

re(t

/°C

)K

2C

O3

(100

w2

/mas

s%

)K

2C

O3

(m2

/mol

kg2

1)d

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)d

230

00

55.5

12.8

3

2.7

0.46

255

.013

.38

2.83

0.46

252

.812

.25

5.1

0.80

449

.010

.99

210

00

59.7

15.2

4

2.58

0.46

257

.014

.51

4.7

0.80

453

.012

.89

00

064

.018

.29

2.43

0.46

259

.516

.08

4.5

0.80

455

.013

.97

100

066

.520

.43

2.11

20.

462

64.8

20.1

5

4.1

0.80

459

.016

.45

200

068

.422

.27

1.95

60.

462

67.4

22.6

3

3.4

0.80

466

.022

.19

a A:

Ice,

H2O

,@7

732-

18-5#

;B

:K

2C

O3•6

H2O

,@1

7033

-98-

6#;C

:K

SC

N•0.

5H2O

,@

#;D

:K

SC

N;@

333-

20-2#

;E

:K

2C

O3•1.

5H2O

,@6

381-

79-9

#.S

eeal

soF

ig.

16.

b Sol

ubili

tyis

othe

rms

wer

eob

tain

edby

the

auth

ors

from

poly

ther

mal

mea

sure

men

ts.

Of

num

erou

sda

tare

port

ed,

only

thos

ere

ferr

ing

to


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Avi

sual

poly

ther

mal

met

hod

used

.In

tota

l,12

sect

ions

ofth

eK

SC

N–

KH

CO 3

–H

2O

syst

emw

ere

inve

stig

ated

,of

whi

chni

neco

rres

pond

edto

10,

20,

30,

40,

45,

49,

54,

58,

and

62m

ass

%K

SC

N,

and

thre

eto

5,10

,an

d15

mas

s%

KH

CO

3.

Mea

sure

men

tsw

ere

carr

ied

out

inan

appa

ratu

sde

scrib

edin

Era

izer

and

Kag

ansk

ii.1T

heso

lubi

lity

vess

el,

equi

pped

with

ath

erm

omet

er,

was

coat

edw

itha

tran

spar

ent

sem

icon

duct

orla

yer

tow

hich

two

heat

ing

silv

erel

ectr

odes

wer

eso

lder

ed.

The

vess

elw

aspl

aced

insi

dea

Dew

arfla

skw

ithtr

ansp

aren

tw

alls

whi

ch,

inm

easu

rem

ents

perf

orm

edbe

low

room

tem

pera

ture

,w

asfil

led

to1/

5of

itsvo

lum

ew

ithliq

uid

nitr

ogen

orso

lidC

O 2.

With

the

solu

bilit

yve

ssel

kept

abov

eth

eco

olan

t,it

was

poss

ible

toco

ntro

lthe

rate

ofco

olin

gor

heat

ing

bym

ovin

gth

eD

ewar

flask

.T

hem

ixtu

rein

the

solu

bilit

yve

ssel

was

stirr

edby

usin

gtw

oex

tern

alel

ectr

omag

nets

,an

dill

umin

ated

toob

serv

edi

sapp

eara

nce

orap

pear

ance

ofcr

ysta

ls.

KS

CN

,che

mic

ally

pure

prod

uct,

was

recr

ysta

llize

dtw

ice

befo

reus

e,an

ddr

ied

at40

°C.

KH

CO 3

was

purifi

edac

cord

ing

toK

arya

khin

and

Ang

elov

,2an

ddr

ied

at40

°C.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 L.N

.E

raiz

eran

dI.

M.

Kag

ansk

ii,Z

avod

skay

aLa

b.33,

119

~196

7!.

2 Yu.

V.K

arya

khin

and

I.I.

Ang

elov

,Pu

reC

he

mic

alS

ub

sta

nce

sR

ussi

aned

.~Khi

miy

a,M

osco

w,

1974!

,p.

140.

Co

~1!

~2!

~3!

Va T/

10 (1 Te


Mea

sure

men

tsw

ere

carr

ied

out

inan

appa

ratu

sde

scrib

edin

Era

izer

and

Kag

ansk

ii.1T

heso

lubi

lity

vess

el,

equi

pped

with

ath

erm

omet

er,

was

coat

edw

itha

tran

spar

ent

sem

icon

duct

orla

yer

tow

hich

two

heat

ing

silv

erel

ectr

odes

wer

eso

lder

ed.

The

vess

elw

aspl

aced

insi

dea

Dew

arfla

skw

ithtr

ansp

aren

tw

alls

whi

ch,

inm

easu

rem

ents

perf

orm

edbe

low

room

tem

pera

ture

,w

asfil

led

to1/

5of

itsvo

lum

ew

ithliq

uid

nitr

ogen

orso

lidC

O 2.

With

the

solu

bilit

yve

ssel

kept

abov

eth

eco

olan

t,it

was

poss

ible

toco

ntro

lthe

rate

ofco

olin

gor

heat

ing

bym

ovin

gth

eD

ewar

flask

.T

hem

ixtu

rein

the

solu

bilit

yve

ssel

was

stirr

edby

usin

gtw

oex

tern

alel

ectr

omag

nets

,an

dill

umin

ated

toob

serv

edi

sapp

eara

nce

orap

pear

ance

ofcr

ysta

ls.

Tem

pera

ture

:pr

ecis

ion

not

repo

rted

.S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 L.N

.E

raiz

eran

dI.

M.

Kag

ansk

ii,Z

avod

skay

aLa

b.33,

119

~196

7!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

otas

sium

sulfa

te;

K 2SO

4;

@777

8-80

-5#W

ater

;H 2

O;

@773

2-18

-5#

P.S

.B

ogoy

avle

nski

iand

G.

V.S

ukm

ansk

aya,

Zh.

Obs

h.K

him

.23

,10

92–

5~19

53!.

riabl

es:

Pre

pare

dB

y:

K:

298,

313

0w

2/m

ass

%:

0–

10.7

6at

298

K13

.1at

313

K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25an

d40

°Cin

wat

eran

daq

ueou

sso

lutio

nsof

K2S

O4

mpe

ratu

re(t

/°C

)K

2S

O4

(100

w2

/mas

s%

)K

2S

O4

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

250

070

.70

24.8

3A

0.04

0.00

7870

.60

24.7

4A1B

400

074

.31

29.7

7A

0.03

0.00

6774

.24

29.6

9A1B

alcu

late

dby

com

pile

r.:

KS

CN

,@33

3-20

-2#;

B:

K2S

O4

,@7

778-

80-5#

.

ditio

nali

nfor

mat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

of13

~at2

5°C

!an

d18

~at4

0°C

!

tura

ted

solu

tions

cont

aini

ng0.

10–

10.7

6an

d0.

13–

13.1

0m

ass

%K

2S

O4

,re

spec

tivel

y,w

here

K 2SO

4w

asth

eeq

uilib

rium

solid

phas

e.es

eda

taar

eno

tsh

own

here

sinc

eth

eyre

fer

toth

eso

lubi

lity

ofK

2S

O4

inso

lutio

nsof

KS

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Sat

urat

edso

lutio

nsw

ere

alyz

edfo

rS

CN2

and

sulfa

teio

ns~m

etho

dsno

tsp

ecifi

ed!,lid

phas

esw

ere

char

acte

rized

byop

tical

mic

rosc

opy.

The

ene

cess

ary

tore

ach

equi

libriu

min

crea

sed

with

incr

easi

ngC

Nco

ncen

trat

ion

inth

esy

stem

,up

to24

–30

hat

KS

CN

ncen

trat

ion

high

erth

an45

mas

s%

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

107107JIRI HALA


the

solu

bilit

yof

KS

CN

wer

ein

clud

edhe

re.

Inot

her

syst

ems,

the

equi

libriu

mso

lidph

ases

wer

eei

ther

ice

orK

2C

O3•6

H2O

.c S

olid

phas

ew

asK

SC

N•0.

5H2O

inal

lcas

es.

d Cal

cula

ted

byco

mpi

ler.

FIG

.16

.S

olub

ility

poly

ther

mof

the

KS

CN

–K 2C

O3–

H2O

syst

em.

Fie

lds

ofcr

ysta

lliza

tion:

I:ic

e;II:

KS

CN

0.5H 2O

;III

:K

SC

N;

IV:

K2C

O3•6

H2O

;an

dV

:K 2

CO

3•1.

5H2O

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Vis

ualp

olyt

herm

alm

etho

dus

ed.

Into

tal,

15se

ctio

nsof

the

KS

CN

–K 2

CO

3–

H2O

syst

emw

ere

inve

stig

ated

,of

whi

chni

neco

rres

pond

edto

10,

20,

30,

40,

45,

55,

60,

66,

and

70m

ass

%K

SC

N,

and

six

to6,

10,

20,

30,

38,

and

44m

ass

%K

2C

O3

.

KS

CN

and

K 2C

O3

wer

ech

emic

ally

pure

prod

ucts

,rec

ryst

alliz

edtw

ice,

and

drie

dat

40an

d10

5°C

,re

spec

tivel

y,be

fore

use.

Est

imat

edE

rror

:

Co

~1!

~2!

~3!

Va T/

10 0–

Te a C b A Ad

sa Th

Me

An

an so tim KS

co

J

g

func

tion

ofth

eco

mpo

sitio

nof

the

mix

ture

s.T

hetr

ansi

tion

from

unsa

tura

ted

tosa

tura

ted

solu

tions

,i.e

.,th

eco

rres

pond

ing

solu

bilit

yva

lue,

was

obta

ined

asa

brea

kon

the

refr

activ

ein

dex

vers

usco

mpo

sitio

npl

ot.

The

met

hod

ofid

entifi

catio

nof

the

solid

phas

ew

asno

tre

port

ed.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#B

oric

acid

;H 3

BO

3;

@100

43-3

5-3#

Wat

er;

H 2O

;@7

732-

18-5#

V.G

.Skv

orts

ov,R

.S.T

sekh

ansk

ii,S

h.V.

Sad

etdi

nov,

and

A.K

.M

olod

kin,

Zh.

Neo

rg.

Khi

m.2

8,26

77–

9~19

83!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

5.6

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25°C

inaq

ueou

sso

lutio

nsof

boric

acid

H3B

O3

00w

2/m

ass

%)

H3B

O3

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

70.5

024

.59

A

4.87

3.11

969

.88

28.4

8A

4.87

3.12

169

.89

28.4

9A1

B

alcu

late

dby

com

pile

r.:

KS

CN

,@33

3-20

-0#;

B:

H3B

O3

,@1

0043

-35-

3#.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofse

ven

satu

rate

dso

lutio

nsnt

aini

ng4.

89–

5.60

mas

s%

H3B

O3

,an

d69

.87

–0

mas

s%

KS

CN

,w

here

H3B

O3

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tow

nhe

resi

nce

they

repr

esen

tth

eso

lubi

lity

ofH

3B

O3

inso

lutio

nsof

KS

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.S

olut

ions

with

exce

ssso

lidw

ere

rred

for

20h,

whi

chw

assu

ffici

ent

for

equi

libriu

mto

beac

hed.

Bor

ate

and

SC

N2

wer

ede

term

ined

inth

esa

tura

ted

lutio

nstit

rimet

rical

ly~m

etho

dsno

tsp

ecifi

ed!,so

lidph

ases

rech

arac

teriz

edby

Sch

rein

emak

ers’

met

hod.

Sol

ubili

tyth

erm

sw

ere

also

confi

rmed

byre

frac

tom

etric

asur

emen

ts.

KS

CN

and

H 3B

O3

wer

ech

emic

ally

pure

prod

ucts

,an

dw

ere

recr

ysta

llize

dbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

otas

sium

sulfa

te;

K 2SO

4;

@777

8-80

-5#~3

!W

ater

;H 2

O;

@773

2-18

-5#

E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9–

52~1

968!

.

Varia

bles

:P

repa

red

By:

T/K

:27

3,29

8,32

310

0w

2/m

ass

%:

0–

7.25

at27

3K

;0

–10

.9at

298

K;

0–

14.1

5at

323

K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eK

SC

N–

K 2S

O4–

H2O

syst

emat

two

tem

pera

ture

s

Tem

pera

ture

(t/°

C)

K2S

O4

(100

w2

/mas

s%

)K

2S

O4

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

064

.40

18.6

2A

0.04

0.00

6464

.35

18.6

0A1B

250

070

.90

25.0

7A

0.18

0.03

570

.32

24.5

3A1

B

500

076

.40

33.3

1A

0.34

0.08

3776

.36

33.7

2A1B

a Cal

cula

ted

byco

mpi

ler.

b A:

KS

CN

,@33

3-20

-0#;

B:

K2S

O4

;@7

778-

80-5#

.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sre

port

edal

soco

mpo

sitio

nsof

12sa

tura

ted

solu

tions

cont

aini

n0.

90–

7.25

,1.4

0–

10.9

0,an

d2.

20–

14.1

5m

ass

%K

2S

O4

at0,

25,a

nd50

°C,r

espe

ctiv

ely,

whe

reth

eeq

uilib

rium

solid

phas

ew

asK

2S

O4

.T

hese

wer

eno

tin

clud

edhe

resi

nce

they

repr

esen

tth

eso

lubi

litie

sof

K2S

O4

inso

lutio

nsof

KS

CN

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ies

wer

eob

tain

edby

grap

hica

lana

lytic

alm

etho

d.1

Ase

ries

ofm

ixtu

res

ofth

esa

ltsan

dw

ater

corr

espo

ndin

gto

ach

osen

sect

ion

inth

etr

iang

ular

diag

ram

,ru

nnin

gfr

omon

epu

resa

ltto

the

oppo

site

leg

ofth

etr

iang

le,

thus

cove

ring

the

field

sof

unsa

tura

ted

and

satu

rate

dso

lutio

ns,

wer

epr

epar

edby

wei

ghin

g.A

fter

equi

libriu

mha

dbe

enat

tain

ed,

refr

activ

ein

dice

sof

the

solu

tions

wer

em

easu

red,

and

plot

ted

asa

KS

CN

,ch

emic

ally

pure

prod

uct,

was

drie

dov

eran

hydr

ous

CaC

l 2.

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co sh Me

Iso

sti

re so we

iso

me


smpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

otas

sium

tetr

abor

ate;

K2B

4O

7;

@133

2-77

-0#W

ater

;H 2

O;

@773

2-18

-5#

V.G

.S

kvor

tsov

,A

.K

.M

olod

kin,

Sh.

V.S

adet

dino

v,an

dR

.S

.Ts

ekha

nski

i,Z

h.N

eorg

.K

him

.26,

3164

–6~

1981

!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

18.0

3J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25°C

inaq

ueou

sso

lutio

nsof

pota

ssiu

mte

trab

orat

e

K2B

4O

7

00w

2/m

ass

%)

K2B

4O

7

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

70.5

024

.59

A

0.85

0.12

469

.73

24.3

9A1

B

0.84

0.12

269

.75

24.4

0A1

B

alcu

late

dby

com

pile

r.:

KS

CN

,@33

3-20

-0#;

B:

K2B

4O

7•4

H2O

,@1

2045

-78-

2#.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofse

ven

satu

rate

dso

lutio

nsnt

aini

ng0.

87–

18.0

3m

ass

%K

2B

4O

7,

and

69.7

0–

0m

ass

%K

SC

N,w

here

K2B

4O

7•4

H2O

was

the

equi

libriu

mso

lidph

ase.

The

seda

tae

not

show

nhe

resi

nce

they

repr

esen

tth

eso

lubi

lity

ofK

2B

4O

7•4

H2O

inso

lutio

nsof

KS

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

ium

was

reac

hed

thin

20h,

whi

chw

asch

ecke

dby

chem

ical

anal

ysis

and

frac

tion

inde

xof

the

satu

rate

dso

lutio

ns.

Bor

ate

and

SC

N2

rede

term

ined

inth

esa

tura

ted

solu

tions

titrim

etric

ally

etho

dsno

tsp

ecifi

ed!,so

lidph

ases

wer

ech

arac

teriz

edby

hrei

nem

aker

s’m

etho

d.

KS

CN

and

K 2B

4O

7w

ere

chem

ical

lypu

repr

oduc

ts,

and

wer

ere

crys

talli

zed

befo

reus

e.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

109109JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

otas

sium

bora

te;

KB

O 2;

@137

09-9

4-9#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

V.G

.Skv

orts

ov,S

h.V.

Sad

etdi

nov,

R.S

.Tse

khan

skii,

and

A.K

.M

olod

kin,

Zh.

Neo

rg.

Khi

m.2

4,20

9–

12~1

979!

.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

0–

18.4

2J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

25°C

inaq

ueou

sso

lutio

nsof

pota

ssiu

mbo

rate

KB

O2

(100

w2

/mas

s%

)K

BO

2

(m2

/mol

kg2

1)a

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)a

Sol

idph

aseb

00

70.5

024

.59

A

0.98

c0.

407

69.6

424

.39

A1B

a Cal

cula

ted

byco

mpi

ler.

b A:

KS

CN

,@33

3-20

-0#;

B:

KB

O2

,@1

3709

-94-

9#.c E

uton

icpo

int.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sal

sore

port

edth

eco

mpo

sitio

nsof

eigh

tsa

tura

ted

solu

tion

cont

aini

ng1.

06–

18.4

2m

ass

%K

BO

2,

and

69.6

7–

0m

ass

%K

SC

N,

whe

reK

BO

2w

asth

eeq

uilib

rium

solid

phas

e.T

hese

data

are

not

show

nhe

resi

nce

they

repr

esen

tth

eso

lubi

lity

ofK

BO

2in

solu

tions

ofK

SC

N.

Als

ore

port

edw

ere

dens

ities

,vi

scos

ities

,an

dre

frac

tion

inde

xes

ofth

esa

tura

ted

solu

tions

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Equ

ilibr

ium

was

reac

hed

with

in24

hun

der

cons

tant

shak

ing

ina

ther

mos

tat.

Bor

ate

and

SC

N2

wer

ede

term

ined

inth

esa

tura

ted

solu

tions

titrim

etric

ally

~met

hods

not

spec

ified!,

solid

phas

esw

ere

char

acte

rized

byS

chre

inem

aker

s’m

etho

dan

dch

emic

alan

alys

is.

KS

CN

was

ach

emic

ally

pure

prod

uct,

sour

ceno

tsp

ecifi

ed.

KB

O2

was

prep

ared

from

boric

acid

and

KO

H.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co ar Me

An

wi

re we

~m Sc

J

–

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Sol

utio

nsco

ntai

ning

exce

ssso

lidw

ere

stirr

edin

ther

mos

tate

dve

ssel

seq

uipp

edw

ithoi

lsea

l.E

quili

briu

mw

asat

tain

edin

6–

8h,

sam

ples

for

anal

ysis

wer

ew

ithdr

awn

afte

r2

–3

days

equl

ibra

tion.

Sat

urat

edso

lutio

nsan

dw

etre

sidu

esw

ere

anal

yzed

for

Mo

byre

duct

omet

rictit

ratio

n,an

dfo

rS

CN2

byVo

lhar

dm

etho

d.S

olid

phas

esw

ere

iden

tified

byS

chre

inem

aker

sm

etho

dan

dby

optic

alm

icro

scop

y.

KS

CN

,ch

emic

ally

pure

,w

astw

ice

recr

ysta

llize

d.A

naly

sis

show

ed99

.86%

purit

y.K 2M

oO4

was

prep

ared

from

chem

ical

lypu

reM

oO3

and

KO

H.

The

prod

uct

was

thre

etim

esre

crys

talli

zed,

and

was

99.9

0%pu

re.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#U

rea;

CH 4

N2O

;@5

7-13

-6#

Wat

er;

H 2O

;@7

732-

18-5#

R.T

urgu

nbek

ova,

K.N

ogoe

v,an

dK

.Sul

aim

anku

lov,

Zh.

Neo

rg.

Khi

m.

17,

1455

–7~

1972

!.

riabl

es:

Pre

pare

dB

y:

K:

288,

303,

and

318

0w

2/m

ass

%:

0–

49at

288

K,

0–

57.5

at30

3K

,0

–64

.5at

8K

J.H

ala

Exp

erim

enta

lDat

aC

ompo

sitio

nof

the

satu

rate

dso

lutio

nsin

the

KS

CN

–ur

ea–

H2O

syst

emat

thre

ete

mpe

ratu

res

mpe

ratu

re(t

/°C

)U

rea

(100

w2

/mas

s%

)U

rea

(100

x 2/m

ole

%)

KS

CN

(100

w1

/mas

s%

)K

SC

N(1

00x 1

/mol

e%

)S

olid

phas

ea

150

068

.31

28.5

6A

2.87

1.94

65.7

027

.39

A

8.55

6.08

63.4

827

.87,

27.8

2b

A

8.76

6.26

63.6

828

.12

B

9.15

6.43

62.3

026

.96

B

12.6

58.

5457

.31

23.8

9B

14.1

59.

0653

.01

20.9

5B

17.2

611

.15

50.8

720

.29

B

22.8

914

.95

46.6

418

.79

B

26.5

017

.01

42.6

016

.90

B

33.4

621

.95

37.8

415

.34

B

40.5

028

.01

34.7

014

.81

B

43.0

031

.27

35.1

415

.79

B1C

300

070

.00

30.2

1A

6.17

4.45

66.4

429

.66

A

8.00

5.79

65.0

029

.09

A1B

10.3

57.

6964

.30

29.5

4B

14.0

09.

7357

.75

24.8

2B

16.3

010

.99

54.1

522

.58

B

21.0

013

.63

48.0

019

.27

B

28.1

818

.51

42.4

917

.26

B

35.0

023

.35

37.5

015

.48

B

43.5

031

.84

35.0

815

.88

B

45.0

033

.21

34.2

015

.61

B1C

450

074

.60

35.2

5A

4.90

3.58

98.0

030

.59

A

8.70

6.42

65.4

029

.85

A

13.7

010

.63

63.6

030

.55

A

14.2

011

.22

63.8

931

.16

A1B

B

15.5

012

.30,

12.4

0b63

.40

31.3

5B

22.0

616

.60

54.8

225

.48

B

24.6

518

.31

51.9

723

.83

B

32.7

024

.25

45.0

020

.61

B

40.0

830

.24

39.5

018

.42

B

43.0

033

.13

38.0

018

.07

B

47.5

337

.45

35.1

817

.11

B

51.0

042

.42

34.6

518

.81,

17.8

1b

B

51.5

643

.06

34.3

717

.74

B1C

a A:

KS

CN

,@33

3-20

-0#;

B:

KS

CN•C

O~N

H2) 2

,@3

7604

-15-

2#;C

:C

O~N

H2) 2

,@5

7-13

-6#.

b The

auth

ors’

mol

e%

data

wer

eco

mpu

ter

reca

lcul

ated

byth

eco

mpi

ler.

Mos

tof

the

data

agre

edw

ithin

60.

02m

ole

%,

the

diffe

renc

esbe

ing

mos

tlik

ely

caus

edby

roun

ding

erro

rs.

Tho

sedi

fferin

gm

ore

are

show

nin

the

tabl

eas

data

mar

ked

with

supe

rscr

ipt

b .


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

otas

sium

mol

ybda

te;

K 2MoO

4;

@134

46-4

9-6#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

Z.

G.

Kar

ov,

I.N

.Le

pesh

kov,

and

S.

B.

Sem

enov

a,Z

h.N

eorg

.K

him

.16

,22

73–

8~19

71!.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

0–

64.6

6J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

solu

tions

ofK 2

MoO

4at

25°C

K2M

oO4

(100

w2

/mas

s%

)K

2M

oO4

(m2

/mol

kg2

1)b

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)b

Sol

idph

asea

00

70.9

125

.08

A

8.83

1.31

662

.99

23.0

0A

15.5

22.

368

56.9

621

.30

A

21.7

13.

392

51.4

119

.68

A

28.9

64.

663

44.9

617

.74

A1B

29.1

44.

710

44.8

817

.78

A1B

29.1

64.

719

44.8

917

.80

A1B

29.2

04.

730

44.8

817

.82

A1B

29.2

44.

739

44.8

517

.81

A1B

a A:

KS

CN

,@33

3-20

-0#;

B:

K2M

oO4

,@1

3446

-49-

6#.b C

alcu

late

dby

com

pile

r.

Add

ition

alin

form

atio

n:

~i!

Com

posi

tion

ofth

esa

tura

tion

solu

tion

atth

eeu

toni

cpo

int

was

repo

rted

tobe

100

w15

44.8

9m

ass

%K

SC

Nan

d10

0w2

529

.61

mas

s%

K 2MoO

4.

The

solu

bilit

yof

KS

CN

inso

lutio

nsof

K 2MoO

4at

25°C

was

expr

esse

dby

the

auth

ors

asS

(in

mas

s%

)570

.912

0.92

43(1

00w

2)0.

99.

~ii!

Inad

ditio

nto

the

data

give

nab

ove,

the

auth

ors

also

repo

rted

com

posi

tions

ofan

othe

rsi

xsa

tura

ted

solu

tions

cont

aini

ng29

.69

64.6

6m

ass

%K 2M

oO4

and

44.2

5–

0m

ass

%K

SC

N.

The

seda

taw

ere

not

incl

uded

inth

eco

mpi

latio

nsi

nce

they

repr

esen

tth

eso

lubi

lity

ofK

2M

oO4

inso

lutio

nsof

KS

CN

.~ii

i!A

lso

repo

rted

wer

ede

nsiti

es,

visc

ositi

es,

refr

activ

ein

dexe

s,su

rfac

ete

nsio

ns,

pH

,an

del

ectr

ical

cond

uctiv

ities

ofth

eK

SC

N–

K 2M

oO4

solu

tions

.

Aux

iliar

yIn

form

atio

n

Co

~1!

~2!

~3!

Va T/

10 31 Te


d ng urea

nce

An

isot

herm

alm

etho

dw

asus

ed;

node

tails

repo

rted

exce

ptth

atth

eco

mpo

sitio

nof

the

KS

CN•C

O~N

H2) 2

com

poun

dw

asco

nfirm

edby

chem

ical

anal

ysis

.F

ound~m

ass

%!:

61.8

9ur

ea,

37.2

2K

SC

N;

calc

ulat

ed~c

ompi

ler!:

38.2

0ur

ea,

61.8

0K

SC

N.

The

auth

ors’

data

wer

eap

pare

ntly

conf

used

bym

ista

ke.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#U

rea;

CH 4

N2O

;@5

7-13

-6#

Wat

er;

H 2O

;@7

732-

18-5#

A.

M.

Bab

enko

and

A.

M.

And

riano

v,Z

h.N

eorg

.K

him

.23,

1344

–8~

1978

!.

riabl

es:

Pre

pare

dB

y:

K:

241

–31

60

w2

/mas

s%

:0

–49

.6J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eK

SC

N–

CH 4

N2O

–H

2O

syst

emas

mea

sure

dby

poly

ther

mal

met

hod

CH

4N

2O

00w

2/m

ass

%)

KS

CN

(100

w1

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

CH

4N

2O

(100

w2

/mas

s%

)K

SC

N(1

00w

1/m

ass

%)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

33.0

02

10.6

A1B

49.6

35.2

843

.0B1

C

30.5

6.95

214

.7A1

B18

.040

.02

30.8

B1C

27.8

14.4

217

.7A1

B21

.738

.02

24.8

B1C

24.0

22.8

221

.0A1

B25

.636

.02

15.7

B1C

20.3

31.8

82

26.4

A1B

28.8

36.0

28.

3B1

C

16.8

39.2

32

31.8

A1B

1C

064

.02

0.8

D1

E

10.4

48.0

230

.8A1

C1

D3.

862

21.

8D

1E

052

.02

30.0

A1D

8.0

60.7

22.

6C1

E

4.81

52.0

231

.6A1

D8.

060

.03.

0C1

E

6.0

58.2

82

8.0

C1D

1E

11.9

460

.212

.0C1

E

36.0

33.9

29.

5A1

B1

C12

.061

.614

.5C1

E

40.0

34.2

19.2

B1C

13.1

662

.426

.0C1

E

43.6

34.9

627

.6B1

C14

.464

.036

.0C1

E

47.6

34.5

837

.6B1

C16

.264

.041

.6C1

E

Sol

ubili

tyis

othe

rms

inth

eK

SC

N–

CH 4N

2O

–H

2O

syst

emb

mpe

ratu

re(t

/°C

)C

H4N

2O

(100

w2

/mas

s%

)C

H4N

2O

(m2

/mol

kg2

1)c

KS

CN

(100

w1

/mas

s%

)K

SC

N(m

1/m

olkg

21)c

Sol

idph

asea

230

00

52.0

11.1

5D

4.75

1.85

052

.512

.64

D

10.3

64.

163

48.2

11.9

7C

10.6

4.16

347

.011

.41

C

13.0

4.78

541

.76

9.49

9A

17.7

6.88

639

.59.

497

C

17.9

77.

136

40.1

9.84

1C

18.3

67.

136

38.8

9.32

0A

220

00

38.8

6.52

4A

00

55.5

12.8

3D

4.42

1.85

055

.814

.43

D

5.2

1.52

237

.92

6.86

0A

6.38

1.85

036

.26.

487

A

6.8

2.82

553

.12

13.6

4C

10.2

4.02

447

.59

11.6

0C

13.0

4.00

933

.06.

288

A

17.5

87.

136

41.4

10.3

9C

21.4

28.

966

38.8

10.0

4C

22.4

47.

136

25.2

4.95

3A

23.0

9.56

536

.96

9.49

9B

23.8

8.66

830

.48

6.86

0B

111111JIRI HALA


Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

inth

eta

ble,

the

auth

ors

also

repo

rted

com

posi

tions

ofan

othe

rse

ven

satu

rate

solu

tions

at15

°Cco

ntai

ning

43.4

6–

49.0

mas

s%

urea

and

29.8

9–

22.3

8m

ass

%K

SC

N,

six

satu

rate

dso

lutio

nsat

30°C

cont

aini

44.4

8–

57.5

0m

ass

%ur

eaan

d31

.37

–28

.86

mas

s%

KS

CN

,an

dse

ven

satu

rate

dso

lutio

nsat

45°C

cont

aini

ng49

.88

–64

.50

mas

s%

and

38.6

3–

35.2

8m

ass

%K

SC

N,w

here

urea

was

the

equi

libriu

mso

lidph

ase.

The

seda

taha

veno

tbee

nin

clud

edin

the

com

pila

tion

sith

eyre

pres

entt

heso

lubi

lity

ofur

eain

solu

tions

ofK

SC

N.A

lso

repo

rted

was

the

phas

edi

agra

mof

the

KS

CN

–ur

ea–

H2O

syst

emat

30°C

~see

Fig

.17

!.

FIG

.17

.S

olub

ility

poly

ther

mof

the

KS

CN

–ur

ea–

H2O

syst

em.

Fie

lds

ofcr

ysta

lliza

tion:

I:ic

e;II:

urea

;III

:K

SC

N•0.

5H2O

;IV

:K

SC

N;

and

V:

KS

CN

urea

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Co

~1!

~2!

~3!

Va T/

10 (1 Te

J

22.5

11.2

244

.113

.59

C

36.2

20.0

933

.811

.59

C

38.6

20.1

329

.47

9.49

7B

39.5

18.1

224

.26.

860

B

40.4

16.0

917

.84.

382

B

42.5

15.3

811

.52.

573

B

200

051

.811

.06

Ee

10.4

44.

163

47.8

11.7

8Ee

16.3

27.

136

45.6

12.3

2Ee

26.9

715

.36

43.8

15.4

2Ee

31.2

718

.78

41.0

15.2

1Ee

33.9

21.9

640

.416

.18

C

46.6

26.4

224

.03

8.41

9C

48.9

827

.17

21.0

7.19

8C

50.0

27.7

520

.06.

860

C

54.8

31.0

615

.82

5.54

1C

55.5

732

.32

15.8

5.67

9C

60.9

038

.85

13.0

5.12

5Bf

66.5

38.8

55.

01.

805

Bf

67.7

38.7

83.

231.

143

Bf

69.0

37.0

60

0Bf

:Ic

e,H

2O

,@7

732-

18-5#

;B

:C

H4N

2O

,@5

7-13

-6#;

C:

KS

CN•

CH

4N

2O

,@3

7604

-15-

2#;D

:K

SC

N•0.

5H2O

,@

#;E

:K

SC

N,@

333-

20-0#

.ol

ubili

tyis

othe

rms

wer

eob

tain

edby

the

auth

ors

from

poly

ther

mal

mea

sure

men

ts.

alcu

late

dby

com

pile

r.w

osa

tura

ted

solu

tions

with

iden

tical

com

posi

tions

,bu

tdi

ffere

ntso

lidph

ases

wer

ere

port

ed.

the

orig

inal

docu

men

t,ur

eais

repo

rted

asth

eso

lidph

ase

ineq

uilib

rium

with

thes

eso

lutio

ns,

evid

ently

bym

ista

ke.

the

orig

inal

docu

men

t,K

SC

Nis

repo

rted

asth

eso

lidph

ase

ineq

uilib

rium

with

thes

eso

lutio

ns,

evid

ently

bym

ista

ke.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ualp

olyt

herm

alm

etho

dus

ed.

Into

tal,

16se

ctio

nsof

the

CN

–ur

ea–

H 2O

syst

emw

ere

inve

stig

ated

,of

whi

chte

nrr

espo

nded

to10

,20

,30

,40

,50

,53

,57

,62

,66

,an

d70

ss%

KS

CN

,an

dsi

xto

10,

20,

30,

35,

40,

and

45m

ass

%ea

.M

easu

rem

ents

wer

eca

rrie

dou

tin

anap

para

tus

desc

ribed

Era

izer

and

Kag

ansk

ii.1T

heso

lubi

lity

vess

el,

equi

pped

with

ther

mom

eter

,w

asco

ated

with

atr

ansp

aren

tse

mic

ondu

ctor

erto

whi

chtw

ohe

atin

gsi

lver

elec

trod

esw

ere

sold

ered

.e

vess

elw

aspl

aced

insi

dea

Dew

arfla

skw

ithtr

ansp

aren

tlls

whi

ch,

inm

easu

rem

ents

perf

orm

edbe

low

room

pera

ture

,w

asfil

led

to1/

5of

itsvo

lum

ew

ithliq

uid

roge

nor

solid

CO 2

.W

ithth

eso

lubi

lity

vess

elke

ptab

ove

cool

ant,

itw

aspo

ssib

leto

cont

rolt

hera

teof

cool

ing

orat

ing

bym

ovin

gth

eD

ewar

flask

.T

hem

ixtu

rein

the

lubi

lity

vess

elw

asst

irred

byus

ing

two

exte

rnal

ctro

mag

nets

,an

dill

umin

ated

toob

serv

edi

sapp

eara

nce

orpe

aran

ceof

crys

tals

.

KS

CN

and

urea

wer

ech

emic

ally

pure

prod

ucts

,tw

ice

recr

ysta

llize

dfr

omw

ater

,an

ddr

ied

at50

°Cbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 L.N

.E

raiz

eran

dI.

M.

Kag

ansk

ii,Z

avod

skay

aLa

b.33,

119

~196

7!.


24.1

58.

966

31.0

7.11

3B

24.6

7.76

122

.62

4.41

0B

210

00

24.0

3.25

0A

00

59.7

15.2

4C

4.08

1.85

059

.216

.59

C,Dd

7.9

1.85

021

.03.

039

A

9.6

2.21

018

.08

2.57

3A

9.6

4.11

151

.52

13.6

4C

13.5

5.52

945

.84

11.6

0C

16.9

24.

163

15.4

2.34

1A

17.1

67.

136

42.8

11.0

0C

25.1

211

.10

37.2

10.1

6C

28.2

12.5

834

.46

9.49

7B

29.0

11.3

328

.46.

860

B

30.0

10.1

921

.04.

410

B

30.4

58.

966

13.0

2.36

6B

31.8

9.70

513

.64

2.57

3B

33.0

9.11

36.

71.

143

B

00

064

.018

.29

E

3.75

1.85

062

.519

.06

E

7.8

3.70

757

.16

16.7

9C

8.8

4.16

356

.016

.37

C

14.5

6.56

648

.73

13.6

4C

16.3

87.

136

45.4

12.2

2C

18.8

8.20

143

.03

11.6

0C

20.1

98.

963

42.3

11.6

0C

24.4

11.1

039

.010

.96

C

28.0

313

.62

37.7

11.3

2C

33.4

16.0

631

.96

9.49

4B

34.2

14.4

226

.32

6.86

0B

35.2

12.9

219

.44

4.41

0B

37.0

12.2

212

.62.

573

B

100

066

.520

.43

E

3.5

1.85

065

.021

.23

E

7.6

4.16

362

.020

.99

E

12.0

5.96

554

.516

.74

C

13.6

87.

136

54.4

17.5

4C

18.6

8.95

146

.813

.92

C

a A b S c C d T e In f In Me

Vis

KS

co ma

ur in a lay

Th

wa

tem

nit

the

he so ele

ap


FIG

.18

.S

olub

ility

ofK

SC

Nin

wat

er–

acet

one

solu

tions

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Not

hing

spec

ified

.N

othi

ngsp

ecifi

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#1,

2-et

hane

diol~

ethy

lene

glyc

ol!;

C2H

6O

2;

@107

-21-

1#W

ater

;H 2

O;

@773

2-18

-5#

Z.

Ada

mco

va´,

Col

l.C

zech

.C

hem

.C

omm

un.34

,31

49–

53~1

969!

;36

,23

38–

41~1

971!

.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

20–

100

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

H 2O

–et

hyle

negl

ycol

mix

ture

sat

25°Ca

C2H

6O

2

(100

w2

/mas

s%

)bK

SC

N(g

/100

gm

ixed

solv

ent!

2022

0

4017

8.7

6013

6.2

8095

.4

9078

.1

9572

.7

100

66.7

quili

briu

mso

lidph

ase

was

KS

CN

,@333

-20-

0#,in

alls

olut

ions

.as

s%

ethy

lene

glyc

olin

the

initi

also

lven

tm

ixtu

re.

ditio

nal

info

rmat

ion:

The

solu

bilit

yof

KS

CN

,S,in

gram

ssa

ltpe

r10

0g

mix

edso

lven

t,as

afu

nctio

nof

solv

ent

com

posi

tion

was

tain

edby

leas

tsq

uare

sm

etho

das

S5

252.

421.

815(

100w

2)2

0.00

112(

100w

2)2

.

lcul

ated

and

expe

rimen

tals

olub

ilitie

sag

reed

with

in6

2%.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

The

glyc

ol–

wat

erm

ixtu

res

repr

epar

edby

wei

ghin

g.M

easu

rem

ents

wer

eca

rrie

dou

tin

rmos

tate

dfla

sks

equi

pped

with

ave

rtic

alst

irrer

.ui

libra

tion

time

was

2h.

Sam

ples

ofth

esa

tura

ted

solu

tions

rew

ithdr

awn

bym

eans

ofa

pipe

ttew

itha

cotto

nw

ad,

and

CN

cont

ent

was

dete

rmin

edby

Volh

ard’

sm

etho

d.T

hegl

ycol

was

foun

dno

tto

affe

ctth

ere

sults

.T

heco

mpo

sitio

nof

the

solid

phas

esw

asch

arac

teriz

edby

Sch

rein

emak

ers’

met

hod.

KS

CN

,ana

lytic

algr

ade~s

ourc

eno

tspe

cifie

d!,w

asre

crys

talli

zed

from

wat

eran

ddr

ied

at10

5°C

.E

thyl

eneg

lyco

l,so

urce

not

spec

ified

,w

aspu

rified

bydi

still

atio

nat

norm

alpr

essu

re.

The

prod

uct

used

show

edth

efo

llow

ing

prop

ertie

s:bo

iling

poin

t19

7.3

°Cat

norm

alpr

essu

re,

refr

activ

ein

dex

1.43

15,

dens

ity1.

1151

gcm

23 .

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n60.

05K

~aut

hor!.

Sol

ubili

ty:

aver

age

expe

rimen

tal

erro

rw

as60.

33m

ass

%re

lativ

e~a

utho

r!.

113113JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!A

ceto

ne;

C 3H

6O

;@6

7-64

-1#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

E.

Wei

tzan

dE

.G

rohr

ock,

Ber

.67,

1085

–91

~193

4!.

Varia

bles

:P

repa

red

By:

T/K

:29

3Vo

lum

e%

acet

one:

0–

100

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofK

SC

Nin

acet

one

–w

ater

solu

tions

at20

°Cw

asre

port

edin

Fig

.18

.

Co

~1!

~2!

~3!

Va T/

10 a E b M Ad

ob Ca

Me

An

we

the

Eq

we

KS

J

the

solid

phas

esw

asch

arac

teriz

edby

Sch

rein

emak

ers’

met

hod.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n60.

05K

~aut

hor!.

Sol

ubili

ty:

aver

age

expe

rimen

tal

erro

rw

as60.

33m

ass

%re

lativ

e~a

utho

r!.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#2,

2 8-@

1,2-

etha

nedi

ylbi

s~oxy

!#bi

s-et

hano

l;ie

thyl

eneg

lyco

l!;C

6H

14O

4;

@112

-27-

6#W

ater

;H 2

O;

@773

2-18

-5#

Z.

Ada

mco

va´,

Col

lC

zech

.C

hem

.C

omm

un.34

,31

49–

53~1

969!

;36

,23

38–

41~1

971!

.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

20–

100

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

H 2O

–tr

ieth

ylen

egly

colm

ixtu

res

at25

°Ca

C6H

14O

4

(100

w2

/mas

s%

)bK

SC

N(g

/100

gm

ixed

solv

ent!

2019

4.5

4014

8.3

6010

6.2

8071

.6

9058

.6

9553

.3

100

48.3

quili

briu

mso

lidph

ase

was

KS

CN

,@333

-20-

0#,in

alls

olut

ions

.as

s%

trie

thyl

eneg

lyco

lin

the

initi

also

lven

tm

ixtu

re.

ditio

nal

info

rmat

ion:

The

solu

bilit

yof

KS

CN

,S,in

gram

ssa

ltpe

r10

0g

mix

edso

lven

t,as

afu

nctio

nof

solv

ent

com

posi

tion

was

tain

edby

leas

tsq

uare

sm

etho

das

S5

250.

222.

955(

100w

2)1

0.00

925(

100w

2)2

.

lcul

ated

and

expe

rimen

tals

olub

ilitie

sag

reed

with

in6

0.88

%.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.T

hegl

ycol

–w

ater

mix

ture

sw

ere

epar

edby

wei

ghin

g.M

easu

rem

ents

wer

eca

rrie

dou

tin

rmos

tate

dfla

sks

equi

pped

with

ave

rtic

alst

irrer

.ui

libra

tion

time

was

24h.

Sam

ples

ofth

esa

tura

ted

lutio

nsw

ere

with

draw

nby

mea

nsof

api

pette

with

aco

tton

wad

,an

dK

SC

Nco

nten

tw

asde

term

ined

byVo

lhar

d’s

met

hod.

The

glyc

olw

asfo

und

not

toaf

fect

the

resu

lts.

The

com

posi

tion

ofth

eso

lidph

ases

was

char

acte

rized

byS

chre

inem

aker

s’m

etho

d.

KS

CN

,ana

lytic

algr

ade~s

ourc

eno

tspe

cifie

d!,w

asre

crys

talli

zed

from

wat

eran

ddr

ied

at10

5°C

.T

rieth

ylen

egly

col,

sour

ceno

tsp

ecifi

ed,

was

purifi

edby

dist

illat

ion

atre

duce

dpr

essu

re.

The

prod

uct

used

show

edth

efo

llow

ing

prop

ertie

s:bo

iling

poin

t20

1.5

°Cat

60m

mH

gpr

essu

re,r

efra

ctiv

ein

dex

1.45

56,d

ensi

ty1.

1260

gcm

23 .

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n60.

05K

~aut

hor!.

Sol

ubili

ty:

aver

age

expe

rimen

tal

erro

rw

as60.

33m

ass

%re

lativ

e~a

utho

r!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!2,

2 8-o

xybi

s-et

hano

l~die

thyl

eneg

lyco

l!;C

4H

10O

3;

@111

-46-

6#~3

!W

ater

;H 2

O;

@773

2-18

-5#

Z.

Ada

mco

va´,

Col

l.C

zech

.C

hem

.C

omm

un.34

,31

49–

53~1

969!

;36

,23

38–

41~1

971!

.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

20–

100

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

H 2O

–di

ethy

lene

glyc

olm

ixtu

res

at25

°Ca

C4H

10O

3

(100

w2

/mas

s%

)bK

SC

N(g

/100

gm

ixed

solv

ent!

2020

1.6

4015

5.3

6011

1.5

8077

.4

100

52.5

a Equ

ilibr

ium

solid

phas

ew

asK

SC

N,@333

-20-

0#,in

alls

olut

ions

.b M

ass

%di

ethy

lene

glyc

olin

the

initi

also

lven

tm

ixtu

re.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

ofK

SC

N,S,

ingr

ams

salt

per

100

gm

ixed

solv

ent,

asa

func

tion

ofso

lven

tco

mpo

sitio

nw

asob

tain

edby

leas

tsq

uare

sm

etho

das

S5

251.

622.

748(

100w

2)1

0.00

742(

100w

2)2

.

Cal

cula

ted

and

expe

rimen

tals

olub

ilitie

sag

reed

with

in6

1.62

%.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

glyc

ol–

wat

erm

ixtu

res

wer

epr

epar

edby

wei

ghin

g.M

easu

rem

ents

wer

eca

rrie

dou

tin

ther

mos

tate

dfla

sks

equi

pped

with

ave

rtic

alst

irrer

.E

quili

brat

ion

time

was

4h.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

bym

eans

ofa

pipe

ttew

itha

cotto

nw

ad,

and

KS

CN

cont

ent

was

dete

rmin

edby

Volh

ard’

sm

etho

d.T

hegl

ycol

was

foun

dno

tto

affe

ctth

ere

sults

.T

heco

mpo

sitio

nof

KS

CN

,ana

lytic

algr

ade~s

ourc

eno

tspe

cifie

d!,w

asre

crys

talli

zed

from

wat

eran

ddr

ied

at10

5°C

.D

ieth

ylen

egly

col,

sour

ceno

tsp

ecifi

ed,

was

purifi

edby

dist

illat

ion

atre

duce

dpr

essu

re.

The

prod

uct

used

show

edth

efo

llow

ing

prop

ertie

s:bo

iling

poin

t17

4.0

°Cat

60m

mH

gpr

essu

re,r

efra

ctiv

ein

dex

1.44

69,d

ensi

ty1.

1181

gcm

23 .

Co

~1!

~2!

~tr

~3!

Va T/

10 a E b M Ad

ob Ca

Me

Iso

pr the

Eq

so


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#P

olye

thyl

eneg

lyco

lsW

ater

;H 2

O;

@773

2-18

-5#

Z.

Ada

mco

va´,

Sci

.P

aper

sIn

st.

Che

m.

Tech

nol.

Pra

gue

B17

,21

7–

24~1

973!

.

riabl

es:

Pre

pare

dB

y:

K:

298

mpo

sitio

nJ.

Hala

Exp

erim

enta

lDat

aTe

rnar

yph

ase

diag

ram

sof

the

KS

CN

–H

2O

–po

lyet

hyle

negl

ycol~

1500

!an

dK

SC

N–

H 2O

–po

lyet

hyle

negl

ycol~

6000

!at

25°C

wer

epo

rted

~see

Fig

s.19

and

20!.N

umer

ical

data

wer

eno

tgiv

en.T

heso

lidph

ase

ineq

uilib

rium

with

H2O

–po

lyet

hyle

negl

ycol

mix

ture

sw

asC

N,@

333-

20-0#

.R

egio

nsin

the

diag

ram

sar

eas

follo

ws:

Iand

VI—

one

liqui

dph

ase;

II—tw

oliq

uid

phas

es;I

II—tw

oliq

uid

phas

esin

equi

libriu

mw

ithlid

poly

ethy

lene

glyc

ol;

IV—

one

liqui

dph

ase

ineq

uilib

rium

with

solid

KS

CN

,@3

33-2

0-0#

~sol

ubili

tycu

rve:

QS!;

and

V—

one

liqui

das

ein

equi

libriu

mw

ithso

lidpo

lyet

hyle

negl

ycol

.

FIG

.19

.P

hase

diag

ram

ofth

eK

SC

N–

H2O

–po

lyet

hyle

negl

ycol~

1500

!.

115115JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!P

olye

thyl

eneg

lyco

l~200

!~3

!W

ater

;H 2

O;

@773

2-18

-5#

Z.

Ada

mco

va´,

Col

l.C

zech

.C

hem

.C

omm

un.36

,23

38–

41~1

971!

.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

H 2O

–P

EG

-200

mix

ture

sat

25°C

The

solu

bilit

yat

25°C

ofK

SC

N,S,

ingr

ams

salt

per

100

gm

ixed

solv

ent,

asa

func

tion

ofso

lven

tcom

posi

tion

was

obta

ined

byle

ast

squa

res

met

hod

asS

524

6.72

3.20

0(10

0w2)1

0.01

156

(100

w2)2

,

whe

re10

0w2

isth

eco

ncen

trat

ion

ofP

EG

-200

inm

ass

%in

the

initi

also

lven

tmix

ture

.Num

eric

alda

taan

deq

uilib

rium

solid

phas

esw

ere

not

repo

rted

.Ave

rage

devi

atio

nof

expe

rimen

tals

olub

ilitie

sfr

omth

eca

lcul

ated

data

was

60.

0167

%.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Toa

mix

ture

ofth

ede

sire

dw

ater

–P

EG

ratio

,th

esa

ltw

asad

ded

inex

cess

,th

em

ixtu

rew

asse

aled

inan

ampo

ule,

and

equi

libra

ted

ina

ther

mos

tat

for

72h.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

bym

eans

ofa

pipe

ttew

itha

cotto

nw

ad,

and

wer

ean

alyz

edfo

rK

SC

Nby

Volh

ard’

sm

etho

d,an

dfo

rw

ater

byF

isch

er’s

met

hod.

The

cont

ent

ofP

EG

-200

was

obta

ined

bydi

ffere

nce.

KS

CN

,ana

lytic

algr

ade~s

ourc

eno

tspe

cifie

d!,w

asre

crys

talli

zed

from

wat

eran

ddr

ied

at10

5°C

.P

olye

thyl

eneg

lyco

lP

EG

-200

was

apr

oduc

tof

Che

mis

che

Wer

ke,

Hu

¨ lls

,A

G,

Ger

man

y.Its

mea

nm

olec

ular

wei

ght,

asde

term

ined

byva

por

phas

eos

mom

etry

,w

as18

2%65%

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n60.

05K

~aut

hor!.

Sol

ubili

ty:

not

repo

rted

.

Co

~1!

~2!

~3!

Va T/

co re KS

so ph

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#M

ethy

lthio

cyan

ate;

C 2H3N

S~C

H3C

NS

);@5

56-6

4-9#

Wat

er;

H 2O

;@7

732-

18-5#

E.S

pacc

amel

aM

arch

etti,

Atti

.Aca

d.S

ci.T

orin

o,C

lase

Fis

.Mat

.N

at.9

4,35

3–

70~1

960!

.

riabl

es:

Pre

pare

dB

y:

K:

293

tioof

H2O

/C2H

3N

Sco

ncen

trat

ions

J.H

ala

Exp

erim

enta

lDat

aP

hase

diag

ram

ofth

eK

SC

N–

C2H

3N

S–

H 2O

syst

emat

20°C

The

tern

ary

phas

edi

agra

mof

the

KS

CN

–C

2H

3N

S–

H 2O

syst

emat

20°C

was

repo

rted~F

ig.

21!.

The

follo

win

gfie

lds

wer

eob

serv

edth

edi

agra

m:

Ian

dII—

one

liqui

dph

ase,

III—

two

liqui

dph

ases

,IV

and

VI—

one

liqui

dph

ase

ineq

uilib

rium

with

solid

KS

CN

,an

dtw

oliq

uid

phas

esin

equi

libriu

mw

ithso

lidK

SC

N.

Num

eric

alda

taw

ere

repo

rted

for

the

solu

bilit

yof

KS

CN

inw

ater

-ric

hH

3N

S–

H 2O

mix

ture

s~cu

rve

RP

inth

edi

agra

m!an

din

C 2H

3N

S-r

ich

C 2H

3N

S–

H 2O

mix

ture

s~cu

rve

QS

inth

edi

agra

m!.

FIG

.21

.P

hase

diag

ram

ofth

eK

SC

N–

CH

3C

NS

–H 2

Osy

stem

at20

°C.

Com

posi

tion

ofth

eso

lutio

nssa

tura

ted

at20

°C

H2O

-ric

hre

gion

C 2H

3N

S-r

ich

regi

on

H2O

(100

w3

/mas

s%

)K

SC

N(1

00w

1/m

ass

%)

C2H

3N

S(1

00w

2/m

ass

%)

H2O

(100

w3

/mas

s%

)K

SC

N(1

00w

1/m

ass

%)

C2H

3N

S(1

00w

2/m

ass

%)

31.5

68.5a

00

0.9b

99.1

30.0

66.9

3.1

2.3

6.8

90.9

28.8

65.2

6.0

5.1

13.0

81.9

28.6

63.2

8.2

12.3

17.2

75.5

28.0

60.5

11.5

27.9

58.2

13.9

a Sol

ubili

tyof

KS

CN

inw

ater

,m15

22.3

8m

olkg

21

~com

pile

r!.b S

olub

ility

ofK

SC

Nin

C 2H

3N

S,m

15

0.09

35m

olkg

21

~com

pile

r!.


FIG

.20

.P

hase

diag

ram

ofth

eK

SC

N–

H2O

–po

lyet

hyle

negl

ycol~

6000

!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

Toa

mix

ture

ofth

ede

sire

dw

ater

–P

EG

ratio

,th

esa

ltw

asad

ded

eith

erin

exce

ss,

whe

nde

term

inin

gth

eso

lubi

lity

isot

herm

,or

inca

lcul

ated

amou

ntw

hen

salti

ng/o

utw

asst

udie

d.T

hem

ixtu

res

wer

ese

aled

inam

poul

es,

and

equi

libra

ted

ina

ther

mos

tat

for

72h.

Afte

rth

ecr

ysta

lsha

dse

dim

ente

dan

dth

eliq

uid

phas

esse

para

ted,

sam

ples

ofth

eliq

uid

phas

esfo

ran

alys

isw

ere

with

draw

nby

mea

nsof

asy

ringe

.T

heK

SC

Nco

nten

tw

asde

term

ined

byVo

lhar

d’s

met

hod,

wat

erco

nten

tby

Fis

cher

’sm

etho

d.T

heco

nten

tof

PE

Gw

asob

tain

edby

diffe

renc

e.

KS

CN

,ana

lytic

algr

ade~s

ourc

eno

tspe

cifie

d!,w

asre

crys

talli

zed

from

wat

eran

ddr

ied

at10

5°C

.P

EG

-150

0w

asa

prod

uct

ofC

hem

isch

eW

erke

,H

u¨ l

ls,

AG

,G

erm

any.

PE

G-6

000

was

apr

oduc

tof

Che

mic

alW

orks

,N

ovak

y,C

zech

oslo

vaki

a.It

cont

aine

d0.

58m

ass

%w

ater

,m

elte

din

the

rang

eof

53–

65°C

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n60.

05K

~aut

hor!.

Co

~1!

~2!

~3!

Va T/

ra in V—

C2


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#E

thyl

thio

cyan

ate;

C 3H5N

S~C

2H

5C

NS

);@5

42-9

0-5#

Wat

er;

H 2O

;@7

732-

18-5#

E.S

pacc

amel

aM

arch

etti,

Atti

.Aca

d.S

ci.T

orin

o,C

lase

Fis

.Mat

.N

at.9

4,35

3–

70~1

960!

.

riabl

es:

Pre

pare

dB

y:

K:

293

tioof

H2O

/C3H

5N

Sco

ncen

trat

ions

J.H

ala

Exp

erim

enta

lDat

aP

hase

diag

ram

ofth

eK

SC

N–

C3H

5N

S–

H 2O

syst

emat

20°C

The

tern

ary

phas

edi

agra

mof

the

KS

CN

–C

3H

5N

S–

H 2O

syst

emat

20°C

was

repo

rted~F

ig.

22!.

The

follo

win

gfie

lds

wer

eob

serv

edth

edi

agra

m:

Ian

dII—

one

liqui

dph

ase,

III—

two

liqui

dph

ases

,IV

and

VI—

one

liqui

dph

ase

ineq

uilib

rium

with

solid

KS

CN

,an

dtw

oliq

uid

phas

esin

equi

libriu

mw

ithso

lidK

SC

N.

Num

eric

alda

taw

ere

repo

rted

for

the

solu

bilit

yof

KS

CN

inw

ater

-ric

hH

5N

S–

H 2O

mix

ture

s~cu

rve

RP

inth

edi

agra

m!an

din

C 3H

5N

S-r

ich

C 3H

5N

S–

H 2O

mix

ture

s~cu

rve

QS

inth

edi

agra

m!.

FIG

.22

.P

hase

diag

ram

ofth

eK

SC

N–

C3H

5N

S–

H 2O

syst

emat

20°C

.

117117JIRI HALA


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Sol

ubili

tycu

rves

wer

eob

tain

edby

titra

tion

am

ixtu

reof

two

com

pone

nts

with

the

third

one

ina

ther

mos

tate

dba

th.

Som

eof

thes

em

easu

rem

ents

wer

eve

rified

bypr

epar

ing

the

tern

ary

syst

ems,

and

obse

rvin

gth

ete

mpe

ratu

reof

hom

ogen

izat

ion.

The

valu

eco

rres

pond

ing

to20

°Cw

asth

enob

tain

edby

inte

rpol

atio

n.B

uret

tes

grad

uate

dby

0.01

cm3w

ere

used

for

titra

tions

.

KS

CN

was

drie

dat

110

°Cbe

fore

use.

No

deta

ilsre

port

edon

C2H

3N

S.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

~2!

~3!

Va T/

ra in V—

C3

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Pot

assi

umth

iocy

anat

e;K

SC

N;

@540

-72-

7#A

cetic

acid

;C 2

H4O

2;

@64-

19-7

#N

,N-d

ieth

ylet

hana

min

e~trie

thyl

amin

e!;C

6H

15N

;21

-44-

8#;or

N,N

-dim

ethy

lben

zene

amin

e;im

etht

yl-A

nilin

e!;

C8H

11N

;@1

21-6

9-7#

Sol

vent

s

T.Ja

sins

kian

dR

.K

orew

a,R

ocz.

Che

m.

~War

saw!

39,

963

–8

~196

5!.

riabl

es:

Pre

pare

dB

y:

K:

293

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nat

20°C

inso

lven

tsin

the

pres

ence

ofam

ines

and

acet

icac

ida

Sol

vent

C2H

4O

2

(c2

/mol

dm2

3)

C6H

15N

(c3

/mol

dm2

3)

C8H

11N

(c3

/mol

dm2

3)

NaS

CN

(c1

/mol

dm2

3)

thyl

acet

ate;

C 4H8O

2;

@141

-78-

6#0.

050

00.

0020

00.

050

0.00

16

0.05

0.05

00.

009b

00

0.05

0.00

26

0.05

00.

050.

0034b

chlo

rom

etha

ne;

CH 2C

l 2;

@75-

09-2

#0.

050

00.

0004

00.

050

0.00

10

0.05

0.05

00.

0026b

00

0.05

0.00

08

0.05

00.

050.

0010b

Ben

zene

;C 6

H6

;@7

1-43

-2#

0.05

0.05

00.

0074b

hlor

oben

zene

;C 6H

5C

l;@1

08-9

0-7#

0.05

0.05

00.

0080b

0.05

00.

050.

0044b

Die

thyl

ethe

r;C 4

H10

O;

@60-

29-7

#0.

050.

050

0.00

92b

olid

phas

esw

ere

not

inve

stig

ated

.ol

ubili

tyof

KS

CN

inth

epr

esen

ceof

the

corr

espo

ndin

gam

mon

ium

acet

ate.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

salt

was

equi

libra

ted

incl

osed

flask

sfo

r5

days

with

20cm3

port

ions

ofth

eso

lutio

nsof

the

amin

e,ac

etic

acid

,or

thei

rm

ixtu

re,

asm

aybe

the

case

,in

the

desi

red

solv

ent.

The

na

10cm3

sam

ple

was

with

draw

n,ad

ded

tow

ater

,an

dth

esa

ltw

asex

trac

ted

into

wat

erby

shak

ing.

The

SC

N2co

nten

tw

asde

term

ined

inth

eaq

ueou

sla

yer

bypo

tent

iom

etric

titra

tion

with

0.01

mol

dm23

AgN

O3

solu

tion.

KS

CN

,re

agen

tgr

ade,

was

twic

ere

crys

talli

zed

from

wat

er,

and

drie

din

anov

ento

cons

tant

wei

ght.

Ace

ticac

id,

sour

ceno

tsp

ecifi

ed,

was

purifi

edby

crys

talli

zatio

nan

ddi

still

atio

n.T

heam

ines

,so

urce

unsp

ecifi

ed,

wer

edr

ied

over

KO

Han

ddi

still

edov

erzi

ncpo

wde

r.C

H 2Cl 2

,ch

loro

benz

ene,

and

ethy

lace

tate

wer

edr

ied

over

P 2O5

,an

ddi

still

edov

eran

hydr

ous

Na

2C

O3

.B

enze

nean

ddi

ethy

leth

erw

ere

drie

dw

ithso

dium

met

al,

and

dist

illed

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.5

K~a

utho

rs!.

Sol

ubili

ty:6

2%~a

utho

rs!.


Com

posi

tion

ofth

eso

lutio

nssa

tura

ted

at20

°C

H2O

-ric

hre

gion

C 3H

5N

S-r

ich

regi

on

H2O

(100

w3

/mas

s%

)K

SC

N(1

00w

1/m

ass

%)

C3H

5N

S(1

00w

2/m

ass

%)

H2O

(100

w3

/mas

s%

)K

SC

N(1

00w

1/m

ass

%)

C3H

5N

S(1

00w

2/m

ass

%)

31.5

68.5a

00

0.9b

99.1

39.7

58.5

1.5

6.3

1.7

92.0

44.1

54.0

1.9

19.3

5.8

74.9

51.5

45.3

3.2

63.3

31.8

4.9

74.4

18.1

7.5

a Sol

ubili

tyof

KS

CN

inw

ater

,m15

22.3

8m

olkg

21

~com

pile

r!.b S

olub

ility

ofK

SC

Nin

C 3H

5N

S,m

15

0.09

35m

olkg

21

~com

pile

r!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Sol

ubili

tycu

rves

wer

eob

tain

edby

titra

tion

am

ixtu

reof

two

com

pone

nts

with

the

third

one

ina

ther

mos

tate

dba

th.

Som

eof

thes

em

easu

rem

ents

wer

eve

rified

bypr

epar

ing

the

tern

ary

syst

ems,

and

obse

rvin

gth

ete

mpe

ratu

reof

hom

ogen

izat

ion.

The

valu

eco

rres

pond

ing

to20

°Cw

asth

enob

tain

edby

inte

rpol

atio

n.B

uret

tes

grad

uate

dby

0.01

cm3w

ere

used

for

titra

tions

.

KS

CN

was

drie

dat

110

°Cbe

fore

use.

No

deta

ilsre

port

edon

C3H

5N

S.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

~2!

~3!

@1 ~d ~4!

Va T/ E

Di C a S b S Me


Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

6.4.

Rub

idiu

mT

hioc

yana

te

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Rub

idiu

mth

iocy

anat

e;R

bSC

N;@387

9-02

-5#W

ater

;H 2

O;

@773

2-18

-5#B

.D

.S

tepi

nan

dI.

N.

Byk

ova,

Tru

dyIR

EA~M

osco

w!N

o.28

,24

6–

50~1

966!

.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofR

bSC

Nin

wat

erat

25°C

The

solu

bilit

yat

25°C

ofR

bSC

Nin

wat

eris

repo

rted

tobe

100

w15

69.2

mas

s%

(m15

15.6

5m

olkg

21;

com

pile

r!.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.R

bSC

Nw

aspr

epar

edfr

omR

b2C

O3

and

NH 4

SC

N~s

ourc

ean

dpu

rity

ofst

artin

gm

ater

ials

not

repo

rted!

acco

rdin

gto

Unm

ack

et

al.1

The

prod

uct

was

recr

ysta

llize

dfr

om70

%et

hano

lan

ddr

ied

at12

0–

160

°C.

Itco

ntai

ned

99.5

%R

bSC

N.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.

Unm

ack,

D.

M.

Rus

t,an

dH

.H

artle

y,P

roc.

R.

Soc

.,S

er.

A12

7,22

8~1

930!

.

119119JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~2

!2-

~2-m

etho

xyet

hoxy!

-N,N

-bis

-2-~2

-met

hoxy

etho

xy!et

hyl

etha

nam

ine$

tris

~dio

xa-3

,6-h

epty

l!am

ine%

;C

15H

33N

O3

;@7

0384

-51-

9#;or

2-m

etho

xy-N

,N-b

is~m

etho

xyet

hyl!e

than

amin

e;$t

ris~o

xa-3

-but

yl!am

ine%

;C

9H

21N

O3

;@3

235-

51-6#

~3!

Dic

hlor

omet

hane

;C

H 2Cl 2

;@7

5-09

-2#

G.S

oula

,Eur

.Par

.App

l.01

6673~

1979

!;F

renc

hA

ppl.

7905

438.

Varia

bles

:P

repa

red

By:

T/K

:un

spec

ified

c 2/m

oldm

23:

0.1

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofK

SC

Nin

CH 2

Cl 2

inth

epr

esen

ceof

amin

esa

Am

ine

KS

CN

~mg

dm2

3 !K

SC

N(c

1/m

oldm

23)b

C15

H33

NO

339

100.

0402

C9H

21N

O3

490

0.00

0504

a Mea

sure

men

tspe

rfor

med

atan

unsp

ecifi

ed,

ambi

ent

tem

pera

ture

.S

olid

phas

esw

ere

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

r.

Add

ition

alin

form

atio

n:T

heso

lubi

lity

ofK

SC

Nin

neat

CH 2C

l 2w

asre

port

edto

bele

ssth

an1

mg

dm23 .

The

solu

biliz

atio

nef

fect

ofC

15H

33N

O3

was

expl

aine

dby

the

auth

ors

inte

rms

ofth

efo

rmat

ion

ofa

1:1

addu

ctof

KS

CN

with

the

amin

ein

the

solu

tion.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

salt

~0.0

01m

ole!

was

equi

libra

ted

with

0.00

1m

ole

amin

ein

10m

LC

H2C

l 2by

stirr

ing.

The

cont

ent

ofth

esa

ltin

the

satu

rate

dso

lutio

nw

asde

term

ined

byfla

me

phot

omet

ry.

C15

H33

NO

3w

aspr

epar

edby

reflu

xing

sodi

umm

etho

xy-2

-eth

anoa

tew

ithch

loro

hydr

ate

oftr

is~c

hlor

o-2-

ethy

l!am

ine

inm

etho

xy-2

-eth

anol

for

12h

at12

5°C

.T

heex

cess

ofso

lven

tw

asth

endi

still

edof

f,ex

cess

ofso

dium

met

hoxy

-2-e

than

oate

deco

mpo

sed

with

conc

entr

ated

HC

l,an

dth

eam

ine

was

dist

illed

at16

5–

180

°Cat

0.5

mm

Hg.

C9H

21N

O3

was

obta

ined

bya

sim

ilar

proc

edur

eus

ing

sodi

umm

etha

noat

ean

dm

etha

nola

sth

eso

lven

t.A

fter

trea

tmen

tof

the

mix

ture

with

HC

l,th

eam

ine

was

extr

acte

din

toC

H2C

l 2,

and

dist

illed

.A

nhyd

rous

CH 2

Cl 2

was

purifi

edfr

omst

abili

zers

.

Co

~1!

~2!

Va T/

Me

An

J

fmpo

nent

s:O

rigin

alM

easu

rem

ents

:

Rub

idiu

mth

iocy

anat

e;R

bSC

N;@387

9-02

-5#T

ri-n-

buty

l~pho

spha

te!;C

12H

27O

4P

;@1

26-7

3-8#

J.H

alaan

dD

.G

.T

uck,

Can

ad.

J.C

hem

.48

,28

43–

6~19

70!.

riabl

es:

Pre

pare

dB

y:

K:

295

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofR

bSC

Nin

tri-n

-but

yl~pho

spha

te!is

repo

rted

tobe

3.4

gsa

ltin

100

gso

lven

tat

22°C

(m

15

0.23

7m

olkg

21;

mpi

ler!.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

ther

mal

met

hod

used

.An

exce

ssof

the

salt

was

shak

ener

nigh

tw

ith5

mL,

dry

solv

ent.

Pre

limin

ary

expe

rimen

tsow

edth

atth

isw

assu

ffici

ent

for

equi

libriu

mto

bere

ache

d.m

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

thro

ugh

ate

r,di

lute

dw

ithac

eton

e,an

dan

alyz

edfo

rth

eth

iocy

anat

ent

ent

bytit

ratio

nag

ains

tA

gNO 3

stan

dard

solu

tion.

Bla

nkat

ions

show

edth

ata

smal

lcor

rect

ion

was

requ

ired

beca

use

the

pres

ence

oftr

i-n-b

utyl~p

hosp

hate!.

RbS

CN

was

prep

ared

byne

utra

lizin

gof

RbO

H~A

lfaIn

orga

nics

!w

ithth

iocy

anic

acid

solu

tion

obta

ined

byio

n-ex

chan

geof

the

sodi

umsa

lton

aD

owex

50W

-X8

colu

mn

inH

form

.T

ri-n-

buty

l~pho

spha

te!~F

ishe

rS

cien

tific

Co.!

was

purifi

edby

reflu

xing

itw

ith0.

5%ca

ustic

soda

solu

tion,

follo

wed

byst

eam

dist

illat

ion.

The

prod

uctw

asdr

ied

first

with

anhy

drou

sM

gSO

4,

and

final

lyva

cuum

/drie

dat

50°C

ina

stre

amof

dry

nitr

ogen

gas.1

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

0.05

gsa

lt/10

0g

solv

ent~a

utho

rs!.

Ref

eren

ces:

1 D.

G.

Tuc

k,J.

Che

m.

Soc

.27

83~19

58!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Rub

idiu

mth

iocy

anat

e;R

bSC

N;@387

9-02

-5#~2

!S

olve

nts

B.D

.Ste

pin,

V.E

.Ply

ushc

hev,

and

Yu.A

.Iva

nova

,Khi

m.P

rom

.~C

hem

.In

dust

ry!40

4–

7~1

962!

.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofR

bSC

Nat

25°C

infiv

eso

lven

tsa

Sol

vent

RbS

CN

(100

w1

/mas

s%

)R

bSC

N(m

1/m

olkg

21)b

Met

hano

l;C

H 4O

;@6

7-56

-1#

16.5

01.

377

Eth

anol

;C 2

H6O

;@6

4-17

-5#

2.75

0.19

7

2-B

utan

one;

C 4H

8O

;@7

8-93

-3#

1.10

0.07

75

Cyc

lohe

xano

ne;

C 6H10

O;

@108

-94-

1#0.

860.

0604

1-P

heny

leth

anon

e;C 8H

8O

;@9

8-86

-2#

0.55

0.03

85

a Sol

idph

ases

not

inve

stig

ated

.b C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.R

efra

ctiv

ein

dice

san

dde

nsiti

es,

resp

ectiv

ely,

both

at20

°C,

oth

eso

lven

tsus

edw

ere

asfo

llow

s:m

etha

nol,

1.32

89,

0.79

08;

etha

nol,

1.36

09,

0.79

87;

2-bu

tano

ne,

1.37

80,

0.80

41;

cycl

ohex

anon

e,1.

4500

,0.

9453

;1-

phen

ylet

hano

ne~a

ceto

phen

one!,

1.53

28,

1.02

70.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

Va T/

co Me

Iso

ov sh Sa

sin

co titr

of


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Ces

ium

thio

cyan

ate;

CsS

CN

;@3

879-

01-4#

Ure

a;C

H 4N

2O

;@5

7-13

-6#

Wat

er;

H 2O

;@7

732-

18-5#

R.

Tur

gunb

ekov

aan

dK

.N

ogoe

v,Ge

tero

ge

nn

yeR

avn

ove

sia

Sis

tem

Ne

org

.O

rg.

So

ed

.~H

eter

ogen

eous

Equ

ilibr

iaof

Sys

tem

sof

Inor

gani

can

dO

rgan

icC

ompo

unds!

~Aka

d.N

auk

Kirg

iz,

SS

R,

1971

!,pp

.34

–35

.

riabl

es:

Pre

pare

dB

y:

K:

288,

303,

and

318

0w

2/m

ass

%:

0–

49at

288

K,

0–

57.5

at30

3K

,0

–64

at8

K

J.H

ala

Exp

erim

enta

lDat

aC

ompo

sitio

nof

the

satu

rate

dso

lutio

nsin

the

CsS

CN

–ur

ea–

H2O

syst

emat

thre

ete

mpe

ratu

res

mpe

ratu

re(t

/°C

)U

rea

(100

w2

/mas

s%

)U

rea

(100

x 2/m

ole

%)

CsS

CN

(100

w1

/mas

s%

)C

sSC

N(1

00x 1

/mol

e%

)S

olid

phas

ea

150

061

.51

8.36

7A

7.08

3.32

957

.51

8.50

4A

29.7

520

.88

46.5

210

.27

A

29.9

821

.46

46.7

610

.53

A1B

31.0

622

.55

46.0

010

.50

B

45.2

616

.11

7.95

0.88

9B

49.0

016

.00

00

B

300

067

.39

10.8

2A

6.97

3.92

263

.44

11.2

3A

30.0

525

.20

50.0

913

.21

A

30.5

526

.10

49.9

613

.42

A1B

30.3

525

.94

50.1

713

.49

B

53.9

522

.99

6.98

0.93

54B

57.5

022

.53

00

A

450

067

.75

11.0

0A

6.08

3.81

067

.35

13.2

7A

30.3

832

.26

53.9

418

.01

A1B

33.4

638

.85

52.2

019

.06

B

33.0

037

.08

52.1

818

.44

B

54.6

526

.72

11.2

91.

736

B

64.0

029

.60

00

B

a A:

CsS

CN

,@38

79-0

1-4#;

B:

CH

4N

2O

,@5

7-13

-6#.

b The

auth

ors’

mol

e%

data

wer

eco

mpu

ter

reca

lcul

ated

byth

eco

mpi

ler.

Mos

tof

the

data

agre

edw

ithin

60.

02m

ole

%,

the

diffe

renc

esbe

ing

mos

tlik

ely

caus

edby

roun

ding

erro

rs.

Tho

sedi

fferin

gm

ore

are

show

nin

the

tabl

eas

data

mar

ked

with

supe

rscr

ipt

b .

Add

ition

alin

form

atio

n:A

lso

repo

rted

wer

eth

eso

lubi

lity

diag

ram

sof

the

CsS

CN

–ur

ea–

H2O

syst

emat

15,

30,

and

45°C

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

exce

ptth

atso

lidph

ases

wer

ech

arac

teriz

edby

Sch

rein

emak

er’s

met

hod.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

121121JIRI HALA


6.5.

Ces

ium

Thi

ocya

nate

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Ces

ium

thio

cyan

ate;

CsS

CN

;@3

879-

01-4#

~2!

Tri-

n-bu

tyl~p

hosp

hate!;

C12

H27

O4P

;@1

26-7

3-8#

J.H

alaan

dD

.G

.T

uck,

Can

ad.

J.C

hem

.48

,28

43–

6~19

70!.

Varia

bles

:P

repa

red

By:

T/K

:29

5J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofC

sSC

Nin

tri-n

-but

yl~pho

spha

te!is

repo

rted

tobe

0.57

gsa

ltin

100

gso

lven

tat

22°C

(m

15

0.02

98m

olkg

21;

com

pile

r!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.A

nex

cess

ofth

esa

ltw

assh

aken

over

nigh

tw

ith5

mL

dry

solv

ent.

Pre

limin

ary

expe

rimen

tssh

owed

that

this

was

suffi

cien

tfo

req

uilib

rium

tobe

reac

hed.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

thro

ugh

asi

nter

,di

lute

dw

ithac

eton

e,an

dan

alyz

edfo

rth

eth

iocy

anat

eco

nten

tby

titra

tion

agai

nst

AgN

O 3st

anda

rdso

lutio

n.B

lank

titra

tions

show

edth

ata

smal

lcor

rect

ion

was

requ

ired

beca

use

ofth

epr

esen

ceof

tri-n

-but

yl~pho

spha

te!.

CsS

CN

was

prep

ared

byne

utra

lizin

gof

CsO

H~A

lfaIn

orga

nics

!w

ithth

iocy

anic

acid

solu

tion

obta

ined

byio

nex

chan

geof

the

sodi

umsa

lton

aD

owex

50W

-X8

colu

mn

inH

form

.T

ri-n-

buty

l~pho

spha

te!~F

ishe

rS

cien

tific

Co.!

was

purifi

edby

reflu

xing

itw

ith0.

5%ca

ustic

soda

solu

tion,

follo

wed

byst

eam

dist

illat

ion.

The

prod

uctw

asdr

ied

first

with

anhy

drou

sM

gSO

4,

and

final

lyva

cuum

/drie

dat

50°C

ina

stre

amof

dry

nitr

ogen

gas.1

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

0.02

gsa

lt/10

0g

solv

ent~a

utho

rs!.

Ref

eren

ces:

1 D.

G.

Tuc

k,J.

Che

m.

Soc

.27

83~19

58!.

Co

~1!

~2!

~3!

Va T/

10 31 Te

J

s

FIG

.23

.S

olub

ility

ofN

H 4S

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

re~num

bers

refe

rto

the

corr

espo

ndin

gre

fere

nces

!.

Sol

ubili

tyof

NH

4S

CN

asa

func

tion

ofte

mpe

ratu

re

mpe

ratu

re(t

/°C

)Te

mpe

ratu

re(T

/K)

NH

4S

CN

(m1

/mol

kg2

1)

Ref

.Te

mpe

ratu

re(t

/°C

)Te

mpe

ratu

re(T

/K)

NH

4S

CN

(m1

/mol

kg2

1)

Ref

.

220

253.

110

.57

920

293.

121

.93

6

210

263.

112

.77

8,9

22.9

5*8

22.

227

0.9

15.4

21

20.8

293.

921

.65

1

027

3.1

15.7

42

25.0

298.

123

.46

2

15.4

28,

923

.45

7

5.0

278.

117

.06

224

.96*

10,1

1

1028

3.1

18.3

16

23.6

912

18.1

48

26.3

329

9.4

24.3

43

18.9

09

28.8

230

1.9

25.4

23

12.9

286.

019

.69

130

303.

125

.80

6

13.0

286.

119

.36

327

.28*

13

16.0

289.

120

.12

233

.030

6.1

27.0

42

18.9

929

2.1

21.6

23

36.3

630

9.5

29.0

53

39.4

431

2.5

30.7

33

obta

inth

ete

mpe

ratu

rede

pend

ence

ofth

eN

H4S

CN

solu

bilit

yin

wat

eras

S/~m

olkg

21!5

0.84

462

5310

52

0.14

824

6310

4~T

/K!1

0.10

381

5310

2~T

/K!2

20.

362

5713

102

1~T

/K!3

10.

631

4773

102

4~T

/K!4

20.

438

6623

102

7~T

/K!5

.

iseq

uatio

nca

nbe

sugg

este

das

yiel

ding

tent

ativ

eso

lubi

lity

valu

esin

the

tem

pera

ture

rang

efr

om25

3to

313

K.

At

tem

pera

ture

sab

ove

313

K,

the

agre

emen

tbe

twee

nso

lubi

lity

data

from

vario

usso

urce

s2

–5

isno

tso

good

,pr

esum

ably

beca

use

atse

tem

pera

ture

sth

esa

tura

ted

solu

tions

are

rath

erco

ncen

trat

ed,

and

even

smal

lerr

ors

inan

alys

ism

ayre

sult

inco

nsid

erab

lede

viat

ions

the

dete

rmin

edso

lubi

lity.

For

this

reas

on,

thes

eda

taha

veno

tbe

enin

clud

edin

the

smoo

thin

gpr

oced

ure.

The

com

posi

tion

atth

eeu

tect

ic~cry

ohyd

ric!

poin

tin

the

NH 4

SC

N–

H 2O

syst

emha

sbe

enre

port

edin

othe

rdo

cum

ents

.14

,15

Inbo

thcu

men

ts,t

heeu

tect

icte

mpe

ratu

rew

asre

port

edto

be24

8K

,the

com

posi

tions

atth

eeu

tect

icpo

intb

eing

100

w15

41.9

5m

ass

%14an

d0

x 15

15m

ole

%15

(100

w15

42.7

mas

s%

;ev

alua

tor

!.F

orth

ese

two

docu

men

tsco

mpi

latio

nsh

eets

wer

eno

tpr

epar

edsi

nce,

exce

pteu

tect

icpo

ints

,no

othe

rda

taor

deta

ilsw

ere

repo

rted

.

fere

nces

:

.R

udor

f,A

nn.

Phy

s.C

hem

.136,

276

~186

9!.

.F.

Zhu

ravl

evan

dM

.N

.B

ychk

ova,

Zh.

Neo

rg.

Khi

m.

4,23

67~1

959!

.

.S

hnid

man

,J.

Phy

s.C

hem

.38

,90

1~1

934!

.

L.K

rupa

tkin

and

L.D

.Vo

robe

va,

Zh.

Obs

h.K

him

.45,

980

~197

5!.

5 M.

I.R

avic

h,V.

Ya.

Ket

kovi

ch,

and

I.S

.R

asso

nska

ya,

Izv.

Sek

tora

Fiz

.K

him

.Ana

l.17

,25

4~1

949!

.6 H

.W

.F

oote

,J.

Am

.C

hem

.S

oc.43,

1031

~192

1!.

7 P.S

.B

ogoy

avle

nski

i,Z

h.F

iz.

Khi

m.32

,20

35~1

958!

.8 A

.M

.B

aben

koan

dA

.M

.And

riano

v,U

krai

n.K

him

.Z

h.45,

1177

~197

9!.

9 A.

M.

Bab

enko

and

A.

M.A

ndria

nov,

Zh.

Neo

rg.

Khi

m.23,

2819

~197

8!.

10V.

G.

Skv

orts

ov,A

.K

.M

olod

kin,

R.

S.

Tsek

hans

kii,

Sh.

V.S

adet

dino

v,an

dF.

V.N

ikon

ov,

Zh.

Neo

rg.

Khi

m.

30,

826

~198

5!.

11S

h.V.

Sad

etdi

nov,

V.G

.S

kvor

tsov

,an

dR

.S

.Ts

ekha

nski

i,S

b.T

rudo

vY

aros

lav.

Gos

ud.

Ped

.In

st.,

No.

169,

72~1

978!

.12

V.J.

Occ

lesh

aw,

J.C

hem

.S

oc.

1892~1

934!

.13

L.S

.B

lesh

insk

aya,

K.

Sul

aim

anku

lov,

M.

D.

Dav

rano

v,an

dZ

.Yu

.Yu

nuso

va,

Dep

.D

oc.

VIN

ITI,

No.

120-

83~1

983!

.14

A.

M.

Vasi

liev,

Zh.

Rus

s.F

iz.

Khi

m.

Obs

h.42,

423

~191

0!.

15E

.K

orde

s,Z

.Ano

rg.A

llg.

Che

m.16

7,97

~192

7!.


6.6.

Am

mon

ium

Thi

ocya

nate

6.6.

1.E

valu

atio

nof

the

NH

4S

CN

–H

2O

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

J.H

ala,

Dep

artm

ent

ofIn

orga

nic

Che

mis

try,

Mas

aryk

Uni

vers

ity,

6113

7B

rno,

Cze

chR

epub

lic,A

ugus

t20

01.

Crit

ical

Eva

luat

ion

The

solu

bilit

yin

the

bina

ryN

H 4S

CN

–H 2

Osy

stem

asa

func

tion

ofte

mpe

ratu

reha

sbe

enre

port

edin

five

docu

men

ts.

Isot

herm

alm

etho

dw

asus

edby

Ru

¨ dor

f,1po

lyth

erm

alm

etho

dw

asus

edin

thre

ela

bora

torie

s,3

–5

and

one

set

ofda

taw

asob

tain

edby

grap

hica

lan

alyt

ical

met

hod.2

Inth

ese

docu

men

ts,

the

solu

bilit

yof

NH

4S

CN

was

repo

rted

over

the

tem

pera

ture

rang

eof

271

–34

4K

.In

addi

tion,

addi

tiona

ldat

aof

the

solu

bilit

yof

NH 4S

CN

inw

ater

atte

mpe

ratu

res

from

253

to30

3K

coul

dbe

extr

acte

dfr

omth

em

easu

rem

ents

onva

rious

tern

ary

syst

ems.6–

13F

rom

the

grap

hw

here

all

the

data

have

been

plot

ted

~Fig

.23

!a

reas

onab

leag

reem

ent

isse

enfo

rth

eso

lubi

lity

data

belo

w31

3K

.The

data

inth

iste

mpe

ratu

rera

nge

have

been

sum

mar

ized

inth

efo

llow

ing

tabl

e.E

xcep

tfo

rth

eth

ree

valu

em

arke

dw

ithan

aste

risk,

the

data

have

been

com

pute

rsm

ooth

edby

alin

ear

regr

essi

onto

afif

thor

der

poly

nom

ial.

Te To Th

the

in do 10 for

Re

1 F 2 E 3 L 4 I.


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Wat

er;

H 2O

;@7

732-

18-5#

L.S

hnid

man

,J.

Phy

s.C

hem

.38

,90

1–

6~1

934!

.

riabl

es:

Pre

pare

dB

y:

K:

286

–34

4.5

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

rea

mpe

ratu

re(t

/°C

)N

H4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(x1)

NH

4S

CN

(m1

/mol

kg2

1)b

13.0

059

.57

0.25

8819

.36

18.9

962

.20

0.28

0321

.62

26.3

364

.95

0.30

4324

.34

28.8

265

.93

0.31

3825

.42

36.3

668

.86

0.34

3529

.05

39.4

470

.05

0.35

6730

.73

46.9

272

.86

0.38

8535

.27

51.3

774

.53

0.40

9238

.44

52.5

074

.94

0.41

5439

.35

57.2

376

.63

0.43

7643

.08

62.4

678

.53

0.46

3748

.05

67.2

180

.18

0.48

9053

.15

71.5

381

.73

0.51

4558

.77

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler

from

the

auth

or’s

mas

s%

data

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lyth

erm

alm

etho

dus

ed.

Wei

ghed

quan

titie

sof

the

solv

ent

dso

lute

wer

ehe

ated

ina

seal

edtu

bero

tate

din

aw

ater

th,

and

the

tem

pera

ture

atw

hich

the

solid

phas

eha

dne

arly

appe

ared

was

note

d.T

heap

para

tus

desc

ribed

inS

unie

r1

was

ed.

Car

ew

asta

ken

inat

tain

ing

true

equi

libriu

mco

nditi

ons

the

solu

bilit

yte

mpe

ratu

reby

slow

heat

ing,

and

ensu

ring

the

pres

ence

ofsm

allc

ryst

als.2In

som

eca

ses,

ther

mos

tatin

gat

the

resp

ectiv

eso

lubi

lity

tem

pera

ture

for

about2

hw

asem

ploy

ed.

Ath

erm

omet

erce

rtifi

edby

the

Bur

eau

ofS

tand

ards

was

used

.

NH

4S

CN

,B

aker

C.

P.gr

ade,

was

twic

ecr

ysta

llize

dfr

omm

etha

nol.

Ano

nhyg

rosc

opic

prod

uct

with

am

eltin

gpo

int

of14

9.7

°Cw

asob

tain

ed.

Itw

asan

alyz

edfo

rN

H3

and

SC

N2by

dist

illat

ion

and

Volh

ard’

sm

etho

ds,

resp

ectiv

ely,

toyi

eld

22.4

0%6

0.06

%N

H 3an

d76

.29%

60.

05%

SC

N2.

Boi

led

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.01

K~a

utho

r!.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.A

.S

unie

r,J.

Phy

s.C

hem

.34,

2582

~193

0!.

2 L.S

hnid

man

,J.

Phy

s.C

hem

.37

,69

3~1

933!

.

123123JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

F.R

udor

ff,A

nn.

Phy

s.C

hem

.136,

276

–84

~186

9!.

Varia

bles

:P

repa

red

By:

T/K

:27

1–

293

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

NH

4S

CN

(g/1

00g

H 2O

)N

H4S

CN

(m1

/mol

kg2

1)c

22.

211

7.4

15.4

2

0b12

2.1

16.0

4

12.9

149.

919

.69

20b

162.

221

.31

20.8

164.

821

.65

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Inte

rpol

ated

valu

esob

tain

edby

the

auth

or;

repo

rted

also

inR

u¨ d

orff.

1

c Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.

The

salt

was

first

shak

enw

ithw

ater

toob

tain

aso

lutio

nsa

tura

ted

ata

tem

pera

ture

slig

htly

abov

eth

ede

sire

don

e.T

hen

the

solu

tion

was

allo

wed

toco

oldo

wn,

and

stan

dat

the

desi

red

tem

pera

ture

for

12h.

The

NH

4S

CN

cont

ent

was

dete

rmin

edin

aw

eigh

edpo

rtio

nof

the

satu

rate

dso

lutio

nby

titra

tion

with

stan

dard

AgN

O 3so

lutio

nag

ains

tK

2C

rO4

asth

ein

dica

tor.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 F.R

udor

ff,B

er.

Deu

tsch

.C

hem

.G

es.

2,68

–70

~186

9!.

Co

~1!

~2!

Va T/

Te a S b C Me

Po

an ba dis

us at

J

IG.2

4.P

hase

diag

ram

ofth

eN

H4S

CN

–H 2

Osy

stem

~a,b

,and

gst

and

for

the

corr

espo

ndin

gfo

rms

ofN

H4S

CN

,L

stan

dsfo

rso

lutio

n!.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

poly

ther

mal

met

hod

was

used

.N

ode

tails

wer

ere

port

edce

ptth

atin

mea

sure

men

tsab

ove

100

°Ccl

osed

vess

els

wer

eed

toav

oid

evap

orat

ion

ofw

ater

.S

epar

ate

expe

rimen

tsow

edth

atat

tem

pera

ture

ssl

ight

lyab

ove

100

°Con

lygl

igib

lefr

actio

n~ab

out

102

2%

)of

NH

4S

CN

was

mer

ized

toth

iour

ea,

whi

le1%

–1.

5%th

iour

eaw

asfo

rmed

lyat

tem

pera

ture

scl

ose

toth

em

eltin

gpo

int

ofth

esa

lt.

NH

4S

CN

,co

mm

erci

al,

chem

ical

lypu

repr

oduc

t,w

asre

crys

talli

zed,

drie

dat

120

°C,

and

kept

over

P2O

5in

ade

ssic

ator

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

n60.

5K

~aut

hors!

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

M.

I.R

avic

h,V.

Ya.

Ket

kovi

ch,

and

I.S

.R

asso

nska

ya,

Izv.

Sek

tora

Fiz

.K

him

.Ana

l.17,

254

–85

~194

9!.

Varia

bles

:P

repa

red

By:

T/K

:34

0–

422.

5J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

rean

dph

ase

diag

ram

ofth

eN

H4S

CN

–H 2

Osy

stem

~see

Fig

.24

!

Tem

pera

ture

t/°C

H2O

(100

w2

/mas

s%

)H

2O

(100

x 2/m

ol%

)N

H4S

CN

(100

w2

/mas

s%

)N

H4S

CNa

(100

x 2/m

ol%

)S

olid

phas

eb

6719

.89

51.2

280

.11

52.9

1A

7118

.53

49.0

081

.47

57.7

6A

72.5

17.5

647

.36

82.4

461

.68

A

76.5

16.3

445

.21

83.6

667

.26

A

8015

.39

43.3

584

.61

72.2

2A

8413

.93

40.6

186

.07

81.1

7A

86.5

13.0

638

.82

86.9

487

.45

A

8912

.31

37.2

387

.31

B

91.5

11.6

535

.78

88.3

5B

9311

.40

35.2

288

.60

B

96.5

10.6

933

.59

89.3

1B

103.

58.

7928

.81

91.2

1B

110

7.34

25.0

792

.66

B

119.

55.

3519

.27

94.6

5B

123

4.71

17.2

795

.29

C

135

2.57

10.0

297

.43

C

149.

5c—

—10

0C

a Cal

cula

ted

byco

mpi

ler.

b A:

g-N

H4S

CN

;B

:b-N

H4S

CN

;C

:a-N

H4S

CN

.c M

eltin

gpo

int

ofN

H 4S

CN

.

F Me

A ex us sh ne iso

on


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Wat

er;

H 2O

;@7

732-

18-5#

I.L.

Kru

patk

inan

dL.

D.V

orob

eva,

Zh.

Obs

h.K

him

.45,9

80–

4~1

975!

.

riabl

es:

Pre

pare

dB

y:

K:

322.

6–

348.

1J.

Ha

´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

rea

empe

ratu

re(t

/°C

)N

H4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)b

49.5

074

.80

38.9

9

60.2

578

.50

47.9

7

63.7

579

.45

50.7

9

64.5

079

.75

51.7

4

65.5

080

.25

53.3

8

66.0

080

.43

53.9

9

66.8

080

.97

55.9

0

68.5

081

.42

57.5

7

71.0

082

.03

59.9

7

75.0

083

.52

66.5

8

olid

phas

ew

asre

port

edto

beN

H4S

CN•

H2O

,@

#,in

alls

olut

ions

.al

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

poly

ther

mal

met

hod

was

used

,no

deta

ilsre

port

ed.

NH

4S

CN

,so

urce

not

spec

ified

,w

asdr

ied

at70

°Cbe

fore

use.

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

125125JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Wat

er;

H 2O

;@7

732-

18-5#

E.

F.Z

hura

vlev

and

M.

N.

Byc

hkov

a,Z

h.N

eorg

.K

him

.4,23

67–

75~1

959!

.

Varia

bles

:P

repa

red

By:

T/K

:27

3–

326

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

inw

ater

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)b

054

.515

.74

5.0

56.5

17.0

6

16.0

60.5

20.1

2

25.0

64.1

23.4

6

33.0

67.3

27.0

4

50.0

72.8

35.1

6

53.0

73.2

35.8

8

a Sol

idph

ase

was

NH 4S

CN

,@17

62-9

5-4#,

inal

lsol

utio

ns.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ies

wer

eob

tain

edby

grap

hica

lana

lytic

alm

etho

d.1,2

Ase

ries

ofm

ixtu

res

ofth

esa

ltan

dw

ater

cove

ring

the

field

sof

unsa

tura

ted

and

satu

rate

dso

lutio

nsw

ere

prep

ared

byw

eigh

ing.

Afte

req

uilib

rium

had

been

atta

ined

,re

frac

tive

inde

xes

ofth

eso

lutio

nsw

ere

mea

sure

d.T

hetr

ansi

tion

from

unsa

tura

ted

tosa

tura

ted

solu

tions

,i.e

.,th

eco

rres

pond

ing

solu

bilit

yva

lue,

was

obta

ined

asa

brea

kon

the

refr

activ

ein

dex

vers

usco

mpo

sitio

ngr

aph.

NH

4S

CN

,so

urce

nots

peci

fied,

was

recr

ysta

llize

dan

ddr

ied

over

anhy

drou

sC

aCl

2.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

2 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.

Co

~1!

~2!

Va T/ T

a S b C Me

A

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Am

mon

ia;

NH 3

;@7

664-

41-7#

W.

P.B

radl

eyan

dW

.B

.A

lexa

nder

,J.

Am

.C

hem

.S

oc.

34,

15–

24~1

912!

.

riabl

es:

Pre

pare

dB

y:

K:

182

–42

1J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–N

H 3sy

stem

NH

3

00w

2/m

ass

%)

Fre

ezin

gpo

int

(t/°

C)

NH

4S

CNa

(100

w1

/mas

s%

)N

H4S

CNa

(m1

/mol

kg2

1)

NH

3

(100

w2

/mas

s%

)

Fre

ezin

gpo

int

(t/°

C)

NH

4S

CNa

(100

w1

/mas

s%

)N

H4S

CNa

(m1

/mol

kg2

1)

014

810

0—

56.1

879

.843

.82

10.2

5

9.89

7790

.11

119.

756

.63

276

.843

.37

10.0

6

13.2

256

86.7

886

.24

57.4

32

75.8

42.5

79.

738

16.5

532

83.4

566

.24

57.7

72

7942

.33

9.60

3

17.6

223

82.3

861

.42

58.6

22

79.8

41.3

89.

274

19.4

010

.380

.60

54.5

859

.22

279

.840

.78

9.04

6

20.9

32

0.3

79.0

749

.63

59.2

92

79.8

40.7

19.

020

21.9

12

5.8

78.0

946

.82

60.0

72

79.8

39.9

38.

733

22.5

02

13.8

77.5

045

.25

60.7

32

84.7

39.2

78.

495

23.2

72

1876

.73

43.3

261

.53

286

.338

.47

8.21

4

23.9

42

2076

.06

41.7

461

.63

284

.338

.37

8.17

9

24.8

92

2275

.11

39.6

462

.33

287

37.6

77.

940

25.6

12

24.3

74.3

938

.16

63.0

52

87.2

36.9

57.

699

26.3

02

25.8

73.7

036

.81

64.5

52

87.3

35.4

57.

215

27.6

72

29.8

72.3

334

.34

65.6

02

88.3

34.4

06.

889

29.1

32

34.8

70.7

831

.96

66.1

12

89.3

33.8

96.

735

29.9

02

39.8

70.1

030

.80

66.4

02

90.8

33.6

06.

648

30.7

52

42.8

69.2

529

.59

66.4

12

91.3

33.5

96.

645

32.2

92

39.8

67.7

127

.55

66.7

92

9533

.21

6.53

2

34.0

12

39.2

65.9

925

.49

67.3

02

9332

.70

6.38

3

36.3

82

38.8

63.6

222

.97

67.9

32

91.8

32.0

76.

202

38.7

62

38.8

61.2

420

.76

68.2

52

90.3

31.7

56.

111

42.0

82

41.3

57.9

218

.08

68.8

42

8931

.16

5.94

6

44.0

82

4255

.92

16.6

769

.65

288

30.3

55.

725

45.4

02

4454

.60

15.8

071

.00

285

.729

.00

5.36

6

47.3

32

47.2

52.6

714

.62

73.7

72

82.7

26.2

34.

671

48.7

62

52.2

51.2

413

.81

76.1

82

81.3

23.8

24.

108

49.7

52

5750

.25

13.2

778

.75

279

21.2

53.

545

51.0

82

60.6

48.9

212

.58

79.3

82

79.2

20.6

23.

413

52.2

02

65.2

47.8

011

.98

83.1

82

78.7

16.8

22.

656

53.9

62

70.8

46.0

411

.21

86.7

82

7813

.22

2.00

1

54.6

52

72.8

45.3

510

.90

90.0

12

779.

991.

458

54.9

02

7345

.10

10.7

993

.50

276

.96.

500.

9133

55.1

32

75.7

44.8

710

.69

94.7

82

76.8

5.22

0.72

35

55.5

22

7744

.48

10.5

294

.90

276

.75.

100.

7060

55.9

12

79.3

44.0

910

.36

100

276

.2—

—

a Cal

cula

ted

byco

mpi

ler.

Equ

ilibr

ium

solid

phas

esan

dth

eir

exis

tenc

ere

gion

sar

esh

own

inth

eph

ase

diag

ram

~Fig

.25

!as

A:

NH 4

SC

N•N

H3

;B

:NH

4S

CN

•3

NH

3;

C:N

H4S

CN•

6N

H3

;D

:NH

4S

CN•

7N

H3

;E

:N

H4S

CN•

8N

H3

.T

heau

thor

sst

ated

that

thei

rda

taw

ere

not

conc

lusi

veab

out

the

hept

aam

mon

iate

,as

wel

las

abou

tN

H4S

CN•

6.5N

H3

or2

NH

4S

CN•

13N

H3

.A

ppro

xim

ate

valu

esof

mel

ting

poin

tsof

amm

onia

tes

A,

B,

C,

D,

and

Ear

e216

°C~m

etas

tabl

e!,2

38°C

,276

°C,2

84°C

,an

d287

°C,

resp

ectiv

ely.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Sul

fur

diox

ide;

SO 2

;@7

446-

09-5#

G.

Jand

eran

dW

.R

uppo

lt,Z

.P

hys.

Che

m.

179,

43–

50~1

937!

.

Varia

bles

:P

repa

red

By:

T/K

:27

3J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

H 4S

CN

inliq

uid

sulfu

rdi

oxid

ew

asre

port

edto

be46

.8g

salt

in10

0g

solv

ent

at0

°C(

m1

/mol

kg2

15

6.14

8;co

mpi

ler!.

Add

ition

alin

form

atio

n:H

igh,

thou

ghun

spec

ified

solu

bilit

yof

NH

4S

CN

inliq

uid

SO 2

was

repo

rted

inF

riedr

ichs2

and

Fra

nklin

.3

Sat

urat

edso

lutio

nsw

ere

repo

rted

tobe

yello

win

colo

ran

dve

ryvi

scou

s.2

Ano

ther

liqui

dph

ase

sepa

rate

dfr

omth

esa

tura

ted

solu

tions

at10

0°C

asa

yello

woi

l.3

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

d.A

bout

10g

SO

2,

care

fully

drie

d,w

aseq

uilib

rate

dw

ithex

cess

solid

at0

°Cin

wat

er–

ice

bath

ina

thre

e-co

mpa

rtm

ent

glas

sve

ssel

inw

hich

equi

libra

ting

and

sam

plin

gco

mpa

rtm

ents

wer

ese

para

ted

bya

com

part

men

tco

ntai

ning

glas

s/w

oolfi

lter.

Equ

ilibr

atio

nw

aspe

rfor

med

for

unsp

ecifi

ed,

prol

onge

dpe

riod

oftim

eun

der

freq

uent

shak

ing.

Afte

req

uilib

rium

had

been

atta

ined

,th

eve

ssel

was

turn

edup

side

dow

n,an

dth

esa

tura

ted

solu

tion

was

filte

red

into

the

empt

ysa

mpl

ing

com

part

men

t,w

hich

was

subs

eque

ntly

cool

edan

dse

aled

off.

Afte

rw

eigh

ing

the

com

part

men

tw

ithth

esa

mpl

e,S

O 2w

asal

low

edto

evap

orat

e,th

ere

sidu

ew

asw

eigh

ed,

diss

olve

din

wat

er,

and

the

cont

ent

ofth

esa

ltw

asde

term

ined

.M

etho

dof

anal

ysis

was

not

spec

ified

.

NH

4S

CN

,so

urce

not

spec

ified

,w

asca

refu

llydr

ied

befo

reus

e.C

omm

erci

ally

avai

labl

eS

O 2w

aspu

rified

bypa

ssin

git

thro

ugh

conc

entr

ated

H 2SO

4an

dov

eras

best

osw

ool,

and

drie

dby

usin

gP 2

O5

.S

peci

ficco

nduc

tivity

ofth

epr

oduc

tw

as4.

53

102

7V

21

~Jan

der

and

Wic

kert!.1

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 G.

Jand

eran

dK

.W

icke

rt,

Z.

Phy

s.C

hem

.17

8,57

~193

6!.

2 F.F

riedr

ichs

,Z

.Ano

rg.A

llgem

.C

hem

ie84,

373

~191

4!.

3 E.

C.

Fra

nklin

,J.

Phy

s.C

hem

.15,

687

~191

1!.

Co

~1!

~2!

Va T/

(1


reap

pear

ance

ofcr

ysta

lsw

asbr

ief,

ther

ew

asno

evid

ence

ofsu

perc

oolin

gin

the

solu

tion.

Tem

pera

ture

was

read

bym

eans

ofa

plat

inum

resi

stan

ceth

erm

omet

erpr

otec

ted

bya

thin

-wal

led

glas

stu

be.

The

ther

mom

eter

was

stan

dard

ized

bym

eans

ofic

ean

dC

O 2–et

her

mix

ture

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Am

mon

ia;

NH 3

;@7

664-

41-7#

H.

W.

Foo

tean

dM

.A

.H

unte

r,J.

Am

.C

hem

.S

oc.

42,

69–

78~1

920!

.

riabl

es:

Pre

pare

dB

y:

K:

276

–32

3J.

Ha´ la

Exp

erim

enta

lDat

aF

reez

ing

poin

tm

easu

rem

ents

inth

eN

H4S

CN

–N

H 3sy

stem

a

mpe

ratu

re(t

/°C

)N

H3

(100

w2

/mas

s%

)N

H4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)b

2.8c

23.1

376

.87

43.6

6

10.0

d22

.51

77.4

945

.22

20.0

d21

.64

78.3

647

.57

23.3

c21

.48

78.5

248

.02

30.0

d19

.99

80.0

152

.58

31.0

c19

.86

80.1

453

.01

33.0

c19

.24

80.7

655

.14

40.0

d18

.50

81.5

057

.87

49.8

c16

.67

83.3

365

.67

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler.

olyt

herm

alm

etho

d.ap

orpr

essu

rem

easu

rem

ent.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

poly

ther

mal

met

hod

and

vapo

rpr

essu

rem

easu

rem

ents

wer

eed

.In

the

poly

ther

mal

met

hod,

aw

eigh

edqu

antit

yof

alu

tion

ofth

esa

ltin

amm

onia

,pr

epar

edby

pass

ing

NH

3ga

ser

the

solid

salt,

havi

nga

know

nco

mpo

sitio

n,w

asse

aled

intu

bew

ithw

eigh

edam

ount

ofN

H 4SC

N.

The

mix

ture

was

ated

until

alld

isso

lved

,th

enco

oled

rapi

dly

tofo

rmsm

all

stal

s.O

nhe

atin

gth

em

ixtu

resl

owly

ina

wat

erba

th,

the

pera

ture

was

dete

rmin

edat

whi

chth

ela

stof

the

crys

tals

diss

olve

d.S

ome

solu

bilit

yva

lues

wer

eob

tain

eddu

ring

vapo

rpr

essu

rem

easu

rem

ents

whe

reN

H3

gas

ata

know

npr

essu

rew

aspa

ssed

thro

ugh

akn

own

amou

ntof

the

salt

ina

ther

mos

tate

dU

tube

until

nofu

rthe

rch

ange

inw

eigh

toc

curr

ed.

The

vapo

rpr

essu

reof

the

satu

rate

dso

lutio

nw

asob

tain

edby

redu

cing

the

pres

sure

until

NH

4S

CN

crys

tals

just

bega

nto

appe

ar,

and

then

incr

easi

ngit

slig

htly

until

they

just

diss

olve

d.

NH

4S

CN

,a

C.P

.pro

duct

,was

recr

ysta

llize

dan

ddr

ied.

Dry

NH

3

gas

was

obta

ined

byw

arm

ing

aco

ncen

trat

edaq

ueou

sso

lutio

nof

amm

onia

and

pass

ing

the

gas

thro

ugh

tow

ers

cont

aini

ngqu

ickl

ime

and

fuse

dca

ustic

pota

sh.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

the

auth

ors

stat

edth

atin

divi

dual

resu

ltsw

ere

not

with

outa

ppre

ciab

leer

ror

whi

ch,h

owev

er,w

asno

tspe

cifie

d,an

dth

atth

etw

om

etho

dsyi

elde

dre

sults

agre

eing

reas

onab

ly.

127127JIRI HALA


FIG

.25

.P

hase

diag

ram

ofth

eN

H4S

CN

–N

H 3sy

stem

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Apo

lyth

erm

alm

etho

dw

asus

ed.

Mea

sure

men

tsw

ere

carr

ied

out

ingl

ass

tube

sco

ntai

ning

wei

ghed

amou

nts

ofth

esa

ltan

dco

nden

sed

NH 3

.T

hetu

bes

wer

ecl

osed

with

asp

ecia

lcap

and

cool

edin

anal

coho

l–et

her

mix

ture

until

the

solu

tion

froz

epa

rtly

.~A

bath

ofw

arm

wat

erw

asus

edat

tem

pera

ture

sab

ove

room

tem

pera

ture

.!

Und

eref

fect

ive

stirr

ing

the

bath

and

spin

ning

the

tube

,th

eba

thw

asal

low

edto

war

mup

slow

lyan

dth

ete

mpe

ratu

reof

disa

ppea

ranc

eof

the

last

crys

tals

was

reco

rded

,At

leas

tth

ree

read

ings

wer

eta

ken

atea

chco

ncen

trat

ion.

Ifth

ein

terv

albe

twee

ndi

sapp

eara

nce

and

NH

4S

CN

,K

ahlb

aum

,w

aspu

rified

byse

vera

lcr

ysta

lliza

tions

from

wat

er,

grou

nd,

and

kept

over

conc

entr

ated

H2S

O4

.T

hepr

oduc

tm

elte

dat

148

°C.

NH 3

gas

was

obta

ined

from

pure

conc

entr

ated

amm

oniu

mhy

drox

ide.

Itw

asdr

ied

over

caus

ticpo

tash

and

byw

ashi

ngw

ithits

own

liqui

dat

itsno

rmal

boili

ngte

mpe

ratu

re.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

Va T/

Te a S b C c P d V Me

A us so ov a he cry

tem

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Met

hano

l;C

H 4O

;@6

7-56

-1#

L.S

hnid

man

,J.

Phy

s.C

hem

.38

,90

1–

6~1

934!

.

riabl

es:

Pre

pare

dB

y:

K:

298

–33

8J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

asa

func

tion

ofte

mpe

ratu

rea

mpe

ratu

re(t

/°C

)N

H4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(x1)

NH

4S

CN

(m1

/mol

kg2

1)b

24.5

837

.11

0.19

897.

752

32.9

440

.05

0.21

948.

776

44.8

044

.70

0.25

3810

.62

54.7

649

.30

0.29

0412

.77

64.5

554

.55

0.33

5615

.77

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler

from

the

mas

s%

data

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lyth

erm

alm

etho

dus

ed.

Wei

ghed

quan

titie

sof

the

solv

ent

dsa

ltw

ere

heat

edin

ase

aled

tube

rota

ted

ina

wat

erba

th,

dth

ete

mpe

ratu

reat

whi

chth

eso

lidph

ase

had

near

lyap

pear

edw

asno

ted.

The

appa

ratu

sde

scrib

edin

Sun

ier

1w

ased

.C

are

was

take

nin

atta

inin

gtr

ueeq

uilib

rium

cond

ition

sth

eso

lubi

lity

tem

pera

ture

bysl

owhe

atin

gan

den

surin

gth

ees

ence

ofsm

allc

ryst

als.2In

som

eca

ses

ther

mos

tatin

gat

the

spec

tive

solu

bilit

yte

mpe

ratu

refo

rab

out2

hw

asem

ploy

ed.

ther

mom

eter

cert

ified

byth

eB

urea

uof

Sta

ndar

dsw

asus

ed.

NH

4S

CN

,B

aker

C.

P.gr

ade,

was

twic

ecr

ysta

llize

dfr

omm

etha

nol.

Ano

nhyg

rosc

opic

prod

uct

with

mel

ting

poin

tat

149.

7°C

was

obta

ined

.It

was

anal

yzed

for

NH

3an

dS

CN2

bydi

still

atio

nan

dVo

lhar

d’s

met

hod,

resp

ectiv

ely,

toyi

eld

22.4

0%6

0.06

%N

H 3an

d76

.29%

60.

05%

SC

N2.

Met

hano

l,B

aker

C.

P.,

was

purifi

edac

cord

ing

toS

hnid

man

.2

Itw

asre

fluxe

dtw

ice

with

lime

over

6h

and

then

dist

illed

thro

ugh

asi

x-bu

lbLe

Bel

–H

enni

ger

colu

mn.

The

frac

tion

boili

ngpo

int

with

in64

.636

0.01

°Cw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.01

K~a

utho

r!.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.A

.S

unie

r,J.

Phy

s.C

hem

.34,

2582

~193

0!.

2 L.S

hnid

man

,J.

Phy

s.C

hem

.37

,69

3~1

933!

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Am

mon

ia;

NH 3

;@7

664-

41-7#

H.

Hun

t,J.

Am

.C

hem

.S

oc.54

,35

09–

12~1

932!

.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aT

hree

resu

ltsw

ere

repo

rted

for

the

solu

bilit

yof

NH

4S

CN

:31

1.9,

312.

4,an

d31

1.6

gin

100

gso

lven

tat

25°C

.F

rom

the

mea

nva

lue

of31

2.0

gsa

lt/10

0g

solv

enta

ndth

ede

nsity

ofliq

uid

amm

onia

of0.

604

gcm

23

at25

°C,t

heau

thor

calc

ulat

edth

eso

lubi

lity

tobe

188.

45g

NH

4S

CN

in10

0cm

3so

lven

t.C

ompi

ler

calc

ulat

edm15

40.9

9m

olkg

21.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.A

mm

onia~1

0–

25g!

was

equi

libra

ted

with

the

salt

inth

ebo

ttom

part

ofa

seal

ed,

two-

com

part

men

tP

yrex

tube

.T

heco

mpa

rtm

ents

wer

ese

para

ted

from

each

othe

rw

itha

narr

owne

ck.

The

salt

was

intr

oduc

edin

toth

etu

bebe

fore

seal

ing

itof

fin

asm

allc

upcl

osed

with

ave

rycl

osel

yw

oven

cotto

ncl

oth.

The

latte

rpe

rmitt

edth

esa

ltto

diss

olve

the

salt

hold

ing

back

the

solid

atth

esa

me

time.

The

syst

emw

aseq

uilib

rate

dfo

r1

–3

wee

ksw

ithoc

casi

onal

shak

ing.

The

nth

etu

bew

asin

vert

edin

the

bath

and

allt

heso

lutio

ndr

aine

din

toth

eem

pty

com

part

men

t,w

hich

was

cool

edan

dse

aled

off.

Whe

nit

reac

hed

room

tem

pera

ture

itw

asdr

ied

and

wei

ghed

,th

eam

mon

iaal

low

edto

boil

off,

the

tube

with

the

salt

war

med

until

allo

dor

ofN

H 3w

asgo

ne,

and

the

salt

was

wei

ghed

.

NH

4S

CN

,B

aker

C.

P.pr

oduc

t,w

asre

crys

talli

zed

and

care

fully

drie

d.C

omm

erci

ally

avai

labl

ean

hydr

ous

NH

3w

asal

low

edto

stan

dov

erm

etal

licso

dium

for

seve

ralw

eeks

befo

reus

e.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.02

5K

~aut

hor!.

Sol

ubili

ty:

5%~a

utho

r!.

Co

~1!

~2!

Va T/

Te a S b C Me

Po

an an dis

us at pr re A


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Eth

anol

;C 2

H6O

;@6

4-17

-5#

L.S

hnid

man

,J.

Phy

s.C

hem

.38

,90

1–

6~1

934!

.

riabl

es:

Pre

pare

dB

y:

K:

291

–33

7J.

Ha´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

inet

hano

las

afu

nctio

nof

tem

pera

ture

a

mpe

ratu

re(t

/°C

)N

H4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(x1)

NH

4S

CN

(m1

/mol

kg2

1)b

18.4

519

.07

0.12

473.

096

33.2

521

.54

0.14

213.

607

36.9

322

.16

0.14

693.

740

43.3

623

.46

0.15

654.

027

57.6

226

.72

0.18

074.

790

64.2

028

.63

0.19

535.

270

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler

from

the

mas

s%

data

.

ditio

nal

info

rmat

ion:

Sol

utio

nsof

NH 4S

CN

inet

hano

ltu

rned

yello

won

stan

ding

,on

expo

sure

tolig

ht,

and

inth

ehe

atin

gpe

riod,

icat

ing

som

ere

actio

nbe

twee

nth

etw

oco

mpo

nent

s.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

lyth

erm

alm

etho

dus

ed.

Wei

ghed

quan

titie

sof

the

solv

ent

dsa

ltw

ere

heat

edin

ase

aled

tube

rota

ted

ina

wat

erba

th,

dth

ete

mpe

ratu

reat

whi

chth

eso

lidph

ase

had

near

lyap

pear

edw

asno

ted.

The

appa

ratu

sde

scrib

edin

Sun

ier

1w

ased

.W

hen

the

wor

kw

asca

rrie

dou

tw

ithsm

allc

ryst

als

they

reso

fine

asto

give

aco

lloid

al,

turb

idop

ales

cent

solu

tion,

dth

eso

lubi

lity

tem

pera

ture

sw

ere

over

step

ped

by1°

orre

.It

was

,th

eref

ore,

nece

ssar

yto

cool

the

solu

tions

slow

lyto

favo

rth

efo

rmat

ion

ofla

rge

crys

tals

.T

rue

solu

bilit

ype

ratu

res

coul

dbe

obta

ined

with

larg

ecr

ysta

lsw

ith10

min

rmos

tatin

g.A

ther

mom

eter

cert

ified

byth

eU

.S

.B

urea

uof

Sta

ndar

dsw

asus

ed.

NH

4S

CN

,B

aker

C.

P.gr

ade,

was

twic

ecr

ysta

llize

dfr

omm

etha

nol.

Ano

nhyg

rosc

opic

prod

uct

with

mel

ting

poin

tat

149.

7°C

was

obta

ined

.It

was

anal

yzed

for

NH

3an

dS

CN2

bydi

still

atio

nan

dVo

lhar

d’s

met

hod,

resp

ectiv

ely,

toyi

eld

22.4

0%6

0.06

%N

H 3an

d76

.29%

60.

05%

SC

N2.

Eth

anol

was

purifi

edac

cord

ing

toS

hnid

man

.2

Itw

asre

fluxe

dtw

ice

with

lime

over

6h

and

then

dist

illed

thro

ugh

asi

x-bu

lbLe

Bel

–H

enni

ger

colu

mn.

The

frac

tion

boili

ngpo

int

with

in78

.4360.

02°C

was

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.01

K~a

utho

r!.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.A

.S

unie

r,J.

Phy

s.C

hem

.34,

2582

~193

0!.

2 L.S

hnid

man

,J.

Phy

s.C

hem

.37

,69

3~1

933!

.

129129JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Ace

toni

trile

;C 2

H3N

;@7

5-05

-8#

A.

Nau

man

n,B

er.4

7,24

7–

56~1

914!

.

Varia

bles

:P

repa

red

By:

T/K

:29

1J.

Hala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

H 4S

CN

isre

port

edto

be0.

0752

gin

1g

solv

ent

at18

°C~com

pile

r:m

15

0.98

8m

olkg

21,

100

w1

57.

00m

ass

%).

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Exc

ess

solid

was

shak

enw

ithth

eso

lven

tin

aw

ater

ther

mos

tat

for

2–

6h.

Atta

inm

ent

ofeq

uilib

rium

was

asce

rtai

ned

byoc

casi

onal

anal

ysis

ofth

eliq

uid

phas

e.T

hesa

tura

ted

solu

tions

wer

era

pidl

yfil

tere

din

tow

eigh

ing

vess

els

kept

at18

°C,

and

the

SC

N2

cont

ent

was

dete

rmin

edtit

rimet

rical

ly.

NH

4S

CN

,so

urce

and

purit

yno

tspe

cifie

d,w

asdr

ied

ina

vacu

umde

ssic

ator

befo

reus

e.A

ceto

nitr

ile~Kah

lbau

m!w

aspu

rified

from

acet

amid

eby

allo

win

gth

eso

lven

tto

stan

dfo

r3

–4

wee

ksov

erP 2

O5

,an

dsu

bseq

uent

dist

illat

ion.

The

frac

tion

boili

ngpo

int

at81

.6°C

was

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.T

here

port

edso

lubi

lity

valu

eis

the

mea

nof

two

dete

rmin

atio

ns,

indi

vidu

alre

sults

wer

eno

tre

port

ed.

Co

~1!

~2!

Va T/

Te a S b C Ad

ind

Me

Po

an an dis

us we

an mo

as tem

the

J

ng re-

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

onni

umth

iocy

anat

e;N

H 4SC

N;@

1762

-95-

4#T

ri-n-

buty

l~pho

spha

te!;C

12H

27O

4P

;@1

26-7

3-8#

J.H

alaan

dD

.G

.T

uck,

Can

ad.

J.C

hem

.48

,28

43–

6~19

70!.

riabl

es:

Pre

pare

dB

y:

K:

295

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofN

H 4S

CN

intr

i-n-b

utyl~

phos

phat

e!is

repo

rted

tobe

11.6

gsa

ltin

100

gso

lven

tat

22°C

(m

15

1.52

4m

olkg

21;

mpi

ler!.

Add

ition

alin

form

atio

n:F

rom

the

ratio

ofth

eso

lven

tan

dN

H4S

CN

conc

entr

atio

nsof

2.46

inth

esa

tura

ted

solu

tions

the

auth

ors

gges

ted

that

the

satu

rate

dso

lutio

nco

ntai

ned

the

diso

lvat

eof

the

salt,

NH

4S

CN•

2C

12H

27O

4P

,w

ithso

me

free

solv

ent.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.A

nex

cess

ofth

esa

ltw

asak

enov

erni

ght

with

5m

Ldr

yso

lven

t.P

relim

inar

ype

rimen

tssh

owed

that

this

was

suffi

cien

tfo

req

uilib

rium

tore

ache

d.S

ampl

esof

the

satu

rate

dso

lutio

nsw

ere

with

draw

nou

gha

sint

er,

dilu

ted

with

acet

one,

and

anal

yzed

for

the

ocya

nate

cont

ent

bytit

ratio

nag

ains

tA

gNO

3st

anda

rdlu

tion.

Bla

nktit

ratio

nssh

owed

that

asm

allc

orre

ctio

nw

asqu

ired

beca

use

ofth

epr

esen

ceof

tri-n

-but

yl~p

hosp

hate!.

NH

4S

CN

,F

ishe

rS

cien

tific

Co.

,w

asus

edw

ithou

tfu

rthe

rpu

rifica

tion.

Tri-

n-bu

tyl~p

hosp

hate!

~Fis

her

Sci

entifi

cC

o.!w

aspu

rified

byre

fluxi

ngit

with

0.5%

caus

ticso

daso

lutio

n,fo

llow

edby

stea

mdi

still

atio

n.T

hepr

oduc

twas

drie

dfir

stw

ithan

hydr

ous

MgS

O4

,an

dfin

ally

vacu

um/d

ried

at50

°Cin

ast

ream

ofdr

yni

trog

enga

s.1

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:6

0.1

gsa

lt/10

0g

solv

ent~a

utho

rs!.

Ref

eren

ces:

1 D.

G.

Tuc

k,J.

Che

m.

Soc

.27

83~19

58!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

N,N

-die

thyl

-eth

anam

ine~t

rieth

ylam

ine!;

C6H

15N

;@1

21-4

4-8#

L.D

.Vor

obev

aan

dI.

L.K

rupa

tkin

,Fa

zovy

eR

avn

ove

sia~P

hase

Equ

ilibr

ia!,

~Kal

inin

.G

osud

.U

niv.

,K

alin

in,

1974!

,pp

.18

–25

.

Varia

bles

:P

repa

red

By:

T/K

:29

3–

298

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

intr

ieth

ylam

ine

asa

func

tion

ofte

mpe

ratu

rea

Tem

pera

ture

(t/°

C)

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)b

2053

.45

15.0

8

2355

.60

16.4

5

2557

.50

17.7

7

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Add

ition

alin

form

atio

n:W

hen

satu

rate

dso

lutio

nsof

NH

4S

CN

intr

ieth

yalm

ine

wer

edi

lute

dw

ithtr

ieth

ylam

ine,

ana

rrow

hom

ogen

eous

regi

onof

unsa

tura

ted

solu

tions

was

first

obse

rved

.O

nfu

rthe

rdi

lutio

n,th

esy

stem

sepa

rate

din

totw

oliq

uid

phas

es,

the

corr

espo

ndi

NH

4S

CN

conc

entr

atio

nsbe

ing

42.5

0,44

.50,

and

46.0

0m

ass

%at

20,

23,

and

25°C

,re

spec

tivel

y.B

ased

onin

frar

edsp

ectr

alm

easu

men

tsth

eau

thor

sas

sum

edth

ata

com

plex

@(C

2H

5) 3

N...

H4N

1#S

CN2

was

bein

gfo

rmed

inth

esy

stem

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.N

H4S

CN

,ch

emic

ally

pure

,w

asdr

ied

toco

nsta

ntw

eigh

tbe

fore

use.

Trie

thyl

amin

e,so

urce

not

spec

ified

,w

asdr

ied

over

anhy

drou

sM

gSO 4

,an

ddi

still

edtw

ice.

The

prod

uctu

sed

boili

ngpo

int

at89

.2°C

,an

dsh

owed

d.of

0.72

32g

cm23

at20

°C.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

Va T/

co su Me

An

sh ex be thr

thi

so re


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Am

mon

ia;

NH 3

;@7

664-

41-7#

Wat

er;

H 2O

;@7

732-

18-5#

H.

W.

Foo

te,

J.A

m.

Che

m.

Soc

.43,

1031

–8~

1921

!.

riabl

es:

Pre

pare

dB

y:

K:

283

–30

30

w2

/mas

s%

:0

–22

.70

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

inaq

ueou

sso

lutio

nsof

amm

onia

atth

ree

tem

pera

ture

sa

mpe

ratu

re(t

/°C

)

NH

3

(100

w2

/m

ass

%)

NH

4S

CN

(100

w1

/m

ass

%)

NH

4S

CN

(m1

/mol

kg2

1)b

Tem

pera

ture

(t/°

C)

NH

3

(100

w2

/m

ass

%)

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)b

100

58.2

318

.31

300

66.2

625

.80

3.49

59.4

02.

8567

.28

6.86

61.0

35.

7968

.30

9.23

62.6

18.

3869

.48

12.3

365

.29

12.1

871

.84

14.5

366

.67

14.4

674

.00

17.1

269

.70

17.0

476

.63

19.7

872

.84

20.0

179

.99

52.5

2

22.7

077

.30

44.7

4

200

62.5

421

.93

3.53

63.5

7

6.23

64.9

9

8.57

66.2

0

11.1

967

.57

12.5

469

.06

15.6

571

.89

18.0

774

.15

21.3

578

.65

48.4

0

H4S

CN

,@17

62-9

5-4#,

was

the

equi

libriu

mso

lidph

ase

inal

lsat

urat

edso

lutio

ns.

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

d1w

asus

ed.

Mea

sure

men

tsw

ere

carr

ied

out

inth

erm

osta

ted

glas

s-st

oppe

red

bottl

es.

Equ

ilibr

ium

was

reac

hed

after

1h

shak

ing.

Sam

ples

for

anal

ysis

wer

ew

ithdr

awn

thro

ugh

apl

ugof

glas

sw

ooli

nto

aw

eigh

edsp

ecim

entu

beun

der

cool

ing

toav

oid

loss

esof

NH

3.

Am

mon

iaw

asde

term

ined

bytit

ratio

nus

ing

cong

ored

asin

dica

tor,

SC

N2by

Volh

ard’

sm

etho

d.S

olid

phas

esw

ere

chem

ical

lyan

alyz

ed.

NH

4S

CN

,so

urce

not

spec

ified

,ch

emic

ally

pure

,w

asre

crys

talli

zed

and

drie

dun

tilit

show

edno

trac

eof

moi

stur

e.D

ryN

H3

gas

was

obta

ined

byw

arm

ing

aco

ncen

trat

edaq

ueou

sso

lutio

nof

amm

onia

and

pass

ing

the

gas

thro

ugh

tow

ers

cont

aini

ngqu

ickl

ime

and

fuse

dca

ustic

pota

sh.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 H.

W.

Foo

tean

dS

.R

.B

rinkl

ey,

J.A

m.

Che

m.

Soc

.43

,10

81~1

921!

.

131131JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

onni

umth

iocy

anat

e;N

H 4SC

N;@

1762

-95-

4#~2

!S

olve

nts

I.L.

Kru

patk

in,

L.D

.Vo

robe

va,

V.P.

Mas

khul

ia,

and,

M.

E.

Vese

lova

,Z

h.O

bsh.

Khi

m.45

,98

5–

90~1

975!

.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

infu

rfur

alan

dm

ethy

leth

ylke

tone

at25

°Ca

Sol

vent

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)b

2-fu

ranc

arbo

xald

ehyd

e~fur

fura

l!;C

5H

4O

2;

@98-

01-1

#10

.30

1.50

9

2-bu

tano

ne~m

ethy

leth

ylke

tone!

;C

4H

8O

;@7

8-93

-3#

10.7

01.

574

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.N

H4S

CN

,so

urce

and

purit

yno

tsp

ecifi

ed,

was

drie

dat

70°C

toco

nsta

ntw

eigh

tbe

fore

use.

The

solv

ents

wer

epu

rified

byst

anda

rdm

etho

ds,

1an

dth

eir

purit

yw

asch

ecke

dth

roug

hph

ysic

alco

nsta

nts.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.W

eisb

erge

r,E

.Pro

skan

zer,

J.R

iddi

ck,a

ndE

.Too

ps,

Org

an

icS

olv

en

ts~R

ussi

antr

ansl

atio

nof

Eng

lish

ed.

!~I

LP

ubl.

Hou

se,

Mos

cow

,19

58!,

pp.

351,

361.

Co

~1!

~2!

~3!

Va T/

10 Te a N b C

J

Pol

ythe

rmal

mea

sure

men

tsfo

rth

ete

rnar

ysy

stem

corr

espo

ndin

gto

the

sect

ion

of15

.00

mol

%N

H4N

O31

85.0

0m

ol%

NH 4

SC

Nb

H2O

(100

x 3/m

ol%

)F

reez

ing

poin

tte

mpe

ratu

re(t

/°C

)S

olid

phas

ea

80.5

12

17.0

A

82.2

22

21.9

A

83.3

52

25.0

A

84.3

92

27.3

A1D

85.2

62

25.4

D

86.3

02

24.0

D

92.3

32

13.8

D

95.8

42

7.2

D

Com

posi

tion

ofin

varia

ntpo

ints

NH

4S

CN

00x 1

/mol

%)

NH

4N

O3

(100

x 2/m

ol%

)Te

mpe

ratu

re(t

/°C

)S

olid

phas

esa

39.5

38.4

68A1

B1

C

12.9

5.7

230

A1

B1

D

:N

H4S

CN

,@17

62-9

5-4#

~mon

oclin

icat

60an

d80

°C,

rhom

boed

rala

t90

°C;

crys

talf

orm

at0

and

30°C

not

repo

rted

;B

:N

H4N

O3

,48

4-52

-2#~t

rigon

alat

60°C

,a-r

hom

boed

rala

t80

and

90°C

;cr

ysta

lfor

mat

0an

d30

°Cno

tre

port

ed;

C:

solid

solu

tions

ofN

H4S

CN

ndN

H 4N

O3

ofva

riabl

eco

mpo

sitio

n;D

:Ic

e,@77

32-1

8-5#

~see

Fig

.26

!.oo

ling

curv

esw

ere

also

obta

ined

for

the

sect

ion

corr

espo

ndin

gto

59.8

0m

ol%

NH

4N

O31

40.2

0m

ol%

NH 4

SC

N,

whe

reN

H 4N

O3

ndic

ew

ere

iden

tified

asth

eso

lidph

ases

.

IG.

26.

Sol

ubili

typo

lyth

erm

for

the

NH 4N

O3–

NH

4S

CN

–H 2

Osy

stem

.(B

1:

cubi

cN

H 4N

O3

;B

2:

trig

onal

NH 4

NO

3;

B3

:-r

hom

boed

ral

NH 4

NO

3;

B4

:b

-rho

moe

dral

NH 4

NO

3;

B5

:he

xago

nal

NH 4

NO

3;

A2

;rh

ombo

edra

lN

H 4S

CN

;A 3

:m

onoc

linic

H4S

CN

;C

:so

lidso

lutio

ns;

D:

ice!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

At

0°C

and

abov

eth

esy

stem

was

stud

ied

isot

herm

ally

.Am

ixtu

reof

solid

salts

~8–

10g!

was

diss

olve

din

wat

erco

mpl

etel

yat

ate

mpe

ratu

reab

ove

the

desi

red

one,

then

the

flask

was

plac

edin

ath

erm

osta

tan

dke

ptat

the

desi

red

tem

pera

ture

tole

teq

uilib

rium

bees

tabl

ishe

d,an

deq

uilib

rium

solid

phas

esto

crys

talli

ze.

Thi

sto

ok12

hat

0°C

,an

d5

hab

ove

0°C

.At

0an

d30

°C,

sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

with

api

pette

preh

eate

dan

d/or

prec

oole

dto

the

corr

espo

ndin

gte

mpe

ratu

re.A

smal

lgla

ssU

tube

with

aw

adof

glas

sw

ooli

nsid

ew

asat

tach

edto

the

pipe

tte.A

t60

°Can

dab

ove,

sam

ples

wer

eta

ken

into

apr

ehea

ted

glas

stu

be.

The

sam

ples

wer

eal

low

edto

crys

talli

zeon

cool

ing

toro

omte

mpe

ratu

rean

dw

eigh

edin

aw

eigh

ing

bottl

e.T

hesa

mpl

esw

ere

anal

yzed

for

NH 41

acid

imet

rical

lyaf

ter

dist

illin

gof

fam

mon

iain

the

pres

ence

ofM

gO,

and

for

SC

N2

byVo

lhar

d’s

met

hod.

The

cont

ent

ofw

ater

was

obta

ined

bydi

ffere

nce.

Sol

idph

ases

wer

eid

entifi

edby

Sch

rein

emak

er’s

met

hod.

NH

4N

O3

and

NH 4

SC

Nw

ere

com

mer

cial

chem

ical

lypu

repr

oduc

ts.

The

yw

ere

recr

ysta

llize

d,dr

ied

at12

0°C

,an

dke

ptin

ade

ssic

ator

over

P 2O5

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Am

mon

ium

nitr

ate;

NH 4

NO

3;

@648

4-52

-2#~3

!W

ater

;H 2

O;

@773

2-18

-5#

M.

I.R

avic

h,V.

Ya.

Ket

kovi

ch,

and

I.S

.R

asso

nska

ya,

Izv.

Sek

tora

Fiz

.K

him

.Ana

l.17,

254

–85

~194

9!.

Varia

bles

:P

repa

red

By:

T/K

:27

3–

363

100

x 2/m

ol%

:3.

6–

53.5

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–N

H 4N

O3–

H2O

syst

emas

afu

nctio

nof

tem

pera

ture

Tem

pera

ture

(t/°

C)

NH

4N

O3

(100

x 2/m

ol%

)N

H4S

CN

(100

x 1/m

ol%

)S

olid

phas

eaTe

mpe

ratu

re(t

/°C

)N

H4N

O3

(100

x 2/m

ol%

)N

H4S

CN

(100

x 1/m

ol%

)S

olid

phas

ea

03.

620

.8A

808.

652

.8A

8.7

19.8

A17

.848

.7A

12.0

18.4

A1B

24.3

47.1

A

14.3

11.1

B33

.348

.0C

16.4

5.6

B35

.148

.0C

308.

428

.5A

38.5

44.1

C

12.2

28.4

A41

.538

.9C

22.1

26.4

A1B

43.9

36.9

C

22.4

15.5

B44

.733

.2B

25.1

10.7

B45

.823

.5B

29.5

5.0

B51

.012

.0B

607.

441

.9A

9012

.856

.8A

14.1

40.8

A22

.252

.7A

25.1

38.5

A28

.152

.7A

27.3

37.9

A30

.451

.5C

32.1

35.8

A37

.647

.7C

34.0

35.5

A1B

40.5

42.6

C

33.5

34.9

B47

.535

.7C

33.8

28.4

B47

.830

.6B

34.2

17.0

B47

.525

.9B

39.6

10.0

B53

.516

.7B

(1 a A @6 a b C a F a N


d

the

com

pila

tion

sinc

eth

eyre

pres

ent

the

solu

bilit

yof

NH

4N

O3

inso

lutio

nsof

NH 4

SC

N.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

yde

term

inat

ions

wer

eca

rrie

dou

tin

ther

mos

tate

dgl

ass-

stop

pere

dbo

ttles

.S

tart

ing

from

the

two-

com

pone

ntso

lutio

nsa

tura

ted

with

NH 4S

CN

,th

eso

lubi

lity

ofth

issa

ltw

asde

term

ined

asa

func

tion

ofin

crea

sing

amou

ntof

NH

4N

O3

,an

dvi

ceve

rsa.

Equ

ilibr

ium

was

reac

hed

afte

r1

hsh

akin

g.S

ampl

esfo

ran

alys

isw

ere

with

draw

nth

roug

ha

plug

ofgl

ass

woo

lint

oa

wei

ghed

spec

imen

tube

unde

rco

olin

gto

avoi

dlo

sses

ofN

H 3.

Am

mon

iaw

asde

term

ined

bytit

ratio

nag

ains

tco

ngo

red

asin

dica

tor,

SC

N2

byVo

lhar

dm

etho

d.T

heco

nten

tof

NH

4N

O3

was

obta

ined

bydi

ffere

nce.

Sol

idph

ases

wer

ean

alyz

edch

emic

ally

.S

epar

ate

expe

rimen

tsw

ere

desi

gned

toco

nfirm

that

nodo

uble

salts

wer

efo

rmed

.

NH

4S

CN

and

NH 4

NO

3w

ere

very

pure

chem

ical

s,th

eir

sour

cew

asno

tsp

ecifi

ed.

The

yw

ere

recr

ysta

llize

dan

ddr

ied

until

they

show

edno

trac

eof

moi

stur

e.D

ryN

H3

gas

was

obta

ined

byw

arm

ing

aco

ncen

trat

edso

lutio

nof

amm

onia

,an

dpa

ssin

gth

ega

sth

roug

hto

wer

sco

ntai

ning

quic

klim

ean

dfu

sed

caus

ticpo

ptas

h.1

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 H.

W.

Foo

tean

dM

.A

.H

unte

r,J.

Am

.C

hem

.S

oc.

42,

69~1

920!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Am

mon

ium

nitr

ate;

NH 4

NO

3;

@648

4-52

-2#W

ater

;H 2

O;

@773

2-18

-5#

P.S

.B

ogoy

avle

nski

i,Z

h.F

iz.

Khi

m.32

,20

35–

41~1

958!

.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

68J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

at25

°Cin

wat

eran

daq

ueou

sso

lutio

nsof

NH

4N

O3

NH

4N

O3

00w

2/m

ass

%)

NH

4N

O3

(m2

/mol

kg2

1)a

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)a

Sol

idph

aseb

00

64.1

23.4

5A

5.17

1.93

761

.524

.24

A

9.97

3.97

958

.73

24.6

4A

15.7

76.

671

54.7

24.3

3A

21.4

99.

910

51.4

224

.93

A

33.0

617

.98

43.9

825

.16

A

38.0

23.2

441

.58

26.7

5A

39.5

25.2

640

.97

27.5

5A1

B

alcu

late

dby

com

pile

r.:

NH

4S

CN

,@17

62-9

5-4#;

B:

NH

4N

O3

;@6

484-

52-2#

.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofse

ven

satu

rate

dso

lutio

nsnt

aini

ng42

.53

–68

.0m

ass

%N

H4N

O3

whe

reN

H 4N

O3

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tsho

wn

here

sinc

eth

eyre

fer

the

solu

bilit

yof

NH 4

NO

3in

solu

tions

ofN

H 4S

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

deta

ilsre

port

ed.

The

com

pile

ras

sum

edth

atth

esa

me

oced

ure

was

adop

ted

asin

the

auth

or’s

prev

ious

wor

kog

oyav

lens

kiia

ndS

ukm

ansk

aya

1 !,i.e

.,is

othe

rmal

met

hod

thch

emic

alan

alys

isof

the

equi

libriu

mliq

uid

phas

es,

and

estig

atio

nof

solid

phas

esby

mea

nsof

optic

alm

icro

scop

y.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 P.S

.B

ogoy

avle

nski

iand

G.V

.S

ukm

ansk

aya,

Zh.

Obs

h.K

him

.23

,10

92~1

953!

.

133133JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Am

mon

ium

nitr

ate;

NH 4

NO

3;

@648

4-52

-2#~3

!A

mm

onia

;N

H 3;

@766

4-41

-7#

H.W

.-F

oote

and

S.R

.Brin

kley

,J.A

m.C

hem

.Soc

.43

,101

8–

31~1

923!

.

Varia

bles

:P

repa

red

By:

T/K

:27

3–

293

100

w2

/mas

s%

:0

–79

.45

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–N

H 4N

O3–

NH

3sy

stem

atth

ree

tem

pera

ture

s

Tem

pera

ture

(t/°

C)

NH

4N

O3

(100

w2

/mas

s%

)N

H4N

O3

(m2

/mol

kg2

1)a

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)a

NH

3

(100

w3

/mas

s%

)S

olid

phas

eb

00

077

.12

44.2

822

.88

A

9.16

5.46

069

.88

43.7

920

.96

A

15.4

59.

848

64.9

543

.53

19.6

0A

19.2

512

.59

61.5

542

.40

19.1

0A

1B

19.2

012

.62

61.8

042

.73

19.0

0A

1B

100

077

.30

44.7

422

.70

A

8.40

5.21

871

.49

46.7

020

.11

A

17.4

912

.24

64.6

647

.59

17.8

5A

21.0

515

.228

61.6

846

.92

17.2

7A

1B

21.0

915

.23

61.6

146

.79

17.3

0A

1B

200

078

.65

48.4

021

.35

A

4.69

2.99

175

.72

50.7

819

.59

A

11.6

48.

025

70.2

450

.93

18.1

2A

16.8

812

.35

66.0

450

.80

17.0

8A

24.7

320

.30

60.0

551

.83

15.2

2A

1B

24.8

620

.45

59.9

551

.85

15.1

9A

1B

a Cal

cula

ted

byco

mpi

ler.

b A:

NH

4S

CN

,@17

62-9

5-4#;

B:

NH

4N

O3

,@6

484-

52-2#

.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

inth

eta

ble,

the

auth

ors

also

repo

rted

com

posi

tions

ofan

othe

rni

nesa

tura

teso

lutio

nsat

0°C

,co

ntai

ning

20.0

6–

76.8

7m

ass

%N

H4N

O3

and

59.9

7–

0m

ass

%N

H 4SC

N,

seve

nsa

tura

ted

solu

tions

at10

°C,

cont

ain-

ing

25.1

1–

78.0

9m

ass

%N

H 4NO

3,

and

56.3

7–

0m

ass

%N

H 4SC

N,

and

nine

satu

rate

dso

lutio

nsat

20°C

,co

ntai

ning

27.9

0–

79.4

5m

ass

%N

H 4N

O3an

d54

.37

–0

mas

s%

NH 4S

CN

,w

here

NH 4

NO

3w

asth

eeq

uilib

rium

solid

phas

e.T

hese

data

have

not

been

incl

uded

in

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co to Me

No

pr ~B wi

inv

J

23.3

13.8

554

.625

.42

14.0

8.32

263

.929

.75

9074

.665

.77

10.5

7.25

1

70.1

60.9

814

.810

.08

61.4

54.5

023

.816

.54

47.0

40.3

537

.725

.35

29.9

26.9

055

.539

.11

15.1

12.7

969

.446

.07

a The

only

solid

phas

esob

serv

edw

ere

two

type

sof

solid

solu

tions

labe

led

asb

and

gin

Fig

.27

.T

heg

solid

solu

tion

cont

aine

dm

ore

NH

4S

CN

than

the

salt

resi

due

ofth

eco

rres

pond

ing

liqui

dph

ase.

Inth

era

nge

ofcr

ysta

lliza

tion

ofth

eb

solid

solu

tions

the

ratio

ofth

eco

ncen

trat

ions

ofbo

thsa

ltsw

asid

entic

alin

the

solid

and

liqui

dph

ases

.b C

alcu

late

dby

com

pile

r.

FIG

.27

.P

hase

diag

ram

sof

the

NH

4S

CN

–K

SC

N–

H 2O

at90

°C~t

op!,

30°C

~bot

tom

left!

,an

d0

°C~b

otto

mrig

ht!.

ditio

nali

nfor

mat

ion:

Pha

sedi

agra

mfo

r60

°Can

dth

eso

lubi

lity

poly

ther

mw

ere

also

repo

rted

.In

addi

tion

toth

eis

othe

rmal

data

,th

eau

thor

sre

port

edal

soso

me

poly

ther

mal

mea

sure

men

tsbe

low

0an

dab

ove

100

°C.

The

resu

ltsha

veno

tbe

enin

clud

edhe

resi

nce

tem

pera

ture

sof

crys

talli

zatio

ndi

ffere

din

som

eca

ses

depe

ndin

gon

whe

ther

seed

ing

was

appl

ied

orno

t,w

hich

indi

cate

dth

eex

iste

nce

ofbo

thst

able

and

met

asta

ble

solid

phas

es.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#~3

!W

ater

;H 2

O;

@773

2-18

-5#

M.

I.R

avic

h,V.

Ya.

Ket

kovi

ch,

and

I.S

.R

asso

nska

ya,

Izv.

Sek

tora

Fiz

.K

him

.Ana

l.17,

254

–85

~194

9!.

Varia

bles

:P

repa

red

By:

T/K

:27

3,30

3,33

3,an

d36

3C

once

ntra

tion

ratio

ofN

H 4SC

Nan

dK

SC

NJ.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–K

SC

N–

H 2O

syst

emat

four

tem

pera

ture

sa

Tem

pera

ture

(t/°

C)

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)b

KS

CN

(100

w2

/mas

s%

)K

SC

N(m

2/m

olkg

21)b

042

.913

.26

14.6

3.53

4

35.7

11.7

524

.46.

292

30.1

11.0

434

.19.

801

29.7

11.2

135

.510

.49

25.0

9.17

339

.211

.26

19.9

7.26

144

.112

.60

10.7

3.95

953

.815

.59

3055

.421

.53

10.8

3.28

7

47.8

19.0

819

.36.

086

46.7

19.6

022

.07.

232

41.0

18.1

329

.310

.15

39.8

18.4

131

.811

.52

29.1

13.2

742

.115

.04

23.2

10.5

848

.017

.15

13.1

5.89

357

.720

.33

6071

.541

.19

5.7

2.57

2

64.4

38.9

813

.96.

591

61.8

38.1

116

.98.

164

59.4

36.2

919

.19.

141

59.2

37.0

319

.89.

702

50.6

30.6

327

.713

.13

36.0

21.3

041

.819

.37

Ad


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Pot

assi

umth

iocy

anat

e;K

SC

N;

@333

-20-

0#W

ater

;H 2

O;

@773

2-18

-5#

A.

M.

Bab

enko

and

A.

M.

And

riano

v,U

krai

n.K

him

.Z

h.45,

1177

–81

~197

9!;s

hort

abst

ract

publ

ishe

din

Zh.

Prik

l.K

him

.51

,23

5~1

978!

.

riabl

es:

Pre

pare

dB

y:

K:

240

–32

50

w1

/mas

s%

:0

–42

0w

2/m

ass

%:

0–

70

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–K

SC

N–

H 2O

syst

emas

mea

sure

dby

poly

ther

mal

met

hod

NH

4S

CN

00w

1/m

ass

%)

KS

CN

(100

w2

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

NH

4S

CN

(100

w1

/mas

s%

)K

SC

N(1

00w

2/m

ass

%)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

42.0

02

25.3

A1B

5.22

47.8

231

.4A1

C

37.6

6.24

224

.7A1

B0

52.0

230

.0A1

C

33.4

13.3

22

26.0

A1B

10.0

51.3

213

.0C1

D

27.4

21.7

82

28.0

A1B

4.0

60.0

2.4

C1E

21.0

31.6

230

.8A1

B0

64.0

20.

8C1

E

19.7

434

.22

32.6

A1B

8.0

60.7

217

.0D1

E

27.3

22.0

227

.8A1

B8.

064

.431

.4D1

E

36.0

10.0

225

.8A1

B8.

060

.015

.0D1

E

13.2

42.6

642

32.6

A1B

9.0

70.0

52.0

D1E

11.4

442

.82

33.0

A1B

1D

21.0

40.0

29.

7B1

D

11.0

47.1

72

23.0

A1C

1D

23.8

40.5

21.

2B1

D

5.0

58.9

25.

0C1

D1

E31

.038

.012

.4B1

D

Sol

ubili

tyis

othe

rms

inth

eN

H 4SC

N–

KS

CN

–H 2

Osy

stem

b

mpe

ratu

re(t

/°C

)N

H4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)c

KS

CN

(100

w2

/mas

s%

)K

SC

N(m

2/m

olkg

21)c

Sol

idph

asea

230

20.0

5.47

332

.06.

860

A

12.0

83.

284

39.6

8.43

3A

10.0

2.80

743

.29.

498

A

5.38

1.45

946

.29.

818

A

21.4

5.96

131

.44

6.86

0B

14.7

4.35

240

.94

9.49

8B

11.2

3.28

444

.010

.10

B

20.6

45.

630

31.2

6.66

6B

19.2

65.

630

35.8

8.19

7B

00

52.0

11.1

4C

5.17

1.45

948

.310

.68

C

220

31.0

6.55

76.

91.

143

A

24.9

5.41

515

.04

2.57

2A

16.0

3.57

425

.24.

410

A

6.4

1.49

737

.44

6.86

0A

6.50

1.45

934

.25.

942

A

00

38.8

6.50

0A

40.0

9.72

16.

01.

149

B

36.2

9.31

712

.76

2.57

2B

31.2

8.51

020

.64

4.41

0B

26.5

7.39

429

.46.

960

B

19.8

6.23

738

.49

9.49

8B

135135JIRI HALA


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Isot

herm

alm

etho

dus

ed.A

mix

ture

ofso

lidsa

lts,

8–

10g,

was

diss

olve

din

wat

erab

ove

the

desi

red

tem

pera

ture

,th

enth

efla

skw

aspl

aced

ina

ther

mos

tat

atth

ede

sire

dte

mpe

ratu

reto

allo

weq

uilib

rium

tobe

esta

blis

hed.

Thi

sto

ok6

–7

hat

0,30

,an

d60

°C,

and

4–

5h

at90

°C.A

t0

and

30°C

,sa

mpl

esof

the

satu

rate

dso

lutio

nsw

ere

with

draw

nw

itha

pipe

ttepr

ehea

ted

and/

orpr

ecoo

led

toth

eco

rres

pond

ing

tem

pera

ture

.A

smal

lgla

ssU

tube

with

aw

adof

glas

sw

ooli

nsid

ew

asat

tach

edto

the

pipe

tte.A

t60

°Can

dab

ove,

sam

ples

wer

eta

ken

into

apr

ehea

ted

glas

stu

be.

The

sam

ples

wer

eal

low

edto

crys

talli

zeon

cool

ing

toro

omte

mpe

ratu

re,

and

wei

ghed

ina

wei

ghin

gbo

ttle.

Sat

urat

edso

lutio

nsw

ere

anal

yzed

for

NH

41,

SC

N2,

and

K1io

ns.

NH 41

was

dete

rmin

edac

idim

etric

ally

afte

rdi

still

ing

amm

onia

off

inth

epr

esen

ceof

MgO

,S

CN

2by

Volh

ard’

sm

etho

d,an

dK1

grav

imet

rical

lyas

K 2S

O4

afte

rev

apor

atio

nof

the

sam

ple

with

exce

ssH

2S

O4

,an

dig

nitio

n.S

olid

phas

esw

ere

iden

tified

byS

chre

inem

aker

s’m

etho

d.

NH

4S

CN

and

KS

CN

wer

ech

emic

ally

pure

prod

ucts

.The

yw

ere

recr

ysta

llize

d,dr

ied

at12

0°C

,an

dke

ptov

erP

2O

5in

ade

ssic

ator

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 10 (1 Te

J

8.96

3.28

455

.215

.84

D

7.8

2.92

457

.16

16.7

8D

1058

.818

.14

00

B

54.4

17.4

14.

561.

143

B

46.4

16.2

416

.08

4.41

0B

41.8

15.7

223

.28

6.86

0B

35.2

13.6

931

.04

9.46

1B

3313

.13

3410

.60

B

28.4

11.0

837

.94

11.5

9B

00

66.5

20.4

2E

3.72

1.45

962

.819

.30

E

2.4

0.94

964

.41

19.9

6E

23.2

9.22

943

.77

13.6

4D

21.6

88.

758

45.8

14.4

9D

17.7

17.

160

49.8

15.7

7D

23.2

9.22

943

.77

13.6

4D

14.1

5.63

053

16.5

7D

8.2

3.28

459

18.5

0D

13.2

5.25

653

.81

16.7

8D

2068

.622

.95

00

B

59.4

21.3

54.

061.

143

B

55.4

20.3

98.

922.

572

B

51.4

19.8

414

.58

4.41

0B

47.0

19.4

121

.26.

860

B

40.5

17.1

628

.59.

460

B

33.6

13.7

024

.19

10.9

2B

54.0

19.7

010

.02.

858

B

00

69.0

22.9

0E

3.45

1.45

965

.521

.70

E

7.56

3.28

462

.221

.16

E

29.5

13.1

341

.014

.30

D

28.6

12.2

340

.69

13.6

4D

20.0

8.75

850

.017

.15

D

18.6

7.94

350

.64

16.9

1D

16.1

57.

107

54.0

18.6

1D

12.9

5.63

057

.019

.48

D

10.7

4.62

958

.93

19.9

7D

:Ic

e,H

2O

,@7

732-

18-5#

;B

:N

H4S

CN

,@1

762-

95-4#

;C

:K

SC

N•0.

5H2O

,@

#;D

:so

lidso

lutio

nsof

mN

H4S

CN•

nK

SC

N;

E:

KS

CN

,33

-20-

2#.ol

ubili

tyis

othe

rms

wer

eob

tain

edby

the

auth

ors

from

poly

ther

mal

mea

sure

men

ts~s

eeF

ig.

28!.

alcu

late

dby

com

pile

r.

FIG

.28

.S

olub

ility

poly

ther

mof

the

NH 4S

CN

–K

SC

N–

H 2O

syst

em.

Fie

lds

ofcr

ysta

lliza

tion:

A:

ice;

II:N

H 4SC

N;

C:

KS

CN•0.

5H2O

;IV

:K

SC

N;

and

V:

solid

solu

tions

mN

H4S

CN•

nK

SC

N.


18.0

5.63

040

.09.

800

B

24.3

67.

073

30.4

6.91

4B

12.6

4.02

946

.32

11.6

0D

10.4

43.

284

47.8

11.7

7D

4.78

1.45

952

.212

.48

C

00

55.5

12.8

3C

210

20.5

3.38

70

0A

19.4

3.28

43

0.39

7A

8.34

1.45

916

.62.

275

A

7.4

1.31

218

.52

2.57

2A

00

243.

249

A

44.8

11.8

45.

521.

143

B

41.0

11.4

111

.82.

572

B

36.0

10.5

519

.24.

410

B

31.6

10.1

127

.36

6.86

0B

25.0

8.42

136

9.49

8B

20.7

97.

073

40.6

10.8

2B

27.6

88.

758

30.8

7.63

3B

49.3

12.7

70

0B

186.

135

43.4

611

.60

D

11.8

4.08

650

.27

13.6

3D

16.6

85.

630

44.4

11.7

3D

00

59.7

15.2

4C

4.38

1.45

956

.214

.67

C

9.68

3.28

451

.613

.71

C

054

.015

.42

00

B

49.6

14.3

65.

041.

143

B

45.8

13.8

710

.84

2.57

2B

41.3

13.2

017

.61

4.41

0B

36.5

12.5

825

.46.

860

B

3010

.82

33.6

9.49

8B

23.2

8.44

340

.70

11.6

0B

00

6418

.29

E

41.

459

6017

.15

E

23.2

28.

758

41.7

12.2

6D

19.2

57.

073

4512

.95

D

17.5

6.48

047

.02

13.6

4D

15.3

65.

630

48.8

14.0

1D

a A @3 b S c C


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Sod

ium

chlo

ride;

NaC

l;@764

7-14

-5#W

ater

;H 2

O;

@773

2-18

-5#

E.

F.Z

hura

vlev

and

M.

N.

Byc

hkov

a,Z

h.N

eorg

.K

him

.4,23

67–

75~1

959!

.

riabl

es:

Pre

pare

dB

y:

K:

278,

298,

323

0w

2/m

ass

%:

0–

26.2

at27

8K

;0

–26

.5at

298

K26

.9at

323

K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–N

aCl–

H 2O

syst

emat

thre

ete

mpe

ratu

res

mpe

ratu

re(t

/°C

)N

aCl

(100

w2

/mas

s%

)N

aCl

(m2

/mol

kg2

1)a

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)a

Sol

idph

aseb

50

056

.517

.06

A

2.3

0.92

355

.116

.99

A

5.1

2.09

253

.216

.76

A1B

5.5

2.21

452

.016

.07

B

9.7

3.33

940

.610

.73

B

13.4

4.13

131

.17.

361

B

19.2

5.21

417

.83.

711

B

22.0

5.83

613

.52.

749

B1C

22.3

5.78

111

.72.

328

C

26.2

6.07

40

0C

250

064

.123

.45

A

1.9

0.92

663

.023

.57

A

4.6

2.30

161

.223

.50

A1B

7.5

3.08

450

.916

.07

B

11.5

4.04

039

.810

.73

B

17.5

5.26

225

.65.

910

B

20.6

5.91

419

.84.

364

B1C

21.0

5.87

117

.93.

820

C

22.6

5.87

611

.62.

315

C

26.5

6.16

90

0C

500

072

.835

.16

A

1.4

0.90

772

.235

.92

A

2.8

1.87

171

.636

.74

A

3.8

2.58

071

.037

.01

A1B

9.5

3.99

349

.816

.07

B

13.6

4.88

838

.810

.70

B

18.1

5.91

029

.57.

395

B1C

21.5

6.06

017

.83.

852

C

23.0

6.01

711

.62.

330

C

26.9

6.29

60

0C

a Cal

cula

ted

byco

mpi

ler.

b A:

NH

4S

CN

,@17

62-9

5-4#;

B:

NH

4C

l,@1

2125

-02-

9#;C

:N

aCl,

@764

7-14

-5#.

137137JIRI HALA


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Vis

ualp

olyt

herm

alm

etho

dus

ed.

Into

tal,

19se

ctio

nsof

the

NH

4S

CN

–K

SC

N–

H 2O

syst

emw

ere

inve

stig

ated

,of

whi

ch11

corr

espo

nded

to0,

10,

20,

30,

40,

50,

53,

57,

62,

66,

and

70m

ass

%K

SC

N,

and

8to

0,10

,20

,30

,35

,40

,50

,an

d60

mas

s%

NH 4

SC

N.

Mea

sure

men

tsw

ere

carr

ied

out

inan

appa

ratu

sde

scrib

edin

Era

izer

and

Kag

ansk

ii.1

The

solu

bilit

yve

ssel

,eq

uipp

edw

itha

ther

mom

eter

,w

asco

ated

with

atr

ansp

aren

tse

mic

ondu

ctor

laye

rto

whi

chtw

ohe

atin

gsi

lver

elec

trod

esw

ere

sold

ered

.T

heve

ssel

was

plac

edin

side

aD

ewar

flask

with

tran

spar

ent

wal

lsw

hich

,in

mea

sure

men

tspe

rfor

med

belo

wro

omte

mpe

ratu

re,

was

fille

dto

1/5

ofits

volu

me

with

liqui

dni

trog

enor

solid

CO 2

.W

ithth

eso

lubi

lity

vess

elke

ptab

ove

the

cool

ant,

itw

aspo

ssib

leto

cont

rolt

hera

teof

cool

ing

orhe

atin

gby

mov

ing

the

Dew

arfla

sk.

The

mix

ture

inth

eso

lubi

lity

vess

elw

asst

irred

byus

ing

two

exte

rnal

elec

trom

agne

ts,

and

illum

inat

edto

obse

rve

disa

ppea

ranc

eor

appe

aran

ceof

last

crys

tals

.

KS

CN

and

NH 4

SC

Nw

ere

reag

ent

grad

epr

oduc

ts,

and

wer

etw

ice

recr

ysta

llize

dfr

omw

ater

,an

ddr

ied

at30

–40

°Cbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 L.N

.E

raiz

eran

dI.

M.

Kag

ansk

ii,Z

avod

skay

aLa

b.33,

119

~196

7!.

Co

~1!

~2!

~3!

Va T/

10 0–

Te

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Am

mon

ium

chlo

ride;

NH 4

Cl;

@121

25-0

2-9#

Wat

er;

H 2O

;@7

732-

18-5#

E.

F.Z

hura

vlev

and

M.

N.

Byc

hkov

a,Z

h.N

eorg

.K

him

.4,23

67–

75~1

959!

.

riabl

es:

Pre

pare

dB

y:

K:

278,

298,

323

0w

2/m

ass

%:

0–

23.8

at27

8K

;0

–28

.6at

298

K33

.5at

323

K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–N

H 4C

l–H

2O

syst

emat

thre

ete

mpe

ratu

res

mpe

ratu

re(t

/°C

)N

H4C

l(1

00w

2/m

ass

%)

NH

4C

l(m

2/m

olkg

21)a

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)a

Sol

idph

aseb

50

056

.517

.06

A

4.7

2.03

953

.016

.46

A

5.9

2.54

652

.416

.46

A1B

250

064

.123

.45

A

3.9

2.05

661

.323

.14

A

5.8

2.88

060

.222

.99

A1B

500

072

.835

.16

A

4.6

3.32

370

.036

.20

A1B

alcu

late

dby

com

pile

r.:

NH

4S

CN

,@17

62-9

5-4#;

B:

NH

4C

l,@1

2125

-02-

9#.

ditio

nali

nfor

mat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

repo

rted

also

com

posi

tions

of16

satu

rate

dso

lutio

nsco

ntai

ning

.6–

23.8

,8.

4–

28.6

,an

d5.

8–

33.5

mas

s%

NH

4C

lat

5,25

,an

d50

°C,

resp

ectiv

ely,

whe

reth

eeq

uilib

rium

solid

phas

ew

asN

H4C

l.es

ew

ere

not

incl

uded

here

sinc

eth

eyre

pres

ent

the

solu

bilit

ies

ofN

H4C

lin

solu

tions

ofN

H 4S

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eso

lubi

lity

was

obta

ined

bygr

aphi

cala

naly

tical

met

hod.

1A

ries

ofm

ixtu

res

ofth

esa

ltsan

dw

ater

corr

espo

ndin

gto

aos

ense

ctio

nin

the

tria

ngul

ardi

agra

m,

runn

ing

from

one

resa

ltto

the

oppo

site

leg

ofth

etr

iang

le,

thus

cove

ring

the

lds

ofun

satu

rate

dan

dsa

tura

ted

solu

tions

,w

ere

prep

ared

byw

eigh

ing.

Afte

req

uilib

rium

had

been

atta

ined

,a

prop

erty

~com

pile

ras

sum

edth

isto

bere

frac

tive

inde

x,as

inth

eau

thor

s’su

bseq

uent

wor

k2 !

ofth

eso

lutio

nsw

ere

mea

sure

d,an

dpl

otte

das

afu

nctio

nof

the

com

posi

tion

ofth

em

ixtu

res.

The

tran

sitio

nfr

omun

satu

rate

dto

satu

rate

dso

lutio

ns,

i.e.,

the

corr

espo

ndin

gso

lubi

lity

valu

e,w

asob

tain

edas

abr

eak

onth

ere

frac

tive

inde

xve

rsus

com

posi

tion

plot

.T

hem

etho

dof

iden

tifica

tion

ofth

eso

lidph

ase

was

not

repo

rted

.

NH

4S

CN

and

NH 4

Clw

ere

chem

ical

lypu

repr

oduc

ts.T

hey

wer

ere

crys

talli

zed

and

drie

dov

eran

hydr

ous

CaC

l2

.D

oubl

ydi

still

edw

ater

was

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

2 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

ies

wer

eob

tain

edby

grap

hica

lana

lytic

alm

etho

d.1

Ase

ries

ofm

ixtu

res

ofth

esa

ltsan

dw

ater

corr

espo

ndin

gto

ach

osen

sect

ion

inth

etr

iang

ular

diag

ram

,ru

nnin

gfr

omon

epu

resa

ltto

the

oppo

site

leg

ofth

etr

iang

le,

thus

cove

ring

the

field

sof

unsa

tura

ted

and

satu

rate

dso

lutio

ns,

wer

epr

epar

edby

wei

ghin

g.A

fter

equi

libriu

mha

dbe

enat

tain

ed,

apr

oper

ty~c

ompi

ler

assu

med

this

tobe

refr

activ

ein

dex,

asin

the

auth

ors’

subs

eque

ntw

ork

2 !of

the

solu

tions

wer

em

easu

red,

and

plot

ted

asa

func

tion

ofth

eco

mpo

sitio

nof

the

mix

ture

s.T

hetr

ansi

tion

from

unsa

tura

ted

tosa

tura

ted

solu

tions

,i.e

.,th

eco

rres

pond

ing

solu

bilit

yva

lue,

was

obta

ined

asa

brea

kon

the

refr

activ

ein

dex

vers

usco

mpo

sitio

npl

ot.

The

met

hod

ofid

entifi

catio

nof

the

solid

phas

ew

asno

tre

port

ed.

NH

4S

CN

and

NaC

lw

ere

chem

ical

lypu

repr

oduc

ts.

The

yw

ere

recr

ysta

llize

dan

ddr

ied

over

anhy

drou

sC

aCl

2.

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

2 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.

Co

~1!

~2!

~3!

Va T/

10 0–

Te a C b A Ad

10 Th

Me

Th

se ch pu fie


6.5

1.05

246

.75

13.1

4

100

059

.018

.90

2.19

0.39

856

.217

.74

4.6

0.84

154

.017

.14

a A:

Ice,

H2O

,@7

732-

18-5#

;B

:(N

H4) 2

SO

4,

@778

3-20

-2#;

C:

NH

4S

CN

;@17

62-9

5-4#.

b Sol

idph

ase

NH 4

SC

N;@

1762

-95-

4#in

alls

olut

ions

.c S

olub

ility

isot

herm

sw

ere

obta

ined

byth

eau

thor

sfr

ompo

lyth

erm

alm

easu

rem

ents

~see

Fig

.29

!.O

fnu

mer

ous

data

repo

rted

,on

lyth

ose

refe

rrin

gto

the

solu

bilit

yof

NH 4

SC

Nw

ere

incl

uded

here

.In

syst

ems

cont

aini

nghi

gher

(NH

4) 2

SO

4co

ncen

trat

ions

,the

equi

libriu

mso

lidph

ases

wer

eei

ther

ice

or(N

H4) 2

SO

4.

d Cal

cula

ted

byco

mpi

ler.

IG.

29.

Sol

ubili

typo

lyth

erm

ofth

eN

H 4SC

N–~

NH

4) 2

SO

4–

H2O

syst

em.

Fie

lds

ofcr

ysta

lliza

tion:

A:

ice;

B:

(NH 4)

2S

O4

;an

dC

:H

4S

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

visu

alpo

lyth

erm

alm

etho

dw

asus

ed.

Into

tal,

11se

ctio

nsof

NH 4

SC

N–~

NH

4) 2

SO

4–

H2O

syst

emw

ere

inve

stig

ated

,of

ich

seve

nco

rres

pond

edto

10,

20,

30,

40,

45,

50,

and

55ss

%N

H 4S

CN

,an

dfo

urto

5,10

,20

,an

d30

mas

s%

H4) 2

SO

4.

Mea

sure

men

tsw

ere

carr

ied

out

inan

appa

ratu

ssc

ribed

inE

raiz

eran

dK

agan

skii.

1T

heso

lubi

lity

vess

el,

uipp

edw

itha

ther

mom

eter

,w

asco

ated

with

atr

ansp

aren

tm

icon

duct

orla

yer

tow

hich

two

heat

ing

silv

erel

ectr

odes

reso

lder

ed.

The

vess

elw

aspl

aced

insi

dea

Dew

arfla

skth

tran

spar

ent

wal

lsw

hich

,in

mea

sure

men

tspe

rfor

med

low

room

tem

pera

ture

,w

asfil

led

to1/

5of

itsvo

lum

ew

ithui

dni

trog

enor

solid

CO 2

.W

ithth

eso

lubi

lity

vess

elke

ptov

eth

eco

olan

t,it

was

poss

ible

toco

ntro

lthe

rate

ofco

olin

gor

heat

ing

bym

ovin

gth

eD

ewar

flask

.T

hem

ixtu

rein

the

solu

bilit

yve

ssel

was

stirr

edby

usin

gtw

oex

tern

alel

ectr

omag

nets

,an

dill

umin

ated

toob

serv

edi

sapp

eara

nce

orap

pear

ance

ofcr

ysta

ls.

NH

4S

CN

and

(NH 4

) 2S

O4

wer

ech

emic

ally

pure

prod

ucts

.T

hey

wer

ere

crys

talli

zed

twic

ebe

fore

use,

and

drie

dat

40°C

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 L.N

.E

raiz

eran

dI.

M.

Kag

ansk

ii,Z

avod

skay

aLa

b.33,

119

~196

7!.

139139JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Am

mon

ium

sulfa

te;

(NH 4

) 2S

O4

;@7

783-

20-2#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

A.

M.

Bab

enko

and

A.

M.

And

riano

v,Z

h.N

eorg

.K

him

.23,

2819

–25

~197

8!.

Varia

bles

:P

repa

red

By:

T/K

:24

8–

280

100

w2

/mas

s%

:0

–39

.8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–~N

H4) 2

SO

4–

H2O

syst

emas

mea

sure

dby

poly

ther

mal

met

hod

(NH

4) 2

SO

4

(100

w2

/mas

s%

)N

H4S

CN

(100

w1

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

(NH

4) 2

SO

4

(100

w2

/mas

s%

)N

H4S

CN

(100

w1

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

39.8

02

19.0

A1B

6.2

38.0

224

.0A1

B1

C

33.0

6.7

218

.2A1

B8.

041

.42

11.6

B1C

27.4

14.5

22

20.0

A1B

6.0

47.0

211

.8B1

C

18.0

24.6

223

.6A1

B5.

052

.25

17.

6B1

C

8.0

36.8

219

.6A1

B0

42.0

225

.3A1

C

14.0

30.0

223

.0A1

B3.

040

.02

22.0

A1C

25.8

14.0

218

.8A1

B

Sol

ubili

tyis

othe

rms

inth

eN

H 4SC

N–~

NH

4) 2

SO

4–

H2O

syst

emb,

c

Tem

pera

ture

(t/°

C)

(NH

4) 2

SO

4

(100

w2

/mas

s%

)(N

H4) 2

SO

4

(m2

/mol

kg2

1)d

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)d

220

00

44.6

10.5

7

2.93

0.39

841

.49.

770

7.0

0.94

937

.28.

758

210

00

49.3

12.7

7

2.68

0.39

546

.411

.76

5.55

0.84

144

.50

11.7

0

00

054

.015

.42

2.44

0.39

851

.214

.51

5.06

0.84

149

.414

.25

F N Me

A the

wh

ma

(N de eq se we

wi

be liq ab

J

chos

ense

ctio

nin

the

tria

ngul

ardi

agra

m,

runn

ing

from

one

pure

salt

toth

eop

posi

tele

gof

the

tria

ngle

,th

usco

verin

gth

efie

lds

ofun

satu

rate

dan

dsa

tura

ted

solu

tions

,w

ere

prep

ared

byw

eigh

ing.

Afte

req

uilib

rium

had

been

atta

ined

,a

prop

erty

~com

pile

ras

sum

edth

isto

bere

frac

tive

inde

x,as

inth

eau

thor

s’su

bseq

uent

wor

k2 !

ofth

eso

lutio

nsw

ere

mea

sure

d,an

dpl

otte

das

afu

nctio

nof

the

com

posi

tion

ofth

em

ixtu

res.

The

tran

sitio

nfr

omun

satu

rate

dto

satu

rate

dso

lutio

ns,

i.e.,

the

corr

espo

ndin

gso

lubi

lity

valu

e,w

asob

tain

edas

abr

eak

onth

ere

frac

tive

inde

xve

rsus

com

posi

tion

plot

.T

hem

etho

dof

iden

tifica

tion

ofth

eso

lidph

ase

was

not

repo

rted

.

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 E.F

.Zhu

ravl

evan

dA

.D.S

heve

leva

,Zh.

Neo

rg.K

him

.5,

2630

~196

0!.

2 E.

F.Z

hura

vlev

and

O.

G.

Nik

itina

,Z

h.N

eorg

.K

him

.13

,54

9~1

968!

.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Bor

icac

id;

H 3B

O3

;@1

0043

-35-

3#W

ater

;H 2

O;

@773

2-18

-5#

V.G

.S

kvor

tsov

,A

.K

.M

olod

kin,

R.

S.

Tsek

hans

kii,

Sh.

V.S

adet

dino

v,an

dF.

V.N

ikon

ov,

Zh.

Neo

rg.

Khi

m.

30,

826

–9

~198

5!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

5.6

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

at25

°Cin

aque

ous

solu

tions

ofbo

ricac

id

H3B

O3

00w

2/m

ass

%)

H3B

O3

(m2

/mol

kg2

1)a

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)a

Sol

idph

aseb

00

65.5

224

.96

A

3.01

1.51

564

.86

26.5

2A

3.02

1.51

964

.82

26.4

8A1

B

alcu

late

dby

com

pile

r.:

NH

4S

CN

,@17

62-9

5-4#;

B:

H3B

O3

,@1

0043

-35-

3#.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

show

nab

ove,

the

auth

ors

also

repo

rted

the

com

posi

tions

ofsi

xsa

tura

ted

solu

tions

ntai

ning

2.99

–5.

60m

ass

%H

3B

O3

,an

d64

.84

–0

mas

s%

NH 4S

CN

,w

here

H 3B

O3

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tow

nhe

resi

nce

they

repr

esen

tth

eso

lubi

lity

ofH

3B

O3

inso

lutio

nsof

NH 4

SC

N.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Sol

utio

nsw

ithex

cess

solid

rest

irred

for

7–

8h,

whi

chw

assu

ffici

ent

for

equi

libriu

mto

reac

hed.

Sol

ubili

tyis

othe

rms

wer

eco

nfirm

edby

frac

tom

etric

mea

sure

men

tsof

the

liqui

dph

ases

.C

ompi

ler

sum

esth

eso

lidph

ases

wer

ech

arac

teriz

edby

hrei

nem

aker

s’m

etho

d,an

dth

atth

esa

tura

ted

solu

tions

wer

eal

yzed

titrim

etric

ally

for

bora

tean

dS

CN

2,

asin

the

thor

s’pr

evio

usw

ork.1

NH

4S

CN

and

H 3B

O3

wer

ech

emic

ally

pure

prod

ucts

,an

dw

ere

recr

ysta

llize

dbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 V.G

.Skv

orts

ov,R

.S.T

sekh

ansk

ii,S

h.V.

Sad

etdi

nov,

and

A.K

.M

olod

kin,

Zh.

Neo

rg.

Khi

m.2

8,26

77~1

983!

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Am

mon

ium

sulfa

te;

(NH 4

) 2S

O4

;@7

783-

20-2#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

E.

F.Z

hura

vlev

and

M.

N.

Byc

hkov

a,Z

h.N

eorg

.K

him

.4,23

67–

75~1

959!

.

Varia

bles

:P

repa

red

By:

T/K

:30

6,32

610

0w

2/m

ass

%:

0–

42.6

at30

6K

;0

–45

at32

6K

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–~N

H4) 2

SO

4–

H2O

syst

emat

two

tem

pera

ture

s

Tem

pera

ture

(t/°

C)

(NH

4) 2

SO

4

(100

w2

/mas

s%

)(N

H4) 2

SO

4

(m2

/mol

kg2

1)a

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)a

Sol

idph

aseb

330

067

.327

.03

A

1.7

0.39

866

.026

.84

A

2.7

0.64

065

.426

.93

A1B

9.4

1.42

840

.910

.76

B

21.0

2.87

323

.75.

630

B

32.0

4.18

910

.22.

318

B

42.6

5.61

60

0B

530

073

.837

.00

A

1.3

0.38

273

.037

.31

A

1.5

0.44

573

.037

.60

A1B

9.5

1.44

340

.710

.73

B

22.9

3.19

523

.25.

644

B

35.0

4.78

99.

72.

304

B

45.0

6.19

10

0B

a Cal

cula

ted

byco

mpi

ler.

b A:

NH

4S

CN

,@17

62-9

5-4#;

B:

(NH

4) 2

SO

4@7

783-

20-2#

. Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solu

bilit

yw

asob

tain

edby

grap

hica

lana

lytic

alm

etho

d.1

Ase

ries

ofm

ixtu

res

ofth

esa

ltsan

dw

ater

corr

espo

ndin

gto

aN

H4S

CN

and

(NH 4

) 2S

O4

wer

ech

emic

ally

pure

prod

ucts

.T

hey

wer

ere

crys

talli

zed

and

drie

dov

eran

hydr

ous

CaC

l2

.D

oubl

y

Co

~1!

~2!

~3!

Va T/

10 (1 a C b A Ad

co sh Me

An

we

be re as Sc

an au


smpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

N,N

-die

thyl

-eth

anam

ine~t

rieth

ylam

ine!;

C6H

15N

;21

-44-

8#W

ater

;H 2

O;

@773

2-18

-5#

L.D

.Vo

robe

vaan

dI.

L.K

rupa

tkin

,Fa

zovy

eR

avo

vesi

a~Pha

seE

quili

bria

!,~K

alin

in.

Gos

ud.

Uni

v.,

Kal

inin

,19

74!,

pp.

18–

25.

riabl

es:

Pre

pare

dB

y:

K:

296,

298

J.H

a´ la

Exp

erim

enta

lDat

aP

hase

ddi

agra

ms

ofth

ete

rnar

ysy

stem

NH

4S

CN

–tr

ieth

ylam

ine

–H 2O

at23

and

25°C

wer

ere

port

ed~Fig

.30

!.F

or20

°Cth

eph

ase

gram

was

repo

rted

tobe

iden

tical

with

that

at23

°C.T

hecr

ysta

lliza

tion

line

AB

repr

esen

tsth

eso

lubi

lity

ofN

H4S

CN

intr

ieth

alam

ine-

Om

ixtu

res

~num

eric

alda

taw

ere

not

repo

rted!.

Low

NH

4S

CN

conc

entr

atio

ns~1

mas

s%

at23

°C,

0.75

mas

s%

at20

°C!

caus

em

ogen

izat

ion

ofth

eH 2O

–tr

ieth

alm

ine

syst

em.

Fur

ther

incr

ease

inth

esa

ltco

ncen

trat

ion

resu

ltsin

stro

ngsa

lting

-out

oftr

ieth

ylam

ine

din

reap

pear

ance

oftw

oliq

uid

phas

es,

ofw

hich

one

ispu

retr

ieth

ylam

ine.

FIG

.30

.P

hase

diag

ram

sof

the

NH

4S

CN

–tr

ieth

ylam

ine

–H 2O

syst

emat

23°C

~rig

ht!

and

25°C

~left!

.R

egio

nsof

exis

tenc

e:I,

Ia:

two

liqui

dph

ases

;II:

unsa

tura

ted

solu

tions

;an

dIII

:so

lidan

dliq

uid

phas

es.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Pha

sedi

agra

ms

wer

eob

tain

edby

isot

herm

alph

ase

titra

tions

.N

H4S

CN

,ch

emic

ally

pure

,w

asdr

ied

toco

nsta

ntw

eigh

tbe

fore

use.

Trie

thyl

amin

e,so

urce

not

spec

ified

,w

asdr

ied

over

anhy

drou

sM

gSO 4

,an

ddi

still

edtw

ice.

The

prod

uctu

sed

boili

ngpo

int

at89

.2°C

,an

dsh

owed

d.of

0.72

32g

cm23

at20

°C.

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

141141JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Am

mon

ium

tetr

abor

ate;

(NH 4)

2B

4O

7;

@120

07-5

8-8#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

Sh.

V.S

adet

dino

v,V.

G.

Skv

orts

ov,

and

R.

S.

Tsek

hans

kii,

Sb.

Tru

dov

Yar

osla

v.G

os.

Ped

.In

st.

No.16

9,72

–5

~197

8!.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

0–

8.76

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

at25

°Cin

wat

eran

don

eaq

ueou

sso

lutio

nof

amm

oniu

mte

trab

orat

e

(NH

4) 2

B4O

7

(100

w2

/mas

s%

)(N

H4) 2

B4O

7

(m2

/mol

kg2

1)a

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)a

Sol

idph

aseb

00

65.5

224

.96

A

1.15

0.17

9465

.34

25.6

2A1B

a Cal

cula

ted

byco

mpi

ler.

b A:

NH

4S

CN

,@17

62-9

5-4#;

B:

(NH

4) 2

B4O

7•4

H2O

,@1

2228

-87-

4#.

Add

ition

alin

form

atio

n:In

addi

tion

toth

eda

tash

own

abov

e,th

eau

thor

sal

sore

port

edth

eco

mpo

sitio

nsof

seve

nsa

tura

ted

solu

tion

cont

aini

ng1.

18–

8.76

mas

s%

(NH

4) 2

B4O

7,

and

65.3

0–

0m

ass

%N

H 4SC

N,

whe

re(N

H 4) 2

B4O

7•4

H2O

was

the

equi

libriu

mso

lidph

ase.

The

seda

taar

eno

tsh

own

here

sinc

eth

eyre

pres

ent

the

solu

bilit

yof

(NH

4) 2

B4O

7•4

H2O

inso

lutio

nsof

NH 4

SC

N.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

ium

was

reac

hed

with

in20

h,w

hich

was

chec

ked

bych

emic

alan

alys

isan

dre

frac

tion

inde

xof

the

satu

rate

dso

lutio

ns.

Bor

ate

and

SC

N2

wer

ede

term

ined

inth

esa

tura

ted

solu

tions

titrim

etric

ally

~met

hods

not

spec

ified!,

solid

phas

esw

ere

char

acte

rized

byS

chre

inem

aker

s’m

etho

d.

NH

4S

CN

and

(NH 4

) 2B

4O

7w

ere

chem

ical

lypu

repr

oduc

ts,

and

wer

ere

crys

talli

zed

befo

reus

e.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

@1 ~3!

Va T/

dia

H2

ho an

J

24.0

11.1

040

.014

.60

210

00

49.3

12.7

7

5.2

1.85

048

.013

.47

10.7

64.

163

46.2

14.1

0

19.7

48.

966

43.6

15.6

2

21.0

9.83

643

.45

16.0

6

22.4

11.1

044

.017

.20

25.9

213

.62

42.4

17.5

8

00

054

.015

.42

4.78

1.85

052

.215

.94

9.84

4.16

350

.816

.96

15.3

7.13

649

.018

.03

18.2

8.96

648

.018

.66

20.8

11.1

048

.020

.21

24.3

13.6

346

.020

.35

32.0

20.4

942

.021

.22

40.0

24.6

733

.016

.06

100

058

.818

.75

4.32

1.85

056

.819

.19

9.12

4.16

354

.419

.59

13.9

27.

136

53.6

21.6

8

16.1

8.96

654

.023

.73

22.5

13.6

350

.023

.89

29.0

20.1

247

.025

.77

olub

ility

isot

herm

sw

ere

obta

ined

byth

eau

thor

sfr

ompo

lyth

erm

alm

easu

rem

ents

~see

Fig

.31

!.O

fth

enu

mer

ous

data

repo

rted

,on

lyos

ew

ere

incl

uded

here

whi

chre

fer

toth

eso

lubi

lity

ofN

H4S

CN

.In

othe

rsy

stem

sth

eeq

uilib

rium

solid

phas

esw

ere

ice

orur

ea.

olid

phas

ew

asN

H 4SC

N,@

1762

-95-

4#in

alls

olut

ions

.al

cula

ted

byco

mpi

ler.

FIG

.31

.S

olub

ility

poly

ther

mof

the

NH 4S

CN

–ur

ea–

H 2O

syst

em.

Fie

lds

ofcr

ysta

lliza

tion:

A:

ice;

B:

urea

;an

dC

:N

H4S

CN

.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Avi

sual

poly

ther

mal

met

hod

was

used

.In

tota

l,15

sect

ions

ofth

eN

H 4S

CN

–ur

ea–

H 2O

syst

emw

ere

inve

stig

ated

,of

whi

chei

ght

corr

espo

nded

to10

,20

,30

,35

,40

,45

,55

,an

d65

mas

s%

NH 4

SC

N,

and

seve

nto

10,

20,

30,

35,

40,

45,

and

55m

ass

%ur

ea.

Mea

sure

men

tsw

ere

carr

ied

out

inan

appa

ratu

sde

scrib

edin

Ref

.1.

The

solu

bilit

yve

ssel

,eq

uipp

edw

itha

ther

mom

eter

,w

asco

ated

with

atr

ansp

aren

tse

mic

ondu

ctor

laye

rto

whi

chtw

ohe

atin

gsi

lver

elec

trod

esw

ere

sold

ered

.T

heve

ssel

was

plac

edin

side

aD

ewar

flask

with

tran

spar

ent

wal

lsw

hich

,in

mea

sure

men

tspe

rfor

med

belo

wro

omte

mpe

ratu

re,

was

fille

dto

1/5

ofits

volu

me

with

liqui

dni

trog

enor

solid

CO 2

.W

ithth

eso

lubi

lity

vess

elke

ptab

ove

the

cool

ant,

itw

aspo

ssib

leto

cont

rolt

hera

teof

cool

ing

orhe

atin

gby

mov

ing

the

Dew

arfla

sk.

The

mix

ture

inth

eso

lubi

lity

vess

elw

asst

irred

byus

ing

two

exte

rnal

elec

trom

agne

ts,

and

illum

inat

edto

obse

rve

disa

ppea

ranc

eor

appe

aran

ceof

the

last

crys

tals

.

NH

4S

CN

and

urea

wer

ech

emic

ally

pure

prod

ucts

,tw

ice

recr

ysta

llize

dfr

omw

ater

,an

ddr

ied

at50

°Cbe

fore

use.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 L.N

.E

raiz

eran

dI.

M.

Kag

ansk

ii,Z

avod

skay

aLa

b.33,

119

~196

7!.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Ure

a;C

H 4N

2O

;@5

7-13

-6#

~3!

Wat

er;

H 2O

;@7

732-

18-5#

A.

M.

Bab

enko

and

A.

M.

And

riano

v,Z

h.N

eorg

.K

him

.23,

2819

–25

~197

8!.

Varia

bles

:P

repa

red

By:

T/K

:24

1–

266

100

w2

/mas

s%

:0–

39J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–C

H 4N

2O

–H

2O

syst

emas

mea

sure

dby

poly

ther

mal

met

hod

CH

4N

2O

(100

w2

/mas

s%

)N

H4S

CN

(100

w1

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

CH

4N

2O

(100

w2

/mas

s%

)N

H4S

CN

(100

w1

/mas

s%

)

Liqu

idus

tem

pera

ture

(t/°

C)

Sol

idph

asea

33.0

02

10.6

A1B

042

.02

25.3

A1C

32.0

6.8

214

.0A1

B6.

040

.02

26.6

A1C

29.8

14.0

42

17.4

A1B

12.4

38.0

227

.6A1

C

27.8

21.6

62

19.8

A1B

19.2

36.0

229

.8A1

C

26.0

25.9

222

.3A1

B23

.17

33.8

232

.2A1

B1

C

26.6

29.3

62

27.8

A1B

24.9

638

.02

29.7

B1C

29.0

35.5

229

.8A1

B28

.836

.02

26.4

B1C

32.0

37.4

220

.6A1

B35

.236

.02

15.6

B1C

39.0

40.0

27.

0B1

C

a A:

Ice,

H2O

,@7

732-

18-5#

;B

:C

H4N

2O

,@5

7-13

-6#;

C:

NH

4S

CN

,@17

62-9

5-4#.

Sol

ubili

tyis

othe

rms

inth

eN

H 4SC

N–

CH 4

N2O

–H

2O

syst

emb,

c

Tem

pera

ture

(t/°

C)

CH

4N

2O

(100

w2

/mas

s%

)C

H4N

2O

(m2

/mol

kg2

1)d

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)d

220

00

44.6

10.5

8

5.68

1.85

043

.211

.10

11.6

84.

163

41.6

11.7

0

21.2

88.

966

39.2

13.0

3

21.0

8.85

339

.513

.14

b S th c S d C Me


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Met

hylth

iocy

anat

e;C 2H

3N

S~C

H3C

NS

);@5

56-6

4-9#

Wat

er;

H 2O

;@7

732-

18-5#

E.S

pacc

amel

aM

arch

etti,

Atti

.Aca

d.S

ci.T

orin

o,C

lase

Fis

.Mat

.N

at.9

4,35

3–

70~1

960!

.

riabl

es:

Pre

pare

dB

y:

K:

293

tioof

H2O

/C2H

3N

Sco

ncen

trat

ions

J.H

ala

Exp

erim

enta

lDat

aP

hase

diag

ram

ofth

eN

H 4SC

N–

C 2H

3N

S–

H 2O

syst

emat

20°C

The

tern

ary

phas

edi

agra

mof

the

NH

4S

CN

–C 2

H3N

S–

H 2O

syst

emat

20°C

was

repo

rted~F

ig.

32!.

The

follo

win

gfie

lds

wer

ese

rved

inth

edi

agra

m:

Ian

dII—

one

liqui

dph

ase,

III—

two

liqui

dph

ases

,IV

and

VI—

one

liqui

dph

ase

ineq

uilib

rium

with

solid

4S

CN

,an

dV

—tw

oliq

uid

phas

esin

equi

libriu

mw

ithso

lidN

H4S

CN

.N

umer

ical

data

wer

ere

port

edfo

rth

eso

lubi

lity

ofN

H4S

CN

inte

r-ric

hC 2

H3N

S–

H 2O

mix

ture

s~cu

rve

RP

inth

edi

agra

m!an

din

C 2H

3N

S-r

ich

C 2H

3N

S–

H 2O

mix

ture

s~cu

rve

QS

inth

edi

agra

m!.

FIG

.32

.P

hase

diag

ram

ofth

eN

H4S

CN

–C

H 3C

NS

–H 2

Osy

stem

at20

°C.

143143JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

~2!

Imid

odic

arbo

nic

diam

ide~b

iure

t!;C

2H

5N

3O

2;

@108

-19-

0#~3

!W

ater

;H 2

O;

@773

2-18

-5#

L.S

.B

lesh

insk

aya,

K.

S.

Sul

aym

anku

lov,

M.

D.

Dav

rano

v,an

dZ

.Yu

.Yu

nuso

va,

Dep

.D

oc.

VIN

ITI

No.

120

–83~

1983

!.

Varia

bles

:P

repa

red

By:

T/K

:30

310

0w

2/m

ass

%:

0–

3.78

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

inaq

ueou

sso

lutio

nsof

biur

etat

30°C

HN

~CO

NH

2) 2

(100

w2

/mas

s%

)H

N~C

ON

H2) 2

(m2

/mol

kg2

1)a

NH

4S

CN

(100

w1

/mas

s%

)N

H4S

CN

(m1

/mol

kg2

1)a

Sol

idph

aseb

00

67.5

027

.28

A

0.62

0.18

2866

.48

26.5

5A

2.52

0.72

6963

.85

24.9

4A

3.78

1.08

262

.32

24.1

5A1

B

3.61

0.99

1361

.06

22.7

0B

3.50

0.64

8844

.17

11.0

9B

2.62

0.37

7330

.02

5.85

5B

2.77

0.32

5914

.78

2.35

5B

3.08

0.30

830

0B

a Cal

cula

ted

byco

mpi

ler.

b A:

NH

4S

CN

,@17

62-9

5-4#;

B:

HN

~CO

NH

2) 2

,@1

08-1

9-0#. Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

atio

nw

asca

rrie

dou

tfo

r8

–9

h,w

hich

was

foun

dsu

ffici

ent

tore

ach

equi

libriu

m.

Sol

idph

ases

wer

ech

arac

teriz

edby

the

met

hod

ofw

etre

sidu

es.

Inth

esa

tura

ted

solu

tions

,S

CN

2w

aspr

ecip

itate

dw

ithst

oich

iom

etric

amou

ntof

AgN

O 3,

and

the

filtr

ates

wer

ean

alyz

edfo

rN

H 41tit

rimet

rical

lyby

the

form

alde

hyde

met

hod,

and

for

tota

lnitr

ogen

byK

jeld

ahlm

etho

d.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

ra ob NH

wa

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Ani

line;

C6H

7N

;@6

2-53

-3#

Wat

er;

H 2O

;@7

732-

18-5#

L.D

.Vo

robe

vaan

dI.

L.K

rupa

tkin

,Ph

ase

Eq

uili

bria~

Rus

sian

editi

on!,

~Kal

inin

.G

osud

.U

niv.

,19

74!,

pp.

26–

31.

riabl

es:

Pre

pare

dB

y:

K:

298

iline

/wat

erco

ncen

trat

ion

ratio

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eN

H 4S

CN

–an

iline

–H 2

Osy

stem

at25

°CC

ompo

sitio

nof

syst

ems

corr

espo

ndin

gto

the

crys

talli

zatio

ncu

rve

inth

eN

H4S

CN

–an

iline

–H 2

Oph

ase

diag

ram

C6H

7N

(100

w2

/mas

s%

)H

2O

(100

w3

/mas

s%

)N

H4S

CN

(100

w1

/mas

s%

)

035

.50

64.5

0a

5.44

33.6

760

.89

16.7

828

.66

54.5

6

20.0

125

.45

49.5

4

40.1

920

.54

39.2

7

53.4

215

.37

31.2

1

72.4

27.

9519

.58

81.5

14.

2614

.23

89.4

70

10.5

9b

olub

ility

ofN

H4S

CN

inw

ater

;m15

23.8

7m

olkg

21

~com

pile

r!.ol

ubili

tyof

NH

4S

CN

inan

iline

;m15

1.55

6m

olkg

21

~com

pile

r!.

FIG

.33

.P

hase

diag

ram

ofth

eN

H4S

CN

–an

iline

–H 2

Osy

stem

at25

°C.

I:tw

oliq

uid

phas

es;

II:ho

mog

eneo

usre

gion

;an

dIII

:so

lidan

dliq

uid

phas

esin

equi

libriu

m.


Com

posi

tion

ofth

eso

lutio

nssa

tura

ted

at20

°C:

H2O

-ric

hre

gion

C 2H

3N

S-r

ich

regi

on

H2O

(100

w3

/mas

s%

)N

H4S

CN

(100

w1

/mas

s%

)C

2H

3N

S(1

00w

2/m

ass

%)

H2O

(100

w3

/mas

s%

)N

H4S

CN

(100

w1

/mas

s%

)C

2H

3N

S(1

00w

2/m

ass

%)

44.2

55.8a

015

.319

.465

.3

41.9

54.1

4.0

11.0

14.2

74.8

41.6

50.8

7.6

7.2

8.1

84.7

41.5

47.3

11.2

4.2

3.1

92.7

42.1

44.0

13.9

01.

9b98

.1

a Sol

ubili

tyof

NH

4S

CN

inw

ater

,m15

16.5

8m

olkg

21

~com

pile

r!.b S

olub

ility

ofN

H4S

CN

inC 2

H3N

S,m

15

0.25

4m

olkg

21

~com

pile

r!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Sol

ubili

tycu

rves

wer

eob

tain

edby

titra

tion

am

ixtu

reof

two

com

pone

nts

with

the

third

one

ina

ther

mos

tate

dba

th.

Som

eof

thes

em

easu

rem

ents

wer

eve

rified

bypr

epar

ing

the

tern

ary

syst

ems,

and

obse

rvin

gth

ete

mpe

ratu

reof

hom

ogen

izat

ion.

The

valu

eco

rres

pond

ing

to20

°Cw

asth

enob

tain

edby

inte

rpol

atio

n.B

uret

tes

grad

uate

dby

0.01

cm3w

ere

used

for

the

titra

tions

.

NH

4S

CN

was

drie

dat

110

°Cbe

fore

use.

No

deta

ilsre

port

edon

C2H

3N

S.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

~2!

~3!

Va T/

an a S b S


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Am

mon

ium

carb

onat

e;(N

H 4)2C

O3

;@5

06-8

7-6#

Am

mon

ia;

NH 3

;@7

664-

41-7#

Wat

er;

H 2O

;@7

732-

18-5#

I.N

.Bel

yaye

van

dE

.A.G

rigor

eva,

Zh

Neo

rg.K

him

.21

,286

6–

8~1

976!

.

riabl

es:

Pre

pare

dB

y:

K:

288

0w

2/m

ass

%:

0–

44J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofN

H4S

CN

inaq

ueou

sam

mon

iaca

lsol

utio

nsof

(NH

4) 2

CO

3at

15°C

(NH

4) 2

CO

3

00w

2/m

ass

%)

NH

4S

CN

(100

w1

/mas

s%

)H

2O

1N

H3a

@100

(w31

w4)/

mas

s% #

Den

sity

~gcm

23 !

Sol

idph

aseb

061

.335

.21.

1354

A

7.2

57.9

31.9

1.14

83A

12.9

55.6

29.0

1.17

54A

14.8

55.0

28.2

1.17

60A

16.9

54.5

26.6

1.18

50A1

B

hesu

mof

conc

entr

atio

nsof

allf

our

com

pone

nts

varie

dw

ithin

95.5

–98

mas

s%

.Att

hesa

me

time,

the

satu

rate

dso

lutio

nsw

ere

repo

rted

cont

ain

2–

4m

ass

%N

H 3.

The

com

pile

ras

sum

edth

atth

efig

ures

give

nin

this

colu

mn

refe

rred

toth

eco

nten

tofw

ater

only

,whi

leth

eiff

eren

cefr

om10

0m

ass

%w

asth

eco

nten

tof

NH

3.

:N

H4S

CN

,@17

62-9

5-4#;

B:

(NH

4) 2

CO

3•2

NH

4H

CO

3,

@#.

ditio

nal

info

rmat

ion:

Inad

ditio

nto

the

data

com

pile

d,th

eau

thor

sal

sore

port

edth

eco

mpo

sitio

nsof

anot

her

13sa

tura

ted

solu

tions

ntai

ning

20.0

–44

.0m

ass

%(N

H4) 2

CO

3an

d49

–0

mas

s%

NH 4S

CN

whe

reth

eeq

uilib

rium

solid

phas

esw

ere

eith

er(N

H4) 2

CO

3

NH

4H

CO

3or

(NH

4) 2

CO

3•H

2O

.T

hese

data

wer

eno

tin

clud

edin

the

com

pila

tion

sinc

eth

eyre

fer

toth

eso

lubi

lity

of(N

H4) 2

CO

3in

lutio

nsof

NH 4

SC

N.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Sam

ples

wer

eeq

uilib

rate

din

ther

mos

tat

byst

irrin

gin

vess

els

equi

pped

with

hydr

osta

tical

.U

nder

cons

tant

stirr

ing

equi

libriu

mw

asat

tain

edw

ithin

10h.

All

solu

tions

cont

aine

d2

–4

mas

s%

ofN

H3

inex

cess

the

stoi

chio

met

ryof

(NH 4)

2C

O3

inor

der

topr

even

tpr

ecip

itatio

nof

NH 4

HC

O3

.S

atur

ated

solu

tions

and

the

solid

phas

esw

ere

anal

yzed

for

SC

N2

byVo

lhar

dm

etho

d,ca

rbon

ate

was

dete

rmin

edby

volu

met

ricm

etho

d,an

dN

H3

was

titra

ted

agai

nst

stan

dard

HC

lsol

utio

n.S

olid

phas

esw

ere

char

acte

rized

byth

em

etho

dof

wet

resi

dues

.

NH

4S

CN

and

(NH 4

) 2C

O3

wer

ech

emic

ally

pure

prod

ucts

,th

ela

tter

was

recr

ysta

llize

dfr

oma

conc

entr

ated

NH

3so

lutio

n.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:i

nsuf

ficie

ntda

tagi

ven

toal

low

for

erro

res

timat

e.T

hesu

mof

H 2O

1N

H3

mas

s%

:62.

0–

4.5.

145145JIRI HALA


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Pha

sedi

agra

mw

asob

tain

edby

isot

herm

alph

ase

titra

tion

~see

Fig

.33

!N

H4S

CN

,ch

emic

ally

pure

prod

uct,

was

drie

dto

cons

tant

wei

ght

befo

reus

e.A

nilin

ew

aspu

rified

bydi

still

atio

n,an

dth

efr

actio

nbo

iling

poin

tat

184.

2°C

was

used

.T

hepr

oduc

tha

dth

ede

nsity

and

refr

actio

nin

dex

of1.

0224

gcm2

3an

d1.

5862

,re

spec

tivel

y.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.1

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

~4!

Va T/

10 (1 a T to d b A Ad

co •2 so Me

An

a se 8–

to

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Mag

nesi

umth

iocy

anat

e;M

g~SC

N) 2

;@3

06-6

1-6#

Ure

a;C

H 4N

2O

;@5

7-13

-6#

Wat

er;

H 2O

;@7

732-

18-5#

R.

Tur

gunb

ekov

a,K

.N

ogoe

v,an

dK

.S

ulay

man

kulo

v,Z

h.N

eorg

.K

him

.17,

2016

–9~

1972

!.

riabl

es:

Pre

pare

dB

y:

K:

288,

303,

318

0w

2/m

ass

%:

0–

55at

288

K,

0–

64at

303

K,

66.5

at31

8K

J.H

ala

Exp

erim

enta

lDat

aC

ompo

sitio

nof

the

satu

rate

dso

lutio

nsin

the

Mg

~SC

N) 2

–ur

ea–

H 2O

syst

emat

thre

ete

mpe

ratu

res

mpe

ratu

re(t

/°C

)U

rea

(100

w2

/mas

s%

)U

rea

(m2

/mol

kg2

1)b

Mg~

SC

N) 2

(100

w1

/mas

s%

)M

g~S

CN

) 2(m

1/m

olkg

21)b

Sol

idph

asea

150

043

.51

5.48

3A

3.52

1.09

042

.69

5.65

0A

15.0

05.

874

42.4

87.

112

A

15.2

46.

025

42.6

47.

207

A1B

15.5

86.

123

42.0

57.

065

B

19.0

07.

432

38.4

36.

427

B

23.3

69.

105

33.9

25.

653

B

27.0

310

.77

31.1

65.

306

B

32.0

513

.55

28.5

65.

162

B

36.7

616

.50

26.1

55.

019

B

46.1

826

.64

24.9

56.

152

B

48.2

029

.73

24.8

06.

539

B1C

48.1

528

.84

24.0

56.

159

C

51.0

030

.43

21.0

95.

380

C

55.0

532

.42

16.6

84.

200

C

54.2

030

.06

15.7

83.

742

D

50.7

019

.93

6.73

1.12

6D

49.0

016

.00

00

D

300

045

.51

5.94

6A

5.05

1.68

545

.03

6.42

2A

8.85

3.15

244

.39

6.75

8A

16.9

67.

307

44.3

98.

176

A

20.0

99.

485

44.6

49.

010

A

20.0

79.

551

44.9

49.

144

A1B

19.4

99.

137

44.9

99.

017

B

25.9

512

.63

39.8

38.

286

B

32.9

717

.01

34.7

57.

664

B

42.5

524

.52

28.5

67.

038

B

49.1

333

.53

26.4

77.

723

B

52.6

938

.41

24.4

77.

627

B

54.7

043

.66

24.4

48.

341

B1C

54.5

141

.94

23.8

57.

846

C

59.1

345

.94

19.4

46.

458

C

63.8

257

.01

17.5

46.

699

C

64.0

055

.16

16.6

86.

146

C1D

63.0

747

.41

14.7

84.

750

D

59.2

527

.92

5.41

1.09

0D

57.5

022

.53

00

D

450

047

.50

6.44

1A

4.85

1.64

245

.96

6.65

2A


6.7.

Mag

nesi

umT

hioc

yana

te

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Mag

nesi

umth

iocy

anat

e;M

g~SC

N) 2

;@3

06-6

1-6#

~2!

Sol

vent

sI.

L.K

rupa

tkin

,E

.M

.O

stro

vska

ya,

L.D

.Vo

robe

va,

and

G.

V.K

amys

hnik

ova,

Zh.

Obs

h.K

him

.48,

957

–60

~197

8!.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofM

g~S

CN

) 2in

thre

eso

lven

tsat

25°Ca

Sol

vent

Mg~

SC

N) 2

(100

w1

/mas

s%

)M

g~S

CN

) 2(m

1/m

olkg

21)b

Wat

er;

H 2O

;@7

732-

18-5#

46.9

56.

30

Ani

line;

C6H

7N

;@6

2-53

-3#

8.72

c—

o-To

luid

ine;

C 7H

9N

;@9

5-53

-4#

2.41

c—

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler

for

anhy

drou

ssa

lt.c T

heau

thor

sdi

dno

tsp

ecify

whe

ther

this

solu

bilit

yva

lue

refe

rred

toth

ean

hydr

ous

orhy

drat

edsa

lt.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

wer

ere

port

ed.

Mg

~SC

N) 2•4

H2O

,ch

emic

ally

pure

,orig

inno

tspe

cifie

d.A

nilin

ean

do-

tolu

idin

ew

ere

purifi

edby

stan

dard

met

hods

.1

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 A.W

eisb

erge

r,E

.P

rosk

auer

,J.

Rid

dick

,an

dE

.Too

ps,

Org

an

icS

olv

en

ts~R

ussi

aned

ition!

,~IL

Pub

l.H

ouse

,Mos

cow

,195

8!,pp

.35

1,36

1.

Co

~1!

~2!

~3!

Va T/

10 0–

Te


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Mag

nesi

umth

iocy

anat

e;M

g~SC

N) 2

;@3

06-6

1-6#

Thi

oure

a;C

H 4N

2S

;@6

2-56

-6#

Wat

er;

H 2O

;@7

732-

18-5#

K.

S.

Sul

aym

anku

lov,

K.

Aby

keev

,an

dS

.Is

akov

a,He

tero

ge

n.

Eq

uil.

Sys

tem

sIn

org

.O

rg.

Co

mp

ds

.~R

ussi

aned

ition!

~Fru

nze,

US

SR

,19

74!,

pp.

9–

12.

riabl

es:

Pre

pare

dB

y:

K:

303

0w

2/m

ass

%:

0–

17.1

7J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

inth

eM

g~S

CN

) 2–

thio

urea

–H 2

Osy

stem

at30

°C

CH

4N

2S

00w

2/m

ass

%)

CH

4N

2S

(m2

/mol

kg2

1)

Mg~

SC

N) 2

(100

w1

/mas

s%

)M

g~S

CN

) 2(m

1/m

olkg

21)

Sol

idph

asea

00

45.5

5.94

3A

4.28

1.45

542

.05

6.93

4A

10.2

12.

738

40.8

5.92

9A

10.2

12.

766

41.3

06.

063

A

11.7

53.

284

41.2

56.

248

A1B

10.4

02.

785

40.5

45.

883

B

10.4

52.

519

35.0

64.

581

B

10.4

92.

255

28.4

3.30

8B

10.4

82.

019

21.3

42.

228

B

13.1

22.

270

10.9

41.

026

B

15.4

22.

545

4.97

0.44

4B

17.7

12.

827

00

B

:M

g~S

CN

) 2•4

H2O

,@

#;B

:C

H4N

2S

,@62

-56-

6#.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed.

Equ

ilibr

ium

was

reac

hed

thin

6–

8h,

node

tails

abou

teq

uilib

ratio

nm

etho

dw

ere

port

ed.

The

satu

rate

dso

lutio

nsw

ere

anal

yzed

for

the

cont

ent

Mg

and

N.

Mag

nesi

umw

asde

term

ined

byco

mpl

exom

etric

atio

nag

ains

ter

ioch

rom

ebl

ack

Tas

indi

cato

r.T

heco

nten

tth

iour

eaw

asob

tain

edfr

omth

eco

nten

tof

Nas

dete

rmin

edby

Kje

ldah

lmet

hod.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

147147JIRI HALA


12.4

64.

866

44.9

07.

496

A

26.0

614

.96

44.9

411

.03

A

27.3

316

.65

45.3

411

.81

A1B

27.5

916

.51

44.5

911

.41

A1B

28.1

717

.03

44.2

911

.45

B

39.0

922

.76

32.3

18.

043

B

44.1

228

.39

30.0

08.

252

B

48.0

432

.18

27.1

07.

761

B

55.6

746

.63

24.4

58.

756

B

56.0

749

.06

24.9

09.

315

B1C

55.3

345

.01

24.2

08.

416

C

58.4

044

.79

19.8

96.

522

C

63.5

055

.45

17.4

36.

507

C

66.4

771

.68

18.0

98.

341

C

65.9

666

.93

17.6

37.

648

C1D

66.1

164

.53

16.8

37.

023

D

63.5

435

.93

7.01

1.69

5D

64.0

029

.60

00

D

a A:

Mg

~SC

N) 2•4

H2O

,@

#;B

:M

g~S

CN

) 2•4

CH

4N

2O

,@3

7954

-71-

5#;C

:M

g~S

CN

) 2•8

CH

4N

2O

,@3

7954

-70-

4#;D

:C

H4N

2O

,@5

7-13

-6#.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.C

ompo

sitio

nof

the

addu

cts

ofM

g~SC

N) 2

with

urea

was

confi

rmed

bych

emic

alan

alys

isof

the

solid

phas

es.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

Va T/

10 (1 a A Me

An

wi

re of titr

of

J

wer

ean

alyz

edfo

rC

atit

rimet

rical

lyag

ains

ta

stan

dard

solu

tion

ofK

MnO

4vi

apr

ecip

itate

dC

aox

alat

e,an

dfo

rS

CN

2by

Volh

ard

met

hod.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Cal

cium

thio

cyan

ate;

Ca~S

CN

) 2;

@209

2-16

-2#S

olve

nts

I.L.

Kru

patk

in,

E.

M.

Ost

rovs

kaya

,L.

D.

Voro

beva

,an

dG

.V.

Kam

yshn

ikov

a,Z

h.O

bsh.

Khi

m.48

,95

7–

60~1

978!

.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

ofC

a~S

CN

) 2in

thre

eso

lven

tsat

25°Ca

Sol

vent

Ca~

SC

N) 2

(100

w1

/mas

s%

)C

a~S

CN

) 2(m

1/m

olkg

21)b

Wat

er;

H 2O

;@7

732-

18-5#

67.3

413

.20

nilin

e;C

6H

7N

;@6

2-53

-3#

7.72

c—

olui

dine

;C 7

H9N

;@9

5-53

-4#

5.28

c—

olid

phas

esw

ere

not

inve

stig

ated

.al

cula

ted

byco

mpi

ler

for

anhy

drou

ssa

lt.he

auth

ors

did

not

spec

ifyw

heth

erth

isso

lubi

lity

valu

ere

ferr

edto

the

anhy

drou

sor

hydr

ated

salt.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed,

node

tails

wer

ere

port

ed.

Ca

~SC

N) 2•3

H2O

prep

ared

acco

rdin

gto

Kar

yaki

nan

dA

ngel

ov.

1

Ani

line

and

o-to

luid

ine

wer

epu

rified

byst

anda

rdm

etho

ds.

2

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 Yu.

B.

Kar

yaki

nan

dI.

I.A

ngel

ov,P

ure

Ch

em

ica

lS

ub

sta

nce

s~R

ussi

aned

ition!

~Khi

mia

,M

osco

w,

1974!

,p.

137.

2 A.W

eisb

erge

r,E

.P

rosk

auer

,J.

Rid

dick

,an

dE

.Too

ps,

Org

an

icS

olv

en

ts~R

ussi

aned

ition!

~IL

Pub

l.H

ouse

,M

osco

w,

1958!,

pp.

351,

361.


6.8.

Cal

cium

Thi

ocya

nate

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Cal

cium

thio

cyan

ate;

Ca~S

CN

) 2;

@209

2-16

-2#~2

!W

ater

;H 2

O;

@773

2-18

-5#A

.K.M

cKer

row

,V.J

.Occ

lesh

aw,a

ndF.

Dra

bble

,J.C

hem

.Soc

.1

–5

~194

6!.

Varia

bles

:P

repa

red

By:

T/K

:27

3–

323

J.H

a´ la

Exp

erim

enta

lDat

aS

olub

ility

ofC

a~S

CN

) 2in

wat

eras

afu

nctio

nof

tem

pera

ture

Tem

pera

ture

(t/°

C)

Ca~

SC

N) 2

(100

w1

/mas

s%

)C

a~S

CN

) 2(m

1/m

olkg

21)b

Sol

idph

asea

055

.44

7.96

3A

856

.11

8.18

2A

1657

.90

8.80

2A

2059

.00

9.21

0A

2359

.80

9.52

1A

2560

.20

9.68

1B

27.5

60.2

69.

705

B

3060

.54

9.82

0B

3560

.94

9.98

6B

4161

.69

10.3

1B

4562

.37

10.6

8B

5063

.27

11.0

3B

a A:

b-m

odifi

catio

nof

Ca~S

CN

) 2•4

H2O

;B

:a-m

odifi

catio

nof

Ca~S

CN

) 2•4

H2O

.

Add

ition

alin

form

atio

n:T

hepo

int

oftr

ansi

tion

from

b-

toa

-mod

ifica

tion

ofC

a~SC

N) 2•4

H2O

occu

rred

at23

.7°C

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

The

salt

was

shak

enw

ithw

ater

inha

rd/g

lass

tube

sun

tila

suffi

cien

tex

cess

ofth

esa

ltre

mai

ned,

and

rota

ted

ina

ther

mos

tat

for

ada

y.In

ocul

atio

nw

asus

ually

requ

ired

toin

duce

crys

talli

zatio

n.T

heso

lidph

ases

wer

ech

arac

teriz

edby

optic

alm

icro

scop

y.S

atur

ated

solu

tions

Ca~

SC

N) 2

,so

urce

not

spec

ified

,w

asre

crys

talli

zed

from

wat

erun

tilth

eC

a/S

CN

ratio

was

satis

fact

ory.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

rs!.

Co

~1!

~2!

Va T/ A

o-T

a S b C c T Me

An


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Cal

cium

thio

cyan

ate;

Ca~S

CN

) 2;

@209

2-16

-2#S

odiu

mth

iocy

anat

e;N

aSC

N;@540

-72-

7#W

ater

;H 2

O;

@773

2-18

-5#

A.K

.McK

erro

w,V

.J.O

ccle

shaw

,and

F.D

rabb

le,J

.Che

m.S

oc.

1–

5~1

946!

.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

590

w1

/mas

s%

:0

–60

.2

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eC

a~SC

N) 2

–N

aSC

N–

H 2O

syst

emat

25°C

NaS

CN

00w

2/m

ass

%)

NaS

CN

(m2

/mol

kg2

1)b

Ca~

SC

N) 2

(100

w1

/mas

s%

)C

a~S

CN

) 2(m

1/m

olkg

21)b

Sol

idph

asea

00

60.2

09.

681

A

3.09

0.99

258

.49

9.74

3A

5.11

1.68

857

.57

9.87

3A

8.78

2.99

955

.11

9.76

8A

9.88

3.41

954

.48

9.78

3A1

B

11.1

03.

869

53.5

29.

682

B

11.1

53.

839

53.0

39.

475

B

14.1

44.

819

49.6

78.

784

B

16.3

65.

427

46.4

67.

997

B

19.5

76.

496

43.2

77.

452

B

21.3

26.

990

41.0

66.

985

B

22.4

07.

331

39.9

16.

777

B

29.3

29.

460

32.4

55.

432

B

32.3

810

.53

29.7

15.

015

B

37.9

112

.29

24.0

74.

052

B

38.8

212

.58

23.1

33.

890

B

41.7

413

.66

20.5

93.

498

B

42.9

913

.98

19.0

93.

222

B1C

42.9

813

.94

19.0

03.

198

C

45.3

714

.47

15.9

72.

643

C

52.0

815

.77

7.19

1.12

9C

58.7

817

.58

00

C

a A:

Ca~

SC

N) 2•4

H2O

,@

#;B

:N

aSC

N,@

540-

72-7#

;C

:N

aSC

N•2

H2O

,@1

7032

-40-

5#.b C

alcu

late

dby

com

pile

r.

See

Fig

.34

and

note

that

the

orig

inal

docu

men

tre

port

edal

soth

eco

mpo

sitio

nof

four

met

asta

ble

syst

ems.

The

seha

veno

tbe

enin

clud

ed

inth

eco

mpi

latio

n.

149149JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Cal

cium

thio

cyan

ate;

Ca~S

CN

) 2;

@209

2-16

-2#~2

!N

,N-D

imet

hyla

ceta

mid

e;C 4H

9N

O;

@127

-19-

5#A

.A.F

edor

ov,L

.B.S

okol

ov,V

.M.S

avin

ov,M

.A.S

hlio

nska

ya,

and

N.

I.F

ilato

va,

Zh.

Prik

l.K

him

.44,

2361

–2~

1971

!.

Varia

bles

:P

repa

red

By:

T/K

:29

5–

298

J.H

a´ la

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofC

a~SC

N) 2

inN

,N-d

imet

hyla

ceta

mid

eis

repo

rted

toc 15

0.24

mol

dm2

3at

22–

25°C

.The

natu

reof

the

equi

libriu

mso

lidph

ase

was

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solv

ent

was

satu

rate

dw

ithan

hydr

ous

salt.

The

na

part

ofth

eso

lven

tw

asdi

still

edof

fto

rem

ove

wat

er,

and

the

satu

rate

dso

lutio

nw

ithex

cess

solid

was

kept

for

3da

ysin

ade

sicc

ator

ina

para

ffine

-coa

ted

flask

.T

heco

nten

tof

wat

erin

the

satu

rate

dso

lutio

nw

asle

ssth

an0.

1%.

The

satu

rate

dso

lutio

nw

asan

alyz

edfo

rth

eco

nten

tof

sulfu

rby

anun

spec

ified

met

hod.

Anh

ydro

usC

a~SC

N) 2

,so

urce

nots

peci

fied,

was

drie

dat

120

°Cfo

r6

h.N

,N-d

imet

hyla

ceta

mid

e,so

urce

not

spec

ified

,w

asfr

eshl

ydi

still

edbe

fore

use.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 10 (1

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Cal

cium

thio

cyan

ate;

Ca~S

CN

) 2;

@209

2-16

-2#P

otas

sium

thio

cyan

ate;

KS

CN

;@3

33-2

0-0#

Wat

er;

H 2O

;@7

732-

18-5#

A.K

.McK

erro

w,V

.J.O

ccle

shaw

,and

F.D

rabb

le,J

.Che

m.S

oc.

1–

5~1

946!

.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

70.7

0w

1/m

ass

%:

0–

60.2

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eC

a~SC

N) 2

–K

SC

N–

H 2O

syst

emat

25°C

KS

CN

00w

2/m

ass

%)

KS

CN

(m2

/mol

kg2

1)b

Ca~

SC

N) 2

(100

w1

/mas

s%

)C

a~S

CN

) 2(m

1/m

olkg

21)b

Sol

idph

asea

00

60.2

09.

681

A

2.13

0.56

358

.99

9.71

0A

5.23

1.45

257

.71

9.96

6A

7.90

2.29

456

.67

10.2

3A

10.4

63.

178

55.6

810

.52

A

13.8

14.

468

54.3

910

.94

A

17.5

46.

166

53.1

911

.63

A

17.7

76.

294

53.1

811

.71

A1B

18.6

26.

481

51.8

211

.22

B

24.0

08.

414

46.6

510

.17

B

26.5

59.

489

44.6

69.

928

B

32.5

612

.29

40.1

79.

428

B

35.3

913

.65

37.9

59.

110

B

36.2

814

.22

37.4

79.

136

B1C

36.8

914

.63

37.1

89.

177

C

39.0

615

.62

35.2

28.

764

C

40.2

216

.19

34.2

28.

568

C

41.1

216

.79

33.6

98.

560

C

42.0

717

.23

32.8

18.

359

C

42.8

417

.59

32.1

18.

204

C

43.5

618

.08

31.6

68.

177

c

43.7

718

.75

32.2

18.

582

C1D

43.7

518

.10

31.3

98.

081

D

44.0

916

.96

29.1

66.

977

D

45.5

716

.85

26.6

16.

122

D

49.3

417

.35

21.4

14.

684

D

53.3

818

.40

16.7

83.

599

D

59.3

220

.23

10.5

12.

229

D

66.1

622

.82

4.01

0.86

0D

70.7

624

.90

00

D

a A:

Ca~

SC

N) 2•4

H2O

,@

#;B

:2

KS

CN•

Ca~

SC

N) 2•3

H2O

,@

#;C

:3

KS

CN•

Ca~

SC

N) 2•3

H2O

,@

#;D

:K

SC

N,@

333-

20-0#

.b C

alcu

late

dby

com

pile

r.c S

olid

phas

eno

tre

port

ed.

Add

ition

alin

form

atio

n:T

heor

igin

aldo

cum

entr

epor

ted

also

the

com

posi

tion

ofei

ghtm

etas

tabl

esy

stem

s.T

hese

are

noti

nclu

ded

here

.In

som

eof

thes

esy

stem

s,C

a~S

CN

) 2•2

H2O

,a

solid

solu

tion

with

aco

mpo

sitio

nap

proa

chin

gth

atof

the

doub

lesa

lt4

KS

CN

•C

a~S

CN

) 2•2

H2O

,an

dan

othe

rm

odifi

catio

nof

Ca

~SC

N) 2•4

H2O

,la

bele

das

theb

mod

ifica

tion,

wer

efo

und

asm

etas

tabl

eso

lidph

ases

~see

Fig

.35!.


FIG

.34

.P

hase

diag

ram

ofth

eC

a~S

CN

) 2–

NaS

CN

–H 2

Osy

stem

at25

°C.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Kno

wn

prop

ortio

nsof

the

salts

wer

esh

aken

with

defin

itevo

lum

esof

wat

erin

hard

-gla

sstu

bes

until

asu

ffici

ent

exce

ssof

solid

rem

aine

d.T

hem

ixtu

res

wer

eth

enhe

ated

until

solu

tion

was

com

plet

e,an

dfin

ally

rota

ted

ina

ther

mos

tat

for

1da

y.S

uita

ble

inoc

ulat

ion

was

usua

llyre

quire

dto

indu

cecr

ysta

lliza

tion.

The

natu

reof

the

solid

phas

esw

asde

term

ined

byth

em

etho

dof

wet

resi

dues

and

byop

tical

mic

rosc

opy.

Filt

ratio

nof

the

satu

rate

dso

lutio

nsw

asca

rrie

dou

tat

25°C

.S

atur

ated

solu

tions

and

the

wet

resi

dues

wer

ean

alyz

edfo

rC

atit

rimet

rical

lyw

itha

stan

dard

KM

nO4

solu

tion

via

prec

ipita

ted

Ca

oxal

ate,

and

for

tota

lS

CN2

byVo

lhar

dm

etho

d.T

heco

nten

tof

NaS

CN

was

obta

ined

bydi

ffere

nce.

Ca~

SC

N) 2

,so

urce

not

spec

ified

,w

asre

crys

talli

zed

from

wat

erun

tilth

eC

a/S

CN

ratio

was

satis

fact

ory.

NaS

CN

was

prep

ared

acco

rdin

gto

Occ

lesh

aw1by

repe

ated

crys

talli

zatio

nfr

omw

ater

ofa

com

mer

cial

prod

uct~s

ourc

eno

tsp

ecifi

ed!.T

here

mai

ning

Na 2

CO

3im

purit

yw

asre

mov

edby

crys

talli

zatio

nfr

om96

%et

hano

land

dryi

ngat

130

°C.

The

anhy

drou

ssa

ltco

ntai

ned

the

theo

retic

alS

CN2

perc

enta

ge.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Ref

eren

ces:

1 V.J.

Occ

lesh

aw,

J.C

hem

.S

oc.

55~1

931!

.

Co

~1!

~2!

~3!

Va T/

10 10 (1


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Cal

cium

thio

cyan

ate;

Ca~S

CN

) 2;

@209

2-16

-2#A

mm

oniu

mth

iocy

anat

e;N

H 4SC

N;@

1762

-95-

4#W

ater

;H 2

O;

@773

2-18

-5#

A.K

.McK

erro

w,V

.J.O

ccle

shaw

,and

F.D

rabb

le,J

.Che

m.S

oc.

1–

5~1

946!

.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

64.3

0w

1/m

ass

%:

0–

60.2

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eC

a~SC

N) 2

–N

H4S

CN

–H 2

Osy

stem

at25

°C

NH

4S

CN

00w

2/m

ass

%)

NH

4S

CN

(m2

/mol

kg2

1)b

Ca~

SC

N) 2

(100

w1

/mas

s%

)C

a~S

CN

) 2(m

1/m

olkg

21)b

Sol

idph

asea

00

60.2

09.

681

A

9.29

3.63

557

.14

10.8

9A

15.2

36.

745

55.1

111

.89

A

17.3

28.

414

55.6

413

.17

A1B

18.4

08.

742

53.9

512

.48

B

20.5

510

.30

53.2

613

.01

B

21.3

810

.96

52.7

613

.05

B

23.3

112

.21

51.6

213

.17

B

24.4

513

.07

50.9

913

.28

B

25.5

513

.80

50.1

313

.19

B1C

25.5

013

.61

49.8

912

.97

B1C

25.9

513

.64

49.0

712

.57

C

26.8

713

.66

47.3

911

.71

C

28.1

514

.44

46.3

411

.55

C

29.0

414

.88

45.3

311

.31

C

31.3

716

.26

43.2

910

.93

C

31.4

816

.34

43.2

210

.93

C

32.8

916

.92

41.5

810

.42

C

34.1

317

.45

40.1

910

.01

C

34.3

517

.25

39.4

99.

661

C

35.2

417

.75

39.0

49.

640

C

36.9

818

.83

37.3

69.

318

C

37.6

719

.54

37.0

19.

355

C1D

37.8

417

.65

34.0

07.

727

D

40.3

816

.52

27.5

25.

487

D

42.7

216

.67

23.6

24.

491

D

49.1

818

.93

16.7

03.

132

D

57.8

521

.80

7.29

1.33

8D

64.2

323

.96

00

D

a A:

Ca~

SC

N) 2•4

H2O

,@

#;B

:7

NH

4S

CN•

6C

a~S

CN

) 2•12

H2O

,@

#;C

:4

NH

4S

CN•

Ca~

SC

N) 2•2

H2O

,@

#;D

:N

H4S

CN

,@17

62-9

5-4#.

b Cal

cula

ted

byco

mpi

ler.

151151JIRI HALA


FIG

.35

.P

hase

diag

ram

ofth

eC

a~S

CN

) 2–

KS

CN

–H 2

Osy

stem

at25

°C.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Kno

wn

prop

ortio

nsof

the

salts

wer

esh

aken

with

defin

itevo

lum

esof

wat

erin

hard

-gla

sstu

bes

until

asu

ffici

ent

exce

ssof

solid

rem

aine

d.T

hem

ixtu

res

wer

eth

enhe

ated

until

solu

tion

was

com

plet

e,an

dfin

ally

rota

ted

ina

ther

mos

tatf

or1

day.

Sui

tabl

ein

ocul

atio

nw

asus

ually

requ

ired

toin

duce

crys

talli

zatio

n.T

hena

ture

ofth

eso

lidph

ases

was

dete

rmin

edby

the

met

hod

ofw

etre

sidu

esan

dby

optic

alm

icro

scop

y.F

iltra

tion

ofth

esa

tura

ted

solu

tions

was

carr

ied

out

at25

°C.S

atur

ated

solu

tions

and

the

wet

resi

dues

wer

ean

alyz

edfo

rC

atit

rimet

rical

lyw

itha

stan

dard

KM

nO 4so

lutio

nvi

apr

ecip

itate

dC

aox

alat

e,an

dfo

rto

talS

CN

2by

Volh

ard

met

hod.

The

cont

ent

ofK

SC

Nw

asob

tain

edby

diffe

renc

e.

Ca~

SC

N) 2

,so

urce

not

spec

ified

,w

asre

crys

talli

zed

from

wat

erun

tilth

eC

a/S

CN

ratio

was

satis

fact

ory.

KS

CN

,Ana

laR

qual

ity,

sour

ceno

tsp

ecifi

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 10 (1

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Cal

cium

thio

cyan

ate;

Ca~S

CN

) 2;

@209

2-16

-2#M

ethy

lthio

cyan

ate;

C 2H3N

S~C

H3C

NS

);@5

56-6

4-9#

Wat

er;

H 2O

;@7

732-

18-5#

E.S

pacc

amel

aM

arch

etti,

Atti

.Aca

d.S

ci.T

orin

o,C

lase

Fis

.Mat

.N

at.9

4,35

3–

70~1

960!

.

riabl

es:

Pre

pare

dB

y:

K:

293

tioof

H2O

/C2H

3N

Sco

ncen

trat

ions

J.H

ala

Exp

erim

enta

lDat

a

Pha

sedi

agra

mof

the

Ca

~SC

N) 2

–C

2H

3N

S–

H 2O

syst

emat

20°C

The

tern

ary

phas

edi

agra

mof

the

Ca

~SC

N) 2

–C

2H

3N

S–

H 2O

syst

emat

20°C

was

repo

rted~F

ig.

37!.

The

follo

win

gfie

lds

wer

e

serv

edin

the

diag

ram

:I

and

II—on

eliq

uid

phas

e,III

—tw

oliq

uid

phas

es,

IVan

dV

I—on

eliq

uid

phas

ein

equi

libriu

mw

ithso

lid

~SC

N) 2

,an

dV

—tw

oliq

uid

phas

esin

equi

libriu

mw

ithso

lidC

a~S

CN

) 2.

Num

eric

alda

taw

ere

repo

rted

for

the

solu

bilit

yof

Ca

~SC

N) 2

wat

er-r

ich

C 2H

3N

S–

H 2O

mix

ture

s~cu

rve

RP

inth

edi

agra

m!an

din

C 2H

3N

S-r

ich

C 2H

3N

S–

H 2O

mix

ture

s~cu

rve

QS

inth

edi

agra

m!.

FIG

.37

.P

hase

diag

ram

ofth

eC

a~S

CN

) 2–

CH

3C

NS

–H 2

Osy

stem

at20

°C.

Com

posi

tion

ofth

eso

lutio

nssa

tura

ted

at20

°C:

H2O

-ric

hre

gion

C 2H

3N

S-r

ich

regi

on

H2O

(100

w3

/mas

s%

)C

a~S

CN

) 2(1

00w

1/m

ass

%)

C2H

3N

S(1

00w

2/m

ass

%)

H2O

(100

w3

/mas

s%

)C

a~S

CN

) 2(1

00w

1/m

ass

%)

C2H

3N

S(1

00w

2/m

ass

%)

40.2

59.8a

012

.820

.966

.3

37.7

56.2

6.1

9.4

14.6

76.0

37.3

53.4

7.6

6.5

11.1

82.4

36.5

48.3

15.2

4.8

7.3

87.9

07.

3b92

.7

a Sol

ubili

tyof

Ca~

SC

N) 2

inw

ater

,m15

9.52

mol

kg2

1~c

ompi

ler!.


FIG

.36

.P

hase

diag

ram

ofth

eC

a~S

CN

) 2–

NH

4S

CN

–H 2

Osy

stem

at25

°C.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Kno

wn

prop

ortio

nsof

the

salts

wer

esh

aken

with

defin

itevo

lum

esof

wat

erin

hard

-gla

sstu

bes

until

asu

ffici

ent

exce

ssof

solid

rem

aine

d.T

hem

ixtu

res

wer

eth

enhe

ated

until

solu

tion

was

com

plet

e,an

dfin

ally

rota

ted

ina

ther

mos

tat

for

1da

y.S

uita

ble

inoc

ulat

ion

was

usua

llyre

quire

dto

indu

cecr

ysta

lliza

tion.

The

natu

reof

the

solid

phas

esw

asde

term

ined

byth

em

etho

dof

wet

resi

dues

and

byop

tical

mic

rosc

opy.

Filt

ratio

nof

the

satu

rate

dso

lutio

nsw

asca

rrie

dou

tat

25°C

.S

atur

ated

solu

tions

and

the

wet

resi

dues

wer

ean

alyz

edfo

rC

atit

rimet

rical

lyw

itha

stan

dard

KM

nO4

solu

tion

via

prec

ipita

ted

Ca

oxal

ate,

and

for

tota

lS

CN2

byVo

lhar

dm

etho

d.T

heco

nten

tof

NH 4S

CN

was

obta

ined

bydi

ffere

nce~s

eeF

ig.

36!.

Ca~

SC

N) 2

,so

urce

not

spec

ified

,w

asre

crys

talli

zed

from

wat

erun

tilth

eC

a/S

CN

ratio

was

satis

fact

ory.

NH

4S

CN

,A

nala

Rqu

ality

,so

urce

not

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

rs!.

Sol

ubili

ty:

insu

ffici

ent

data

give

nto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

ra ob Ca

in


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Cal

cium

thio

cyan

ate;

Ca~S

CN

) 2;

@209

2-16

-2#A

mm

oniu

mth

iocy

anat

e;N

H 4SC

N;@

1762

-95-

4#A

mm

onia

;N

H 3;

@766

4-41

-7#

A.S

tasi

ewic

z,A

nn.U

niv.

M.C

urie

/Skl

odow

ska,

Lubl

in,P

olan

d14

,S

ect.

AA

,49

–57

~195

9!.

riabl

es:

Pre

pare

dB

y:

K:

291

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofC

a~SC

N) 2

inliq

uid

amm

onia

teof

NH 4

SC

Nis

repo

rted

tobe

c 15

1.80

mol

dm2

3or

100

w15

30.0

mas

s%

at°C

.T

heco

mpo

sitio

nof

the

solv

ent

corr

espo

nded

toth

em

olar

ratio

NH

3/N

H4S

CN5

2.7.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eam

mon

iate

ofN

H 4SC

N,

acl

ear

liqui

d~de

nsity

of0.

9345

cm2

3 !,w

asob

tain

edby

actio

nof

NH 3ga

son

toso

lid

4S

CN

atat

mos

pher

icpr

essu

re.

The

prep

arat

ion

ofth

elv

ent,

and

solu

bilit

ym

easu

rem

ents

wer

eca

rrie

dou

tin

adr

yx

unde

ra

stre

amof

dry

NH 3ga

s.

Ca~

SC

N) 2

was

prep

ared

byth

ere

actio

nof

Ca

~OH

) 2w

ithN

H4S

CN

.T

heco

mpo

sitio

nof

the

salt

prep

ared

was

not

spec

ified

.N

H 4S

CN

,A

rgon

-Lod

z,w

asre

peat

edly

recr

ysta

llize

d,an

ddr

ied

ina

dess

icat

orov

erco

ncen

trat

edH

2S

O4

,fir

stat

norm

alpr

essu

rean

dth

enun

der

vacu

umfo

r1

mon

th.A

mm

onia

was

drie

dw

ithN

am

etal

ina

stee

lcon

tain

er.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

153153JIRI HALA


b Sol

ubili

tyof

Ca~

SC

N) 2

inC

2H

3N

S,m

15

0.50

4m

olkg

21

~com

pile

r!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Sol

ubili

tycu

rves

wer

eob

tain

edby

titra

tion

am

ixtu

reof

two

com

pone

nts

with

the

third

one

ina

ther

mos

tate

dba

th.

Som

eof

thes

em

easu

rem

ents

wer

eve

rified

bypr

epar

ing

the

tern

ary

syst

ems,

and

obse

rvin

gth

ete

mpe

ratu

reof

hom

ogen

izat

ion.

The

valu

eco

rres

pond

ing

to20

°Cw

asth

enob

tain

edby

inte

rpol

atio

n.B

uret

tes

grad

uate

dby

0.01

cm3w

ere

used

for

the

titra

tions

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

~2!

~3!

Va T/

18 Me

Th

g NH

so bo

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Str

ontiu

mth

iocy

anat

e;S

r~S

CN

) 2;

@188

07-1

0-8#

Am

mon

ium

thio

cyan

ate;

NH 4S

CN

;@17

62-9

5-4#

Am

mon

ia;

NH 3

;@7

664-

41-7#

A.S

tasi

ewic

z,A

nn.U

niv.

M.C

urie

/Skl

odow

ska,

Lubl

in,P

olan

d14

,S

ect.

AA

,49

–57

~195

9!.

riabl

es:

Pre

pare

dB

y:

K:

291

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofS

r~SC

N) 2

inliq

uid

amm

onia

teof

NH 4

SC

Nis

repo

rted

tobec

15

1.68

mol

dm2

3or

100

w15

36.5

mas

s%

at18

°C.

eco

mpo

sitio

nof

the

solv

ent

corr

espo

nded

toth

em

olar

ratio

NH

3/N

H4S

CN5

2.7.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eam

mon

iate

ofN

H 4SC

N,

acl

ear

liqui

d~de

nsity

of0.

9345

cm2

3 !,w

asob

tain

edby

actio

nof

NH 3ga

son

toso

lid

4S

CN

atat

mos

pher

icpr

essu

re.

The

prep

arat

ion

ofth

elv

ent,

and

solu

bilit

ym

easu

rem

ents

wer

eca

rrie

dou

tin

adr

yx

unde

ra

stre

amof

dry

NH 3ga

s.

Sr~S

CN

) 2w

aspr

epar

edby

the

reac

tion

ofS

r~O

H) 2

with

NH

4S

CN

.T

heco

mpo

sitio

nof

the

salt

prep

ared

was

not

spec

ified

.N

H 4S

CN

,A

rgon

-Lod

z,w

asre

peat

edly

recr

ysta

llize

d,an

ddr

ied

ina

dess

icat

orov

erco

ncen

trat

edH

2S

O4

,fir

stat

norm

alpr

essu

rean

dth

enun

der

vacu

umfo

ra

mon

th.A

mm

onia

was

drie

dw

ithN

aM

etal

ina

stee

lcon

tain

er.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.


6.9.

Str

ontiu

mT

hioc

yana

te

Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Str

ontiu

mth

iocy

anat

e;S

r~S

CN

) 2;

@188

07-1

0-8#

~2!

Sol

vent

sI.

L.K

rupa

tkin

,E

.M

.O

stro

vska

ya,

L.D

.Vo

robe

va,

and

G.

V.K

amys

hnik

ova,

Zh.

Obs

h.K

him

.48,

957

–60

~197

8!.

Varia

bles

:P

repa

red

By:

T/K

:29

8J.

Hala

Exp

erim

enta

lDat

aS

olub

ility

ofS

r~SC

N) 2

inth

ree

solv

ents

at25

°Ca

Sol

vent

Sr~S

CN

) 2(1

00w

1/m

ass

%)

Sr~S

CN

) 2(m

1/m

olkg

21)b

Wat

er;

H 2O

;@7

732-

18-5#

56.4

36.

356

Ani

line;

C6H

7N

;@6

2-53

-3#

7.21

c—

o-To

luid

ine;

C 7H

9N

;@9

5-53

-4#

1.73

c—

a Sol

idph

ases

wer

eno

tin

vest

igat

ed.

b Cal

cula

ted

byco

mpi

ler

for

anhy

drou

ssa

lt.c T

heau

thor

sdi

dno

tsp

ecify

whe

ther

this

solu

bilit

yva

lue

refe

rred

toth

ean

hydr

ous

orhy

drat

edsa

lt.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

wer

ere

port

ed.

Sr

~SC

N) 2•3

H2O

prep

ared

acco

rdin

gto

Kar

yaki

nan

dA

ngel

ov.

1

Ani

line

and

o-to

luid

ine

wer

epu

rified

byst

anda

rdm

etho

ds.

2

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 Yu.

B.

Kar

yaki

nan

dI.

I.A

ngel

ov,P

ure

Ch

em

ica

lS

ub

sta

nce

s~R

ussi

aned

ition!

~Khi

mia

,M

osco

w,

1974!

,p.

137.

2 A.W

eisb

erge

r,E

.P

rosk

auer

,J.

Rid

dick

,an

dE

.Too

ps,

Org

an

icS

olv

en

ts~R

ussi

aned

ition!

~IL

Pub

l.H

ouse

,M

osco

w,

1958!,

pp.

351,

361.

Co

~1!

~2!

~3!

Va T/

Th

Me

Th

g NH

so bo


irmpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#W

ater

;H 2

O;

@773

2-18

-5#I.

L.K

rupa

tkin

,E

.M

.O

stro

vska

ya,

L.D

.Vo

robe

va,

and

G.

V.K

amys

hnik

ova,

Zh.

Obs

h.K

him

.48,

957

–60

~197

8!.

riabl

es:

Pre

pare

dB

y:

K:

298

J.H

ala

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofB

a~SC

N) 2

inw

ater

at25

°Cis

repo

rted

tobe

100w15

63.0

4m

ass

%(m

15

6.73

mol

kg2

1;

com

pile

r!.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

isot

herm

alm

etho

dw

asus

ed,

deta

ilsno

tre

port

ed.

Ba

~SC

N) 2

was

prep

ared

asdi

hydr

ate

acco

rdin

gto

Kar

yaki

nan

dA

ngel

ov.1

Dou

bly

dist

illed

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Ref

eren

ces:

1 Yu.

B.

Kar

yaki

nan

dI.

I.A

ngel

ov,P

ure

Ch

em

ica

lS

ub

sta

nce

s~R

ussi

aned

ition!

~Khi

miy

a,M

osco

w,

1974!

,p.

137.

155155JIRI HALA


6.10

.B

ariu

mT

hioc

yana

te

6.10

.1.

Eva

luat

ion

ofth

eB

a„S

CN…

2–

H2O

Sys

tem

Com

pone

nts:

Eva

luat

or:

~1!

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#~2

!W

ater

;H 2

O;

@773

2-18

-5#J.

Hala

,D

epar

tmen

tof

Inor

gani

cC

hem

istr

y,M

asar

ykU

nive

rsity

,61

137

Brn

o,C

zech

Rep

ublic

,Apr

il20

02.

Crit

ical

Eva

luat

ion

The

solu

bilit

yof

Ba~S

CN

) 2in

wat

erha

sbe

enre

port

edin

four

docu

men

ts.

Of

thes

e,m

easu

rem

ents

wer

epe

rfor

med

at29

8.1

Kin

thre

edo

cum

ents

.T

heso

lubi

lity

repo

rted

byO

ccle

shaw

1~6

2.61

mas

s%

;m15

6.60

6m

olkg

21,

com

pile

r!is

inex

celle

ntag

reem

ent

with

that

ofF

oote

and

Hic

key2~6

2.63

mas

s%

;m15

6.61

1m

olkg

21).

Kru

patk

ine

ta

l.3re

port

eda

slig

htly

high

erva

lue~6

3.04

mas

s%

;m

15

6.73

mol

kg2

1),

but

did

not

repo

rtan

yin

form

atio

non

the

met

hod

used

.T

here

fore

,th

eso

lubi

lity

ofB

a~S

CN

) 2of

6.61

mol

kg2

1is

reco

mm

ende

das

ate

ntat

ive

valu

e,ba

sed

onth

em

easu

rem

ents

inO

ccle

shaw

1an

dF

oote

and

Hic

key.2

Inth

est

udy

ofth

eB

a~S

CN

) 2–

urea

–H 2

Osy

stem

at28

8.1,

303.

1,an

d31

8.1

K,

Tur

gunb

ekov

ae

ta

l.4al

sore

port

edth

eso

lubi

lity

ofB

a~SC

N) 2

.A

lthou

ghit

isdi

fficu

ltto

dete

rmin

eth

eex

act

cour

seof

the

solu

bilit

yve

rsus

tem

pera

ture

func

tion

from

the

thre

em

easu

rem

ents

,in

terp

olat

ion

ofth

eda

tapo

ints

toth

eso

lubi

lity

ofB

a~SC

N) 2

inw

ater

at29

8.1

Kto

bebe

twee

n6.

9an

d7.

0m

olkg

21 ,a

valu

eco

nsid

erab

lyhi

gher

than

thos

eof

Occ

lesh

aw1

and

Foo

tean

dH

icke

y.2T

here

ason

for

this

isno

tcl

ear

sinc

eno

deta

ilsw

ere

repo

rted

onth

eex

perim

enta

lmet

hod

used

.It

coul

dbe

rela

ted

toth

ete

nden

cyof

conc

entr

ated

Ba

~SC

N) 2

solu

tion

tofo

rmm

etas

tabl

esy

stem

s.

Ref

eren

ces:

1 V.J.

Occ

lesh

aw,

J.C

hem

.S

oc.

2282~1

931!

.2 H

.W

.F

oote

and

F.C

.H

icke

y,J.

Am

.C

hem

.S

oc.

59,

648

~193

7!.

3 I.L.

Kru

patk

in,

E.

M.

Ost

rovs

kaya

,L.

D.

Voro

beva

,an

dG

.V.

Kam

yshn

ikov

a,Z

h.O

bsh.

Khi

m.

48,

957

~197

8!.

4 R.

Tur

gunb

ekov

a,K

.N

ogoe

v,an

dK

.S

ulai

man

kulo

v,Z

h.N

eorg

.K

him

.18

,28

47~1

973!

.

Co

~1!

~2!

Va T/

Me

An

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#S

odiu

mth

iocy

anat

e;N

aSC

N;@540

-72-

7#W

ater

;H 2

O;

@773

2-18

-5#

V.J.

Occ

lesh

aw,

J.C

hem

.S

oc.

55–

60~193

1!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

58.8

0w

1/m

ass

%:

0–

62.6

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eB

a~SC

N) 2

–N

aSC

N–

H 2O

syst

emat

25°Ca

NaS

CN

00w

2/m

ass

%)

NaS

CN

(m2

/mol

kg2

1)b

Ba~

SC

N) 2

(100

w1

/mas

s%

)B

a~S

CN

) 2(m

1/m

olkg

21)b

00

62.6

16.

606

12.9

64.

296

49.8

35.

283

19.9

36.

728

43.5

34.

700

24.6

48.

530

39.7

34.

399

31.1

111

.30

34.9

34.

058

39.3

316

.32

30.9

44.

105

41.5

216

.80

27.9

93.

621

41.6

016

.87

27.9

93.

631

46.0

316

.60

19.7

72.

280

54.1

417

.22

7.07

0.71

9

58.7

8c17

.59

00

tabl

eeq

uilib

rium

solid

phas

esin

the

syst

emw

ere

NaS

CN

•2

H2O

,@1

7032

-40-

5#an

dB

a~SC

N) 2•3

H2O

,@6

8016

-36-

4#~s

eeF

ig.

38!.

No

oubl

esa

ltsex

ist

inth

esy

stem

at25

°C.

alcu

late

dby

com

pile

r.ol

ubili

tyof

NaS

CN

inw

ater

asth

em

ean

offo

urcl

osel

yag

reei

ngde

term

inat

ions

~indi

vidu

alre

sults

not

repo

rted!

onso

lutio

nssh

aken

rbe

twee

n2

days

and

1m

onth

.

FIG

.38

.P

hase

diag

ram

ofth

eB

a~S

CN

) 2–

NaS

CN

–H 2

Osy

stem

at25

°C.

Add

ition

alin

form

atio

n:T

heco

mpo

sitio

nof

NaS

CN•2

H2O

was

char

acte

rized

bych

emic

alan

alys

is~SC

Nfo

und

48.5

6%–

49.6

7%,

calc

ulat

edfo

rth

edi

hydr

ate

49.6

0%!.T

hete

mpe

ratu

reof

the

tran

sitio

nfr

omN

aSC

N•2

H2O

toan

hydr

ous

NaS

CN

was

dete

rmin

edto

be30

.4°C

dila

tom

etric

ally

,an

d30

.3°C

ther

mom

etric

ally

.


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#~2

!N

,N-D

imet

hyla

ceta

mid

e;C 4H

9N

O;

@127

-19-

5#A

.A.F

edor

ov,L

.B.S

okol

ov,V

.M.S

avin

ov,M

.A.S

hlio

nska

ya,

and

N.

I.F

ilato

va,

Zh.

Prik

l.K

him

.44,

2361

–2~

1971

!.

Varia

bles

:P

repa

red

By:

T/K

:29

5–

298

J.H

a´ la

Exp

erim

enta

lDat

aT

heso

lubi

lity

ofB

a~SC

N) 2

inN

,N-d

imet

hyla

ceta

mid

eis

repo

rted

tobec

15

0.24

mol

dm2

3at

22–

25°C

.T

hena

ture

ofth

eeq

ui-

libriu

mso

lidph

ase

was

not

inve

stig

ated

.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

The

solv

ent

was

satu

rate

dw

ithan

hydr

ous

salt.

The

na

part

ofth

eso

lven

tw

asdi

still

edof

fto

rem

ove

wat

er,

and

the

satu

rate

dso

lutio

nw

ithex

cess

solid

was

kept

for

3da

ysin

ade

sicc

ator

ina

para

ffine

-coa

ted

flask

.T

heco

nten

tof

wat

erin

the

satu

rate

dso

lutio

nw

asle

ssth

an0.

1%.

The

satu

rate

dso

lutio

nw

asan

alyz

edfo

rth

eco

nten

tof

sulfu

rby

anun

spec

ified

met

hod.

Anh

ydro

usB

a~SC

N) 2

,so

urce

nots

peci

fied,

was

drie

dat

120

°Cfo

r6

h.N

,N-d

imet

hyla

ceta

mid

e,so

urce

not

spec

ified

,w

asfr

eshl

ydi

still

edbe

fore

use.

Est

imat

edE

rror

:S

olub

ility

:in

suffi

cien

tda

tare

port

edto

allo

wfo

rer

ror

estim

ate.

Co

~1!

~2!

~3!

Va T/

10 10 (1 a S d b C c S fo


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#P

otas

sium

thio

cyan

ate;

KS

CN

;@3

33-2

0-0#

Wat

er;

H 2O

;@7

732-

18-5#

V.J.

Occ

lesh

aw,

J.C

hem

.S

oc.

55–

60~193

1!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

70.9

0w

1/m

ass

%:

0–

62.6

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eB

a~SC

N) 2

–K

SC

N–

H 2O

syst

emat

25°Ca

KS

CN

00w

2/m

ass

%)

KS

CN

(m2

/mol

kg2

1)b

Ba~

SC

N) 2

(100

w1

/mas

s%

)B

a~S

CN

) 2(m

1/m

olkg

21)b

00

62.6

16.

606

14.4

54.

985

55.7

27.

369

19.4

67.

308

53.1

47.

651

19.5

07.

255

52.8

47.

536

26.0

49.

794

46.6

06.

719

28.9

510

.88

43.6

66.

288

34.0

213

.20

39.4

55.

866

34.4

713

.42

39.1

05.

836

37.1

814

.84

37.0

45.

668

43.9

218

.56

31.7

35.

141

45.0

019

.10

30.7

55.

002

47.6

720

.99

28.9

64.

889

48.2

821

.56

28.6

84.

911

52.4

221

.75

22.7

83.

624

62.3

223

.37

10.2

41.

472

70.8

925

.06

00

tabl

eeq

uilib

rium

solid

phas

esin

the

syst

emw

ere

KS

CN

,@3

33-2

0-0#,

Ba~

SC

N) 2•3

H2O

,@68

016-

36-4#

~see

Fig

.39!,

and

the

doub

lesa

ltK

SC

N•2

Ba~

SC

N) 2•5

H2O

,@

#.al

cula

ted

byco

mpi

ler.

FIG

.39

.P

hase

diag

ram

ofth

eB

a~S

CN

) 2–

KS

CN

–H 2

Osy

stem

at25

°C.

Add

ition

alin

form

atio

n:T

hedo

uble

salt

3K

SC

N•2

Ba~

SC

N) 2•5

H2O

was

prep

ared

bycr

ysta

lliza

tion

at25

°Cfr

oma

solu

tion

cont

aini

ngth

eco

mpo

nent

sin

the

stoi

chio

met

ricra

tio.

The

salt

drie

dby

suct

ion

inai

rco

ntai

ned,

inm

ass

%,

32.9

1–

33.0

9K

SC

Nan

d56

.63

–57

.29

Ba~S

CN

) 2;

calc

ulat

edfo

r3

KS

CN•

2B

a~S

CN

) 2•5

H2O

:32.

91K

SC

N,

56.9

9B

a~SC

N) 2

.

157157JIRI HALA


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Sin

ceus

uale

quili

brat

ion

did

not

alw

ays

give

the

stab

leso

lidph

ase,

the

mix

ture

sw

ere

mad

eup

from

wei

ghed

amou

nts

ofso

lids

with

suffi

cien

tw

ater

togi

veun

ders

atur

ated

solu

tions

thro

ugh

whi

chdr

y,fil

tere

dai

rat

25°C

was

draw

nun

tilsu

ffici

ent

solid

phas

ese

para

ted.

The

mix

ture

sw

ere

then

shak

enin

ath

erm

osta

tfo

rpe

riods

vary

ing

from

2da

ysto

4w

eeks

.E

ven

soin

mos

tca

ses

the

mix

ture

sha

dto

bein

ocul

ated

with

solid

NaS

CN

•2

H2O

toin

duce

sepa

ratio

nof

the

stab

leso

lidph

ase.

Sam

ples

ofth

esa

tura

ted

solu

tions

wer

ew

ithdr

awn

with

aw

arm

edpi

pette

with

agl

ass

–w

oolfi

lter,

and

anal

yzed

grav

imet

rical

lyfo

rB

aan

dS

CN

asB

aSO 4

and

AgS

CN

,re

spec

tivel

y.S

olid

phas

esw

ere

char

acte

rized

byth

em

etho

dof

wet

resi

dues

.

Ba~

SC

N) 2•3

H2O

was

obta

ined

from

aco

mm

erci

alpr

oduc

t~s

ourc

eno

tspe

cifie

d!by

repe

ated

crys

talli

zatio

nan

ddr

ying

over

fuse

dC

aCl 2.

Sm

all

amou

ntof

amm

oniu

msa

ltw

asre

mov

edpr

ior

the

final

crys

talli

zatio

nby

boili

ngth

eso

lutio

nw

itha

slig

htex

cess

ofB

a~OH

) 2,

and

rem

ovin

gth

eex

cess

ofth

ela

tter

bypa

ssin

gth

roug

ha

cold

solu

tion

ofB

a~S

CN

) 2a

stre

amof

CO 2

.N

aSC

Nw

aspr

epar

edby

repe

ated

crys

talli

zatio

nfr

omw

ater

ofa

com

mer

cial

prod

uct~

sour

ceno

tsp

ecifi

ed!.T

here

mai

ning

Na 2

CO

3im

purit

yw

asre

mov

edby

crys

talli

zatio

nfr

om96

%et

hano

lan

ddr

ying

at13

0°C

.T

hean

hydr

ous

salt

obta

ined

cont

aine

dth

eth

eore

tical

SC

Npe

rcen

tage~7

1.64

%!.

Dis

tille

dw

ater

was

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

r!.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

Va T/

10 10 (1 a S 3 b C

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#A

mm

oniu

mth

iocy

anat

e;N

H 4SC

N;@

1762

-95-

4#W

ater

;H 2

O;

@773

2-18

-5#

V.J.

Occ

lesh

aw,

J.C

hem

.S

oc.

55–

60~193

1!.

riabl

es:

Pre

pare

dB

y:

K:

298

0w

2/m

ass

%:

0–

64.3

0w

1/m

ass

%:

0–

62.6

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eB

a~SC

N) 2

–N

H4S

CN

–H 2

Osy

stem

at25

°C

NH

4S

CN

00w

2/m

ass

%)

NH

4S

CN

(m2

/mol

kg2

1)b

Ba~

SC

N) 2

(100

w1

/mas

s%

)B

a~S

CN

) 2(m

1/m

olkg

21)b

Sol

idph

asea

00

62.6

16.

606

A

15.4

87.

010

55.5

17.

548

A

20.7

511

.02

54.5

18.

692

A

24.7

014

.86

53.4

79.

663

A

24.6

914

.97

53.6

59.

771

A1B

25.6

416

.05

53.3

710

.03

B

26.7

316

.79

52.3

69.

878

B

27.4

117

.18

51.6

39.

717

B

28.8

518

.23

50.3

69.

556

B

29.5

218

.72

49.7

69.

474

B

29.6

418

.83

49.6

89.

477

B

30.7

819

.96

48.9

69.

533

B

31.0

019

.89

48.5

29.

346

B

31.5

220

.65

48.4

39.

529

B

31.8

521

.11

48.3

39.

619

B1C

34.7

319

.33

41.6

66.

961

C

38.9

519

.35

34.6

05.

160

C

42.7

219

.76

28.8

84.

012

C

52.3

621

.28

15.3

11.

868

C

57.7

222

.37

8.38

0.97

52C

64.3

323

.69

00

C

a A:

Ba~

SC

N) 2•3

H2O

,@6

8016

-36-

4#;B

:B

a~S

CN

) 2•N

H4S

CN•

H2O

,@

#;C

:N

H4S

CN

,@17

62-9

5-4#.

b Cal

cula

ted

byco

mpi

ler.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Sin

ceth

eso

lutio

nsw

ere

very

conc

entr

ated

and

visc

ous,

the

mix

ture

sw

ere

rota

ted

ina

ther

mos

tat

for

perio

dsva

ryin

gup

to7

days

.S

ince

the

syst

ems

read

ilyfo

rmed

met

asta

ble

mix

ture

s,in

ocul

atio

nw

ithth

eap

prop

riate

equi

libriu

mso

lidph

ase

was

carr

ied

out

inor

der

toen

sure

the

atta

inm

ent

ofst

able

equi

libriu

m.

Sam

ples

ofth

esa

tura

ted

solu

tions

and

wet

equi

libriu

mso

lidph

ases

wer

ean

alyz

edgr

avim

etric

ally

for

Ba

and

SC

Nas

BaS

O4

and

AgS

CN

,re

spec

tivel

y.S

olid

phas

esw

ere

char

acte

rized

byth

em

etho

dof

wet

resi

dues

,an

dth

edo

uble

salt

also

byop

tical

mic

rosc

opy.

The

doub

lesa

ltco

uld

beis

olat

edfr

omso

lutio

nsco

ntai

ning

31.8

5–

24.6

9m

ass

%N

H4S

CN

and

48.3

3–

53.6

5m

ass

%B

a~SC

N) 2

,an

dco

uld

beai

r/dr

ied

atlo

wer

tem

pera

ture

s.It

was

char

acte

rized

bych

emic

alan

alys

is.

Ba~

SC

N) 2•3

H2O

was

obta

ined

from

aco

mm

erci

alpr

oduc

t~s

ourc

eno

tspe

cifie

d!by

repe

ated

crys

talli

zatio

nan

ddr

ying

over

fuse

dC

aCl 2.

Sm

all

amou

ntof

amm

oniu

msa

ltw

asre

mov

edpr

ior

the

final

crys

talli

zatio

nby

boili

ngth

eso

lutio

nw

itha

slig

htex

cess

ofB

a~OH

) 2,

and

rem

ovin

gth

eex

cess

ofth

ela

tter

bypa

ssin

gth

roug

ha

cold

solu

tion

ofB

a~S

CN

) 2a

stre

amof

CO 2

.N

H4S

CN

was

anA

.R.

qual

itypr

oduc

t,so

urce

not

spec

ified

.D

istil

led

wat

erw

asus

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

r!.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.


Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Mix

ture

spr

epar

edfr

omw

eigh

edam

ount

sof

the

two

salts

and

wat

erw

ere

war

med

toob

tain

aho

mog

eneo

usso

lutio

n.T

his

was

cool

edto

25°C

,an

yso

lidse

para

ting

was

diss

olve

dby

the

addi

tion

ofa

little

wat

er,

and

then

rota

ted

ina

ther

mos

tat

for

2–

7da

ysat

25°C

.S

ampl

esof

the

satu

rate

dso

lutio

nsw

ere

with

draw

nw

itha

war

med

pipe

ttew

itha

glas

s–

woo

lfilte

r,an

dan

alyz

edgr

avim

etric

ally

for

Ba

and

SC

Nas

BaS

O4

and

AgS

CN

,re

spec

tivel

y.S

olid

phas

esw

ere

char

acte

rized

byth

em

etho

dof

wet

resi

dues

.

Ba~

SC

N) 2•3

H2O

was

obta

ined

from

aco

mm

erci

alpr

oduc

t~s

ourc

eno

tspe

cifie

d!by

repe

ated

crys

talli

zatio

nan

ddr

ying

over

fuse

dC

aCl 2.

Sm

all

amou

ntof

amm

oniu

msa

ltw

asre

mov

edpr

ior

the

final

crys

talli

zatio

nby

boili

ngth

eso

lutio

nw

itha

slig

htex

cess

ofB

a~OH

) 2,

and

rem

ovin

gth

eex

cess

ofth

ela

tter

bypa

ssin

gth

roug

ha

cold

solu

tion

ofB

a~S

CN

) 2a

stre

amof

CO 2

.K

SC

Nw

asan

A.R

.qu

ality

prod

uct,

sour

ceno

tsp

ecifi

ed.

Dis

tille

dw

ater

was

used

.

Est

imat

edE

rror

:Te

mpe

ratu

re:6

0.05

K~a

utho

r!.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

Va T/

10 10 (1


was

dete

rmin

edby

titra

tion

with

stan

dard

HC

lsol

utio

nus

ing

nitr

azin

eye

llow

asin

dica

tor,

SC

N2w

asde

term

ined

byVo

lhar

dm

etho

d.S

olid

phas

esw

ere

iden

tified

byS

chre

inem

aker

sm

etho

d.

Tem

pera

ture

:60.

03K

~aut

hors!

.S

olub

ility

:in

suffi

cien

tda

tagi

ven

toal

low

for

erro

res

timat

e.

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#M

ethy

lthio

cyan

ate;

C 2H3N

S~C

H3C

NS

);@5

56-6

4-9#

Wat

er;

H 2O

;@7

732-

18-5#

E.S

pacc

amel

aM

arch

etti,

Atti

.Aca

d.S

ci.T

orin

o,C

lase

Fis

.Mat

.N

at.9

4,35

3–

70~1

960!

.

riabl

es:

Pre

pare

dB

y:

K:

293

tioof

H 2O

/C2H

3N

Sco

ncen

trat

ions

J.H

ala

Exp

erim

enta

lDat

aP

hase

diag

ram

ofth

eB

a~S

CN

) 2–

C2H

3N

S–

H 2O

syst

emat

20°C

The

tern

ary

phas

edi

agra

mof

the

Ba

~SC

N) 2

–C

2H

3N

S–

H 2O

syst

emat

20°C

was

repo

rted~F

ig.

40!.

The

follo

win

gfie

lds

wer

ese

rved

inth

edi

agra

m:

Ian

dII—

one

liqui

dph

ase,

III—

two

liqui

dph

ases

,IV

and

VI—

one

liqui

dph

ase

ineq

uilib

rium

with

solid

~SC

N) 2

,an

dV

—tw

oliq

uid

phas

esin

equi

libriu

mw

ithso

lidB

a~S

CN

) 2.

Num

eric

alda

taw

ere

repo

rted

for

the

solu

bilit

yof

Ba

~SC

N) 2

wat

er-r

ich

C 2H

3N

S–

H 2O

mix

ture

s~cu

rve

RP

inth

edi

agra

m!an

din

C 2H

3N

S-r

ich

C 2H

3N

S–

H 2O

mix

ture

s~cu

rve

QS

inth

edi

agra

m!.

FIG

.40

.P

hase

diag

ram

ofth

eB

a~S

CN

) 2–

CH

3C

NS

–H 2

Osy

stem

at20

°C.

159159JIRI HALA


Com

pone

nts:

Orig

inal

Mea

sure

men

ts:

~1!

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#~2

!B

ariu

mhy

drox

ide;

Ba~O

H) 2

;@1

7194

-00-

2#~3

!W

ater

;H 2

O;

@773

2-18

-5#

H.

W.

Foo

tean

dF.

C.

Hic

key,

J.A

m.

Che

m.

Soc

.59

,64

8–

50~1

937!

.

Varia

bles

:P

repa

red

By:

T/K

:29

810

0w

2/m

ass

%:

0–

8.5

J.H

ala

Exp

erim

enta

lDat

aS

olub

ility

inth

eB

a~SC

N) 2

–B

a~O

H) 2

–H

2O

syst

emat

25°C

Ba~

OH

) 2(1

00w

2/m

ass

%)

Ba~

OH

) 2(m

2/m

olkg

21)b

Ba~

SC

N) 2

(100

w1

/mas

s%

)B

a~S

CN

) 2(m

1/m

olkg

21)b

Sol

idph

asea

00

62.6

36.

611

A

2.05

0.33

361

.97

6.79

5A

3.16

0.52

561

.73

6.93

6A1

B

3.18

0.52

761

.61

6.90

3A1

B

4.75

0.73

157

.34

5.96

7B

6.16

0.91

454

.49

5.46

3B

8.49

1.22

351

.00

4.96

6B1C

8.45

1.21

350

.88

4.93

5B1C

5.89

0.73

847

.51

4.02

2C

3.44

0.28

726

.54

1.49

5C

3.58

0.25

915

.83

0.77

5C

4.48

90.

274

00

C

a A:

Ba~

SC

N) 2•3

H2O

,@6

8016

-36-

4#;B

:B

a~O

H!S

CN

,@#;

C:

Ba~

OH

) 2•8

H2O

,@1

2230

-71-

6#.b C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed.

Mix

ture

sof

the

thre

eco

mpo

nent

sin

suita

ble

prop

ortio

nsw

ere

rota

ted

ina

ther

mos

tat

for

seve

rald

ays.

Equ

ilibr

ium

was

reac

hed

in2

days

.S

ampl

esof

the

satu

rate

dso

lutio

nsw

ere

with

draw

nth

roug

has

best

osor

glas

sw

oolfi

lters

and

wei

ghed

.B

a~O

H) 2

Ba~

SC

N) 2

was

apr

oduc

tof

high

purit

y~sou

rce

not

spec

ified!

and

was

used

with

out

furt

her

purifi

catio

n.B

a~O

H) 2•8

H2O

was

recr

ysta

llize

dbe

fore

use

inan

appa

ratu

sw

hich

excl

uded

CO

2.

Est

imat

edE

rror

:

Co

~1!

~2!

~3!

Va T/

Ra

ob Ba

in

J

mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#U

rea;

CH 4

N2O

;@5

7-13

-6#

Wat

er;

H 2O

;@7

732-

18-5#

R.T

urgu

nbek

ova,

K.N

ogoe

v,an

dK

.Sul

aim

anku

lov,

Zh.

Neo

rg.

Khi

m.

18,

2847

–9~

1973

!.

riabl

es:

Pre

pare

dB

y:

K:

288,

303,

and

318

0w

2/m

ass

%:0

–53

.5at

288

K,

0–

57.5

at30

3K

,64

.0at

318

K

J.H

ala

Exp

erim

enta

lDat

aC

ompo

sitio

nof

the

satu

rate

dso

lutio

nsin

the

Ba

~SC

N) 2

–ur

ea–

H 2O

syst

emat

thre

ete

mpe

ratu

res

mpe

ratu

re(t

/°C

)U

rea

(100

w2

/mas

s%

)U

rea

(100

m2

/mol

kg2

1)b

Ba~

SC

N) 2

(100

w1

/mas

s%

)B

a~S

CN

) 2(1

00m

1/m

olkg

21)b

Sol

idph

asea

150

062

.32

6.52

5A

4.97

2.48

861

.77

7.32

6A

9.43

5.39

061

.44

8.32

0A

12.8

28.

284

61.4

19.

401

A

13.8

19.

348

61.5

99.

877

A1B

13.5

58.

759

60.6

99.

294

B

16.0

310

.08

57.5

08.

569

B

19.3

112

.08

54.0

88.

017

B

25.9

418

.16

50.2

88.

341

B

31.2

025

.10

48.1

09.

167

B

35.1

831

.78

46.3

99.

930

B

41.8

751

.11

44.4

912

.87

B

48.1

043

.04

B

53.4

242

.04

B

53.5

340

.61

C

52.5

036

.15

C

50.6

842

.15

29.3

05.

774

C

50.1

432

.47

24.1

53.

706

C

49.0

025

.90

19.5

02.

442

C

48.6

020

.64

12.2

01.

228

C

48.5

017

.71

5.90

0.51

0C

49.0

016

.00

00

C

300

064

.47

7.15

8A

4.72

2.51

364

.00

8.07

1A

8.32

4.93

063

.58

8.92

6A

11.4

77.

824

64.1

210

.36

A

13.4

210

.35

65.0

011

.88

A1B

12.8

29.

367

64.3

911

.15

B

15.2

510

.94

61.5

410

.46

B

20.1

514

.81

57.2

09.

962

B

23.1

318

.20

55.7

110

.39

B

26.3

923

.34

54.7

811

.48

B

31.0

335

.68

54.4

914

.85

B

32.0

240

.15

54.7

016

.25

D

34.5

035

.64

49.3

812

.08

D

39.5

741

.10

44.4

010

.93

D

49.0

040

.65

D

54.8

439

.68

D

55.3

938

.79

C

53.6

528

.58

C


Com

posi

tion

ofth

eso

lutio

nssa

tura

ted

at20

°C

H2O

-ric

hre

gion

C 2H

3N

S-r

ich

regi

on

H2O

(100

w3

/mas

s%

)B

a~S

CN

) 2(1

00w

1/m

ass

%)

C2H

3N

S(1

00w

2/m

ass

%)

H2O

(100

w3

/mas

s%

)B

a~S

CN

) 2(1

00w

1/m

ass

%)

C2H

3N

S(1

00w

2/m

ass

%)

37.5

62.5a

015

.023

.261

.8

35.8

59.2

5.0

9.4

16.1

74.5

35.0

55.9

9.1

4.7

10.0

85.3

4.0

8.1

87.9

03.

8b96

.2

a Sol

ubili

tyof

Ba~

SC

N) 2

inw

ater

,m15

6.57

5m

olkg

21

~com

pile

r!.b S

olub

ility

ofB

a~S

CN

) 2in

C2H

3N

S,m

15

0.15

6m

olkg

21

~com

pile

r!.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

Sol

ubili

tycu

rves

wer

eob

tain

edby

titra

tion

am

ixtu

reof

two

com

pone

nts

with

the

third

one

ina

ther

mos

tate

dba

th.

Som

eof

thes

em

easu

rem

ents

wer

eve

rified

bypr

epar

ing

the

tern

ary

syst

ems,

and

obse

rvin

gth

ete

mpe

ratu

reof

hom

ogen

izat

ion.

The

valu

eco

rres

pond

ing

to20

°Cw

asth

enob

tain

edby

inte

rpol

atio

n.B

uret

tes

grad

uate

dby

0.01

cm3w

ere

used

for

the

titra

tions

.

Not

hing

spec

ified

.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Co

~1!

~2!

~3!

Va T/

10 0–

Te


mpo

nent

s:O

rigin

alM

easu

rem

ents

:

Bar

ium

thio

cyan

ate;

Ba~S

CN

) 2;

@209

2-17

-3#A

mm

oniu

mth

iocy

anat

e;N

H 4SC

N;@

1762

-95-

4#A

mm

onia

;N

H 3;

@766

4-41

-7#

A.S

tasi

ewic

z,A

nn.U

niv.

M.C

urie

/Skl

odow

ska,

Lubl

in,P

olan

d14

,S

ect.

AA

,49

–57

~195

9!.

riabl

es:

Pre

pare

dB

y:

K:

291

J.H

ala

Exp

erim

enta

lDat

a

The

solu

bilit

yof

Ba~S

CN

) 2in

liqui

dam

mon

iate

ofN

H 4S

CN

isre

port

edto

bec 1

51.

10m

oldm

23

or10

0w

15

29.6

mas

s%

at

°C.

The

com

posi

tion

ofth

eso

lven

tco

rres

pond

edto

the

mol

arra

tioN

H3

/NH

4S

CN5

2.7.

Aux

iliar

yIn

form

atio

n

thod

ÕApp

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

eam

mon

iate

ofN

H 4SC

N,

acl

ear

liqui

d~de

nsity

of0.

9345

cm2

3 !,w

asob

tain

edby

actio

nof

NH 3ga

son

toso

lid

4S

CN

atat

mos

pher

icpr

essu

re.

The

prep

arat

ion

ofth

elv

ent,

and

solu

bilit

ym

easu

rem

ents

wer

eca

rrie

dou

tin

adr

yx

unde

ra

stre

amof

dry

NH 3ga

s.

Ba~

SC

N) 2

was

prep

ared

byth

ere

actio

nof

Ba

~OH

) 2w

ithN

H4S

CN

.T

heco

mpo

sitio

nof

the

salt

prep

ared

was

not

spec

ified

.N

H 4S

CN

,A

rgon

-Lod

z,w

asre

peat

edly

recr

ysta

llize

d,an

ddr

ied

ina

dess

icat

orov

erco

ncen

trat

edH

2S

O4

,fir

stat

norm

alpr

essu

rean

dth

enun

der

vacu

umfo

r1

mon

th.A

mm

onia

was

drie

dw

ithN

am

etal

ina

stee

lcon

tain

er.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

161161JIRI HALA


54.6

238

.36

21.6

73.

606

C

54.9

629

.97

14.5

01.

873

C

57.5

022

.53

00

C

450

067

.11

8.04

9A

6.35

3.73

065

.30

9.08

6A

11.0

67.

122

63.0

89.

623

A

20.5

918

.45

60.8

312

.92

A

25.2

329

.07

60.3

216

.47

A

29.5

946

.48

59.8

122

.26

A1D

29.3

840

.57

58.5

619

.16

D

31.6

139

.37

55.0

216

.23

D

34.5

441

.08

51.4

614

.50

D

42.3

047

.84

D

45.5

347

.33

D

50.9

847

.48

C

52.0

041

.77

C

53.0

335

.81

C

54.7

928

.39

C

58.4

844

.12

19.4

53.

477

C

60.1

836

.49

12.3

61.

776

C

64.0

029

.60

00

C

a A:

Ba~

SC

N) 2•3

H2O

,@6

8016

-36-

4#;B

:B

a~S

CN

) 2•2

CO

~NH

2) 2

,@

#;C

:C

O~N

H2) 2

,@5

7-13

-6#;

D:

Ba~

SC

N) 2•3

CO

~NH

2) 2

,@

#.b C

alcu

late

dby

com

pile

r.

Aux

iliar

yIn

form

atio

n

Met

hodÕ

App

arat

usÕP

roce

dure

:S

ourc

ean

dP

urity

ofM

ater

ials

:

An

isot

herm

alm

etho

dw

asus

ed,

node

tails

repo

rted

.N

othi

ngsp

ecifi

ed.

Est

imat

edE

rror

:Te

mpe

ratu

re:

prec

isio

nno

tre

port

ed.

Sol

ubili

ty:

insu

ffici

ent

data

repo

rted

toal

low

for

erro

res

timat

e.

Co

~1!

~2!

~3!

Va T/

18 Me

Th

g NH

so bo

J

ata of

7. Appendix

List of systems for which the original documents were not available to the editor, and systems for which only duncertain quality exist.

NaN3–chloroform,n-hexane, CCl4 , trichloroethylene, ethylacetate1

NaN3 or KN3–benzene2

NH4N3– SO23,4 ~two liquid phases separate at saturation!

NaOCN or KOCN–water5

NaOCN or KOCN–benzene2

KOCN, KCN, or KSCN–POCl36

NaCN–NaCl–NH37

NaCN–NaOH–Na2CO3– NH38

KCN–dimethylsulfoxide9

KCN–polyethyleneglycol~400!9

LiSCN, NaSCN, KSCN, or CsSCN–poly~methyl glycidyl ether!25

NaSCN–nitrobenzene10

NaSCN, KSCN, or NH4SCN–CF3COOH11

NaSCN or KSCN–acetone–water12a

NaSCN or KSCN–phenol–water13

NaSCN, KSCN, or NH4SCN–cresols–water14

NaSCN–K2SO4–water15

NaSCN or RbSCN–1-butanol–water16

NaSCN, KSCN, or NH4SCN–triethylamine–water22

NaSCN or KSCN–acetone–methanol26

KSCN–SO2– H2O17

KSCN–methylmetacrylate18

KSCN–furfural–water19

KSCN–CH3CN–water34

KSCN–1-butanol16,20,24

KSCN–Na2SO4– H2O15

KSCN–poly~ethylene oxide!21

KSCN, RbSCN, CsSCN, or NH4SCN–1-butanol–water23a

CsSCN–1-butanol–water16,32a

NH4SCN–SO2–water17,27

NH4SCN–SO2–formamide27

NH4SCN–phenol–water28,35

NH4SCN–thiourea–water36

NH4SCN–diethylether–water37

Mg~SCN)2–acetamide–water33a

Ba~SCN)2– SO229

Ba~SCN)2–amines30

Ba~SCN)2–methanol–propylene31

aOriginal document not available to the editor.

References to the Appendix1F. Hudswell, J. S. Nairn, and K. R. Gadsby, J. Appl. Chem.1, S137~1951!.2J. A. Cranston and A. Y. Livingstone, J. Chem. Soc. 501~1926!.3F. Fridrichs, J. Am. Chem. Soc.35, 1866~1913!.4F. Fridrichs, Z. Anorg. Allgem. Chem.84, 373 ~1914!.5J. Roth, J. Chem. Phys.30, 596 ~1959!.6V. Gutmann, Monatsh. Chem.83, 279 ~1952!.7B. B. Vasiliev, J. L. Ettinger, and M. P. Golovkov, Z. Anorg. Allgem. Chem.219, 341 ~1934!.8G. Tinelli and R. Rohmer, Compt. Rend.259, 157 ~1964!.9E. Santaniello, A. Manzocchi, and P. Sozzani, Tetrahedron Lett.47, 4581~1979!.10O. L. Hughes and T. H. Mead, J. Chem. Soc. 2282~1929!.11R. Hara and G. H. Cady, J. Am. Chem. Soc.76, 4285~1954!.12F. I. Ivanova and I. Danilova, Fiz. Khim. Izuch. Neorg. Soed., No. 3,3 ~1976!; Chem. Abstr.86, abstract no. 34853~1977!.13L. D. Vorobeva and I. L. Krupatkin,Fazovye Ravnovesia~Phase Equilibria! ~Kalinin. Gosud. Univ., USSR, 1975!, p. 32.14I. L. Krupatkin and L. D. Vorobeva, Zh. Obsh. Khim.45, 980 ~1975!.15O. G. Nikitin and E. F. Zhuravlev, Zh. Neorg. Khim.14, 2200~1969!.16M. I. Bakeev and I. P. Akimova, Dep. Doc. VINITI No. 1148~1976!.17Ch. J. Hansen, Ber.66, 447 ~1933!.18N. Gallo, V. D. Bianco, and S. J. Doronzo, J. Inorg. Nucl. Chem.34, 2374~1972!.19E. Speccamela-Marchetti, Ann. Chim.~Rome! 58, 801 ~1968!.20M. V. Ionin, Z. B. Kuznetsova, and T. I. Moleva, Zh. Neorg. Khim.14, 2850~1969!.21H. Ohno and K. Ito, Polymer34, 4171~1993!.22L. D. Vorobeva and I. L. Krupatkin,Fazovye Ravnovesia~Phase Equilibria! ~Kalinin. Gosud. Univ., USSR, 1975!, p. 18.

0047-2689Õ2004Õ33„1…Õ162Õ176Õ$39.00 J. Phys. Chem. Ref. Data, Vol. 33, No. 1, 2004162

163163JIRI HALA

23R. S. Andamasov, Izv. Nats. Akad. Nauk Resp. Kazakhstan, Ser. Khim. No.2, 3 ~1994!.24Z. B. Kuznetsova and T. I. Moleva, Trudy Gorkov. Politekh. Inst., USSR28, 30 ~1974!.25M. Dumont, D. Boils, P. E. Harvey, and J. Prudhomme, Macromolecules24, 1791~1991!.26F. C. Thyrion and O. M. Landauer, Fluid Phase Equilibria130, 253 ~1997!.27A. W. Francis, J. Chem. Eng. Data10, 45 ~1965!.28R. N. Mertslin, V. S. Petelina, N. I. Nikurashina, and N. G. Bylinkina, Zh. Neorg. Khim.16, 227 ~1971!.29A. I. Shattenshtein and A. I. Viktorov, Acta Physicokhim. USSR7, 883 ~1937!.30H. McKee Elsey, J. Am. Chem. Soc.42, 2083~1920!.31A. W. Francis, J. Chem. Eng. Data11, 96 ~1966!.32M. I. Bakeev, Trudy Khim. Met. Inst., Akad Nauk Kazakh. SSR, No.17, 138 ~1972!.33K. Abykeev, K. Sulaimankulov, and M. Ismailov, Izv. Akad. Nauk Kirgiz. SSR, No.6, 36 ~1974!.34A. W. Francis, Chem. Eng. Sci.22, 627 ~1967!.35R. V. Mertslin, Zh. Obsh. Khim.10, 1865~1940!.36A. Smits and A. Kettner, Proc. Kungl. Akad. Wet.~Amsterdam! 15, 683 ~1912!.37V. I. Nesterova and N. N. Petin, Zh. Obsh. Khim.1, 272 ~1931!.


Diammo--

8. System Index

Page numbers preceded by E refer to evaluation texts whereas those not preceded by E refer to compiled tables.nium, trisodium, etc. salts are indexed under ammonium, sodium, etc. The symbol~aq! stands for water as additional component in the respective system.

Ammonium azide 1 ammonia 191 benzene 181 diethyl ether 181 ethanol 181 methanol 181 water 18

Ammonium thiocyanate 1 acetonitrile 1291 ammonia 126-1281 ammonia1 water 1311 ammonium carbonate1 ammonia1 water 1451 ammonium chloride1 water 1381 ammonium nitrate1 ammonia 1331 ammonium nitrate1 water 132, 1331 ammonium sulfate1 water 139, 1401 ammonium tetraborate1 water 1411 aniline 1 water 144-1451 barium thiocyanate1 ammonia 1611 barium thiocyanate1 water 1581 boric acid1 water 1401 2-butanone 1311 calcium thiocyanate1 ammonia 1531 calcium thiocyanate1 water 151-1521 ethanol 1291 2-furancarboxaldehyde 1311 imidodicarbonic diamide 1431 methanol 1281 methylthiocyanate1 water 143-1441 potassium thiocyanate1 water 134-135, 135-1371 sodium chloride1 water 137-1381 sodium thiocyanate1 water 76-771 strontium thiocyanate1 ammonia 1541 sulfur dioxide 1261 tri-n-butylphosphate 1301 triethylamine 1301 triethylamine1 water 1411 urea1 water 1421 water E122, 123-125

Barium azide 1 ethanol 241 water E24, 24, 25

Barium thiocyanate 1 ammonium thiocyanate1 ammonia 1611 ammonium thiocyanate1 water 1581 barium hydroxide1 water 1591 N,N-dimethylacetamide 1561 methylthiocyanate1 water 159-1601 potassium thiocyanate1 water 157-1581 sodium thiocyanate1 water 156-1571 urea1 water 160-1611 water E155, 155

Calcium azide 1 ethanol 201 water 201 potassium azide1 water 21

Calcium thiocyanate 1 ammonium thiocyanate1 ammonia 1531 ammonium thiocyanate1 water 151-1521 aniline 1481 N,N-dimethylacetamide 1491 methylthiocyanate1 water 152-1531 potassium thiocyanate1 water 150-1511 sodium thiocyanate1 water 149-1501 o-toluidine 1481 water 148

Cesium azide 1 ethanol 181 water 18

Cesium thiocyanate 1 tri-n-butylphosphate 1211 urea1 water 121

Lithium azide 1 ethanol 8

0047-2689Õ2004Õ33„1…Õ164Õ176Õ$39.00 J. Phys. Chem. Ref. Data, Vol. 33, No. 1, 2004164

165165JIRI HALA

1 water 8-9Lithium cyanide 1 tetraethylammonium perchlorate1 propylene carbonate 25Lithium thiocyanate 1 ammonia 54

1 N,N-dimethylacetamide 54, 551 boric acid1 water 561 lithium borate1 water 571 lithium chloride1 water 561 lithium tetraborate 571 tri-n-butylphosphate 551 tris~dioxa-3,6-heptyl!amine1 dichloromethane 591 tris~oxa-3-butyl!amine1 dichloromethane 591 urea1 water 581 water E52, 52-53

Magnesium thiocyanate 1 aniline 1461 thiourea1 water 1471 o-toluidine 1461 urea1 water 146-1471 water 146

Potassium azide 1 ethanol 161 ethanol1 water 171 water E15, 161 strontium azide1 water 23

Potassium cyanate 1 ammonia 501 ethanol1 water 511 18-dibenzo-crown-61 N,N- dimethylformamide 511 18-dicyclohexyl-crown-61 N,N- dimethylformamide 511 water 50

Potassium cyanide 1 acetone1 water 431 acetonitrile1 water 411 ammonia E36, 36-371 N,N-dimethylformamide1 water 441 1,4-dioxane1 water 451 1,2-ethanediol~ethyleneglycol! 421 ethanol E37, 381 ethanol1 water 411 ethylenecarbonate1 water 431 formamide1 water 401 hydrogen cyanide 351 methanol 381 methanol1 water 401 2-methyl-2-propanol~tert-butanol! 1 water 451 potassium hydroxide1 water 391 1,2,3-propanetriol~glycerol! 391 1,2,3-propanetriol1 water 441 propylene carbonate 341 sulfinylbis~methane! ~dimethylsulfoxide! 1 water 421 sulfur dioxide 351 water 33-34

Potassium thiocyanate 1 acetone E91, 92, 981 acetone1 water 1131 acetonitrile 891 ammonia 88-891 ammonium thiocyanate1 water 134-135, 135-1371 barium thiocyanate1 water 157-1581 boric acid1 water 1081 1-butanol E94, 941 2-butanone E93, 991 calcium thiocyanate1 water 150-1511 cyclohexanone 991 diethyleneglycol1 water 1141 N,N-dimethylacetamide 971 N,N-dimethylaniline1 acetic acid1 benzene 1181 N,N-dimethylaniline1 acetic acid1 chlorobenzene 1181 N,N-dimethylaniline1 acetic acid1 dichloromethane 1181 N,N-dimethylaniline1 acetic acid1 diethylether 1181 N,N-dimethylaniline1 acetic acid1 ethylacetate 1181 1,2-ethanediamine 901 1,2-ethanediol1 water 1131 ethanol E90, 91, 991 ethylacetate 93



1 ethylthiocyanate1 water 117-1181 furfural 991 methanol 98, 991 methylacetate 921 methylthiocyanate1 water 116-1171 1-pentanol 971 1-phenylethanone 991 polyethyleneglycols1 water 115-1161 potassium borate1 water 1091 potassium bromide1 water 1021 potassium carbonate1 water 106-1071 potassium chloride1 water 100-1011 potassium hydrogencarbonate1 water 105-1061 potassium iodide1 water 1021 potassium molybdate1 water 1101 potassium nitrate1 water 103-1041 potassium nitrite1 water 1031 potassium sulfate1 water 107-1081 potassium tetraborate1 water 1091 pyridine E95, 961 sodium thiocyanate1 water 75-761 sulfolane 951 sulfur dioxide 871 triethylamine1 acetic acid1 benzene 1181 triethylamine1 acetic acid1 chlorobenzene 1181 triethylamine1 acetic acid1 dichloromethane 1181 triethylamine1 acetic acid1 diethylether 1181 triethylamine1 acetic acid1 ethylacetate 1181 triethyleneglycol1 water 1141 tri-n-butylphosphate 981 tris~dioxa-3-butyl!amine1 dichloromethane 1191 tris~dioxa-3,6-heptyl!amine1 dichloromethane 1191 urea1 water 110-1121 water E82-E83, 83-86, 871 water1 1-butanol 1001 water-d2 86-87

Rubidium azide 1 ethanol 171 water 17

Rubidium thiocyanate 1 2-butanone 1201 cyclohexanone 1201 ethanol 1201 methanol 1201 1-phenylethanone 1201 tri-n-butylphosphate 1201 water 119

Sodium azide 1 ammonia 131 sodium amide1 ammonia 13-141 N,N-dimethylformamide 121 ethanol 9, 111 ethanol1 water 111 methanol 121 sulfinyl-bis~methane! ~dimethylsulfoxide! 121 water 9, 101 18-dibenzo-crown-61 acetone 141 18-dibenzo-crown-61 acetone1 methanol 151 18-dibenzo-crown-61 acetonitrile 141 18-dibenzo-crown-61 acetonitrile1 methanol 151 18-dibenzo-crown-61 benzene1 methanol 151 18-dibenzo-crown-61 2-butanone 141 18-dibenzo-crown-61 2-butanone1 methanol 151 18-dibenzo-crown-61 cyclohexanone 141 18-dibenzo-crown-61 cyclohexanone1 methanol 151 18-dibenzo-crown-61 N,N- dimethylformamide 141 18-dibenzo-crown-61 N,N-dimethylformamide1 methanol 151 18-dibenzo-crown-61 1,4-dioxane1 methanol 151 18-dibenzo-crown-61 ethanol 141 18-dibenzo-crown-61 heptane1 methanol 151 18-dibenzo-crown-61 sulfinyl-bis~methane! 141 18-dibenzo-crown-61 sulfinyl-bis~methane! 1 methanol 151 18-dibenzo-crown-61 tetrahydrofurane1 methanol 15


167167JIRI HALA

Sodium cyanate 1 ammonia E46, 46-471 ammonium chloride1 ammonia 481 ammonium nitrate1 ammonia 491 18-dibenzo-crown-61 o-dichlorobenzene 481 18-dicyclohexyl-crown-61 o-dichlorobenzene 481 18-dibenzo-crown-61 N,N- dimethylformamide 481 18-dicyclohexyl-crown-61 N,N- dimethylformamide 481 diethylether1 methanol 491 ethanol 47

Sodium cyanide 1 ammonia 271 ethanol 281 2-furancarboxaldehyde~furfural! 291 methanol 281 sodium chloride1 water 32-331 sodium hydroxide1 water E29, 30-321 sulfur dioxide 271 water E26, 26

Sodium thiocyanate 1 acetone E67, 67-681 ammonia 63-641 ammonium chloride1 water 741 ammonium thiocyanate1 water 76-771 barium thiocyanate1 water 156-1571 boric acid1 water 77-781 2-butanone 691 calcium thiocyanate1 water 149-1501 1,2-ethanediamine 701 ethanol 61, E65, 661 2-furancarboxaldehyde~furfural! 691 methanol 64, 681 methylacetate 701 methylthiocyanate1 water 801 N,N-dimethylacetamide 711 N,N-dimethylacetamide1 water 721 N,N-dimethylaniline1 actic acid1 benzene 811 N,N-dimethylaniline1 actic acid1 chlorobenzene 811 N,N-dimethylaniline1 actic acid1 dichloromethane 811 N,N-dimethylaniline1 actic acid1 diethylether 811 N,N-dimethylaniline1 actic acid1 ethylacetate 811 N,N-dimethylformamide 711 N-methyl-2-pyrrolidone 711 potassium thiocyanate1 water 75-761 2-propen-1-ol~allylalcohol! 661 sodium borate1 water 781 sodium chloride1 water 73-741 sodium molybdate1 water 791 sodium sulfate1 water 751 sodium tetraborate1 water 791 sulfur dioxide 631 tri-n-butylphosphate 721 tris~dioxa-3,6-heptyl!amine1 dichloromethane 811 triethylamine1 actic acid1 benzene 811 triethylamine1 actic acid1 chlorobenzene 811 triethylamine1 actic acid1 dichloromethane 811 triethylamine1 actic acid1 diethylether 811 triethylamine1 actic acid1 ethylacetate 811 tris~oxa-3-butyl!amine1 dichloromethane 811 water E59-E60, 60-62

Stronitum azide 1 ethanol 221 water E21, 22-231 potassium azide1 water 23

Strontium thiocyanate 1 ammonium thiocyanate1 ammonia 1541 aniline 1541 o-toluidine 1541 water 154


.

1

1, 99,

83

4, 45

34-137,

6-157

0


9. Registry Number Index

Page numbers preceded by E refer to evaluation texts whereas those not preceded by E refer to compiled tables

56-81-5 1,2,3-propanetriol~glycerol! 39, 4457-13-6 Urea 58, 110-112, 121, 142, 146, 160-1660-29-7 Diethyl ether 18, 49, 81, 11862-53-3 Aniline 144-145, 146, 148, 15462-56-6 Thiourea 14764-17-5 Ethanol 8, 9, 11, 14, 16, 17, 18, 20, 22, 24, 28, E37, 38, 41, 47, 51, 61, E65, 66, E90, 9

120, 12964-19-7 Acetic acid 81, 11867-56-1 Methanol 12, 15, 18, 28, 38, 40, 49, 65, 68, 98, 99, 120, 1267-64-1 2-propanone~acetone! 14, 15, 43, E67, 67, 68, E91, 92, 98, 1167-68-5 Sulfinyl-bis methane~dimethylsulfoxide! 12, 14, 15, 4268-12-2 N,N-dimethylformamide 12, 14, 15, 44, 48, 51, 7171-36-3 1-butanol E94, 94, 10071-41-0 1-pentanol 9771-42-371-43-2 Benzene 15, 18, 81, 11874-90-8 Hydrogen cyanide 3575-05-8 Acetonitrile 14, 15, 41, 89, 12975-09-2 Dichloromethane 59, 81, 118, 11975-12-7 Formamide 4075-65-0 2-methly-2-propanol~tert-butanol! 4578-93-3 2-butanone~methyl ethyl ketone! 14, 15, 69, E93, 99, 99, 120, 13179-20-9 methylacetate 70, 9295-50-1 o-dichlorobenzene 4895-53-4 o-toluidine 146, 148, 15496-49-1 1,3-dioxolan-2-one~ethylene carbonate! 4398-01-1 2-furancarboxaldehyde~furfural! 29, 69, 99, 13198-86-2 1-phenylethanone 99, 120107-15-3 1,2-ethanediamine~ethylenediamine! 70, 90107-18-6 2-propen-1-ol~allylalcohol! 66107-21-1 1,2-ethanediol~ethyleneglycol! 42, 113108-19-0 Imidodicarbonic diamide~biuret! 143108-32-7 4-methyl-1,3-dioxalan-2-one~propylene carbonate! 25, 34108-90-7 Chlorobenzene 81, 118108-94-1 Cyclohexanone 14, 15, 99, 120109-99-9 Tetrahydrofurane 15110-86-1 Pyridine E95, 96111-46-6 2,28-oxybis-ethanol~diethyleneglycol! 114112-27-6 2,28-@1,2-ethanediyl bis~oxy!#bis-ethanol

~triethylene glycol!114

121-44-8 N,N-diethylethanamine~triethylamine! 81, 118, 130, 141121-69-7 N,N-dimethylbenzeneamine~dimethyl-aniline! 81, 118123-91-1 1,4-dioxane 15126-33-0 Tetrahydro-1,1-thiophene dioxide~sulfolane! 95126-73-8 Tri-n-butyl~phosphate! 55, 72, 98, 120, 121, 130127-19-5 N,N-dimethylacetamide 54, 55, 71, 72, 97, 149, 156141-78-6 Ethylacetate 81, 93, 118142-82-5 Heptane 15143-33-9 Sodium cyanide E26, 27, 28, E29, 30, 31, 32, 33151-50-8 Potassium cyanide 33, 34, 35, 36, 37, E37, 38, 39, 40, 41, 42, 43, 4298-14-6 Potassium hydrogencarbonate 105306-61-6 Magnesium thiocyanate 146-147330-20-2 Potassium thiocyanate 75-76, E82-E83, 83-90, E90, 91, E91, 92, E93, 93, E94, 94, 95, E95, 96-119, 1

150-151, 157-158506-87-6 Ammonium carbonate 145540-72-7 Sodium thiocyanate E59, E60, 60, 61, 62, 63, 64, 65, E65, 66, E67, 67-81, 149, 15542-90-5 Ethylthiocyanate 117-118556-64-9 Methylthiocyanate 80, 116-117, 143-144, 152-153, 159-16556-65-0 Lithium thiocyanate E52, 52, 53, 54, 55, 56, 57, 58, 59584-08-7 Potassium carbonate 106-107590-28-3 Potassium cyanate 50, 51872-50-4 N-methyl-2-pyrrolidone 71917-61-3 Sodium cyanate E46, 47, 48, 491234-91-1 1,4-dioxane 45


, 161

3, 145,

2, 53-152,,

-157

169169JIRI HALA

1303-96-4 Sodium tetraborate decahydrate 791310-58-3 Potassium hydroxide 391310-73-2 Sodium hydroxide E29, 30, 31, 321332-77-0 Potassium tetraborate 1091762-95-4 Ammonium thiocyanate 76-77, E122, 123-145, 151-152, 153, 154, 1582092-16-2 Calcium thiocyanate 148-1532092-17-3 Barium thiocyanate E155, 155-1612408-36-8 Lithium cyanide 252567-83-1 Tetraethylammonium perchlorate 253235-51-6 2-methoxy-N,N-bis~methoxyethyl!ethaneamine

~tris~oxa-3- butyl!amine!59, 81, 119

3879-01-4 Cesium thiocyanate 1213879-02-5 Rubidium thiocyanate 119, 1206381-79-96484-52-2 Ammonium nitrate 49, 132, 1337446-09-5 Sulfur dioxide 27, 35, 63, 87, 1267447-40-7 Potassium chloride 100, 1017447-41-8 Lithium chloride 567631-95-0 Sodium molybdate 797647-14-5 Sodium chloride 32-33, 73, 74, 137-1387664-41-7 Ammonia 13, 19, 27, 36, 37, E46, 47, 48, 49, 50, 54, 63, 64, 88-89, 126, 127, 128, 131, 13

153, 154, 1617681-11-0 Potassium iodide 1027732-18-5 Water 8-11, E15, 16-18, 20, E21, 22-24, E25, E26, E29, 30- 34, 39-45, 50, 51, E52, 5

56-58, E59, E60, 61, 62, 72-80, E82-E83, 83-87, 100-117, 119, 121, 122-125, 131154, E155, 155, 156, 157, 158, 159, 16

7757-79-1 Potassium nitrate 103, 1047757-82-6 Sodium sulfate 757758-02-3 Potassium bromide 1027758-09-0 Potassium nitrite 1037775-19-1 Sodium borate 787778-80-5 Potassium sulfate 107, 1087782-92-5 Sodium amide 137783-20-2 Ammonium sulfate 139, 1407789-20-0 Water-d2 86, 8710043-35-3 Boric acid 56, 77, 78, 108, 14010102-40-6 Sodium molybdate dihydrate 7910555-76-7 Sodium borate tetrahydrate 7812007-58-8 Ammonium tetraborate 14112007-60-2 Lithium tetraborate 5712045-78-2 Potassium tetraborate tetrahydrate 10912047-22-2 Barium azide monohydrate 2512125-02-9 Ammonium chloride 48, 74, 138, 13712164-94-2 Ammonium azide 18, 1912228-87-4 Ammonium tetraborate tetrahydrate 14112230-71-6 Brium hydroxide octahydrate 15913446-49-6 Potassium molybdate 11013453-69-5 Lithium borate 5713709-94-9 Potassium borate 10914187-32-7 18-dibenzo-crown-6 14, 15, 48, 5116712-20-2 Lithium chloride monohydrate 5617032-40-5 Sodium thiocyanate dihydrate 61, 73, 74, 74, 75-76, 79, 149-150, 15617033-98-6 Potassium carbonate hexahydrate 106-10717194-00-2 Barium hydroxide 15918807-10-8 Strontium thiocyanate 15418810-58-7 Barium azide E24, 2519465-88-4 Calcium azide 20, 2119465-89-5 Strontium azide E21, 22, 2319579-69-4 Lithium azide 8, 920762-60-1 Potassium azide E15, 16, 17, 21, 2322208-76-0 Barium azide monohemihydrate 2522119-71-7 Calcium azide with 0.5H2O 2022119-72-8 Calcium azide with 1.5H2O 2022119-73-9 Calcium azide with 4H2O 2022750-57-8 Cesium azide 1822756-36-1 Rubidium azide 1725178-25-0 Sodium cyanide dihydrate 26, 30, 31-32, 32-3326628-22-8 Sodium azide 10, 11, 12, 12, 13, 14, 15


-161

7

. This list


34204-05-2 Lithium azide monhydrate 837195-62-3 Lithium tetraborate trohydrate 5737604-15-2 Potassium thiocyanate•urea 110-111, 111-11237954-70-4 Magnesium thiocyanate•8-urea 146-14737954-71-5 Magnesium thiocyanate•4-urea 146-14741514-73-2 Lithium thiocyanate•2-urea 5841514-74-3 Lithium thiocyanate•1-urea 5852075-71-5 Strontium azide hexahydrate 22-2352075-72-6 Strontium azide dihydrate 22-2352214-22-9 Strontium azide tetrahydrate 22-23, 2361088-24-8 Sodium tetraborate 7968016-36-4 Barium thiocyanate trihydrate 156-157, 157-158, 158, 159, 16070384-51-9 2-~2-methoxyethoxy!-N,N-bis-2-~2-methoxyethoxy!ethyl

~tris~dioxa-3,6-heptyl!amine!59, 81, 119

84372-58-7 Lithium thiocyanate dihydrate 53, 55, 57, 5897034-69-8 Lithium thiocyanate monohydrate 53

Ammonium azide diammoniate 19Ammonium azide pentaammoniate 19NH4SCN•H2O 1257NH4SCN•6Ca~SCN!2•12H2O 151-1524NH4SCN•Ca~SCN!2•2H2O 151-152~NH4!2CO3•2NH4HCO3 145Ba~OH!SCN 159Ba~SCN!2•NH4SCN•H2O 158Ba~SCN!2•2CO~NH2!2 160-161Ba~SCN!2•3CO~NH2!2 160-161Calcium thiocyanate tetrahydrate 149-151, 151-1522KSCN•Ca~SCN!2•3H2O 150-1513KSCN•Ca~SCN!2•3H2O 150-1512KSCN•2Ba~SCN!2•5H2O 157-158Lithium thiocyanate pentahydrate 53Lithium thiocyanate trihydrate 5318-dicyclohexyl-crown-6 48, 51Lithium azide tetrahydrate 8Polyethylenegylcol~200! 115Polyethylenegylcol~1500! 115-116Polyethylenegylcol~6000! 115-116Magnesium thiocyanate tetrahydrate 146-147Dipotassium calcium azide tetrahydrate 21Sodium azide trihydrate 10Sodium azide hexaammoniate 13Strontium azide pentahydrate 23Dipotassium stronitum azide tetrahydrate 23Sodium hydroxide monohydrate 31-32NaCH•NaOH 31-32Sodium thiocyanate monohydrate 60NaSCN•C3H6O 67NaSCN•C4H9NO 723NaSCN•4C4H9NO 72NaSCN•2C4H9NO 722NaSCN•5C4H9NO 72KSCN•0.5H2O 101, 104, 105, 106, 111-112, 135-13

10. Author Index

Page numbers preceded by E refer to evaluation texts whereas those not preceded by E refer to compiled tablesdoes not include the authors listed under the References in the Auxiliary Data.

Abe, S. E46, 47, 48, 49Abykeev, K. 147Adamcova, Z. 113, 114, 115-116Akimova, I. P. E82-E83, E94, 100Akhrap, L. K. E26


142

142

3

140

4

2

9

171171JIRI HALA

Alexander, R. 12Alexander, W. B. 126-127Andrianov, A. M. E82-E83, 101, 104, 105-106, 106, 111-112, E122, 135-137, 139,Ariizumi, M. E46, 46Babenko, A. M. E82-E83, 101, 104, 105-106, 106, 111-112, E122, 135- 137, 139,Bakeev, M. I. E82-E83, E94, 100Basanov, A. N. 55Basanova, N. A. 55Bassett, H. 39Batura, Z. E. E59-E60, 62, 73Belyayev, I. N. 145Blandamer, M. J. 34, E37, 40-45Bleshinskaya, L. S. E122, 143Blytas, G. C. 54, 64, 88Bogoyavlenskii, P. S. E82-E83, 100,102, 103, 105, 107, E122, 13Bradley, W. P. 126-127Brighton, T. B. 33, 50Brinkley, S. R. 133Browne, A. W. 18, 19Bump, C. K. E59-E60Burgess, J. 34, E37, 40-45Bychkova, M. N. E59-E60, 61, 73, 74, 75, 76-77, E122, 125, 137-138, 138,Bykova, I. N. 119Chang, T. L. E82-E83, 87Chretien, A. E82-E83, 85Corbet, A. S. 39Cothran, J. C. 18Cranston, J. A. 11, 47Curtius, T. 8, 9, E15, 16, 17, 18, 20, E21, 22, E24, 2Dahmlos, J. 35Daniels, F. 54, 64, 88Darrin, M. E59-E60Davranov, M. D. E122, 143DeBruyn, C. A. L. E37, 38Dernini, S. E67, 68, E91, 98DeSantis, R. E67, 68, E91, 98Dingle, H. E. 11Drabble, F. E59-E60, 148, 149-150, 150-151, 151-15Duffield, A. J. 34, E37, 40-45Efimov, A. Yu. 56Ernst, G. 20Ettinger, J. L. 27Fedorov, A. A. 54, 71, 97, 149, 156Fedorov, V. M. E59-E60, E82-E83Fedotova, G. F. E90, 91Filatova, N. I. 54, 71, 97, 149, 156Foote, H. W. E82-E83, 84, E122, 127, 131, 133, E155, 15Fredenhagen, K. 35Friedrichs, F. 19Frost, O. I. E26, 26Frost, W. S. 18Gadsby, K. R. 12Gerzhberg, Yu. I. E67, 68, 69, E90Ghaspar, E. D. E82-E83, 105Gode, G. K. E59-E60, 77Golovkov, M. P. 27Golyand, S. M. E59-E60, 74Gopal, R. 95Grigoreva, E. A. 145Grohrock, E. E91, 113Hala, J. 55, 72, 98, 120, 121, 130Hara, R. E46, 46Henstock, H. 28Hickey, F. C. E155, 159Hoffer, O. E82-E83, 85Howard, D. H. 19Hsieh, Y. Y. E82-E83, 87Hudswell, F. 12


, 155

2

40

618, 158


Hughes, O. L. E59-E60, 60, 65, E65, 66, E67, 67Hunt, H. 50, 63, 128Hunter, M. A. 127Husain, M. M. 95Ionin, M. V. E94, 94Isakova, S. 147Isbin, H. S. 70, 90Ivanova, Yu. A. E90, E93, 99, 120Iwase, E. E52, 52Izutsu, K. 25Jander, G. 27, 35, 63, 87, 126Jasinski, T. 81, 118Johnson, S. E. J. E26, E29, 31-32Johnson, W. C. E36, 36Kamyshnikova, G. V. 146, 148, 154, E155, 155Karchmarchik, O. S. E59-E60, 62, 71, 72Karov, Z. G. E59-E60, 79, E82-E83, 110Kawakami, T. 13-14Kertesz, D. J. 54Ketkovich, V. Ya. E122, 124, 132, 134Khripun, M. K. 56King, F. E. E65, 66Kireev, V. A. E26, E29, 30Kirschner, H. 20, 21, E21, 22, 23, E24, 25Klyavina, L. A. E59-E60, 77Ko, E. C. F. 12Kobe, K. A. 70, 90Kordes, E. E82-E83, E122Korewa, R. 81, 118Kraczek, F.C. E82-E83, 86Kravchenko, L. N. 14, 15Krumboltz, O. F. E36, 36Krumgalz, B. S. E67, 68, 69, E90, 91Krupatkin, I. L. 55, 69, E93, 99, E122, 125, 130, 131, 141, 144-145, 146, 148, 154, E155Kukulieva, E. I. E59-E60, 79Kumoa, S. E46, 46Kutuzova, M. L. 56Kuznetsova, Z. B. E94, 94Lavrova, O. A. E59-E60, 71, 72Lepeshkov, I. N. E59-E60, 79, E82-E83, 110Lewis, G. N. 33, 50Lieber, E. 11Lilis, L. S. 56Livingstone, A. Y. 11, 47Ludkovskaya, B. G. E59-E60, 74Mac, Y. C. 12Mai, L. S. E26Maier, H. E. 21Marianowska, J. 86Marrelli, L. E67, 68, E91, 98Mashkulia, V. P. 69, E93, 99, 131McKerrow, A. K. E59-E60, 148, 149-150, 150-151, 151-15Mead, T. H. E59-E60, 60, 65, E65, 66, E67, 67Mokosina, N. N. E59-E60, 62, 71, 72Moleva, T. I. E94, 94Molodkin, A. K. 56, 57, E59-E60, 78, 79, E82-E83, 108, 109, E122, 1Moroto, S. 13-14Nairn, J. S. 12Nakamura, T. 25Naumann, A. 89, 129Nikitina, I. P. E90, 91Nikitina, O. G. E59-E60, 75-76, E82-E83, 108Nikolaev, V. I. E52, 53Nikonov, F. V. E122, 140Nogoev, K. 58, E82-E83, 110-111, 121, 146-147, E155, 160-1Occleshaw, V. J. E59-E60, E82-E83, E122, 148, 189-150, 150-151, 151-152, E155, 156-157, 157-15Odanaka, S. E26, 32-33Okabe, T. E46, 47, 48, 49


4

141

141

-160

-161

141

61

, 155

173173JIRI HALA

Okuwaki, A. 49Oliver, G. D. E26, E29, 31-32Ossendowski, A.M. 39Ostrovskaya, E. M. 146, 148, 154, E155, 155Paar, W. 23Parker, A. J. 12Partington, J. R. E59-E60, 61, E65, 66, E82-E83, 84Plyushchev, V. E. E90, E93, 99, 120Radl, K. H. E24, 25Rao, C. N. R. 11Rassonskaya, I. S. E122, 124, 132, 134-135Ravich, M. I. E122, 124, 132, 134-135Rissom, J. 8, 9, E15, 16, 17, 18, 20, E21, 22, E24, 2Rollet, A. P. 8-9Roth, H. E. E21, 22RXdorff, F. E82-E83, 83, E122, 123Ruppolt, W. 27, 35, 63, 87, 126Sadetdinov, Sh. V. 56, 57, E59-E60, 78, 79, E82-E83, 108, 109, E122, 140,Savinov, V. M. 54, 71, 97, 149, 156Schenk, P. W. E36, 37, 88-89Schimmel, F. A. E52, 53Schroeder, J. 70, 92Selecki, A. 86Semenova, S. B. E82-E83, 110Shlionskaya, M. A. 54, 71, 97, 149, 156Shnidman, L. E122, 123, 128, 129Shuvaeva, T. M. 14, 15Skvortsov, V. G. 56, 57, E59-E60, 78, 79, E82-E83, 108, 109, E122, 140,Smirnova, V. A. E67, 68, 69, E90Sokolov, L. B. 54, 71, 97, 149, 156Soper, W. E. E59-E60, 61, E65, E82-E83, 84Soula, G. 59, 81, 119Spacamella Marchetti, E. E59-E60, 80, 116-117, 117-118, 143-144, 152-153, 159Srivastava, P. 95Stasiewicz, A. 153, 154, 161Steiner, M. 70, 92Stepin, B. D. E90, E93, 99, 119, 120Sukmanskaya, G. V. E82-E83, 107Sulaimankulov, K. 58, E82-E83, 110-111, E122, 143, 146-147, 147, E155, 160Syui, K. M. E82-E83, 100, 102Takeshita, J. 49Tarasov, A. K. 48Teetsow, J. 11Thompson, M. R. 28, E37, 38Titova, V. A. E59-E60, 62, 73Torkar, K. 20, E21, 22, E24, 25Traber, D. G. E90, 01Trimble, F. 29Tsekhanskii. R. S. 56, 57, E59-E60, 78, 79, E82-E83, 108, 109, E122, 140,Tuck, D. G. 55, 72, 98, 120, 121, 130Tulhoff, H. E36, 37, 88-89Turgunbekova, R. 58, E82-E83, 110-111, 121, 146-147, E155, 160-1Tyminski, B. 86Vagranskaya, L. I. E26, E29, 30Van, L. E82-E83, 103Vasilevoy, L. A. 34Vasiliev, B. B. 27Vassiliev, A. M. E82-E83, E122Veselova, M. E. 69, E93, 99, 131Voinilovich, G. I. E26Von Laszczynski, S. E91, 92, 93, E95, 96, 97Vorobeva, L. D. 69, E93, 99, E122, 125, 130, 131, 140, 144-145, 146, 148, 154, E155Wagner, K. L. E95, 96Weitz, E. E91, 113Winterton, R. J. E65, 66Wohlgemuth, J. 8-9, 10, E15, 16Yajima, K. E26, 32-33Yashio, H. 49


, 140

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Yastrebov, L. N. 14, 15Yunusova, Z. Yu. E122, 143Zerner, E. E95, 96Zhuravlev, E. F. E59-E60, 61, 73, 74, 75-76, 76-77, E82-E83, 108, E122, 125, 137-138, 138Zlobin, V. A. 48

Editor-in-ChiefM. Salomon

Sub-EditorSolid/Liquid Systems

W. Voigt

EDITORIAL BOARDChr. Balarew~Bulgaria! C. Magalhaes~Portugal!M.W. Chase~USA! H. Miyamoto ~Japan!R. Cohen-Adad~France! J. Sangster~Canada!J. Eysseltova` ~Czech Republic! K. Sawada~Japan!P.G.T. Fogg~UK! M.-Th. Saugier Cohen-Adad~France!H. Gamsja¨ger ~Austria! P. Scharlin~Finland!M. Gaune-Escard~France! D.G. Shaw~USA!A. Goto ~Japan! A. Skrzecz~Poland!C. Guminski~Poland! R.P.T. Tomkins~USA!G.T. Hefter~Australia! J. Vanderdeelen~Belgium!E. Konigsberger~Australia! V.M. Valyashko~Russia!J.W. Lorimer~Canada! W. E. Waghorne~Ireland!

Managing EditorM. W. Chase

National Institute of Standards and Technology

SOLUBILITY DATA SERIES

Volume 1 H.L. Clever,Helium and NeonVolume 2 H.L. Clever,Krypton, Xenon and RadonVolume 3 M. Salomon,Silver Azide, Cyanide, Cyanamides, Cyanate, Selenocyanate and ThiocyanatVolume 4 H.L. Clever,ArgonVolume 5/6 C.L. Young,Hydrogen and DeuteriumVolume 7 R. Battino,Oxygen and OzoneVolume 8 C.L. Young,Oxides of NitrogenVolume 9 W. Hayduk,EthaneVolume 10 R. Battino,Nitrogen and AirVolume 11 B. Scrosati and C.A. Vincent,Alkali Metal, Alkaline Earth Metal and Ammonium Halides, Ami

SolventsVolume 12 C.L. Young,Sulfur Dioxide, Chlorine, Fluorine and Chlorine OxidesVollume 13 13 S. Siekierski, T. Mioduski and M. Salomon,Scandium, Yttrium, Lanthanum and Lanthani

NitratesVolume 14 H. Miyamoto, M. Salomon and H.L. Clever,Alkaline Earth Metal HalatesVolume 15 A.F.M. Barton,Alcohols with WaterVolume 16/17 E. Tomlinson and A. Regosch, Antibiotics: 1,b-Lactam AntibioticsVolume 18 O. Popovych,TetraphenylboratesVolume 19 C.L. Young,Cumulative Index: Volumes 1-18Volume 20 A.L. Horvath and F.W. Getzen, Halogenated Benzenes, Toluenes and Phenols with WaterVolume 21 C.L. Young and P.G.T. Fogg,Ammonia, Amines, Phosphine, Arsine, Stibine, Silane, Germane

Stannane in Organic Solvents


in

clic

clic

ium,

ter

ter,

175175JIRI HALA

Volume 22 T. Mioduski and M. Salomon,Scandium, Yttrium, Lanthanum and Lanthanide HalidesNon-aqueous Solvents

Volume 23 T.P. Dirkse,Copper, Silver, Gold and Zinc, Cadmium, Mercury Oxides and HydroxidesVolume 24 W. Hayduk,Propane, Butane and 2-MethylpropaneVolume 25 C. Hirayama, Z. Galus and C. Guminski,Metals in MercuryVolume 26 M.R. Masson, H.D. Lutz and B. Engelen,Sulfites, Selenites and TelluritesVolume 27/28 H.L. Clever and C.L. Young,MethaneVolume 29 H.L. Clever, Mercury in Liquids, Compressed Gases, Molten Salts and Other ElementsVolume 30 H. Miyamoto and M. Salomon, Alkali Metal Halates, Ammonium Iodate and Iodic AcidVolume 31 J. Eysseltova and T.P. Dirkse,Alkali Metal OrthophosphatesVolume 32 P.G.T. Fogg and C.L. Young, Hydrogen Sulfide, Deuterium Sulfide and Hydrogen SelenideVolume 33 P. Franzosini,Molten Alkali Metal AlkanoatesVolume 34 A.N. Paruta and R. Piekos,4-Aminobenzenesulfonamides. Part I: Non-cyclic SubstituentsVolume 35 A.N. Paruta and R. Piekos,4-Aminobenzenesulfonamides. Part II: 5-membered Heterocy

SubstituentsVolume 36 A.N. Paruta and R. Piekos,4-Aminobenzenesulfonamides. Part III: 6-membered Heterocy

Substituents and Miscellaneous SystemsVolume 37 D.G. Shaw,Hydrocarbons with Water and Seawater. Part I: Hydrocarbons C5 to C7Volume 38 D.G. Shaw, Hydrocarbons with Water and Seawater. Part II: Hydrocarbons C8 to C36Volume 39 C.L. Young,Cumulative Index: Volumes 20-38Volume 40 J. Hala,Halides, Oxyhalides and Salts of Halogen Complexes of Titanium, Zirconium, Hafn

Vanadium, Niobium and TantalumVolume 41 C.-Y. Chan, I.N. Lepeshkov and K.H. Khoo,Alkaline Earth Metal PerchloratesVolume 42 P.G.T. Fogg and W. Gerrard,Hydrogen Halides in Non-aqueous SolventsVolume 43 R.W. Cargill,Carbon MonoxideVolume 44 H. Miyamoto, E.M. Woolley and M. Salomon,Copper and Silver HalatesVolume 45/46 R.P.T. Tomkins and N.P. Bansal,Gases in Molten SaltsVolume 47 R. Cohen-Adad and J.W. Lorimer,Alkali Metal and Ammonium Halides in Water and Heavy Wa

(Binary Systems)Volume 48 F. Getzen, G. Hefter and A. Maczynski,Esters with Water. Part I: Esters 2-C to 6-CVolume 49 F. Getzen, G. Hefter and A. Maczynski, Esters with Water. Part II: Esters 7-C to 32-CVolume 50 P.G.T. Fogg, Carbon Dioxide in Non-aqueous Solvents at Pressures Less Than 200 kPaVolume 51 J.G. Osteryoung, M.M. Schneider, C. Guminski and Z. Galus, Intermetallic Compounds in

MercuryVolume 52 I. Lambert and H.L. Clever,Alkaline Earth Hydroxides in Water and Aqueous SolutionsVolume 53 C.L. Young,Cumulative Index: Volumes 40-52Volume 54 W.E. Acree, Jr.,Polycyclic Aromatic Hydrocarbons in Pure and Binary SolventsVolume 55 S. Siekierski and S.L. Phillips,Actinide NitratesVolume 56 D. Shaw, A. Skrzecz, J.W. Lorimer and A. Maczynski,Alcohols with HydrocarbonsVolume 57 W. Hayduk,EtheneVolume 58 W.E. Acree, Jr.,Polycyclic Aromatic Hydrocarbons: Binary Non-aqueous Systems, Part I:

Solvents A-EVolume 59 W.E. Acree, Jr.,Polycyclic Aromatic Hydrocarbons: Binary Non-aqueous Systems, Part II:

Solvents F-ZVolume 60 A.L. Horvath and F.W. Getzen,Halogenated Methanes with WaterVolume 61 C.-Y. Chan, K.H. Khoo, E.S. Gryzlova and M.-T. Saugier-Cohen Adad,Alkali Metal and

Ammonium Perchlorates, Part I: Lithium and Sodium PerchloratesVolume 62 P. Scharlin,Carbon Dioxide in Water and Aqueous Electrolyte SolutionsVolume 63 H.U. Borgstedt and C. Guminski,Metals in Liquid Alkali Metals, Part I: Be to OsVolume 64 H.U. Borgstedt and C. Guminski,Metals in Liquid Alkali Metals, Part II: Co to BiVolume 65 J.J. Fritz and E. Ko¨nigsberger,Copper(I) Halides and PseudohalidesVolume 66 J. Eysseltova´ and T.P. Dirkse,Ammonium Phosphates, JPCRD27„5…, 1289~1998!.Volume 67 A.L. Horvath, F.W. Getzen and Z. Maczynska,Halogenated Ethanes and Ethenes with Wa

JPCRD28„2…, 395 ~1999!.Volume 68 A.L. Horvath and F.W. Getzen,Halogenated Aliphatic Hydrocarbons C3-C14 with Water,JPCRD

28„3…, 649 ~1999!.


nd

d


Volume 69 A. Skrzecz, D. Shaw and A. Maczynski,Ternary Alcohol-Hydrocarbon-Water Systems,JPCRD28„4…, 983 ~1999!.

Volume 70 Yu.P. Yampol’skii, R. Paterson and P.G.T. Fogg,Gases in Glassy Polymers,JPCRD,28„5…, 1255~1999!.

Volume 71 V. Sazonov, G.T. Hefter and K.N. Marsh,Binary Nitromethane Systems,JPCRD,29„5…, 1165~2000!.

Volume 72 V. Sazonov and G.T. Hefter,Nitromethane with Water or Organic Solvents: Ternary aQuaternary Systems,JPCRD,29„6…, 1447~2000!.

Erratum SDS volume 66,Ammonium Phosphates,JPCRD,29„6…, 1643~2000!.Volume 73 Chr. Balarew and T.P. Dirkse,Metal Formates,JPCRD,30„1…, 1 ~2001!.Volume 74 J. Ha´la, Actinide Carbonates and Carbon-Containing Compounds,JPCRD,30„2…, 531 ~2001!.Volume 75 H.U. Borgstedt and C. Guminski,Non-Metals in Liquid Alkali Metals, JPCRD,30„4…, 835~2001!.Volume 76 P.G.T. Fogg,Ethynes, JPCRD,30„6…, 1693~2001!.Volume 77 V. P. Sazonov and D. G. Shaw,Nitroalkanes with Water or Organic Solvents: Binary an

Multicomponent Systems, JPCRD,31„1…, 1 ~2002!.Volume 78 V. P. Sazanov and D. G. Shaw,Acetonitrile binary systems, JPCRD31„4…, 989 ~2002!.Volume 79 J. Ha´la, Alkali and alkaline earth metal pseudohalides,JPCRD,33„1…, 1 ~2004!.

Volumes 1-53 published by Pergamon PressVolumes 54-65 published by Oxford University PressVolumes 66 and above published in theJournal of Physical and Chemical Reference Data~JPCRD! under the titleIUPAC-NIST Solubility Data Series.


IUPAC-NIST Solubility Data Series. 79. Alkali and Alkaline

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Transcript of IUPAC-NIST Solubility Data Series. 79. Alkali and Alkaline