APPLICATIONS OF ION-SELECTIVE ELECTRODES IN...

Pure & Appi. Chem., Vol. 55, No. 12, pp. 2029—2065, 1983. 0033—4545/83 $3.00+0.00Printed in Great Britain Pergamon Press Ltd.

©1983 IUPAC

INTERNATIONAL UNION OF PUREAND APPLIED CHEMISTRY

ANALYTICAL CHEMISTRY DIVISION

COMMISSION ON ELECTROANALYTICAL CHEMISTRY*

APPLICATIONS OF ION-SELECTIVEELECTRODES IN NONAQUEOUS AND

MIXED SOLVENTS

Prepared for publication byE. PUNGOR', K. TOTH1, P. G. KLATSMANYI' and K. IZUTSU2

1lnstitute for General and Analytical Chemistry, Technical University,Budapest, Hungary

2Faculty of Science, Shinshu University, Matsumoto, Japan

*Membership of the Commission during the preparation of this report (1979—1981) was asfollows:

Chairman: J. F. COETZEE (USA); Secretary: J. JORDAN (USA); Titular Members:A. K. COVINGTON (UK); K. IZUTSU (Japan); J. JUILLARD (France); R. C.KAPOOR (India); E. PUNGOR (Hungary); Associate Members: R. A. DURST (USA);M. GROSS (France); K. M. KADISH (USA); R. KALVODA (Czechoslovakia);Y. MARCUS (Israel); L. MEITES (USA); T. MUSSINI (Italy); H. W. NURNBERG(FRG); P. PAPOFF (Italy); M. SENDA (Japan); D. E. SMITH (USA); N. TANAKA(Japan); National Representatives: D. D. PERRIN (Australia); W. C. PURDY(Canada); R. NEEB (FRG); K. TOTH (Hungary); H. V. K. UDUPA (India);Z. GALUS (Poland); B. BIRCH (UK); M. BRANICA (Yugoslavia).

APPLICATIONS OF ION-SELECTIVE ELECTRODES IN NONAQUEOUS AND

MIXED SOLVENTS

1. Introduction2. Problems of potentiometry in nonaqueous media3. Potential response of ion—selective electrodes3.1. pH-sensitive glass electrodes3.2. Cation-sensitive glass electrodes3.3. Non-glass based ion-selective electrodes4. Application of ion-selective electrodes in nonaqueous

media4.1. Application of pH-sensitive glass electrodes4.2. Application of cation-sensitive glass electrodes4.3. Application of non-glass based ion-selective electrodes

1. INTRODUCTION

The processes taking place in nonaqueous, mixed and partially aqueous mediaare far more complex than those occuring in water. However, studies on theprocesses in these media with potentiometric technique employing differention-selective electrodes opened up new possibilities for the further develop-ment in the field. Thus, determinations can be accomplished which are notfeasible in aqueous media. At the same time the use of such solvent systemsmade possible a thorough examination of acid-base and complex equilibria, andof the mechanism and kinetics of different chemical reactions, as well as theinvestigation of ion-transport processes in solvent mixtures.

As it is known, in the interpretation of processes in nonaqueous media it isimportant to take into consideration the properties of the solvent (1-4) aswill be described in Section 3.1. The application of ion-selective electrodesin nonaqueous solvents involves a series of problems in connection with theselection of the sensors and the measuring techniques. Among the ion-selectiveelectrodes applied in nonaqueous and mixed solvents pH sensitive glass elec-trodes have found most extensive use. Consequently a series of questionsregarding the mechanism of the operation of the electrodes in different non--aqueous solvents was investigated (e.g. pH—scales. liquid junction, poten-tial response, etc.). The appearance of non—glass based ion—selective elec-trodes since the 1960's, offered new possibilities for the further developmentand widespread application of potentiometric techniques. Moreover their usein nonaqueous systems is expected.

2. Problems of potentiometry in nonaqueous media

Sources of errors which are encountered in ion—selective electrode potentio-metry in aqueous solutions have been reviewed, for example, by Durst (1,6-8).In the ion—selective electrode potentiometry in non—aqueous solvents, someadditional problems other than those in aqueous solutions should be takeninto account, as have been discussed by Pungor and Tóth (3). In the followinga brief description will be given about problems and possibilities of the useof ion-selective sensors in non-aqueous, mixed and partially aqueous solvents.

Ion-selective electrodes: Ion-selective electrodes nowadays available havebeen prepared for use in aqueous solutions, and many of them are difficultto apply in non-aqueous solutions (not speaking about the pH-sensitive glasselectrodes). Besides the problem of the proper response of the electrode, thematerials constructing the electrode should not be damaged in the solventunder study. In general, it is true that the establishment of a well-definedphase boundary at the detector-solution interface is a condition of the useof an ion—selective electrode in nonaqueous solvents.

2030

Applications of ion—selective electrodes 2031

From the point of view of the application of potentiometric measuring tech-niques, the sensitivity, the Nernstian behaviour and selectivity of an mdi-cator electrode is very important. From this point, glass electrodes and somesolid membrane electrodes are promising. Ion-selective electrodes applicablein non-aqueous solvents and their conditioning will be described in Sections3. and 4.

Cells, salt bridges, and reference electrodes: Two types of cells are usuallyemployed for potentiometric study, i.e., cells with and without liquidjunctions as shown by (1) and (2), respectively,

indicator solution salt-bridge•• reference

electrode to be tested electrolyte electrode type(l)

indicator solution referenceelectrode to be tested electrode type(2)

where indicates a solution-electrode interface, and a liquid junction.Cells of type (1) are usually used. In these cells, liquid junction potenti-als at J1 and J2 influence the emf of the cell. The liquid junction potentials

should be reproducible and constant during a series of measurements. It ispreferable that the solvent of the reference electrode is the same as thatof the test solution. Moreover, if possible, it is recommended to eliminatethe liquid junction potentials either (1 ) by adding an appropriate indifferentelectrolyte to all solutions in the three compartments of cell, or (2) byusing a high concentration of an equitransferent electrolyte solution in thesalt bridge. It often occurs, however, that an aqueous electrode of the secondkind (aqueous SCE, for example) is employed as the reference electrode. Inthose cases, big liquid junction potentials may be observed at the boundarybetween aqueous and non-aqueous (9) and the potential may be influencedsignificantly by the composition of the solutions at the boundary (10). Theaqueous reference electrode should be connected to the test solution onlythrough a salt bridge of appropriate non-aqueous solutions.

In cells of type (2), there is no liquid junction. However, this cell can beused only when the behaviour of the reference electrode in the test solutionis exactly known.

The problem of the reference electrode is extremely important in potentiometryin non—aqueous solvents. Unfortunately no reference electrode in non—aqueoussolvents is reliable enough in respect of stability and reproducibility ofits potential. Detailed reviews (11-13) will be of help in choosing suitablereference electrodes.

Calibration of ion-selective electrodes: In general for the calibration of anion—selective electrode other than the pH—sensitive glass electrode, a seriesof stable electrolyte solutions of different concentrations are prepared fromwell-defined, high purity salts. The effect of salt concentration on theactivity coefficients of ionic species is often larger in non-aqueous solu-tions than in aqueous solutions, and the effect can be estimated by using anappropriate form of the Debye-HUckel equation. Correction should also be madefor the effect of salt concentration on the liquid junction potential betweenthe test solution and the salt bridge. The Henderson equation may be used forthis. If there is no salt available which dissociates completely in the sol-vent under study, solutions of a salt of known dissociation equilibrium shouldbe employed. In this case, of course, the calculation of ionic activitiesbecomes more complicated. The purity of the solvent may also be very important.Small amounts of acidic and/or basic impurities, including residual water,may influence the calibration curve significantly.

3. Potential response of ion—selective electrodes

3.1. pH—sensitive glass electrodes

The fundamental principle of the operation of a pH-sensitive glass electrodeis the interfacial potential difference between the hydrogen ions fixed in themembrane phase and solvated hydrogen ions in the solution

E =E + —— ln aHl(1)l,(l) o zH+F aH,(l)

2032 CONNISSION ON ELECTROANALYTICAL CHEMISTRY

where E is the phase—boundary potential,E is a constant, 1 means the glass membrane phase,

while (1) the solution phase, the other terms have their usualmeaning

In practice the electrode process was found to be different from that de—scibed by equation (1). Boksay and Csákváry (14) have explained this fact inthe following way: when an ion leaves the glass phase and enters the solution,a vacancy is produced in the glass surface. In the reverse process the ionentering the glass from the solution can occupy a vacancy only,

vacancy + H H1) (2)

then the phase-boundary potential can be rewritten

E1(1) _ E0 +ln {cv a:(l)

where c = the concentration of vacanciesv

Thus, the potential of the pH-sensitive glass electrode depends both on theactivity of the hydrogen ion and the concentration of the vacancies.

In the case of a given type of glass and solvent, resp., the concentration ofthe vacancies can be regarded as constant provided that the rearrangement ofthe bond in the glass and the interfering effect of the molecules are ex-cluded:

cv = const.thus

0 RT RT aHlE =E +—lnc + —ln ' (4)l,(l) F v F a

H, 1

E0

However, in the course of the penetration of another solvent into the glassthe concentration of the vacancies may change due to the change in the ion—-exchange processes. So in the case of the measurements carried out in non—aqueous solvents, this fact must always be taken into consideration. Thisjustifies and shows the importance of the conditioning, i.e. the preliminarysoaking of the electrode in the given solvent.

The papers dealing with the problems related to the potential response of pH-—sensitive glass electrodes have been summarized in Table 1. The main pointof view discussed is the role of the internal reference solution and theeffect of pretreatment of glass electrodes. There are different views re-garding the selection of the internal filling solution (15-21).

The dynamic response of the commercially available glass electrodes was stu-died in detail by several authors (17,18,22-26) and it was found that thepre-conditioning of the glass electrode has shortened the time required forthe establishment of a stable equilibrium potential. The acid error of glasselectrodes in nonaqueous media was discussed also in some of the papers (27,28).The pH-sensitive glass electrode has been extensively used for thermodynamicstudies in different media. In this context considerable effort has devotedto study the effect of non—aqueous solvents on acid-base equilibria.The extent of reactions in which protons are taking part depends on bothelectrostatic and chemical interactions. Changes in the nature of the sol-vents alter the position of equilibria of a protolytic reaction as well asthe activity coefficient of ions. Due to this when ions are transfered fromone solvent to another the so-called "transfer effect" can be observed. Thetransfer effect is a measure of the change in the free energy of transfer.Several papers have dealt with the correlation between of permittivity of thesolvent and the transfer effect (29-37) mainly on the basis of the Borntheory. In work (1,32) there are detailed and critical surveys on these prob-lems. On the basis of the above mentioned publications it can be stated thatthe Born equation does not give a satisfactory explanation for the observedvariations in the PKa values. Certain attempts were made using methanol-water


mixtures (32) to get a linear correlation between the pKa values of p-substi-tuted phenols and the l/& of the corresponding solvent media on the onehand, and between the Harnrnett'5 and l/& on the other. However, the expec-ted linearity predicted on the basis of the simple Born equation was not ob-served in any of the cases studied. These results gave also a confirmation ofthe limited applicability of the simple electrostatic treatment to the trans-fer problems of ions.

In paper (33) a study is given dealing with the behaviour of a series of or-ganic acids in nonaqueous media. Three different binary solvent systems wereemployed each extending over the range of C =5-30. The solvents were chemi-cally inert, nonleveling and nonreactive (benzene—nitrobenzene, benzene—nitro—methane and benzene—acetone systems). The slopes of the HNP vs. PKa curvesplotted against the dielectric constants of different solvent systems resultdifferent curves depending on the nature of the solvent system, indicatingthat the permittivity on its own is not sufficient to describe the phenomena.

In other papers (31,33,38-41) there are also data on the relationship betweenPI<a or pKb values obtained in pure water and the half neutralization potenti-als (HNP) in potentiometric titrations of acids and bases in different non-aqueous media. To eliminate the shifts caused by electrostatic effects, liquidjunction potentials, etc. it was expedient to use a reference standard, so tocalculate instead of HNP of each acid or base with the differential half neu-tralization potential ( HNP)(40). In other cases good results were obtainedby extrapolating the data to zero dielectric constant (33).

Korolev (42) studied the dissociation constants of NH- and OH-type organicacids in water and various organic solvents. Other authors examined amines innitromethane (43) NaCl in nitromethane (35), organic acids in propylene car-bonate (44), alkali metal chlorides (45) and HC1 (46) in dimethyl sulfoxide-water mixtures (45), chloride ion in tert-butanol (47), HC1 in N-methylacet-amide-water mixtures (48), NaCl in aqueous glycerol solutions (49). Thesepublications have dealt with the problem of solvation of ions in differentorganic solvents and in mixed solvents. The papers on the effect of solventsare summarized in Table 2.

3.2. Cation-sensitive glass electrodes

Nernstian response: Many investigators have confirmed the Nernstian responseof cation-sensitive glass electrodes in different aqueous and nonaqueous sol-vent mixtures. Eisenman (50) showed that the glass electrode may be used tomeasure the activities of alkali metal ions in methanol (MeOH). McClure andReddy (51) reported that a cation-sensiiveglass eectrode (Beckman, 39047)responds in a nearly Nernstian way o K ,Na and Li in acetonitrile (AN) andpropylene carbonate (PC)nd to K in dimethylformide (DMF) in the concen-tration range between 10 and 1O2M in the pesence f O.1M Bu4NC1O4 as anindifferent electrolyte. The response for Na and Li in DMF, however, wasunsatisfactory. Each electrode was in contact with_9nly ne kind of solventthroughout the work: the electrode stored in PC(l0 M Li ) showed no sign ofdeterioration even after six months, but the electrode stored in AN becamepitted and ceased to respond after three months. The response of the elec-trodes was rapid, and an equilibrium potential within 1 mV was attained in5 to 10 s. Chantooni and Kolthoff (52) used the sme kind of electrode(Beckman, 39047) to detrmine the activitiesof K in AN, DMF, and dimethylsulfoxide (DMSO) anda in AN and DMSO. (Na in DMSO gave a Nernstian re-sponse only above 10 M.) About 10 mm was required to get stable potentialsreproucibe withi ±2 mV. The same electrode was also confirmed to repondto Rb , Tl and NHA in AN with a Nernstian slope, but the slope for Cs inAN was ca. 43 mV (3).

Mukherjee and Boden (.54) studied the response charcteristics of a glasselectrode (Beckman, 39137) insoluions of pue Li salt in PC and in thepresence f such cations as K , NH , and Et4H at a concentration of .25M.Only Et4N did not interfere with he reponse of the electrode to LiKlthoff nd Chanooni (55) calibrated K -electrode (Makson Co., 1002) forK and Tl and Na -electrode (Markson Co., 1001) for Na in MeOH, AN, PC andDMSO. The electrodes were conditioned for 3-4 days in a O.O1M÷solution of theperchlorate or picrate salt in the same solvent in which paM )÷was meaured.The slopes of the calibration curve for pe9hlorates of Na , K and Tl (forthe concentration ranges of ca. 10 - 5xlO 0M) in AN, PC, DMO and MeOH werealmost Nerstian (59.1 + 0.5 mV/pa(M ) at 25 C), except for K in DMSO (63.8mV) and Tl in PC (54 mV). Stable potentials to within ±1 mV were obtainedin 5 mm, except in PC which required 10-20 mm.PAAC 55:12—L

2034 COMMISSION ON ELECTROANALYTICAL CHEMISTRY

çparison of activities in different solvents: Eisenman (50 ) compared thepotentials of a cation-sensitive glass electrode (NAS 11-18) vs. Ag/AgC1 ref-erence electrode in saturated solutions of NaCl in pure H20, pure MeOH, andmixtures of HO and MeOH. The potential values were the same within a frac-tion of a miltivolt, showing that there was no special solvent effect on thesurface of the glass electrode and that the electrode can be used to compareionic activities in those solvents. For (NAS 27-3 + 3ZnO) glass electrode,however, the potentials in HO and MeOHdiffered by 15-20 mV, indicating theexistence of some solvent eftect on the surface properties. Cells with acation-sensitive glass electrode and an Ag/AgC1 reference electrode (type (2))have been used to obtain free energies of transfer of alkali metal chloridesfrom water to various aqueous organic solvents (56—61). Covington and Thain(62) determined free energies of transfer of alkali metal fluorides and chlori-des from water to aqueous MeOH by using cation—sensitive glass electrodes andas a reference electrode an F-selective electrode (Orion, 94-09) for fluoridesand a Cl -selective electrode (Orin, 94-17) for chlordes. They comparedseveral glass electrodes (Orion Na , 94-llA; E.I.L. a , GEA 3313 or 33-1048--100; Corning univalent cation, 476200; and E.I.L. K , 33-1057-200) as to thespecific solvent effect on the electrode potentials.

Nakamura (63) studied the response of a cation-sensitive glass electrode(Beckman, 39047) to the activities of various univalent cations in differentsolvents. He compared emfs of cells (3) and (4),

M(Hg) MClO4, O.OlM Et4NC1O4(D)ff O.lM Et4NC1O4(AN)I( 5xlO3M AgNO3(AN)/Ag(3)x

Glass electrode JMC1O4, O.OlM Et4NC1O4(D) ft O.1M Et4NC1O4(AN) II 5xlO3M

AgNO3 (AN ) lAg+

where D i AN* PC, MeOH, H20, DMF or DMSO, and M+ is Li+, a+ K, Rb , Cs+,Tl or Ag . ( Ag wire was used instead of Ag amalgam for M = Ag .) The re-sults are shown in Fig.l, choosing AN as a reference solvent (Fig.l.). It isapparent that, in many cases, the glass electrode behaved in the same way asthe cprresponding amalgam elctrodes. There are some exceptions, however, inwhich deviations occured. Ag in AN deviated significantly, and some cationsin H20 also deviated to a smaller extent

Cox et al. (64,65) obtained free energies of transfer of Li and Na from PCto DMA, DMSO, and DMA-PC, DMSO-PC mixtures by measuring emfs of cell (5),

Glass electrode/0.1M MCl04(PC or D )I1O.1M Et4NPic(PC)lt O.O1M AgC1O4(PC)/Ag

(5)where the glass electrode is Coning univalent cation—sensitive electrodeand D shown solvents to which M is transferred. The liquid junction potentalat J was considered to be negligible (66). Free energies of transfer for Nawere also obtained using an amalgam electrode, fair agreements being obtainedbetween both results. They also calculated the free energies of transfer ofthese cations from the successive formation constants of complexing of theseions in PC with DMA and DM50, by assuming that interaction energies outsidethe first coordination sphere were independent of the solvent species. Thevalues provided by calculations agreed well with the experimental valuesobtained with cell (5).

From these results it is apparent that the cation-sensitive glass electrodescan be applied to compare ionic activities in different solvents. But it isnecessary to confirm beforehand, by some appropriate methods, that the poten-tials of the electrode to be used are not affected specifically by the sol-vents in question.Note on the selectivities of cation-sensitive glass electrodes. Some resultshave been reported on the selectivities of cation-sensitive glass electrodesin non-aqueous solvents (50,51,67,68), but no systematic investigation hasbeen carried out. When the glass electrode can respond in a Nernstian way tothe activities of univalent cations in different solvents, the solvent effectto the selectivity constants of the electrode is considered to be determinedmainly by the changes of solvation energies of the cations.

3.3. Non-glass based ion—selective electrodes

As it was proved by a number of scientists, similar calibration curves can beobtained in general for different ion-selective electrodes in nonaqueous and


in mixed media as in aqueous solutions.

Manyauthors examined (69,70,71,72,73,74,75,76,77,78,80—86) the potentialresponse of silver iodide electrodes as well as that of silver bromide elec-trodes (72-74, 78) in detail. Publications on silver chloride ion selectiveelectrodes (72-74, 87-90) deal with certain theoretical problems important inrespect of applications in nonaqueous media. In connection with fluoride ion—-selective electrode there are numerous publications (87,91-96) but only afew papers deal with the potential response of copper (97-99) and lead ion--selective electrodes (100-104). The data published in the papers alreadymentioned are summarized in Table 3. according to the solvents applied. Theapplication conditions are discussed in detail in Section 4.3.

There are publications reporting on electrodes containing new electrode activematerials, which are summarized in Table 4. On the basis of the above litera—ture data it can be stated that the investigation of potential response,dynamic properties, selectivity, etc. of non-glass based ion-selective elec—trodes requires further research work in the future not only from practicalbut also from theoretical points of view.

4. Application of ion-selective electrodes in nonaqueous media

Although most of the applications of ion-selective electrodes are limited toaqueous solutions, the number of examples of successful applications in non-—aqueous solutions is increasing steadily. The present report will reviewthese applications of ion—selective electrodes in non—aqueous solutions.

Ion—sensitive electrodes in organic solvents have been used as:

(i) an indicator electrode for physicochemical studies, including thoseon ion association and complexation of univalent cations

(ii) an indicator electrode for analytical titrations of univalentcations and of reagents which can complex univalent cations (macro—cyclic polyethers, for example),

(iii) a reference electrode in the solutions containing univalent cations.

4.1. Application of pH-sensitive glass electrodes

The majority of papers are dealing with determination of analytical concen-tration values of organS1d bases. At the same time, from the potentio—metric data first of all thermodynamic constants, e.g. stability constantsof complexes containing organic ligands, acid-base equilibrium constants oforganic compounds, etc. are determined. These papers are summarized in Tab-les 5—10.

4.2. Application of cation-sensitive glass electrodes

The cation-sensitive glass electrodes are very convenient+for the study ofcomplexing of univalent cations. Frensdorff (105) used Na -selective electrode(Corning NAS lll8, 476lO)and nivalentcation-sensitive electrode (Corning,476220) for Na and Li , K , Cs and NH4 , respectively, to study the complexformation constants of these cations in MeOH with macrocyclic polyethers.(The cation electrode was conditioned for each new cation by soaking it over-night in a O.O1-0.lM solution of its chloride. One such electrode cracked onimmersion in MeOH, but other electrodes were successfully used in MeOH bystepwise conditioning in aqueous solution of increasing MeOH content up topure MeOH, in which they could be kept indefintely) Kothof and Chntooni(55) studied complex formation constants of Na , K , Rb , Cs and Tl in AN,PC and DMSO with various macrocyclic poyethers. Izutsu et al. (106) deter-mined complex formation 8onstants of Na in AN with several macrocycic p8ly-ethers t 10, 25, and 40 C and obtained thermodynamic parameters(G ,and S ) for the 1:1 complexing processes. In such protophobic solvents asAN and PC, alkali metal ions form stable 1:1 complexes with macrocyclic poly-ethers. Thus, the glass electrodes are convenient for potentiometric titra-tions of alkali metal ions with polyethers and vice versa.

Izutsu et al. (53,107,108) and Nakamura (109,110) used a glass electrode(Beckman, 39047) to study the complexing of univalent cations in AN with +

oter olvet mlecules,+and obtained successive formation constants of LiNa , K , Rb Tl and NH4 with such solvents as MeOH, dimethylacetamide(DMA)(DMF), dimethylthioformamide, DMSO, pyridine and hexamethylphosphoric tn-amide (HMPA). Izutsu et al.(lO6) also used the electrode to obtain thermo-

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AIISIJIHD IVDIIA1VVOIIDTI MO MOISSINJ4OD 9COZ


Kazaryan et al. (90,117) investigated the behaviour of homogeneous Ci-selec-tive electrode in non-aqueous MeOH, ethanol, propanol, isopropanol, acetoneand DMF, and in their 10-90% mixtures with H20. The slopes of the calibrationcurves, obtained in solutions of Et4NC1, were 35-40 mV/pCl for pure organicsolvents an 38-50 mV/pCl for mixed solvents. The lower detection limit forCl was 10 M in pure MeOH, ethanol and DMF, lO7M in propanol, and lO8M inisopropanol and acetone. A Cl— se+ective electrode was used in AN titrateCl in the presence of Br with Ag after the selective oxidation of Br withKMnO4 or Ce(S04)2 (88).

Izutsu et al. (118) used ceramic halide-selective electrodes (Ag2S.AgX) inMeOH, ethanol and PC. Test solutions of (Et4X + O.01M EtANC1O4)were connectedto the reference electrode (Ag/O.005M AgC1O4, O.OlM Et4NlO4) through a saltbridge of O.05M Et4NC1O4. Thel -slective electrode( Matsushita, IE-560l03)gave Nernstian slopes to 2x10 -10 M Cl in all solvents tested, but thedissolution of the electrode surface was considerable in PC containing highconcentrations of Cl . The response of Br—selective electrode (Matsushita, IE--560104) to Br was Nernstian in MeOH and ethanol, but super-Nernstian (95±1mV/pBr for lO5-lOM Br)in PC. The electrode surface was also etched in PC.The response of C-selective electrode (Matsushita, IE-560l05) to 1 wassuper-Nernstian in all solvents tested (83 mV in MeOH, 93 mV in ethanl and68 mV in PC). All these electrodes responded in a Nernstian way to Ag in allsolvents, They attributed the super—Nernstian responses of the ceramic elec—trodes to the slow rates of dissolution of the electrode materials (Ag2S.AgX).

Homogeneous halide—selective electrodes can be used as indicator electrodesin anhydrous alcohols, but their responses are not always Nernstian. Thus,for physicochemical uses, the potential response of the electrode should betested beforehand. In aprotic solvents containing high concentrations of halideions, slow dissolution of electrode materials occurs because the halide ionsform stable complex ions [AgX with AgX of the electrodes. Although Nernstianresponses are sometimes obtained in aprotic solvents, the electrodes are notdurable for long time in those solvents.

Fluoride Ion-Selective Electrodes:

Single Crystal lanthanum fluoride electrodes for F ion can be used in organicand aqueous organic srlvents wich do not damage the electrode and the elec-trode body. Among those organic solvents are MeOH, ethanol, acetone, AN andPC, and even DMSO has been reported to be a such solvent (93).

Lingane (91,92) showed that the response of an F-selective electrode (Orionproduct) to F in 60% aqueous ethanol was Nernstian and that the addition of60-70% ethanol was vy efctive timprove the potentiometric titrationcurves of F with Th , La and Ca . Heckel and Marsh (119) could titrate,using and F -electrode (Orion 96-09), subnanomole quantities of F in 2 mlsolutions in polar solvents (MH, ethanol, propanol, acetone and 1,4-dioxane)containing 5% of water with La . F —selective electrodes are often used inaqueous organic solvents in titrations of F with metal ions ad of meta+ionswith F . Zhukov et al. (120) used the electrode to titrate SO4 with Ba in40-90% acetone or ethanol containing a known amount of NaF.

Bixler and Bond (121) investigated the behaviour of an F-electrode (Orion94-09A) in MeOH and applied it to study the stabilities of alkaline earthmonofluoride complexes [MF3 in MeOH and aqueous MeOH. Coetzee and Martin (96)recently investigated, by direct potentiometry and potentiometric titrations,the response of an F —electrode (Orion 94—09) in a variety of alcohols anddipolar aprotic solvents and their mixtures with water. In direct potentio-metry, the electrode was calibrated in EtANF containing O.OlM EtdNClOd orBu NC1O . The reference electrode, a modifled-SCE in alcohols and Ag/O.O1MAglO4(N) in other solvents, was used with a salt bridge of O.lM Et4NCIO4 inthe pertinent solvent. To obtain stable potentials ca. 10 mm was required.The slopes of the calibration curves and the lower limits of detection areshown in Table 13. The response in anhydrous soventg was somewhat super--Nernstian, especially for F activities in lO -10 M range. The responsebecame almost Nernstian when some water was added. The response of the F --electrode was more ideal in potentiometric titrations of F with metal ions.Coetzee and Martin applied the titration method to determine solubility productconstants of LaF3 in various solvents and of NaF, NiF2 and MnF2 in AN. Theyalso showed that the addition or organic solvents to aqueous samples couldimprove the sensitivity of direct potentiometry by up to 1 decade, and thatof potentiometric titration by 2-3 decades.

2038 CONMISSION ON ELECTROANALYTICAL CHEMISTRY

Menard et al. (122) used a LaF3 electrode to measure F activities in anhyd-rous HF and HF-H20 mixtures. Because of the strong corroding action of anhyd-rous HF, the use of a commercial electrode was impossible. They built an HF--resistant electrode with a Teflon sleeve.

Solid-State Heavy MetalIon-lective Electrodes:

Various organic solvents are often added to aqueous solutions to improve theresults of potentiometric titrations with solid-state heavy metal ion-selec-tive electrodes. In the analyses of inorganic sulfate (123), organic sulfur(124,125) and oxalate (l26, for exampl4 aqueous 1,4-dioxane was used as asolvent to titrate with PbZ+ using a Pb -selective electrode. The behaviourof Pb2+_selective electrode (Orion 94-82 A) in various organic solvents wasstudied recently (103,104).

Solid-state heavy metal ion-selective electrodes can also be used in2nhydrousorganic solvents. Rechnitz and his coworkers studied the use of a Cd -selec-ti electrode in the titration of Cd(N03)2 in DMSO with EDTA (127), and of aCu -selective electrode in the titration of Cu(Cl04)2 in MeOH, acetone andAN with EDTA, tetraethylenepentamine and 5,6-dimethyl-l,10-phenanthroline (97).Heerman and Rechnitz (128) used a cuprous sulfide-membrane electrode for thepotentiometric measurements of Cu(I) in AN containing 0.1M Et4NC1O4 or NaClO4as an indifferent electrolyte. The electrode showed near-Nernstian response(55-5 mV/decade) for Cu(I) down to 10 M in pure solutions and at least3x10 'M in the presence of complexing ligands. The electrode was used to meas-ure successive formation constants of Cu(I) complexes with halide ions andthiourea in AN. Recently, Coetzee and Istone (99) studied the response of aCu(II) ion-selective electrode having a composition of Ag1 ç5Cu0 45S in solu-tions of Cu(II) in various alcohols and aprotic solvents aM their mixtureswith water. In all solvents, except AN, the slope in the linear region wasNernstian or slightly sub-Nernstian and the lower limit of the linear regionwas at 4-5 pCu. They used the electrode to estimate free energies of transferof Cu(II) between different solvents and solvent mixtures. Coetzee et al. (98)studied the reason why the electrode did not work correctly in AN and showedby ESCA and other studies that, in solutions of certain Cu(II) salts in AN,the electrode failed because Cu(II) replaced Cu(I) and Ag(I) ion was leachedfrom the electrode.

In Tables 12-19 the trends of application of non-glass based ion-selectiveelectrodes in non-aqueous media are summarised.

On this basis it can be stated that the application of ion-selective electrodesin non-aqueous and mixed solvent is continuously gaining ground, while incontrast, the properties and response mechanism of these electrodes in thevarious media are not sufficiently known yet, so that further research activ-ity is. required in this area in the future.

Moreover, it can also be concluded that the needs for analytical and physico-chemical applications of ion-selective electrodes in non-aqueous solvents arenow increasing rapidly, and the development of new ion-selective electrodeswhich can be used for other ions in non-aqueous solvents is highly desired.

(0)

500

Fig. 1. Comparison of emfs of cells 3 & 4> 300E A&Bforcell3; C&Dforcell4

A&CshowenifD emfD=ANforM other than Ag

(00 BshowsemfD emfD=ANforM=AgD shows emf D for M= Ag

0M: I Li, 2 Na, 3 K, 4 Rb, 5 Cs, 6 Ti

&7AgD: 0 AN, PC, H20, DMF, and DMSO.

-400 -200 0 200(B)

M(Hg) or Ag wire electrode, mV

Applications of ion—selettive electrodes 2039

SOLVENT Studies made Ref.

iso-PrOH, methyl ethylkand its biner systems

etan, Stability af a glasslAg/AgC1cell was investigated

22

liq. ammania The electrade respands ta NH ian 129

water-MeOH DMF-water The effect af the campasitian afinner salutian was studied

17,18

MeOH, DMF, AN The rale af the canditianing af theelectrade in the apprapriate salvent(dehydratian af the gel layer)

24

isa-PrOS The cause af the slaw respanse wasinvestigated (dehydratian af the glasssurface)

25

sulfalane Camparisan af glass and hydragenelectrade

130

30% aqueaus DMSO The cell functianed narmally at 25 and 131

aliphatic alcahals,ketanes and their binersystems with water

The acid errar af pH-glass electradeswas investigated in cancentratedaqueaus acids and in arganic salvents

132

Table 2. Effect af salvents

SOLVENTS Subject Ref.

dipalar apratic salvents classificatian af arg. salvents, acid--base equilibria, effect af hydragen--band, titrn. af very weak bases andacids, effect af dielectric canstant, etc.

2

effect af the dielectric praperties af 29mixed salvents an the liquid junctianand the H+ian, resp.

water—n—PrOH Dissaciatian canstants af same ligandsand farmatian canstants af metal chelatesin a dielectric canstant range af 30-80

benzene—AN titratian and pKa values af numerausacids and bases in mixed systems withdielectric cantants in the range af 5-35

33

pyridine titratian af same arganic acids, effect 39af salvent an their half neutralizatianpaint

Table 1. Patential respanse af glass electrades

biner systems (water-dipalarapratic salvents)

benzene—AN, benzene—nitra—benzene, benzene—nitra——methane, benzene—acetane

30

31

Relatianships between the pKa af acidsand their half neutralizatian paint,effect af the af salvent systems


cont. Table 2.

SOLVENTS Subject Ref.

AN, pyridine, 4-methyl-2- titration of substituted aromatic acids, 40-pentanone, 2—nitropro— relationship of half neutralization pointpane, 0-nitrotoluene, with PKa and Hammett's cnitrobenzene, DMF, chloro—benzene, bromobenzene

glacial acetic acid, relationship is given between pK(H2O) of 41acetone, AN, iso-PrOH, some organic bases and their halt neutrali-nitromethane zation points

dioxane—water titration of some sulpha-drugs in biner sol- 36vent systems, correlation of mole fractionof dioxane and pK values

iso-PrOH, tert.-butanol titration of dibasic organic acids, effect 133of the .

methanol-nitromethane Changing in solvation of NaC1 and activity 35coefficients in organic systems in therange of & = 32,1-81

nitromethane Change of solvation of substituted ammonium 43ions on the basis of the slope of thecorrelation between PKa values and Taftconstants

nitromethane, AN, DMSO Solvation of ions and effect of substituents 42on the acidity of NH- and OH-acids

methanol-water Solvation of some 4-substituted phenols, 32the validity of the Born equation and theHammett function in biner systems

iso-PrOH, tert.-butanol, Acid-base equilibria, solvation constant of 47n-hexanol chloride ion in tert.-butanol

water-glycerol solvation of NaCl in biner systems, activity 49coefficients, data in comparison with thoseobtained in ethylene glycol

MeOH-nitromethane Solvation of NaCl, the trend of change in 35solvation and activity coefficients, resp.with the composition of solvent system

DMSO-water Solvation and activity coefficients of HC1 46and changing with the dimethyl sulphoxidecontent of the solvent

water-dioxane Protonation constants of glycine and stability 134constants of their metal complexes in functionof solvent composition

AN-water, MeOH-water, Acid-base equilibria, proton.ligand stability 135dioxane—water constants in various solvent systems

tert.-butanol, pyridine, The effect of the solvents on the electrode 329acetone, iso-PrOH potential of the glass electrode is discussed

AN The calibration of the glass electrode in AN 330was investigated in detail


Table 3. Potential response of non-glass based ion-selectiveelectrodes

ELECTRODE Subject, Media Ref.

silver iodide, Potential response in methanol, ethanol, 69silicone rubber based propanol, isopropanol and their mixtures

with water

Potential response and swelling in aqueous 70mixtures of methanol, ethanol, benzene, aceto—nitrile and dimethyl formamide

Detection limit and solubility products in 71methanol, ethanol, propanol, isopropanol, dimethylformamide, methanol-benz ene mixtires

Applicability in mixtures with water of acetone 72and dimethyl formamide

Determination of solubility product values in 73,74aliphatic alcohols, acetone and dimethylformamide

Potential response and applicability in pure 75nonaqueous solvents

silver iodide Potential response and detection limit in aqueous 76aliphatic alcohols

Determination of solubility product values in 77aqueous aliphatic alcohols

The effect of organic solvent content of medium 78on the potential response

Determination of the mean activity coefficient 79,80,values in pure nonaqueous solvents as follows:8l,82,83,EtOH, n-PrOH, MeOH, n-BuOH, n-heptanol, n- 84,85,86-octanol

silver bromide, Applicability in aqueous mixtures of acetone 72silicone rubber based and DMF

Determination of solubility product values in 73,74aliphatic alcohols, acetone and DMF

The effect of organic solvent content of medium 78on the potential response

silver chloride, Applicability in aqueous mixtures of acetone and 72silicone rubber based DMF

Determination of solubility product values in 73,74aliphatic alcohols, acetone and DMF

silver chloride Determination of free energy of transfer of 87alkali chlorides in methanol + water mixtures

Applicability in AN 88

Potential response and detection limit in iso- 89propanol and in its mixtures with water

Potential response and other properties in MeOH, 90EtON, PrOH, iso-PrOH, aceton and DMF

lanthanum fluoride, Determination of free energy of transfer of alkali 87single crystal fluorides in methanol + water mixtures

2042 COIMISSION ON ELECTROANMYTICAL CHEMISTRY

cont. Table 3.

ELECTRODE Subject, Media Ref.

The role of organic solvent content on applica-bility of the electrode in aqueous ethanol

Properties of the electrode in aqueous ethanol

Applicability in DMSO

Potential response and detection limit in aqueousMeOH, EtOH, PrOH, acetone and dioxane

Properties in aqueous MeOH, EtOH, acetone and 94dioxane

Applicability in MeOH, acetone and AN 97

Potential response studies in connection with the 98change of the electrode surface in AN

Determination of free energy of transfer of copper 99ion in water-propanol, isopropanol, ethyleneglycol and sulfolane mixtures

Applicability in MeOH, DMSO, 1,4-dioxane and AN 100

Preparation and applicability in aqueous acetone 101

Applicability in dioxane 102

Effect of permittivity on the electrode in aqueous 103mixtures of MeOH, EtOH, acetone, DMSO and dioxane

Potential response in aqueous MeOH, EtOH, PrOH, 104ethylene glycol and glycerol

91

92

93

136

95

96

Potential response in MeOH

Potential response and other properties in al-cohols, dipolar approatic solvents and theirmixtures with water

lanthanum fluoride,polycrystal line

copper

lead

Table 4. Ion-selective electrodes based on different electroactivematerials

Ion, for ELECTRODE, MEDIA Ref.

chlorideanions

bivalent cations

and Cl

4,7-DPP anion

SCN

picrate

phenolate anions

Ion-exchange type, in amylalcohol 137

ion-exchange type, in aqueous MeOH, EtOH and PrOH 138

ion-exchange type in aqueous PrOH 139

ion-exchange type in pure EtOH 140

Silver complex of 4,7-diphenylphenantroline 141(4,7-DPP), in aqueous EtOH and acetone

AgSCN electrode, in different aqueous mix- 116tures of EtOH, acetone, DMF, dioxane and DMSO

picrate salt of crystal violet, in a two-phase 142system of nitrobenzene, toulene or chloroformwith water

phenolate salt of crystal violet, in two-phase 143system of nitrobenzene and water


cont. Table 4.

ELECTRODE, MEDIA

As2S3, arsenous sulfide, in alcohols

Pelargonate salt of crystal violet in two-phasesystems

Picrate salt of crystal violet in two-phasesystems

Tetrabutylammonium tetraphenylborate in PVC inaqueous EtOH

Table 5. Stability constants of metal chelates

SOLVENT SUBJECT Ref.

Metal chelate stabilities of Ni(II) and Zn(II) 30complexes of picolin. and pipecolinic acids

Study on the stability of Ni complexes of dialkyl-148dithiocarbamates. Stability constants data aregiven

A critical survey of hydroxo complexes of Be 149

Stability data of Ni, Zn, Cd, Hg(II), Pb(II) and 150U02( II)complexes of some monothio- -ketones were

determined

Stability constants of binary complexes of 151lanthanides with thiotropolone

Study on equilibrium constants of U02(II)-malonic 152acid complexes

Stability constants of some Schiff base complexes 153with Cs, Ag., Zn, Cd, Hg(II) and Co are given anddiscussed

Potentiometric study of the complexes of In( III) 154with some azo dyes. Stability data are given

Formation contants of Cu, Ni, Co and Zn chelates 155of 2-hydroxy-l-naphtalidene-2 5'-dimethoxyaniline

Formation constants of vanadyl complexes of 156benzoyl- and nicotinyl hydrazines

Stability constants of 2-mercaptomethylbenzyli- 157midazole complexes with Zn, Co and Ni are reported

Formation constants of 2-hydroxy-5-methylbenzo- 158phenoneanil with Cu, Zn, Cd, Ni, Co, Mn are givenand discussed

Stability of complexes of Ni with monoethanol- 159amine is discussed

Potentiometric study on Cu and Zn complexes of 134glycine

Potentiometric study on some protonated and non- 160protonated divalent metal ion complexes with—. -furan-2-aldoxime

Ion, for

sulfide

anions of C9-C18aliphatic acids

picrate

+R N cations

Ref.

144

145

146

147

aqueous n—PrOH

DMF

aqueous MeOH, EtOH,acetone

3:1 dioxane—water

50% aqueous dioxane

aqueous dioxane

60% aqueous MeOH

50% aqueous dioxane

75% aqueous dioxane

aqueous DMF

50% aqueous acetone

60% aqueous dioxane

0-64% aqueous EtOH

10-70% aqueousdioxane

40-60% aqueousdioxane


cont. Table 5.


60% aqueous dioxane Studies on etái chelatesof2-hydroxy--5-methyl-acetophenoneani 1

161

75% aqueous dioxane Formation constants of the divalent metal ioncomplexed of 2-hydroxy-l-napthalidene- .-napthyl-amine

162

70% aqueous dioxane Stability constant data of Cu and Ni chelateswith some substituted 4—pyrazolone dyes are givenand discussed

163

Table 6. Equilibrium constants of organic compounds

SUBJECT

Dissociation constants are given for perchloricacid, picric acid, 2,4-dinitrophenol and benzoicacid

The variation of the relative dissociation of 165acetic and benzoic acid was studied in 4 binersystems

The pK values of some acid-base indicators are 166reported

Studies made on acid-base equilibria of a series 167of diazonium salts

Comparison of provisional dissociation constants 130of some acids in the two solvents

Dissociation constants are given for some organic 168salts

Ionization contants of benzoic acid at different 169water content are reported. The H0 and TS°values for the ionization process have been alsocalculatedIonization constants of 57 aliphatic and aromatic 43amines were determined

pK values of naphtalene derivatives were deter- 170mined and investigated

The ionization constants of numerous organic 171acids are reported

The dissociation of malonic, succinic and dimethyl 172malonic acid was studied

The solvation of Na+ and Cl ions were investi- 49gated in comparison with the results obtained inethylene glycolDissociation constants and metal chelate stabili- 30ties of picolin and picolinic acids are studiedin the range of = 30-80

pK and half-neutralization potential data are 31reported in the case of numerouos organic compound

Ionization constants of p-substituted phenols 32are reported and studied

SOLVENT

tert-butanol

aqueous acetone , DMSO

Ref.

164

ethylene glycol

DMSO

sulpholane, AN

acetic acid, AN,acetonewater-DMSOmixtures

nitromethane

50% aqueous acetone

methyl ethyl ketone

DMF

aqueous glycerol

water—n—PrOH mixtures

benzene—acetoni trilebiner systems

water—methanol binersystems


cont.Table 6.

The hydrolysis of berillium ion was studied in 149mixed solvents

pK data are given for 8 p-substituted pyridinium ion 34

A method is reported for the determination of pK 173values in amphiprotic solvents

Dissociation constants of some aminobenzolides 174

Dissociation constants of 6-substituted purine 175derivatives are given

pK values of aliphatic mono carboxylic acids are 176reported

Dissociation constants of malonic, succinic, 133maleic and phtalic acids and of their methyl esterswere determined

pK values of some aromatic carboxylic acids are 177listed

Ionization constant values of some quinolinol 178derivatives were determinedAcid-basic properties of hydroxypyridine deriva- 179tives were investigated to determine their struc-ture

Protonation contants of substituted benzoyl 180hydrazines were determined

pK values of picric acid and some acid-base 181indicators were determined

The dissociation constants of some N-aryl hydroxa- 182mic acids were described

Dissociation constants of some methoxybenzoic acid 183derivatives were investigated

Determination of the ionization constants of 18 184organic compounds are described

pK values of some sulphophtaleine derivatives are 185listed

The problem of solvation of HC1 was investigated 48on the basis of thermodynamic parameters

pK values of R-saturated dicarboxylic acids are 186given compared with those obtained in water

pK values of some NH- and OH acids are listed 42

Ionization constants of 21 phenol derivatives are 187given

pK values of phenol and 9 mono-, di- and trisubsti-188tuted phenols are described

SUBJECT Ref.

Correlation between the half neutralization point 33and PKa values were investigated

SOLVENT

benzene—nitrobenzenebenzene-nitromethanebenzene—AN binersystems

aqueous MeOH, EtOH,acetone biner systems

aqueous methanolmixtures

water-aliphaticalcohol mixtures

acetic acid, acetoneMeOH

DMSO

80% aqueous DMSO

n-PrOH, tert-butanol

80% aqueous DMSO

dioxane-water

ni tromethane

water-DMF,water—dioxane

acetone

50% aqueous EtOH

dioxane—waterbiner systems

PC

AN, DMSOdioxane—water

90% aqueousN-methylacetamide

DMF

nitromethane, AN,DMSO

AN

nitromethane


cant. Table 6.


AN, acetoneDMF, DMSO

pK values of 2,4,6-trinitrophenol are given 189

aqueous AN Hydrolytic constants of tallium(III)ion aredescribed, and the thermodynamic parameters ofthe hydrolytic process were evaluated

190

aqueous EtOH Critical study of potentiometric methods fordetermination of some substituted benzamidesacidity constants

37

PC Dissociation constants of some protonated aminesare given

191

dioxane-waterbiner systems

The acidic dissociation of some N-arylhydroxamicacids were investigated

192

80% aqueous DMSO pK values of 10 acid-base indicators were deter-mined

193

80% aqueous2-methoxyethanol

Dissociation constants of the E- and Z-c,(-di-arylacrylic acids are investigated

194

2-methoxyethanol PKa and pKb values of 20 purine and pyrimidinederivatives were studied

195

MeOH, acetone,DMF, DMSO

pK values of 22 flavonoids were determined andcompared with those obtained in water

196

Table 7. Determination of organic acids


tert.-butanol A method was developed for the evaluation of the 164dissociation constant of weak acids. Data arereported

MeOH-water, Potentiom. titration of weak acids with strong 197MeOH, acetone,EtOH bases employing glass/calomel and Mo/Ag electrode

systems

alcohols, ketones, Titration of organogermanium compounds with KOH 198AN or K-methoxyde as titrants

DMSO, 1:10 DMSO + Titration of fulvic acid in arnmonical and aqueous 199iso-PrOH acetone extracts

dichlorometane Titration of rosin with KOH 200

AN Potentiometric titration method for the determi- 201nation of 4-hydrxybenzoyl and alkyihydroxy-iso-phtalic acids with N-tetraethylammonium hydroxydeas a titrant

DMSO + rnethylamine Potentiometric titration of carboxy-groups in+ ethanolamine cellulose and its derivatives with Na-methoxyde 202

in dimethyl sulphoxyde as titrant

1:2 acetone + ben- Potentiometric analysis of formic and butanoic 203zene, 1:2 acetone acids in mixed solvents with KOH titrant in+ chloroform, 1:2 different solventstert.-butanol + carbontetrachioride, 1:2 2--hexanone+chloro form


cont. Table 7.


tert. -butanol The use of tert.-butanol as differentiatingsolvent for the titration of some organic acidshas been evaluated

Determination of sulphanilamide preparations bypotentiometric titration with KOH in differentsolvents

328

Determination of inorganic acids and phenols in 206the presence of heavy pyridine bases by potentio-metric titration

75% aqueous MeOH Differential potentiometric titration of 2-ethyl- 207hexylphosphoric acid

50% aqueous acetone pKavalues was determined of substituted naphtols 170by potentiometric titration

ethylmethyl ketone Determination of pK -values of some organic acids 171by potentiometric atitration with tetraethyl-arnmonium hydroxyde as titrant

Ionic equilibrium of malonic, succinic and di-methylmalonic acids was investigated

169

Potentiometric titration of mixtures of halo- 208-substituted aliphatic monocarboxylic acids withK-isopropylate in isopropanol as titrant

acetone Determination of pyromellitic, trimellitic andbenzophenonetetracarboxylic acids using triethyl-amine as titrant

aqueous acetone Potentiometric titration of acetic acid with al-coholic KOH as titrant in the presence of HC1

210

Potentiometric microtitration of phenols, 211carboxylic and phenolic acids with Na-methoxydein DMF

benzene+ MeOH

10-90% MeOH + watermixtures

benzene + nitrobenzenebenz ene—nitromethanebenzene-acetone

glacial acetic acid,DMF, AN

Titration of -lactam antibiotics with tetra-butylarnmonium hydroxyde as titrant

Investigation of PKa values of 4-substitutedphenols by potentiometry

PKa values of a series of acids are given: rela-tionships between the pKa and the half neutrali-zation point were determined

Titration of some l,4-benzodiazepines withtetrabutylammonium hydroxyde in 10% methanol-benzene as titrant

212

32

33

213

DMF Differentiating potentiometric titration of aspi- 214rin, acetaminophen and salicylamide mixtures withtetrabutylainmonium hydroxyde standard solution

1:3 iso-PrOH +dioxane

AN + benzene indifferent ratiosAN, butanone

50% aqueous EtOH,acetone

Potentiometric titration of diketones with KOHin isopropanol as titrant

Titration of organic acids and acid mixtures,HNP and pKa data are given in the range of =5-35

204

31

205

DMSO + watermixtures in differentratios

DMF

acetone, tert.--butanol

The PKa values of benzoic acid increase withincreasing dimethyl sulphoxide concentrationof the solvent

172

DMF

209


cont. Table 7.


methanol+water mix- pK values and dissociation enthalpies of p- 34tures —substituted pyridinium ions are giv'n

DMF Potentiometric titration of intermediates of 215orotic acid syntheses with tetraethylammoniumhydroxyde as titrant

acetone Potentiometric determination of orotic acid in 216mixtures with its derivatives

isobuthyl-methyl Potentiometric titration of p-toluic and 217ketone terephthalic acids and methyl terephthalate with

tetrabutylammonium hydroxyde in isopropanol astitrant

EtOH Potentiometric determination of 4,6-dinitro-o- 218-cresol in the technical grade product with KOHin ethanol as titrant

pyridine, ethylene Differential potentiometric titration of binary 219diamine and ternary mixtures of benzanilides with a

benzene + methanol solution of tetraethylammoniumhydroxyde

80% aqueous DMSO Titration of aliphatic mono carboxylic acids 176

5:1 benzene-EtOH Separate determination of thioglycolic and dithio-220glycolic acids by potentiometric titration

DMF, acetone, pyridine Determination of benzotrioxifuran by potentiomet- 221tetramethyl guanidine, nc titration with tetrabutylammonium hydroxydeDMSO

acetone, ethylmethyl Potentiometric titration of some acid triphenyl- 222ketone, DMF, iso- methane dyes with tributyl-methylammoniumbutyl-methyl ketone, hydroxyde in benzene-methanol (10:1) as titrantAN

2-ethylhexanol, iso- Titrimetric determination of mixtures of higher 223dodecyl alcohol aldehydes and acetals as impurities in 2-ethyl-

hexanol and in sododecyl alcohol after oximationvia liberated H ions

tert.-butanol, DMSO Potentiometric titration of succinic acid with 133methanolic tetraethylammonium hydroxyde as tit-rant

80% aqueous DMSO Potentiometric titration of some aromatic carboxy-l77lic acids

50% aqueous tributyl Titration of weak carboxylic acids in the presence 224phosphate, 50% aque- of HC1ous butyl acetate

aqueous dioxane Potentiometric titration of 2-hydroxy-oxime 225extractants

DMF, DMSO Potentiometric behaviour of extracted humic acids 226

aqueous DMF and di- Potentiometric titration of p-substituted benzoyl 180oxane hydrazines to determine the PKa values

acetone Determination of dissociation constants of picric 181acid by direct potentiometric method

50% aqueous EtOH Potentiometric study of some N-aryl hydroxamic 182acids


cont. Table 7.

SOLVENT

50% aqueous acetone

dimethyl acetamide

80% aqueous acetone

acetone, AN

Pyridine, tetramethylguanidine, hexa-methylphosphoramideDMF

nitromethane

AN

iso-PrOH

ni trome thane

AN, acetone, DMF, DMSO

tert. butanol

DMF, acetone, aceticacid, and their mix-tures

10-50% aqueous dioxane

80% aqueous DM50

80% aqueous 2-methoxy-ethanol

1:1 iso-PrOH-benzene

(0,4—0,57): 0,31 EtOH—-benzene, 0,58: (0,02--0,12) xylene-water

1:14 water—nitro—methane

1:24 formic acid—-ethylmethylketon1:8 acetic acid-ethyl-methylketonPAAC 55:12—11

SUBJECT Ref.

Determination of sulphamerazine and suipha- 227proxyline in tablets by differential potentio-metric titration

Potentiometric titration of phenolic end groups 228in monomeric and macromolecular structures

Determination of phenylbutazone by potentio- 229metric titration

Potentiometric titration of carbazole and nitro- 230carbazoles

Potentiometric microtitration of 1,3,5-trinitro- 231-1,3, 5-triazacyclohexane and its derivatives

Potentiometric titration of some saturated di- 186carbocylic acids

Potentiometric titration of 3,5-dinitrobenzoic 42acid were carried out to study the solvation

Potentiometric study on the effect of alkylthio 187group on phenols

Potentiometric titration of fumaric, maleic 232acids and maleic anhydride

Study on acid-base properties of substituted 188phenols by potentiometric titration

Potentiometric titration of 2,4,6-trinitrophenol 189in methanol—benzene mixtures. pK data are givenin different solvents a

Determination of substituted benzophenone oxime 233reagents used in copper extraction processes

Differential potentiometric titration was devel- 234oped for determining nitroaminobenzanilides

The acid dissociation of some N-aryl-hydroxamic 192acids were investigated by potentiometric tit-ration

Potentiometric titration of 10 acid-base mdi- 193cators

On the basis of potentiometric titration of E- 194- and Z-o-diarylacrylic acids was studied thestructure of 36 compounds

Potentiometric determination of l,2,3-benzotria- 235zole nd N-hydroxy-l,2,3—benzotriazole is given

Quantitative potentiometric determination of 236organic acids or their anhydrides

Potentiometric analysis of mixtures of some amino 237acids with their N-tert.-butoxycarbonyl deriva-tives

Determination of binary mixtures of amino acids 238is described


cant. Table 7.


acetane Patentiarnetric determinatian af acidic im- 239purities in 1 ,2-naphtaquinane-2-diazide-5--sulfanyl chlaride is given

acetane Determinatian af hydraxamic and carbaxylic acids 240in a flatatian agent was develaped

DMF Indirect patentiametric titratian far determina- 241tian af maleic anhydride by the marfaline methad

1: (4-5 )N-methyl-2- Quantitative determinatian af dicarbaxylic acids 242-pyrralidinone-PC is described

aqueaus isa-PrOH- Quantitative determinatian af arganic acids ar 243-heptane systems their anhydrides

isa-PrOH Determinatian af phthalimide and patassium 244phthalimide in technical grade mixtures

2-methaxyethanal Patentiametric differential titratian af purine 195and pyrimidine derivatives

23:7 DMF-benzene Patentiametric determinatian af 5,5-dimethyl- 245hydantain in reactian mixtures

acetane Patentiametric titratian af an isadithiabiuret 247derivative with different standard salutians

1:8 EtOH-benzene Methad far deterrninatian af acid number af 246mineral ails

chloroform-water H2A+ type dipratic acids can be titrated in 248twa—phase systems with gaad results

tert.-butanal,pyri- The use af tetrabutyl ammanium hydraxide asdine, acetane and titrant far weak and very weak acids is discus— 329isa-PrOH sed

Table 8. Determinatian af arganic bases


acetic anhydride Determinatian af m-taluic diethylamide by 249patentiam. titratian with HC1O4 in diaxaneas titrant

butanane Mixtures af aminophenazane with Na-barbital, Na- 250-phenalbarbital, Na-benzaate and Na-salicylatewere determined with HC1O4 stack salutian

1:1 acetic anhydride- Differential patentiametric titratian methad 251-acetic acid 1:1 was develaped ta determine cadeine phasphateacetic anhydride-di— and same drugs in mixturesaxane 3:10:10 prapia-nic acid-prapianic an-hydride—benz ene

2-butanane-benzene Analysis af same ingredients af rubbers by 252patentiametric titratian

MeOH, MeOH-DMF Determinatian af same antibiatics is given by 253patentiametric titratian

50% aqueaus EtOH Patentiametric titratian af heavy pyridine bases 206or acetone


cont. Table 8.

SOLVENT Ref.

1:2:1 chloroform-AN- 254—acetone

1:1 acetic acid-tn chloromethane

iso-PrOH, AN

acetic anhydride

nitromethane

acetic acid-dioxane

acetic acid, DMF, AN

acetic acid

90% aqueous phenol

acetic acid

dioxane

acetic acid,acetone, MeOH

acetic acid, MeOH,pyridine, 1,1,3,3—-tetramethylguanidine

nitromethane

1:2:4 chloroform-acetic anhydride-benz ene

acetone

nitromethane

dioxane

nitromethane

acetic acid

acetic anhydride

2-methoxyethanol

nitromethane

SUBJECT

Potentiometric titration method for determina-tion of amidopyrine, quaiacyl-o-hydroxybenzoatenicotinate and lidocaine HC1

Potentiometric titration of methaqualone andits dosage forms

Determination of sulphanlamide preparationsby potentiometric titration

Potentiometric titration of 36 differentphenothiazine derivatives

Study of basicity of aliphatic and aromaticamines by potentiometric titration

Indirect potentiometric titration of hydro-chlorides of nitrogenous bases

Study of nonaqueous potentiometric titrationof 1, 4-benzodiazepines

Study on the chemistry of potentiometric titra-tion of chloropromazine

Determination of organic basby potentiometrictitration

Potentiometric titration of (-lactam antibiotics

Determination of adenosine by potentiometrictitration

Potentiometric titration of some aminobenzolides

Investigation of the standardization of standardsolutions using in nonaqueous titrimetry

Potentiometric titration of dipiperidylbenzami-nals

Potentiometric titration of caffeine

Potentiometric titration of triphenyltin com-pounds

Determination of dipiperidylbenzaminals

Potentiometric titration of 2-hydroxyoximes

Potentiometric titration of hydroxypyridinederivatives

Improved method for potentiometric titrationof salts of organic bases by adding Bi(N03)3

Micro-determination of nitroguanidine bypotentiometric titration

Determination of 6-benzylaminopurine by poten-tiometric titration

potentiometric titration of some dipiperidylderivatives in piperidine

255

205

256

170

257

213

258

259

212

260

174

261

262

263

264

265

225

179

266

267

268

184


cant. Table 8.


acetic acid Patentiametric titratian of several amine salts 269

20-80% aqueaus AN, Potentiometric titratian af nicatinyl and benzayl 135MeOH, diaxane hydrazines

aqueaus EtOH Patentiometric titratian af same substitutes 37benzamides

PC Patentiametric determinatian af several pratanated 191amines

diaxane Methad is given far determinatian af Na-salicy-- 270late, amydapyrine and caffeine and their mixturesin Pyrasalafen tablets

acetic acid Patentiametric titratian af nitro-.aminobenzanili- 234des

aqueaus EtOH, diaxane Patentiametric determinatian af difurfuralidin- 271acetane

80% aqueaus DMSO Patentiametric titratian af 10 acid-base indica- 193tars

1:1 nitrabenzene- Patentiametric titratian af Katamin AB in 272-chlarafarm mixtures with rasin and terpentine with picric

acid

2-methaxyethanal Patentiametric differential titratian af pyrimi- 195dines and purines

acetane Analysis af 4,4'-diamina-3,3' dihydraxydiphenyl- 273methane by patentiam. titratian

ethylmethylketane Evaluation af titratian methad af C1618 alkyl- 274propylamines is impraved by the use af Gran methad

Table 9. Determinatian af inarganic campaunds


1:1 DMF + iso-PrOH Differentiated titratian af Sc, Y and La salts 28with KOH in isoprapanal

acetane Analysis af KC1, H SO4, KNO3 and K3P04 by 275patentiametric titation

15:15:2 acetic an- Determinatian af alkaline nitrates 276hydride-acetic acid-—farmic acid

MeOH, EtOH, acetane Determinatian af H TiCl6 and H2TiF6 in the 277ethyl-methyl ketan, presence af HC1 an HF by patentiametric titra-3: 1 MeOH-acetone tianaqueaus acetane Determination of HC1 and acetic acid in the 210

presence af ian(III)aqueaus MeOH Indirect titratian af sodium sulphate in 278

anianic surfactantsaqueaus MeOH Determinatian af fluoraphaspharic acids and their 279

mixtures with other inorganic acids

acetone, iso-PrOH, Differentiated titration of a mixture of 280ethyl-methylketon ammonium perchlarate with perchloric and

hydrochloric acids


cont. Table 9.


iso-PrOH, tert. — Study on acid-base equilibria of HC1 and HBrbutanol, n—hexanol

47

PC Potentiometric study of protonation of waterin comparison with other methods

281

1:1 ethylene glycol- Determination of sulphuric acid and ethylacetone sulphate

282

alcohols, ketones Study of acid-base properties of Nb, Ta, V, Monitromethane and V02 chlorides

284

3:2 acetone-trichlo- Determination of HC1 and iron(III chloride inrometane, acetone—sec. hydrochlorination processesbutyl chloride1: (7-25) water-acetone Determination of sulphuric acid and sulphonic

acids in mixtures

283

285

acetic acid Determination of boric acid 286

acetone Determination of sulphuric acid in a mixture 287

acetone Determination of phosphoric acid in a reactionmixture

288

Table 10. Determination of organic and inorganic compoundsin their mixtures


20650% aqueous EtOH oracetone

Determination of heavy pyridine bases in thepresence of inorganic acids or salts

aqueous acetone Determination of HC1 and acetic acid in amixture by potentiom. titration

210

50% aqueous tributylphosphate or butylacetate

Potentiometric titration of weak carboxylicacids in a mixture with HC1

224

EtOH

chlorobenzene-acetonebiner system

Determination of L-carnitine HC1 in thepresence of NH4C1Determination of S2Cl2 in mixtures withphthalimid, potassium phthalimide and N,N'--dithiobis (phthalimide)

289

290

1:1 ethylene glycol-—acetone

Determination of sulphuric acid, and ethyl-hydrosulphate in a mixture

282

3:2 acetone-trichloro-methylmethane oracetone- sec. butylchloride

Determination of HC1 and iron(III) chloridein the presence of organic compounds

.

283

l:(7-25) water-acetone

Quantitative determination of sulphuric acidand sulphonic acids in a mixture

285


Table 11. Cation—selective glass electrodes

SOLVENT ION SUBJECT Ref.MEASURED

AN,PC andK+, Na+, Li+ The Beckman 39047 electrode was studied 51

DMF K+ after etching in solution of the measuredion in the appropriate solvent. Lifetime,response and stability data are given

AN, DMF, DM50 The response time, reproducibility of the 52

+ Beckman 39047 electrode are reportedAN, DMSO Na

AN Rb+,Tl+,NH,Cs+ The response of the Beckman 39047 elec- 53trode was investigated

.+PC Li The response characteristics of the 54

Beckman 39137 electrode ad seectivity +data in the presence of K ,

NH4 and Et4N ions

MeOH, AN K+,Tl+; Reponse characteristics of a K+ and a 55PC, DMSO Na Na -sensitive electrode are investigated

and applied to study the complex-formaionofsome÷macrocylic polyethers with Na , KRb , Cs and Tl ions

MeOH Na + + + Complex formation was studied with macro- 105Na ,Li ,K ,Cs cyclic polyethers

NH4

AN Na+,Li+ Thermodynamic data of some macrocyclic 106compound complexes were determined

.+ + + +AN Li÷,Na +K ,Rb , A brief study of complexation of uni- 108Tl , NH4 valent ions with a series of solvents e.g.

MeOH, DMF, etc.,by a Beckman 39047 electrode

+ .+PC Na ,Li Complex formation of ions with dirnethyl lii,

sulfoxide was investigated 112

MeOH,EtOH,n- Na,I The mean activity coefficient of ions 79-86-PrOH,n-BuOH was determined using a Na -selectiven-pentanol, glass electrode Radelkis OP-Na-711 Dn—heptanol,n—octanol

liq.arnmonia NH Measurement were made by a Beckman 39137 113type cation-sensitive glass electrode

fused univalent and The respgnse of a Pyrex bulb electrode 67.ammonium some divalent at 190 C was studied 115nitrate cations

various organic Determination of free energy of transfer 56,solvents of alkali metal chlorides 57

different sol- KLi++Na+,b+, The response of the Beckman 39047 elec- 63vents e.g. Cs ,Tl , Ag trode was studiedAN,PC etc.

different Studied made on the selectivities of 50.solvents cation-sensitive glass electrodes 51,

67,68

aqueous methanol Investigation of transfer of alkali 87fluorides and chlorides from waterto aqueous methanol using severalglass electrodes as reference. Thespecific solvent affect of the latterwas also studied

DMSO


Table 12. Application of fluoride ion-selective electrode

Condition of potentiometric titration offluoride ion with Th(IV)-, La(III)- and CqII )-—ions in aqueous ethanol is presented

Potentiometric titration of fluoride ions by 92lanthanum ions as titrant. The organic solventgives better results then the unbuffered aqueousmedia

The titration curves taken by a fluoride-selective 93electrode did not give satisfactory resultsin this solvent

A method is described for rapid determination 291of organically bonded fluorine after combustion

Microdetermination of fluorine content of 292

organic compound containing phosphorus isgiven. After combustion the fluoride ion wastitrated with La(III)

Determination of Si,Al,Fe,Ca and Mg with a 293fluoride ion selective electrode is reportedby an indirect titration method

294

The formation constants of HF and (HF)2 were 295determined using a fluoride ion-selectiveelectrode

The Orion and a self-constructed LaF (dopedwith SrF2) fluoride ion-selective elctrodewere investigated, both by direct and indirectpotentiometric technique. A procedure for tit-ration with thorium nitrate is given. The bestmedia for the electrode is the 30% dioxane-watercomposition. Inorganic and organic fluorinecompounds were determined, resp.

60% aqueousEtOH

60-70% aqueousEtOH

SOLVENT

—SUBJECT Ref.

91

80% aqueousEtOH

50% aqueousEtOH

30-70% aqueousEtOH

50% aqueousMeOH, 60% aqueousiso-PrOH

20,40,60, 80% aqueousdioxane

50% aqueous (Et0H,iso-PrOH, acetone

DMF, AN), dioxane

Direct measurements as well as titrationsof fluoride ion with La(III) using a fluorideion-selective electrode

296

80% aqueous EtOH The potentiometric titration of Al(III)-La(III)- and Th(III)- ions is described byusing a fluoride ion-selective electrode

297

MeOH-waterbiner A method is given for the determinatIon of 298systems methanol content in biner systems using ion-

—selective electrodes

water-(MeOH, EtOH, Determination of fluoride ion by direct potentio- 136PrOH, acetone, metry in organo—aqueous biner systemsdioxane)biner systemsaqueous EtOH Determination of fluoride ion content in Sn(II)-

-Ni(II) electrolytes with a CuF2 doped LaF3electrode is described

299

40-90% aqueous Determination of sulphate ions by potentiometric 120acetone or EtOH titration using Ba(II) as titrant in the presence

of known amount of sodium fluoride

80-90% aqueous EtOH Indirect titrimetric determination of tungstenand phosphorus via titration of excess sulfate

300

ion after precipitation with Ba-salt, filtration,finally addition of known amount of sodium sulfate

MeOH, aqueous MeOH Determination of stability of alkaline earthmonofluoride complexes

121

MeOH, EtOH, PrOHacetone, dioxane

Titration subnanomo quantities of fluorideof fluoride with La is described

119

aqueous acetone Determination of sulfate ions with Ba in the 120or EtOH presence of known amount of sodium fluoride is

given


Table 13. Response of fluoride ion-selective electrode invarious solvents (96)

slopesolvent3'(pF)

—-

for slope for lower limit of

5 5 <pF >6 usable range, pF

H2058.1 x 6.0

MeOH 62.0 90 6.8

MeOH+l mol% H20 59.5 60 6.7

MeOH+lO mol% H20 59.3 58 6.5

EtOH 64.0 80 7.0

EtOH+l mol% H20 59.5 71 6.3

EtOH+ 10 mol% H20 59.0 63 6.7

l-PrOH 65.0 101 6.0

l-PrOH+l mol% H20 62.5 80 6.5

l—PrOH+lO mol% H20 61.0 77 6.52-PrOH 66.0 x 5.0AN+lO mol% H20 57.8 x 5.6PC+l0 mol% H20 62.0 62 6.5

XSlope gradually changed to less negative values with this region.

Table 14. Application of silver sulfide ion-selective electrode


20% aqueousglycerol

30% aqueousacetone

Potentiometric titration method for determina-tion of some tetrazoles

A method is given for determining H)S contentin air samples after absorbing by standardaddition technique

Determination of some metal ions using sulphur--containing organic reagents by potentiometrictitration method

Potentiometric titration is described fordetermination of captax

301

308

309

74% aqueous aceticacid

80% aqueous aceticacid

70% aqueousMeOH or acetic

Automatic titration method is presented for thedetermination of small amounts of halogenides

A semi-automatic halogen determination is de- 302scribed for organic compounds after decomposi-tion by argentometric titration

Titration method is proposed for determination 303of water-insoluble mercaptans with silver ionsas titrant

EtOH-benz enebiner system

80% aqueous acetic Microdetermination of organically bonded chlorine 304acid and bromine in volatile compounds after combus-

tion is described

A method is given for determination of hydrogen 305sulfide and thiols in petroleum products bypotentiometric titration

90% aqueous EtOH Argentometric titration method is proposed todetermine the radiolytically produced chloridecontent in chlorobenzene solution

MeOH-waterbiner system

MeOH

A method is described for the determination ofmethanol content in biner aqueous system

306

298

307

EtOH 310


cont Table 14.

EtOH A new sulfide ion-elective is proposed fordetermination of S ion and thiourea. The

144

electrode is a Pt coated wire with As2S3electroactive material

80% aqueous acetic Method is given for determination chlorine and 311bromine in volatile organic compounds

Table 15. Application of iodide ion—selective electrode


MeOH, EtOH, r- Determination of iodide ion by direct 76-PrOH, iso-PrOH potentiometric methodand their mixtureswith water

aqueous MeOH, Potentiometric titration for determination of 77EtOH, n-PrOH iodide ioni so-PrOH

methanol-water A method is described for the determination of 298biner systems methanol content in its biner aqueous system20% aqueous MeOH Potentiometric titration of large inorganic 312

and organic anions with quaternary ammoniumhalides

aqueous MeOH Indirect potentiometric titration for deter- 313mination of L-ascorbic acid, p—(methylamino)--phenol sulfate and hydroquinone after treatingwith iodide solution in methanol, then the iodideproduced was determined

Table 16. Application of bromide ion-selective electrode


n-butanol Determination of bromo-content in organic 314compounds after combustion by potentiometrictitration

methanol-water A method is described for the rapid determina- 298biner system tion of methanol content in MeOH-H20 biner systems

Table 17. Application of chloride ion-selective electrode


80% ueous dixane- - - —

315Microdetermination of chloride in the presenceof azide by potentiometric titration withmercurv(II) perchlorate as titrant

The titration of halide ions using a chloride- 88-selective electrode only in the presence ofoxidizing agents or strong acids gives satis-factory results

90-100% iso-PrOH Direct potentiometric determination of a seriesof alkali- and alkaline earth metal chloridesand tetramethyl- and tetramethylammonium chloridesis given with 0,9% rel. error

89


AN


SOLVENT SUBJECT

cont.Table 17.

50% aqueous dioxane

tributyl phosphate

formic acid

3:2 acetone - dil.HNO3

methanol —waterbiner system

aqueous acetone,iso-PrOH orethyl methyl ketone

A potentiometric titration method is proposedfor determination mixtures of alkali chlorideand fluoride

Potentiometric investigation of some metalchloro-complexes

296

316

Kinetic studies on the rates of reaction of 317formolysis of benzoyl chloride and p-substitutedbenzoyl chlorides

Organic chloro-compounds were determined afterdecomposition by potentiometric titration withan chloride ion-selective electrode

A method is described for the determination ofmethanol content in its biner aqueous system

Determination of HC1 content in a mixture ofammonium perchlorate, perchloric and hydro-chloric acid

318

298

280

Determination of sulphate ion by potentio-metric titration using lead perchlorate astitrant

123

Potentiometric titration method is described 124for determining sulphur content of organiccompounds after combustion, via sulphate ion

Determination lead in galvanic mixtures by 319potentiometric titration

Potentiometric titration for determining ofmolybdenum with lead ions

Indirect determination of sulphate ion con-centration in galvanic mixtures

Determination method is given for tungsten bytitration with lead perchlorate as titrant

A new PbS-Ag2S electrode has been used for 101determination of sulphate ions by titrationwith lead nitrate standard solution

Determination of trace sulphur in petroleum 125products by potentiometri c titrationDetermination of lead content in paints 303

Determination of sulphate by titration with 304lead ions

Method is given to determinate the sulphate 320content in food colors by potentiometric tit-ration with lead nitrate as titrant

Comments on the determination of concentrated 321sulphate solutions by potentiometric titrationwith lead perchlorate

Ref.

50% aqueous dioxane

Table 18. Application of lead ion-selective electrode


60% aqueousdioxane

50% aqueous MeOH

50% aqueous MeOH

aqueous dioxane

aqueous dioxane

50% aqueous acetone

50% aqueous dioxane

50% aqueous MeOH

50% aqueous MeOH

50% aqueous dioxane

70% aqueous EtOH


cont Table 18.SOLVENT SUBJECT REF.

50-70% aqueous MeOH Potentiometric determination of drug sulphateswith lead perchlorate

322

aqueous acetone Potentiometric determination of sulphate inwhite and green liquors. The use of acetoneinstead of ethanol gave better results

323

80% aqueous EtOH Potentiometric method is given for determinationof sulphur in secondary alumina after combustionwith a newly developed lead selective electrode

384

aqueous MeOH Determination of sulphur content in organiccompounds by potentiometric titration

325

Table 19. Application of copper ion-selective electrode

SOLVENT SUBJECT REF.

MeOH, acetone, AN Direct potentiometric method and complexometrictitrations of copper(II) ions with several ligandsare Presented

97

50% aqueous acetic Some hydrazines were titrated with copper(II) ionsacid

45% aqueous EtOB Direct potentiometric titration of copper(II)ion with EDTA in the presence of iron(III) ions

326

327

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MeOHEtOHn-PrOHiso-PrOHDMFDMSOPCAN

Abbreviations

methanolethanoln-propanoli sopropanoldimethyl formamidedimethyl sulfoxidepropylene carbonateacetonitri le

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