PREDICT - MW Softwaremwsoftware.com/dragon/manual.pdf · PREDICT can execute compatibly with most...

PREDICTChemical Thermodynamic & Transport

Properties of Interest to Chemical Engineers andChemists

Version 4.0

Users Manual

Dragon Technology, Inc.P.O. Box 585

Golden, CO 80402-0585

Voice and FAX:303-526-5404

PREDICT Version 4.0

Copyright 1985-1995 Dragon Technology, Inc.

Warranty and Disclaimer

THIS SOFTWARE AND MANUAL ARE SOLD "AS IS" AND WITHOUT WARRANTIESAS TO THE PERFORMANCE OR MERCHANTABILITY. THE SELLER MAY HAVE MADESTATEMENTS ABOUT THIS SOFTWARE. ANY SUCH STATEMENTS DO NOTCONSTITUTE WARRANTIES AND SHALL NOT BE RELIED ON BY THE BUYER INDECIDING WHETHER TO BUY THE PROGRAM.

DRAGON TECHNOLOGY, INC. MAKES NO WARRANTIES, EITHER EXPRESSEDOR IMPLIED, REGARDING THE LICENSED SOFTWARE, MERCHANTABILITY OR FITNESSFOR ANY PARTICULAR PURPOSE. IN NO EVENT WILL DRAGON TECHNOLOGY, INC. BELIABLE FOR DIRECT, INDIRECT, INCIDENTAL OR CONSEQUENTIAL DAMAGESINCURRED BY USERS WHETHER ARISING IN TORT OR CONTRACT, RESULTING FROMANY DEFECT IN DRAGON TECHNOLOGY, INC.'S LICENSED SOFTWARE OR ANY REPAIROR REPLACEMENT THEREOF, EVEN IF DRAGON TECHNOLOGY, INC. HAS BEENADVISED OF THE POSSIBILITY OF SUCH DAMAGES; IT BEING EXPRESSLYUNDERSTOOD THAT THE ROYALTY FEE FOR THE LICENSED SOFTWARE HAS BEENSET WITH THE FOREGOING EXCLUSIONS AND LIMITATIONS OF WARRANTIES AND THESOLE REMEDY FOR BREACH OF THIS WARRANTY SHALL BE REPLACEMENT OF THESOFTWARE.

DRAGON TECHNOLOGY, INC. does not and cannot warrant that the Licensed Software willoperate error free.

License Agreement For Predict

Serial No.

By using the software diskettes the user agrees to use the software on no more than onemicrocomputer system. The user is allowed, under this license, to make one (1) back-up copy ofthe program for archival purposes only, to be used in case of failure of the original. At no time isthe back-up copy to be used on a second micro-computer. Use of this software package on anetwork of microcomputers is strictly prohibited. The user also agrees not to permit copies to bemade by other persons for the purpose of using the program on another microcomputer.

The user acknowledges that the unauthorized distribution or use of this software, received fromDRAGON TECHNOLOGY, INC., will cause material damage to DRAGON TECHNOLOGY, INC.

ONLY REGISTERED USERS WILL BE NOTIFIED OF UPDATES! Please fill out the enclosedregistration, sign it and return it to:

DRAGON TECHNOLOGY, INC.P.O. Box 585Golden, CO 80402-0585

Telephone & FAX: 303-526-5404

Page iv PREDICT Version 4.0

Copyright - 1985-1995 Dragon Technology, Inc.

INSTALLATION

Hardware Requirements

PREDICT Version 4.0, requires a 386 or higher PC computer and 4 MB of RAM.If a 386 computer is being used, a 387, math coprocessor, is also required. On 486’sand Pentium computers, the math coprocessor is included in the main processor. About2 MB of hard disk space are required for storage of the program and supporting files.

Before You Install - Back It Up

Before installing PREDICT, make a copy of the install disk and save it as abackup (see your DOS Manual for instructions). During the installation process, do notremove the write protection tab on the installation floppy. The install program neverneeds to write to the floppy disk. The current distribution of PREDICT consists of asingle floppy containing a compressed self extracting file and an instillation program.

Floppy Disk Inventory

PRED40x.EX_ Self Extracting set of files for PREDICTINSTPRED.EXE An installation program for creating a directory on the hard disk,

copying PRED40x.EX_ to the hard disk as PRED40x.EXE,extracting the PREDICT system from PRED40x.EXE and deletingthe no longer needed file PRED40x.EXE.

Installing PREDICT

To install PREDICT, move to the floppy by typing,

A: (Return)

(or B:)

then

INSTPRED (Return)

(running A:INSTPRED will not work, you must run from the floppy)

PREDICT Version 4.0 Page v


The install program will ask which hard disk to install on and the directory to install into.The install program will check for necessary hard disk space (2 MB are required) forexisting files and that all directories are created properly. If the program installs properlythe files listed below should be on the hard disk

Files Installed to the Hard Disk

Files Contained within PRED400.EXE

PREDICT.EXE 1,084,909 08-01-95 12:00p - Main PREDICT Executab leCMPDNAME.DAT 65,408 08-01-95 12:00p - Compound Data Base NamesCMPDDB.DAT 143,080 08-01-95 12:00p - Compound Data Base Prop DataPROP.DAT 123,375 08-01-95 12:00p - Data File for Various PREDICT MethodsSCREEN.DAT 198,000 08-01-95 12:00p - Data file of Group ContributionsHELP.MSG 231,000 08-01-95 12:00p - Full Screen Help MessagesHELP2.MSG 76,960 08-01-95 12:00p - Half Screen Help MessagesDEV.CFG 146 08-01-95 12:00p - Printer and Screen Configuration FilePRED.PIF 545 08-01-95 12:00p - Information File for MS-WindowsPREDICT.ICO 766 08-01-95 12:00p - MS-Windows Icon

Optional Manual Installation

To manually install, copy PRED40x.EX_ to the hard disk as PRED40x.EXE,where “x” is the current revision number.

COPY B:PRED40x.EX_ C:\PRED40\PRED40x.EXE

then execute pred40x

PRED40x

The file PRED40x.EXE is no longer needed and can be deleted,

DEL PRED40x.EXE

All of the files listed above should now be in the PRED40 directory.

Modifying the Configuration File

The system comes installed for VGA and HP LaserJet printer on LPT1. Thedevice configuration information is stored in the DEV.CFG file.

Page vi PREDICT Version 4.0


The video device and the printer/plotter are setup with parameters in theDEV.CFG file It should be noted that these settings only affect the graphics display andprinting and not standard text display and property printing. The default settings in thefile are:

VGA2$HPLJ3$LPT1:$

To change the devices simply edit this file with the DOS editor and modify thevalues. Line 1 is the monitor type, line 2 is the printer and line 3 is the printer port.Available options are listed in the following table.

Currently Supported Video Graphics Devices

Video Code Resolution Colors Tested at DragonCGA1$ 320x200 4 YCGA2$ 320x200 4 YCGA3$ 640x200 2 YEGA1$ 320x200 16 YEGA2$ 640x200 16 YEGA3$ 640x350 2 YEGA4$ 640x350 16 YVGA1$ 640x480 2 YVGA2$ 640x480 16 YVGA3$ 320x200 256 YHGC1$ 720x348 2 NHGC2$ 720x328 2 N

Various graphics printers that are available as well. However, only a few of theprinters and plotters have actually been tested at Dragon Technology.

PREDICT Version 4.0 Page vii


Currently Supported Graphics Printers

Printer Code Resolution Page Size PrinterHPLJ1$* 750x600 10x8 HP Laser/Desk JetsHPLJ2$* 1000x800 10x8 "HPLJ3$* 1500x1200 10x8 "HPLJ4$* 3000x2400 10x8 "PS1$* 3000x2400 10x8 Postscript PrintersHPGL1$* 1016/inch HPGL compatible PlotterHPGL2$ 1016/inch HP Laserjet III (HPGL/2)

* These printers/plotters have been tested at Dragon. Other printers that are availablebut have not been tested at Dragon are shown in the table below.

Other Graphics Printers Available, but Not Tested at Dragon

Printer Code Resolution Page Size PrinterEPS1$ 720x480 10x8 Epson 9-pin NarrowEPS2$ 720x960 10x8 Epson 9-pin NarrowEPSW1$ 816x720 13.6x10Epson 9-pin WideEPSW2$ 1632x720 13.6x10Epson 9-pin WideOKI1$ 720x480 10x8 Okidata 9-pin NarrowOKI2$ 720x960 10x8 Okidata 9-pin NarrowHPPJ1$ 900x720 10x8 HP PaintJet - 2 ColorHPPJ2$ 900x720 10x8 HP PaintJet - 4 ColorHPPJ3$ 900x720 10x8 HP PaintJet - 8 ColorHPPJ4$ 900x720 10x8 HP PaintJet - 16 ColorHPPJ5$ 1800x1440 10x8 HP PaintJet - 2 ColorHPPJ6$ 1800x1440 10x8 HP PaintJet - 4 ColorHPPJ7$ 1800x1440 10x8 HP PaintJet - 8 ColorDMPL1$ 1000/inch Houston Inst Plotter

Printer Port Specifications

The following printer ports are available for specification:LPT1:$LPT2:$COM1:$COM2:$

Page viii PREDICT Version 4.0


If COM1: or COM2: are used a mode command must be execute before runningPREDICT that establishes the baud rate for the printer. As an example, if the printer isconfigured at 2400 baud on serial port 1 (COM1) the following MODE command isnecessary:

MODE COM1:, 24

Also in the DEV.CFG file, each line must end in a $, as the variousconfigurations are different length.

In summary to select a different monitor or printer for PREDICT graphics, editthe DEV.CFG file and replace the appropriate parameter with a new one, making surethat the line ends in a dollar sign, $.

Configuring and Executing Under MS Windows

A pif file (PRED.PIF) is included for running PREDICT under MS Windows. Toinstall PREDICT in windows, select the File, New, Program Item from ProgramManager. Type PREDICT in as the title, PRED.PIF in on the command line,C:\PRED400 as the working directory, or whatever directory was used in the above DOSinstallation. Select, Change Icon and type C:\PRED400\PREDICT.ICO to select theenclosed icon. PREDICT operates best as a full screen application, not windowed.

To copy data or other information from PREDICT to the Windows clipboard forpasting into other program, you must first put PREDICT in a “window”. To do this, press<ALT><ENTER>. This will put PREDICT into a window (note that the property plots willonly work when PREDICT is full screen). Once in a “window”, click on the “dash” in theupper left corner with the mouse and then select Edit, Mark. Then select the area to becopied with the mouse. Finally, click on the “dash” again, followed by Edit, Copy. Themarked information is now in the Windows clipboard and can be pasted to otherWindows programs.

Possible Incompatibility with Memory Resident Programs

PREDICT 4.0 is written using the 386 DOS-Extender from Phar-Lap to takeadvantage of extended memory, memory higher than 1 MB. You will notice that thePREDICT executable is about 1.5 MB in size and could never run within the standardDOS limitation of 640K of memory. Because PREDICT is running in extended memory itis possible that other programs also trying to run in the same area may interfere withPREDICT. The following attempts to address various types of possibilities and whetheror not there might be a problem with PREDICT.

PREDICT Version 4.0 Page ix


Memory Resident Programs

Memory resident programs, also referred to as "terminate stay resident" (TSR)programs are usually installed in memory when DOS is initialized, through a line in theCONFIG.SYS or AUTOEXEC.BAT files. These programs can cause compatibilityproblems because they take over interrupts. Interrupts are used to enable the programto "pop-up". Some TSRs are also in extended memory.

PREDICT can execute compatibly with most memory resident programs. Thefollowing discusses some particular programs.

RAM Disks and Disk Cache Programs

The only problem PREDICT will have with these types of programs is in their useof extended memory. PREDICT is compatible with programs following the VDISKstandard, the BIOS extended memory size determination standard or the technique usedby Microsoft RAMDRIVE program for allocating extended memory.

If memory resident programs that allocate extended memory do not follow one ofthese standards there will probably be problems with PREDICT.

EMS Emulators

EMS refers to the Lotus-Intel-Microsoft Expanded Memory Specificationestablished to enable standard DOS applications to access more memory. Originally thiswas implemented in hardware.

With the 386/486 family of processors a new set of EMS emulator programswere developed.

In most cases PREDICT will refuse to run if an XMS (extended memorymanager) driver that supports VCPI is not present. This usually occurs when you havetold the driver to load itself (as well as other TSR's, etc.) in the memory availablebetween 640 KB and 1 MB and have done one of the following:• installed Quarterdeck's QEMM with the "noems" option• installed Compaq's CEMM with the argument "cemm off"• installed Microsoft's EMM386 with the 'noems" option or specified

"emm386 off" on the command line• installed 386MAX with the "ems=0" option"

PREDICT will run correctly with the above mentioned drivers when these driversdo not report themselves as VCPI hosts. PREDICT will still fail if this condition isencountered with other XMS drivers. The only option is to turn the EMS emulator off,which switches the 386/486 processor back to real mode so that PREDICT can run.

Page x PREDICT Version 4.0


Other Memory Resident Programs

Most other available memory resident programs run wholly in real mode of the386/486. These programs generally take over hardware interrupts to enable them to"pop-up". In general PREDICT has no compatibility problems with this class of program,because PREDICT doesn't take over any interrupts.

PREDICT Version 4.0 Page i


Table of Contents

Installation iv

Hardware Requirements ivBefore You Install - Back It Up ivFloppy Disk Inventory ivInstalling PREDICT ivOptional Manual Installation vModifying the Configuration File vCurrently Supported Video Graphics Devices viCurrently Supported Graphics Printers viiConfiguring and Executing Under MS-Windows viiiPossible Incompatibility with Memory Resident Programs viii

I. Introduction I-1

I.1 Properties Available I-2I.2 What’s New I-3

II. Description of Physical Property Prediction Methods II-1

II.1 Critical Temperature II-1II.2 Critical Pressure II-3II.3 Critical Volume II-5II.4 Acentric Factor, Riedel Factor and Polarity Factor II-7II.5 Normal Boiling Point II-11II.6 Ideal Gas Heat of Formation II-14II.7 Ideal Gas Free Energy of Formation II-16II.8 Vapor Pressure II-17II.9 Heat of Vaporization II-22II.10 Liquid Density II-25II.11 Surface Tension II-30II.12 Liquid Viscosity II-32II.13 Gas Viscosity II-34II.14 Liquid Heat Capacity II-36II.15 Ideal Gas Heat Capacity II-38II.16 Liquid Thermal Conductivity II-42II.17 Gas Thermal Conductivity II-43II.18 Important Nomenclature II-45

Page ii PREDICT Version 4.0


III. Regression III-1

III.1 Regression System III-1III.2 Using the Regression System III-5III.3 ASPEN Simulator Output III-8III.4 Data Regression Files III-8

IV. References IV-1

V. Program Operation V-1

V.1 Help V-1V.2 Group Contribution Screens V-1V.3 Exiting and Quiting V-2V.4 Error Recovery V-2V.5 Yes/No Questions and Selections from Menus V-2V.6 Output Units V-3V.7 User Specified Input Units V-3V.8 Extensive Error Checking on User Inputs V-5V.9 Internal Property Storage V-6V.10 Property Database and Empirical Formula Entry V-6V.10.1 Saving Data to the PREDICT User Database V-8V.10.2 References to Data Supplied with PREDICT V-8V.11 Saving Data to ASCII Data Files V-8V.12 Displaying and Printing Graphs V-9V.13 Executing Under MS-Windows V-9V.14 Example Calculations V-9V.14.1 Example 1, Critical Temperature Prediction by Joback and Ambrose,

Saving Data to the User Database and Use of Help Files V-10V.14.2 Example 2, Retrieve 2,2,5-Trimethylhexane data from the Database,

Calculate the Vapor Pressure in English Units, save Data to a File and Regress the Data to a Standard Equation V-17

V.14.3 Example 3, Retrieve Cyclohexane data from the Database, Calculate the Liquid Heat Capacity, Inputing Ideal Gas Heat Capacity Polynomial and Display the Results in SI Units V-26

V.14.4 Example 4, Calculate the Ideal Gas Heat Capacity using Benson’s Method for Methyl Ethyl Ketone V-31

PREDICT Version 4.0 Page iii


VI. Appendix VI-1

Lydersen Critical Constants Group Contributions VI-1Ambrose Critical Constant Group Contributions VI-2Klinewicz & Reid Critical Constant Group Contributions VI-3Joback Critical Constant Group Contributions VI-4Fedors Critical Temperature Group Contributions VI-5Fedors Critical Volume Group Contributions VI-6Joback Point Property Group Contributions VI-7Ideal Gas Heat of Formation Bond Contributions VI-8Franklin Ideal Gas Heat of Formation Group Contributions VI-9VanKrevelen Charmin Ideal Gas Free Energy of Formation Group ContributionsVI-10Benson Ideal Gas Heat of Formation Group Contributions VI-11Pitzer Vapor Pressure Parameters VI-19Halm Stiel Vapor Pressure Parameters VI-20Pitzer Heat of Vaporization Parameters VI-21Halm Stiel Heat of Vaporization Parameters VI-22Halm Stiel Liquid Density Parameters VI-23Bhirud Liquid Density Parameters VI-24Morris Liquid Viscosity Group Contributions VI-25Joback Liquid Viscosity Group Contributions VI-26Reichenburg Gas Viscosity Group Contributions VI-27Missenard Liquid Heat Capacity Group Contributions VI-28Yuan Stiel Liquid Heat Capacity Parameters VI-29Rihani Doraiswamy Ideal Heat Capacity Group Contributions VI-30Joback Ideal Gas Heat Capacity Group Contributions VI-31Benson Ideal Gas Heat Capacity Group Contributions VI-32Harrison Seaton Ideal Gas Heat Capacity Parameters VI-41

PREDICT Version 4.0 Page I-1


I. INTRODUCTION

Some physical properties are required on nearly every chemical involved in aprocess design. Usually some of these properties can be found in databases of somesort, or in the literature. However, as is often the case with new, developmentalchemicals, these properties are unavailable. Ideally the properties should be measuredin a laboratory, but for a host of reasons, including long lead times, no pure chemicalavailable or no experimental method available, the properties needed cannot always beobtained from experiment. Therefore, these properties must be estimated or predicted.

For almost every property of interest there exists an estimation method. Someare much better than others, indeed some are no more than guesses. Most of thesemethods are complex and awkward to use. To help the chemical engineer better decidewhich estimation method should be used for a particular application and then accuratelyapply the selected method PREDICT was written.

PREDICT, Version 4.0 contains 64 group contribution and corresponding stateprediction routines for 19 chemical engineering physical properties. Group contributionmethods sum up a series of contributions from various molecular groups in thecompound to obtain the desired property. Corresponding states methods relate thedesired property to constants characteristic of the compound, usually critical properties.

PREDICT is designed to be a "user friendly" program that any engineer can pick-up and use with little, if any, instruction. The properties are called from a series ofmenus and all inputs are "prompted" for. All inputs can be entered in a variety of units,the default units are listed on the input form, alternative units are explained in the HELPscreen available by pressing F1. Group contribution methods are made simple to use bydisplaying the complete list of molecular groups on the screen for the user to easilyselect from, again HELP screens are available explaining how to select groups as well asexamples of each type of group contribution method.

Some of the important features of PREDICT include it's ability to rapidly comparethe various methods that might be included in the program for a particular property or testthe sensitivity of the calculated result to the various input values. The tabulated resultsof the program can be displayed on the screen (and subsequently to the printer). Graphsof results can be displayed on the screen or printed on various printers. The predictedresults can be regressed by least squares methods to common physical propertyequations. Finally, the predicted data can be stored in a file that can interface with otherprograms including the ASPEN family of process simulators. PREDICT is also suppliedwith a database of point properties on over 1000 common chemicals. These can beeasily retrieved and used to calculate additional properties. In addition, any of the pointproperties calculated with PREDICT can be stored in a user database for later retrievaland reuse. The HELP screens are available to the user at various locations in the

Page I-2 PREDICT Version 4.0


program giving an explanation of the prediction methods in the program, theirapplicability, and recommendations for their use.

It cannot be stressed too often or too strongly that the accuracy of any estimationis directly related to the quality of the input parameters. If these inputs are alsoestimated it can increase the expected error greatly. This is most common when criticalproperties are estimated and then used to predict other temperature correlatedproperties. The errors listed generally throughout this document are assuming goodinputs. This is where the features of PREDICT can come in very handy in testing thesensitivity of calculated outputs to potential errors in the inputs.

I.1 Properties Available

Properties available in this program can be divided into two categories, PointProperties and Temperature Correlated Properties. The point properties are a singlevalue property. Temperature correlated properties are defined over a range oftemperatures. The point properties that can be calculated by PREDICT include:

Critical TemperatureCritical PressureCritical VolumeAcentric FactorPolarity FactorRiedel Factor

Ideal Gas Heat of Formation @ 298KIdeal Gas Free Energy of Formation @ 298K

Normal Boiling PointThe Temperature Correlated Properties included in the current version of the

program are:Vapor Pressure

Heat of VaporizationLiquid Density

Surface TensionLiquid ViscosityGas Viscosity

Liquid Heat CapacityIdeal Gas Heat Capacity

Liquid Thermal ConductivityGas Thermal Conductivity

Prediction of the critical temperature and critical pressure are by groupcontribution methods. The critical volume can be calculated either by the groupcontribution methods or by corresponding states. The temperature correlated prediction

PREDICT Version 4.0 Page I-3


methods included are generally corresponding states methods, with the exception of thethree ideal gas heat capacity methods (Joback, Benson, and Rihani-Doraiswamy), twoliquid viscosity methods (Joback and Morris), one gas viscosity method (Reichenberg),one heat of vaporization method (Joback) and one liquid heat capacity method(Missenard) which are group contribution methods.

An important concept used in this program is the awareness that any knowninput, such as one of the point properties, is better than a prediction. Therefore, anypoint property can be entered when needed. There are also properties that require someother temperature correlated property in their estimation. These other properties caneither be estimated by any method included or entered by the user as a polynomial. If aproperty is entered by the user as a polynomial it has no temperature limits associatedwith it. Further if several temperature correlated estimation methods must be used, themost restrictive temperature limit will prevail. Also advantage is taken of reference datapoints and other input data, when known.

The majority of the methods used have been recommended by Reid et al.1 andReid et al.66 in their books on physical property estimation, or by the AIChE's DIPPR(Design Institute for Physical Property Research)2 committee on Data Prediction. Theopen literature was also searched for methods that might have been overlooked by thesefine references.

The author sincerely hopes that this program fills a serious need of chemicalengineers to be able to reliably and accurately predict physical properties when needed(and not available elsewhere) using the most appropriate method.

I.2 What’s New

The last version, 3.9, saw the introduction of several new calculation procedures,including those of Benson for ideal gas heat capacity, Joback for critical properties,normal boiling boiling point, heat of formation and free energy of formation. Also, addedin that version was a new point property database of over 300 common chemicals.

This version adds the feature of automatically regressing the Benson set of idealgas heat capacity predictions at discrete temperatures, to a continuous function oftemperature allowing estimation of ideal heat capacity at intermediate temperatures.Also added are two additional ideal gas heat capacity methods, that of Joback and ofHarrison and Seaton, including an automatic regression of the Harrison-Seaton discretevalues to a continuous temperature function. The Harrison-Seaton method is particularlyinteresting because it only requires the compound’s empirical formula and it canaccommodate any element. Using information developed by the AIChE DIPPR68 project,more accurate group contributions for silicon containing compounds were added to theAmbrose and Lydersen critical property methods and the Fedors critical volume method.The DIPPR project also improved the silicon, boron and aluminum group contributions to

Page I-4 PREDICT Version 4.0


the Benson ideal gas heat of formation (at 298 K) method, which was added with theseimprovements to PREDICT in this version. Additional methods by Joback for heat ofvaporization and liquid viscosity were also added. Finally, a very useful method for theestimation of normal boiling point from any vapor pressure point, typically at pressuresless than atmospheric, was added. This method uses the group contributions ofLydersen, Ambrose or Joback and the vapor pressure prediction method of Pitzer toiterate on a normal boiling point given a vapor pressure/temperature data point other than1 atmosphere.

The pure component database was expanded to over 1000 chemicals with theuser added compounds moved to a separate database that can be edited by the user.The user database allows the user to modify properties from the system database andstore for reuse or to store a completely new compound for later retrieval and reuse later.

PREDICT Version 4.0 Page II-1


II. DESCRIPTION OF PHYSICAL PROPERTY PREDICTION METHODS

II.1 Critical Temperature

Five group contribution methods, Lydersen3, Ambrose4, Klincewicz and Reid5,Fedors6, and Joback65 have been included for estimation of critical temperature.

Historically, Lydersen's method, developed in 1955, was found to be the mostaccurate method available for TC prediction for hydrocarbons and organics7,8. In 1978Ambrose used the considerable amount of new data available to develop a new moreaccurate, but also more complex prediction method. Klincewicz and Reid used the dataamassed by Ambrose to come up with a scheme that was nearly as accurate asAmbrose's but not as complex. Very recently, Joback took advantage of the new criticaldata that has become available since Lydersen’s original work in 1955 to modifiedLydersen’s scheme slightly and develop a method that is as accurate as Ambrose, butagain, not as complex. All four of these methods have merit and are therefore included.Klincewicz and Reid and Joback will be the most useful, but the Ambrose method doesinclude some molecular groups not found in the former correlations. Lydersen is stillimportant for comparisons, as it was the standard for over 20 years. Myers68 working forthe AICHE DIPPR project has modified the silicon group contributions used by Lydersen,Ambrose and Fedors. Those new groups are included in this version of PREDICT.

The fifth method, Fedors6 is important because it does not require the normalboiling point, as do all of the other methods. This method is not as accurate as theothers, but can be very useful if that basic physical property, normal boiling point, is notavailable. Finally a sixth method is included for a quick reference only. Klincewicz andReid5, in their investigation of critical temperature methods found that a simple correlationusing only the normal boiling point and the molecular weight will give nearly the sameresult as a complicated group contribution scheme. While this method has higher errorthan all of the others, it is useful for a quick estimate or when the compound in questionis not covered by the existing group contributions.LYDERSEN, Critical Temperature

TC = TB / [0.567 + ∑∆TL - (∑∆TL)2] (1)

where, ∆TL : Group Contributions from Appendix Table 1.

Page II-2 PREDICT Version 4.0


AMBROSE, Critical Temperature

TC = TB (1 + φT + ∑∆TA) / (φT + ∑∆TA) (2)

where, ∆TA : Group Contributions from Appendix Table 2.φT : 1.570 for Perfluorocarbons, 1.242 Otherwise.

KLINCEWICZ-REID (Group Contribution), Critical Temperature

TC = 45.4 - 0.77 MW + 1.55 TB + ∑∆TK (3)

where, ∆TK: Group Contributions from Appendix Table 3KLINCEWICZ-REID (Simple), Critical Temperature

TC = 50.2 - 0.16 MW + 1.41 TB (4)

FEDORS, Critical Temperature

TC = 535 log10(∑∆TF) (5)

where, ∆TF: Group Contributions from Appendix Table 5.JOBACK, Critical Temperature

TC = TB / [0.584 + 0.965 Σ∆TJ - (Σ∆TJ )2] (6)

where, ∆TJ : Group Contributions from Appendix Table 4.Expected Errors Klincewicz and Reid5, Reid, Prausnitz and Poling66 and

Joback65 made a very complete analysis of the error of all of the above methods. Usingthe database of 396 polar, nonpolar, organic and organometallic compounds developedby Ambrose9 they found that the mean error using the Ambrose method was 0.7% and95% of the errors were within 3.7%, while the error using the Joback method was 0.8%.The Klincewicz and Reid method had a mean error of 1.2% with 95% of the errors within4.3%. The Klincewicz and Reid simple method had a mean error of about 3%. The olderLydersen method had a mean error of 1.4% and 95% of the errors within 5.1% Fedors'method showed an average error of 4%. The DIPPR report2 only studied the Ambroseand Lydersen methods. They found an average error, using 195 data points of 1.53% forLydersen and 1.05% for Ambrose. They also broke down the error summary bycompound class. Significant is the fact that the Ambrose method has considerably lowererrors for alcohols, anhydrides and ketones.

Considering the complexity of the Ambrose method as compared to Joback’s



method, Joback is recommended for most compounds except compounds containingsilicon groups.

Calculation Hints When more than one critical property is predicted using thesame method (Lydersen, Ambrose or Klincewicz and Reid) for the same compound, thestructure will need to be entered only once.

The program will allow the user to freely move the cursor around on the groupcontribution menus. Simply locate the groups that are present in the molecule, move tothat group and enter the number of that group that are present. If there are groups in themolecule that do not appear in the menu, quit and try a different method. The screencan be cleared of all numbers using a function key or a single entry can be removed bymoving to it and entering a zero. When all groups have been selected to the userssatisfaction, a function key, DONE is pressed.

II.2 Critical Pressure

Four group contributions methods are presented for critical pressure. As with thecritical temperature, Lydersen's3 method has long been the preferred method.Ambrose10 used the new data measured since Lydersen and improved upon the earliermethod. Klincewicz and Reid5 took a little different approach to their correlation, resultingin a form different than that of Lydersen or Ambrose with simpler group contributions.Joback, as with Ambrose, took advantage of the new data available but kept a form verysimilar to Lydersen. As with the critical temperature correlations the Ambrose method isthe most accurate but only slightly more so than that of Joback which is much lesscomplex than Ambrose. Klincewicz and Reid or Lydersen methods, while simpler thanAmbrose are not as accurate as Joback. As with critical temperature the new siliconcontaining group contributions developed by Myers68 were included for the Lydersen andAmbrose methods.

Klincewicz and Reid5 also offer a simple method that does not include a groupcontribution, but rather requires only the molecular weight and the number of atoms inthe molecule. As with their simple critical temperature method this correlation will beuseful for a quick reference or for the prediction of a compound's critical pressure whosegroups are not listed. The result being less accurate than any of the other methods.LYDERSEN, Critical Pressure

PC = MW / (0.34 + ∑∆PL)2 (7)

where, ∆PL: Group Contributions from Appendix Table 1.AMBROSE, Critical Pressure ,

PC = MW / [1.01325 (φP + ∑∆PA)2] (8)



where, ∆PA: Group Contributions from Appendix Table 2.φP: 1.00 for Perfluorocarbons, 0.339 Otherwise

KLINCEWICZ-REID (Group Contribution), Critical Pressure ,

PC = MW / [1.01325 (0.348 + 0.0159 MW + ∑∆PK)2] (9)

where, ∆PK: Group Contributions from Appendix Table 3.Note: The constants in equation 8 are different than the original reference.11

KLINCEWICZ-REID (Simple), Critical Pressure ,

PC = MW / [1.01325 (0.335 + 0.009 MW + 0.019 nA)2] (10)

where, nA: Number of atoms in molecule.JOBACK, Critical Pressure

PC = [(0.113 + 0.0032nA - Σ∆PJ)-2]/1.01325 (11)

where, nA : Number of Atoms in the Compound.∆PJ: Group Contributions from Appendix Table 4.Expected Errors As with the errors in critical temperature the good reviews are

contained in Klincewicz and Reid5, Reid, et. al.66 and Joback65. Reid, et al. and Jobackused a database of 390 compounds and found average errors of 2.1 bar or 5.2% forJoback’s method. This is compared with 4.6% using Ambrose's method (95% of allerrors within 13%), 8.9% using Lydersen's method (95% of all errors within 38%) and7.8% using Klincewicz's method (95% of all errors within 25%). Finally the simple methodof Klincewicz and Reid had an average error of 12%.

The DIPPR2 project again compared only the Lydersen and Ambrose methods.Their findings, using 139 compounds of various classes, showed an average error forLydersen of 5.61% and Ambrose of 4.52%. They also point out that the Lydersenmethod was significantly better than Ambrose for aldehydes and anhydrides whileAmbrose was much better than Lydersen for acids and all halides.

As with critical temperature, considering the extra complexity of the Ambrosemethod, Joback's method will prove to be very useful.

II.3 Critical Volume

Group contribution methods as well as corresponding states methods are givenfor the prediction of critical volume. This, the third of the three critical properties is



usually the most difficult to measure, so consequently the database of good experimentalcritical volume data is smaller. Also, it is quite common that experimental values of thecritical pressure and temperature for the compound in question might be available. Inthat case using the corresponding states methods, which utilize these properties, mightgive a better estimate than the group contribution methods.

Five group contribution methods, Lydersen3, Ambrose10, Klincewicz and Reid5,Joback65 and Fedors12 are given. Along with these are two corresponding statesmethods, those of Halm and Stiel13 and Pitzer et al.14

The group contribution methods followed the same development as the criticaltemperature and pressure. That is, the Lydersen was improved upon by Joback and bythe more complex Ambrose method while Klincewicz and Reid somewhat simplified theAmbrose method. The Fedors method is a fairly simple group contribution method and isthe only method recommended by DIPPR.

Again as with the other critical property methods Klincewicz and Reid presenteda simple correlation that does not use group contributions, nor corresponding statesmethods. This simple method uses only the compound's molecular weight and numberof atoms. Again this can be useful if other critical data is not available and thecompounds structure is not given in any of the group contribution methods.

As with the other critical properties, the new work by Myers68 on the groupcontributions for silicon containing compounds is included. For some reason, Myers onlyreported actual Si group contributions for the Fedors method. Dragon Technology usedthe Si VC data reported by Myers68 and developed the Si group contributions for theLydersen and Ambrose methods.LYDERSEN, Critical Volume

VC = 40 + ∑∆VL (12)

where, ∆VL: Group Contributions from Appendix Table 1.AMBROSE, Critical Volume

VC = 40 + ∑∆VA (13)

where, ∆VA: Group Contributions from Appendix Table 2.



KLINCEWICZ-REID (Group Contribution) Critical Volume

VC = 25.2 + 2.8 MW + ∑∆VK (14)

where, ∆VK: Group Contributions from Appendix Table 3.KLINCEWICZ-REID (Simple) Critical Volume

VC = 20.0 + 0.088 MW + 13.4 nA (15)

FEDORS Critical Volume

VC = 26.5 + ∑∆VF (16)

where, ∆VF: Group Contributions from Appendix Table 6.JOBACK, Critical Volume

VC = 17.5 + Σ∆VJ (17)

where, ∆VJ: Group Contributions from Appendix Table 4.Expected Error, Group Contribution Klincewicz and Reid5 evaluated three of

the methods given here. Using the database of Ambrose9 which contains about 200compounds for critical volume the Lydersen method was found to have an average errorof 3.1% with 95% of the errors less than 10%. Ambrose's method had a mean error of2.8% with 95% of the errors less than 9.6%. Klincewicz and Reid's method had a meanerror of 2.9% and 95% less than 8.5%. The simple Klincewicz and Reid method wasfound to have an average error of about 5.2%.

Fedors method was not reviewed by Klincewicz and Reid, but in Fedors12 originalpaper he reported an average deviation of 3.15% for 160 compounds. This is comparedwith an average error for the same compounds (given by Fedors) using Lydersen'smethod of 3.26%.

Reid et. al.66 and Joback65 report an absolute error using the Joback criticalvolume method of 7.5 cc/mole or 2.3% for 310 compounds. These are the samecompounds used in the earlier comparison by Klincewicz and Reid5.

In summary Joback's method has both the lowest error and, as stated earlier, iseasier and more accurately applied that Ambrose's. The Fedors method is ofcomparable accuracy to the Lydersen method and has a very simple group contributionprocedure. Ambrose and Fedors methods have the advantage of new parameters for Sicontaining groups.

Corresponding States Methods The other two methods included are



corresponding states methods based on the critical temperature, critical pressure andother parameters. The two methods, by Pitzer14 and Halm and Stiel13, arecompressibility factor (Z) correlations evaluated at the critical point.

The Pitzer correlation uses the acentric factor as a third parameter for thecorrelation of Z. The exact error is not known but the critical region is within the range ofthe correlation which was fit to data within a very close deviation. It must be pointed outthat, as with all of the three parameter corresponding states correlations used in thisprogram, it will be accurate only for "normal fluids". A "normal fluid" is nonpolar or onlyslightly polar. That means that it does not exhibit a dipole, quadrupole or highermoments, nor are there hydrogen bonding forces present. An example of a "normalfluid" would be hexane or carbon tetrachloride, polar compounds would be water ormethyl chloride.PITZER, Critical Volume

VC = R TC (0.291 - 0.080 ω) / PC (18)

The Halm and Stiel method uses the acentric factor of Pitzer plus a fourthparameter, the polarity factor. This fourth parameter will allow polar forces to bedescribed by the equation. The correlation works quite well for most polar substances,indeed much better than the three parameter correlation of Pitzer. However, theequation will give largest errors for very complex polar molecules where a simple fourthparameter is still not enough to describe the forces. Obviously the disadvantage of thismethod over Pitzer's is the requirement of more data, the polarity factor. Halm and Stielfound the average error of 15 polar substances to be 1.4%.HALM & STIEL, Critical Volume

VC = (0.291 - 0.114ω - 1.42x + 0.069ω2 - 7.05x2 + 1.51xω)RTC / PC (19)

II.4 Acentric Factor, Riedel Factor and Polarity Factor

The acentric factor is defined by Pitzer14 to be:

x = - log PVR (@ TR = 0.7) - 1.000 (20)

The Riedel factor was defined by Riedel16 as:

αCVR

R

d Pd T

=lnln

(21)



This can be evaluated at the critical point given the following:

ddT

C

R

α= 0, @ TR = 1 (22)

Finally, the polarity factor, defined by Halm and Stiel15 as:

x P T P TVP R VR RDATA CALC= = − =log (@ . ) log (@ . )0 6 0 6 (23)

where, PVRCALC: Reduced Vapor Pressure calculated from Eq. 55.

These three factors have been defined as additional parameters incorresponding states theory. None have much value by themselves but are extremelyuseful in correlation of other properties, as has been seen already in the case of VC andwill be seen more later.

These properties are not usually calculated from their definitions exactly, as thevapor pressure at TR = 0.7 or TR = 0.6 exactly, or the vapor pressure slope at the criticalpoint are usually not known. More commonly some other vapor pressure points will beknown and by using the corresponding states vapor pressure correlations involving theacentric factor or Riedel factor or polarity factor these factors can be calculated. Ideally,any correlation that involves these parameters, liquid density, liquid heat capacity,surface tension, etc. could be used with physical property data to calculate them.However, because all are defined by vapor pressure, only vapor pressure (and heat ofvaporization, which is easily calculated from vapor pressure) will be used to calculatethese parameters.

For the calculation of acentric factor, two methods are included. The Pitzer14

correlations of heat of vaporization, see section II.9, and vapor pressure can be used tocalculate the acentric factor.PITZER Acentric Factor from Vapor Pressure

ω = [log10PVR - P(0)] / P(1) (24)

where, P(0) and P(1) are Tabulated functions of TR, see Appendix Table 12.As will be pointed out in the section on vapor pressure the original Pitzer

correlation for vapor pressure was good only for the temperature range of 0.56 to 1.00reduced temperature. This was extended by Carruth and Kobayashi17 to a reducedtemperature of 0.25. The program checks these temperature limits and will not acceptany data outside these limits.PITZER Acentric Factor from Heat of Vaporization ,



ω = [(HVAP/T) - S(0)] / S(1) (25)

where, S(0) and S(1) are Tabulated functions of TR, see Appendix Table 14.As with the Pitzer vapor pressure correlation the original heat of vaporization

function was tabulated for reduced temperatures of 0.56 to 1.00. Carruth andKobayashi17 also extended this correlation. The extension, down to a reducedtemperature of 0.30, is used in this program. Again as with the vapor pressure, no dataoutside of these temperature limitations will be accepted.

The Riedel factor can be calculated using the vapor pressure correlationdeveloped by Riedel16 or from a correlation with the acentric factor. More commonly theacentric factor will be listed in a database and can here be used to calculate the RiedelFactor. Pitzer et al.14 offered a correlation to relate the two, the DIPPR2 project hasmodified that original correlation. The DIPPR correlation is used here.RIEDEL FACTOR from Vapor Pressure

αC = 0 1368

0 036410

10

. log

. log

−

−

P

TVR

R

(26)

ζ = 36TR

+ 96.7 log10TR - 35 - TR6 (27)

RIEDEL FACTOR from the Acentric Factor

αC = 5.811 + 4.919 ω (28)

The polarity factor, as described earlier is defined based on the calculation of thePitzer vapor pressure equation (55). Therefore, in order to calculate the polarity factor,the acentric factor must be known. Or, if two data points are available, both the acentricfactor and the polarity factor can be calculated from the Halm and Stiel15 correlations for



vapor pressure and heat of vaporization. The user is given the following options fromwhich to calculate the polarity factor;

1. Two Vapor Pressure Data Points2. Two Heat of Vaporization Data Points3. One Vapor Pressure and One Heat of Vaporization Point4. One Vapor Pressure Data Point and the Acentric Factor5. One Heat of Vaporization Point and the Acentric Factor

In the first three cases both the acentric factor and the polarity factor are calculated.POLARITY FACTOR, Given Two Vapor Pressure Data Points

x = [ ]

[ ]log / log

/

( ) ( ) ( ) ( )

( ) ( ) ( ) ( )

10 1 10

10

21

10 2 20

12

11

22

21

P P P P P P

P P P P

VR VR+ + − −

−(29)

ω=− + −P xP P

PVR1

01

210 1

11

( ) ( )

( )

log(30)

where, P(0), P(1) and P(2) are Tabulated functions of TR, see Appendix Table 13.The temperature limitations for this correlation are 0.44 to 1.0 reduced

temperature, as always the program will not except any vapor pressure data outside ofthis range. Additionally, because the tabulated function P(2), which is multiplied by thepolarity factor, is zero above TR = 0.7, the data points must be less than TR = 0.7 tocalculate a meaningful x.POLARITY FACTOR, Two Heat of Vaporization Data Points

x =( )( )

( )H T S S S H T S

S S S S

VAP VAP2 2 20

21

11

1 1 10

21

12

11

22

− − −

−

( ) ( ) ( ) ( )

( ) ( ) ( ) ( )

/ /

/(31)

=− +H T S x S

SVAP1 1 1

012

11

/ ( ) ( )

( ) (32)

where, S(0), S(1) and S(2) are Tabulated functions of TR, see Appendix Table 15.The heat of vaporization functions are tabulated only for the temperature range

of .56 to .72 reduced temperature. Therefore, only data in that range will be accepted.



POLARITY FACTOR, One Vapor Pressure Data Point and One Heat ofVaporization Data Point

( )( )( )x

P P P S H T S

P P S S

VR VAP=

+ + −

−

log / /

/

( ) ( ) ( ) ( )

( ) ( ) ( ) ( )

10 1 10

11

21

2 2 20

12

11

22

21

(33)

where, P(0), P(1), P(2), S(0), S(1) and S(2) are Tabulated functions of TR, see AppendixTable 13 & 15.

In this case the acentric factor, ω, can be calculated either by equation 30 or 32.This relationship will have the same temperature limitations for the vapor pressure andheat of vaporization data as pointed out earlier.POLARITY FACTOR One Vapor Pressure Data Point and Acentric Factor

x = [log10PVR + P(0) + ω P(1)] / P(2) (34)

where, P(0), P(1), and P(2) are Tabulated functions of TR, see Appendix Table 13.POLARITY FACTOR, Given One Heat of Vaporization Data Point and theAcentric Factor,

x = [S(0) + ω S(1) - HVAP/T] / S(2) (35)

where, S(0), S(1) and S(2) are Tabulated functions of TR, see Appendix Table 15.

II.5 Normal Boiling Point

The normal boiling point has been defined as the boiling temperature of acompound under one atmosphere pressure. This very common physical property isusually the first property measured for a compound. Because of it's very commonavailability and usefulness it is commonly used in estimation schemes. Obviously therewill be times when even this fundamental property will not be available, and for many ofthe reasons stated in the introduction will not be easily obtained. So rather than forgosome of the useful estimation methods using this property, it can be estimated.

A word of caution is due here, if it is at all possible to get an experimental valuefor the normal boiling point, get it and use it! Do not estimate it unless it is absolutely thelast resort.

While “normal boiling point” is quite often used in estimation methods, sometimesa single boiling point at a pressure other than 1 atmosphere is available. Generallymeasurements of boiling points are made at lower pressures for extremely high boilingcompounds or for compounds that decompose before they boil at atmospheric pressure.Using the correlations of Lydersen, Ambrose or Joback for critical temperature as a



function of TB and structure, critical pressure as a function of structure, and a vaporpressure method such as Pitzer as a function of TC and PC, TB can be estimated from aboiling point at any pressure.

The method for estimation of TB given another vapor pressure, uses the Pitzervapor pressure equation and one of the critical property prediction methods toapproximate the normal boiling. The Pitzer vapor pressure equation gives vaporpressure as a function of temperature, acentric factor, critical temperature and criticalpressure. If the critical properties were known the Pitzer equation could be solved fortemperature when the vapor pressure is one atmosphere (normal boiling point).Lydersen, Ambrose and Joback give the critical pressure as a function of structure andmolecular weight, so PC can be calculated directly. These methods also give criticaltemperature as a function of structure and normal boiling point. Using the Pitzer vaporpressure, one of the critical temperature prediction equations and a vaporpressure/temperature point, the normal boiling point, critical temperature and acentricfactor can be solved for.

Joback65 used the same approach to developed a method for normal boilingpoint as he used to develop a method for critical temperature. The resulting method is afunction of structure only.

A method is also given for estimation of the normal boiling point by Miller18. Thismethod takes advantage of the fact that in the Lydersen critical property methods onlythe critical temperature calculation requires the normal boiling point. The others, criticalpressure and volume use only the molecular weight and compound's structure. Furtherby using the Rackett19 liquid density method which uses all three critical properties andthe Tyn and Calus20 prediction of the liquid density at the normal boiling point the normalboiling point can be predicted. Obviously there are many ways in which variouscorrelation routines could be combined to give the normal boiling point, but this one hasbeen tested and recommended21.JOBACK, Normal Boiling Point

TB = 198 + Σ∆BJ (36)

where, ∆BJ: Group Contributions from Appendix Table 7.MILLER, Normal Boiling Point

TB = (θ/R) eβ (37)

β =( )[ ]ln . ( ) ln .

( )

/ /

/

V PC C1 0 04822 1 12547

1

2 7 2 7

2 7

− − + − +

−(38)



θ = 0.567 + ∑∆TL - ∑∆TL2 (39)

PC = MW / (0.34 + ∑∆PL)2 (40)

VC = 40 + ∑∆VL (41)

where, ∆TL, ∆PL, ∆VL: Group contributions, see Appendix Table 1.Normal Boiling Point, Given another Vapor Pressure/Temperature Data PointCalculate TC/TB from Lydersen, Joback or Ambrose

TC / TB = 1.0 / [0.567 + ∑∆TL - (∑∆TL)2] Lydersen (42a)

TC / TB = (1 + φT + ∑∆TA) / (φT + ∑∆TA) Ambrose (42b)

TC / TB = 1.0 / [0.584 + 0.965 Σ∆TJ - (Σ∆TJ )2] Joback (42c)

Calculate PC from Lydersen, Ambrose or Joback

PC = MW / (0.34 + ∑∆PL)2 Lydersen (43a)

PC = MW / [1.01325 (φP + ∑∆PA)2] Ambrose (43b)

PC = [(0.113 + 0.0032nA - Σ∆PJ)-2]/1.01325 Joback (43c)

Calculate ω from Pitzer given TB/TC from above

ω = [ log10(1/PC) - P(0)(TB/TC) ] / P(1)(TB/TC) (44)

Estimate TC, and Iterate on Pitzer Equation using VP Data Point

TR EST = TDATA/ TC EST (45)



log10(PDATA/PC) = P(0)(TR EST) + ω· P(1)(TR EST) (46)

where: ∆TL, ∆PL: Lydersen Group contributions, see Appendix Table 1.∆TA, ∆PA: Ambrose Group contributions, see Appendix Table 2.∆TJ, ∆PJ: Joback Group contributions, see Appendix Table 4.P(0) P(1) : Tabulated functions of TR, see Appendix Table 12.

PDATA, TDATA: Vapor Pressure and Temperature data point.TC EST : Initial Estimate of TC .Expected Error The expected error when calculating TB from a

temperature/vapor pressure data point not at one atmosphere will depend on how far thatpoint is from one atmosphere. As an extreme, if the measured point is more than 100 Caway then the error in TB would be expected to be as high as in the TC estimation used inthe calculation. The error in TC will range from 0.7% to 1.5%. If the average TC is about600 K, that error would be about 4 to 9 K. The absolute error would migrate to the TBresulting in an error of 4 to 9 K in TB. If, however, the measured vapor pressure /temperature data point is closer to the calculated TB, then a lower error would beexpected.

Reid, et al.66 report an absolute error of 12.9 K (or 3.6%) for 438 compoundsusing the method of Joback. These errors do not appear high, but if TB is used for theestimation of other properties, such as TC, the error in TC will be compounded over thesmall errors indicated for TC with an experimentally determined TB with low error.

There are too many different estimation methods included in the Miller process toaccess the amount of error in the result. Perry's Handbook21 indicates that it was testedfor 25 compounds and an average error of 10% was found.

II.6 Ideal Gas Heat of Formation

The heat of formation or enthalpy of formation, as it is also known, is given hereas a point property at the temperature of 298 K for an ideal gas. The heat of formation isthe isothermal enthalpy change during the formation of the molecule from its elements attheir standard states. The value given in PREDICT is for an ideal gas, so the pressureand phase are not of concern. The property is function of temperature. That functionalityis given by the ideal heat capacity, but is not calculated in this version of PREDICT. Thetemperature of 298 K was chosen because, this is the typical standard state, manyprocess simulators require this point property.

Because this property is an ideal gas property with no intermolecular forces,there are no corresponding states correlations. The four methods given here are allgroup contribution. The first is actually a bond contribution method and the remainderare group contribution methods. The group contribution methods of Franklin56,57 andJoback65 are more accurate than the bond contribution method because they can



account for interactions of bonds within a group, rather than just the bond itself. The last,more complicated method, that of Benson49,55,67 uses the proximity of other groups aswell as the group contribution method. The method of Benson goes beyond the standardset of groups and includes organometallic groups. The organometallics include, tin, lead,chromium, zinc, titanium, vanadium, cadmium, aluminum, germanium, mercury,phosphorous, boron and silicon. The recent work by the AIChE DIPPR project 68

updated the contributions for silicon, aluminum and boron.BOND CONTRIBUTION, Heat of Formation

The bond contribution method used is that given by Benson49. This is a simplermethod than most, but gives as good a result as can be expected from such a simpleapproach.

∆ Σ∆HF HBC298° = (47)

where, ∆HBC: are Bond Contributions from Appendix Table 8.FRANKLIN, Heat of Formation

∆ Σ∆HF HF298° = (48)

where, ∆HF are Group Contributions from Appendix Table 9.JOBACK, Heat of Formation

∆ Σ∆HFo

HJ298 68 29= + . (49)

where ∆HJ are Group Contributions from Appendix Table 7BENSON, Heat of Formation

∆ Σ∆HFo

HB298 41868= / . (50)

where ∆HB are Group Contributions from Appendix Tables 11Expected Errors As is quite often the case the simplest method, here the bond

contribution, is also the least accurate. For 25 compounds tested by Reid, et al.1 theaverage error for the bond contribution method was 4.5% with three errors in the 18% to22% range. Reid et al.1 reported errors for the Benson and Franklin methods for 28 and23 compounds respectively, Reid et al.66 reported errors on the same compounds forJobacks method. These compounds encompassed all types except organometallics.The errors are summarized in the following table.

Errors for ∆HFo

298 of non-organometallic compounds



Method No. Cmpds Ave. Err. Std. Dev Max. Err. kcal/mol kcal/mol kcal/molBenson 28 0.9 2.8 2.2Franklin23 1.0 3.9 2.2Joback 28 3.4 17.0 8.1

Only the Benson method estimated the heat of formation for organometallic compounds.Error estimates for these types of compounds are found in the original publication byBenson, et al.67. The group contributions for Si, Al and B were enhanced for the DIPPRproject by Myers68. For these compound types the errors of Myers are reported.

Errors for ∆HFo

298 of organometallic compounds using the Benson methodOrganometallic Expected ErrorCompound Type kcal/molPhosphorus(P) 0.9 to 3.6Boron (B) 3.2 (max. 26.9)Tin (Sn) 0.7 to 2.8Zinc (Zn) 2.5Titanium (Ti) 2 to 3 (max.16)Vanadium (V) 2Chromium (Cr) 2Mercury (Hg) 0.9 to 2.7Silicon (Si) 2 (max. 28%)Aluminum (Al) 1.2 (max. 2.5)

II.7 Ideal Gas Free Energy of Formation

As with the ideal gas heat of formation, given earlier, the Free Energy ofFormation is also given here only as a point property at 298 K. The ideal gas free energyof formation is also calculated using contribution methods. The bond contributionmethod, by Benson49 actually calculates the entropy of formation for the ideal gas at 298K. Using this property in connection with the heat of formation at the same temperaturewill result in the free energy of formation. The other two methods given are groupcontribution methods. The methods of Van Krevelen and Chermin 59,60 and of Joback65

calculate this property directly.



BOND CONTRIBUTION, Free Energy of Formation

∆ ∆G H SF F F298 298 298298° ° °= − (51)

SF SBC298° = Σ∆ (52)

where, ∆SBC are Bond Contributions from Appendix Table 8, and ∆HF298° is calculated

from equation 48.van KREVELEN and CHERMIN, Free Energy of Formation,∆ Σ∆GF GKC298

° = (53)where,: ∆GKC are Group contributions from Appendix Table 10.JOBACK, Free Energy of Formation

∆ Σ∆GFo

GJ298 68 29 41868= +[ . ] / . (54)

where, ∆GJ: Group Contributions from Appendix Table 7.

Expected Errors The average absolute error of the Joback method, asreported by Joback65, for 43 compounds was 1.1 kcal/mol. The standard deviation of theerror was 1.6 kcal/mol. Joback also reported the error of the van Krevelen and Cherminmethod for these compounds as 3.1 kcal/mol with a standard deviation of 4.1 kcal/mol.The error for the van Krevelen and Chermin method was report by Reid et al.1 as about 5kcal/mole. Reid indicated that the bond contribution method would be expected to beeven poorer.

As with other methods for free energy, these errors are probably not acceptablefor reaction equilibrium calculations. Free energy should be determined by experimentalmethods for accurate reaction equilibrium calculations.

II.8 Vapor Pressure

Four vapor pressure methods are included, two are old methods that will predictthe properties of non-polar, "normal" fluids. The other two are more general and can beused to predict the vapor pressure of polar compounds.

Pitzer realized that earlier two parameter corresponding states correlationswould work fine for "simple fluids". That is, fluids that are spherical and have no polarforces present, such as some of the noble gases, like argon. To describe more complexmolecules that are not spherical but rather might be globular or elongated, a thirdparameter was required. This parameter, linked to the actual vapor pressure at a



reduced temperature of 0.7 is called the acentric factor. Now with three parameters, thecritical temperature, critical pressure and acentric factor a corresponding states vaporpressure model was developed to describe the vapor pressure of "normal fluids". "Normalfluids" are limited to nonpolar or slightly polar molecules. That equation and tables areused here as Pitzer's14 Vapor Pressure method.PITZER Vapor Pressure

log10PVR = P(0) + ω P(1) (55)

where, P(0) and P(1) are Tabulated functions of TR, Appendix Table 12.The following, inverse reduced temperature, interpolation equation is used for alltabulated functions,

( ) ( ) ( )[ ]( ) ( )F F

F F T T

T Tdd

= +− −

−12 1 1

2 1

1 1

1 1

/ /

/ /(56)

where, F1 and F2 are any of the tabulated functions at temperatures T1 and T2,respectively, and Fd is that function at the desired temperature Td.

Expected Errors Pitzer in his original article claims that the error using thiscorrelation will be less than 2%, at temperatures at or above the normal boiling point. Atlower temperatures expect the error to increase to about 5%. However, great careshould be taken with that quote. First of all that error assumes good values for criticalpressure, critical temperature and the acentric factor. The final results of this calculationwill depend greatly on these values. Secondly, the correlation should be used only oncompounds meeting the definition of a "normal fluid". If the compound is not a "normalfluid" the expected error will be higher.

Temperature Limitations As pointed out earlier the temperature limitation forthe original Pitzer correlation is 0.56 to 1.0 reduced temperature. Carruth andKobayashi17 extended the range of the tabulated functions down to a reducedtemperature of 0.25. These extended correlations are used in this program. Above areduced temperature of 0.56 the tables of Carruth and Kobayashi are identical to that ofPitzer.

The program will not allow the calculation and reporting of any vapor pressuresby this method outside the allowable reduced temperature range of 0.25 to 1.00.

Riedel16 Shortly before Pitzer developed the acentric factor to account for theextra complexity of "normal fluids" Riedel defined a similar factor, the Riedel Factor, αC.Please see equations 21 & 22 for the definition of the Riedel Factor. Using a generalcorrelating equation, that has the proper character to predict the S shape of the vapor



pressure curve, the Riedel Factor can be used to calculate the vapor pressure.Like the Pitzer correlation this is a three parameter equation and will accurately

predict only the vapor pressure of simple or "normal fluids".RIEDEL Vapor Pressure

log ''

' log '10 106P A

BT

C T D TVRR

R R= + + + (57)

Q = 0.0364 (3.7582 -αC) (58)

A’ = - 35 Q (59)

B’ = 36 Q (60)

C’ = 96.7 Q + αC (61)

D’ = - Q (62)

Expected Error The error to be expected from this correlation will be similar tothat for the Pitzer correlation or a little higher. Carruth and Kobayashi17 reported an errorof 10.9% for this method in their study of various vapor pressure prediction methods.

Temperature Limitations This correlation will predict the vapor pressure fromthe triple point (approximately the melting point) to the critical point. However, becausethe triple point is so rarely known, no lower temperature limit is imposed by the program.The upper temperature is limited to the critical temperature, as that must be known touse the correlation.GOMEZ-NIETO-THODOS 22,23,24 Vapor Pressure This method is based on the sameoriginal correlation proposed by Riedel16 to describe the S shape of the vapor pressurecurve when represented in the form ln(P) vs. T. In the following equation,

ln( ) **

*P AB

TC T

Rm R= + + 7 (63)



The parameters A*, B*, and C* are fit using experimental data to the correlatingparameter, s, given by the following equation,

sT P

T TB C

C B

=−

ln( )(64)

The parameters A*, B* and C* were successfully fit to the data23 of various nonpolarorganic and inorganic compounds with a function of the s parameter. It should be notedthat this follows the earlier work of Pitzer that indicates, in corresponding states theorythat 3 parameters are needed to model nonpolar properties, in this case TB, TC and PCare used.

For polar compounds Gomez and Thodos24 found that not only would a differentformulation of the A*, B* and C* parameters be required, but that compounds thatexhibited hydrogen bonding would need a fourth parameter. The result is a correlation,still with the s parameter only, for polar compounds that are not hydrogen bonded and adifferent correlation for compounds exhibiting hydrogen bonding using the s parameterplus the molecular weight.

The equations used here for the Gomez-Nieto and Thodos vapor pressuremethod are as follows (eq. 63 is rearranged to eq. 65),

( )[ ] [ ]ln * / *P B T C TVR Rm

R= − + −1 1 17 (65)

sT P

T TB C

C B

=−

ln( )(66)

( )a

T

TBR

BR

=−

−

1 1

1 7

/(67)

( )b

T

T

BRm

BR

=−

−

1 1

1 7

/(68)



Non-Polar

Bs s s

* ..

exp( . )

.

exp( . / ). .= − − +4 267022179

0 03848

3 8126

2272 442 5 2 5 2 (69)

C* = a s + b B* (70)

m ee

ss= −0 78425

8 52170 0893150 74826.... (71)

Polar, but not Hydrogen Bonded

BC a s

b*

*=

−(72)

C e x TC* . .=−

0 08594 7 462 10 4

(73)

m TC= 0 466 0 166. . (74)

Polar, Hydrogen Bonded

BC a s

b*

*=

−(75)

CMW

e x MW TC*. .=

−2 464 9 8 10 6

(76)

m MW TC= 0 0052 0 29 0 72. . . (77)

Expected Errors The only data regarding errors on this method are from theoriginal investigators. They found an average error for the nonpolar correlation of 0.97%for 6290 data points of 113 different hydrocarbon and inorganic compounds. The polarcorrelation was fit to the data of 25 polar compounds (1343 data points) with an averageerror of 1.44%. The authors tried to use data that covered the entire range from thetriple point to the critical point if at all possible. Predicted properties for compounds notincluded in the original study will probably have higher errors, and will depend greatly on



the quality of the input parameters, TB, TC, PC and MW.Temperature Limitations This correlation is good from the triple point

(approximately the melting point) to the critical point. The triple point or even the meltingpoint is usually not known for a compound with limited data available, so the programdoes not impose a lower temperature limit. The critical temperature must be known forthe estimation and is used as an upper limit. The program will not calculate the propertyabove the TC.

Halm and Stiel15 provide the fourth and final vapor pressure method offered.Halm and Stiel introduce a fourth parameter to the corresponding states theory of Pitzer.With this fourth parameter, the polarity factor, the Halm-Stiel vapor pressure equationhas the ability to predict the properties of polar compounds. As stated earlier, polarcompounds have at least one more force, usually a dipole moment, that nonpolarcompounds do not. This fourth parameter allows the corresponding states methods tomodel this additional force. There are some limitations to a simple additional parameterbecause the polar forces it is describing can become very complex. Therefore, thismodel will have difficulty with complex polar molecules, but will still offer advantages overthe three parameter relationship. Again, as was pointed out earlier, this does requiremore data, the polarity factor in addition to the others.

It should be pointed out that the polar effects are only felt at lower reducedtemperatures, below 0.7 reduced temperature. Above this temperature the correlation isidentical to that of Pitzer.

The polarity factor was described earlier as to it's definition and calculation.HALM & STIEL, Vapor Pressure

log10PVR = - P(0) - ω P(1) + x P(2) (78)

where, P(0), P(1) and P(2) are Tabulated functions of TR, see Appendix Table 13.Expected Errors Halm and Stiel15 in their original work state that the worst

error was 4.5% with water. This is a very complex polar compound, so the error onsimpler compounds could be expected to be less.

Temperature Limitations The tabulated functions are given for reducedtemperatures from 0.44 to 1.00. The program will not attempt to calculate any vaporpressures using this method outside of that temperature range.

II.9 Heat of Vaporization

Reid et al.1 points out that there are three ways of calculating the heat of vaporization.First, the heat of vaporization is related to the vapor pressure by the Clausisus Clapeyronequation. So if vapor pressure has been established, the heat of vaporization can becalculated from it. Second, are the methods that are developed from corresponding



states theory, following the Clausisus Clapeyron equation but not requiring that thedifferences in the liquid and vapor saturated densities be calculated. Finally the heat ofvaporization can be predicted at the normal boiling point and scaled to othertemperatures using the Watson25 equation. Only the last two methods are used here, asthey don't require the saturated vapor density (not calculated in this program).

Given here are three methods of calculating the heat of vaporization. First,Pitzer's14, which is related to the earlier described vapor pressure relationship. Also aheat of vaporization model developed by Halm and Stiel15 in the same manner as theirvapor pressure model. The third model, Watson, allows scaling to other temperatures ofa heat of vaporization given at one temperature. The heat of vaporization is commonlytabulated at the normal boiling point. Using that one heat of vaporization andtemperature point, others can be calculated. Additionally, three methods, Riedel61,Chen62 and Joback65 are given for the calculation of the heat of vaporization at thenormal boiling point. The first two of these methods (Riedel and Chen) use only thecritical temperature, pressure and normal boiling point as parameters, Joback is a groupcontribution method. All three can be used with the Watson equation.

Pitzer Pitzer used the Clausisus Clapeyron equation in combination with hisvapor pressure and compressibility factor (volume) equations to develop a function (notrequiring the direct calculation of either) for the heat of vaporization. The resultingequation will have similar properties to the vapor pressure, most importantly it is limitedto "normal fluids".PITZER, Heat of Vaporization

HVAP / T = S(0) + ω S(1) (79)

where, S(0) and S(1) are Tabulated functions of TR, see Appendix Table 14.Expected Error At temperatures between the normal boiling point and the

critical temperature errors can be expected to be around 2%, again depending on thequality of the critical constants and the acentric factor. At lower temperatures the errorwill increase as it did with the vapor pressure equations. A 5% error at lowertemperatures is probable.

Temperature Limitations The tabulated functions were defined by Pitzer overa reduced temperature range of 0.56 to 1.00. This was later extended by Carruth andKobayashi17 to a reduced temperature of 0.30. This extension is used in this program sothe effective temperature range for calculation is 0.30 < TR < 1.0.

Halm and Stiel15 Again this heat of vaporization technique was developed froma related vapor pressure equation, this time the Halm-Stiel. The heat of vaporizationexpression like the vapor pressure uses the fourth parameter, the polarity factor, allowingit to predict the heat of vaporization of polar compounds.HALM & STIEL, Heat of Vaporization



HVAP / T = S(0) + ω S(1) - x S(2) (80)

where, S(0), S(1) and S(2) are Tabulated functions of TR, see Appendix Table 15.Expected Error Halm and Stiel15 found that the error for polar compounds at a

temperature of 0.6 to be <1.0%. The error for nonpolar compounds should be the sameas Pitzer's, as this relationship reduces to Pitzer's when x = 0.

Temperature Limitation Due to a lack of good data the original investigatorsonly tabulated the S(2) function from a reduced temperature of 0.56 to TR = 0.72. Theprogram will not allow calculations outside of this region.

Watson25 This method models the temperature variation of the heat ofvaporization, using one data point as a reference. Several authors have studied thisrelationship63,64 most agreeing that the power, n, while it does vary somewhat, should be0.38. Silverberg and Wenzel64 found that for 44 substances the average value of n to be0.378.

H HT

TVAP VAPR

R

n

REF

REF

=−

−

1

1(81)

where, n = 0.38Expected Error If the reference heat of vaporization is good the errors

expected should be in the range of those for Pitzer's correlation. The errors will be leastbetween the reference point and the critical point, and increasing at lower temperatures.

Temperature Limitation The temperature is limited physically to the criticaltemperature on the high end. The program does not impose a lower temperaturelimitation, but the user should use caution at temperature significantly lower than thereference point.

Riedel HVAP @ TB Riedel61 uses a modification of the Clapeyron equation,evaluated at the HVAP @ TB.

( )( )H T R T T

P

TVAP B C BR

C

BRREF

@ .ln

.=

−

−

10931

0 93(82)

where, R = 1.987 cal/gmole KThe errors for this calculation are given by Reid, et al. 1 to be about 1% to 2%, with someexcursions to 5%.

Chen HVAP @ TB Chen's62 method uses a corresponding states approach thateliminates the acentric factor. When this is applied at the normal boiling point the



following correlation is the result.

( )H T R T T

T P

TVAP B C BRBR C

BR

@. . . ln

.=

− +

−

3 978 3 938 155

107(83)

where, R = 1.987 cal/gmole KThe errors will be similar to those of the Riedel correlation.

Joback HVAP @ TB Joback’s65 method uses a group contribution method, basedon the same set of groups by Joback for various other point property calculations.

H TVAP B HVJ@ = +3657 Σ∆ (84)

where, ∆HVJ are Bond Contributions from Appendix Table 7.The expected errors for this method are slightly higher than for Riedel or Chen.

With errors generally between 2 and 3%. However, this method is not dependent onother properties, such as critical properties, as are the previous two methods. Therefore,the errors given for Riedel and Chen could be higher if the supporting properties are inerror. This method is recommended if there is question about the error in supportingproperties.

II.10 Liquid Density (Saturated)

Four methods for the estimation of saturated liquid density are offered here. Twoof these methods (Gunn and Yamada and Rackett) are primarily for nonpolar or "slightly"polar compounds. The other two (Halm and Stiel and Bhirud) were specifically designedfor polar compounds, each with it's own unique fourth parameter.

Gunn and Yamada26 This corresponding states method was selected becauseof its general applicability, high accuracy and wide temperature application. As will bestated later, the error for many different types of compounds is very low.

Another important feature of this method is it's ability to use a reference density.Quite often a liquid density near ambient temperature will be known, using this to tiedown the equation will greatly decrease the error. Without a reference the criticalpressure is incorporated to calculate a pseudo reference state, this also works quite well.GUNN & YAMADA, Liquid Density

( )110

ρωΓ= −V VSC R

( ) (85)



( )VR T

PSCC

C

= −0 2970 0 0967. . ω (86)

( ) ( )V

V T TSC

REF

R R RREF REF

=−

1

10

/

@ @( )

ρ

ωΓ(87)

V T T T TR R R R R( ) . . . . .0 2 3 40 33593 0 33953 151941 2 02512 111422= − + − + (88)

0.2 ≤ TR ≤ 0.8

( ) ( ) ( )( )

V T T T

TR R R R

R

( ) /. . log .

.

0 1 210

210 13 1 1 0 50879 1

0 91534 1

= + − − − − −

−(89)

0.8 < TR < 1.0

Γ = − −0 29607 0 09045 0 04843 2. . .T TR R (90)

Expected Errors Gunn and Yamada investigated 32 different compoundsfinding the average error, as compared to this correlation to be < 0.5% with maximumdeviations < 2.2% (excepting highly polar substances). At temperatures below TR = 0.8the maximum deviations were usually < 0.5%. The correlation is a three parametercorresponding states relationship and would not be expected to perform well for highlypolar substances.

As pointed out many times before the estimate of error depends on the quality ofthe inputs. In this case, if a reference density is used that will tend to determine the errorof the prediction.

Temperature Limitations The temperature range of this correlation extendsfrom a reduced temperature of 0.20 to just below the critical temperature. This shouldeasily cover the most needed areas. The program will not calculate any properties withthis method outside of this range, nor except a reference point outside of this range.

Rackett19 This correlation is extremely simple and was originally developedusing only the three critical properties, TC, PC and VC. Even in this form the correlation isvery accurate. Spencer and Danner27 later found that if a reference saturated liquiddensity was used instead of the critical volume that the accuracy could be furtherimproved. A later study by Spencer and Adler28 compared this method with manycompounds and found that for all, except very highly associated (polar) compounds, thiswas the superior method.

As with the Gunn and Yamada correlation the Rackett works best with a



reference data point. However, if a data point is not available the program will use thecritical volume and still give a reasonable result.RACKETT, Liquid Density

( )1 1 12 7

ρ=

+ −

R T

PZC

CRA

TR/

(91)

ZP VR TRA

C C

C= , without a reference data point (92)

( )( )

ln ln/ZT

P

R TRA

R

C

REF CREF

=+ −

1

1 12 7 ρ

, with a reference data point (93)

Expected Error Spencer and Adler28 studied the estimation of saturated liquiddensity data on 75 hydrocarbons, 71 other organics and 19 inorganics by this method.Their finding were; errors of less than 0.5% for all classes of compounds except organicacids and alcohols. Errors for these compounds were reported to be between 1% and1.5%. This is the same result found earlier by Spencer and Danner and would beexpected because this is only a three parameter equation. A fourth parameter is reallyneeded to predict the density of highly polar compounds.

Temperature Limitations This correlation is good from the triple point to thecritical. However, because the triple point is not usually known for compounds where thismethod would be used, no lower temperature limit is imposed by the program. The useris only cautioned not to over extend the calculation.

The upper temperature limit is the critical temperature and the program will notcalculate any properties above that point nor except a reference point from thisunrealistic region.

Halm and Stiel13 This method is an extension of the Pitzer14 correlation. ThePitzer density method was limited, as is the Pitzer vapor pressure correlation, to nonpolarcompounds. The Pitzer method is not included as other nonpolar expressions (Gunn andYamada or Rackett) are superior. However, the Halm-Stiel correlation with it's fourthparameter, x, is noteworthy. By adding a fourth parameter to the original threeparameter corresponding states expression this method fairly well predicts polarsaturated liquid densities.

This method can be used for all types of polar compounds, with caution beingexercised only in regard to highly associated compounds that even four parameterscannot describe.



The fourth parameter used is the polarity parameter, x, defined by Halm andStiel15 in their vapor pressure and heat of vaporization equations. Currently the programallows direct entry of this parameter, or it can be calculated from vapor pressure or heatof vaporization data. At this time there is no provision to calculate this parameter fromliquid density data.HALM & STIEL, Liquid Density

[ ]1 0 1 2 2 3 2 4 5

ρω ω ω= + + + + +

R T

PV V x V V x V x VC

C

( ) ( ) ( ) ( ) ( ) ( ) (94)

where, V(0), V(1), V(2), V(3), V(4) and V(5) are Tabulated functions of TR, see AppendixTable 16.

Expected Error Joffe and Zudkevitch29 in their study of polar liquid densitycorrelations found that the error of this method was 1.9% for 12 polar compounds attemperatures less than TR = 0.85. For 16 polar compounds with data at temperaturesgreater than TR = 0.85 the average error was 3.8%. The errors varied somewhat, aswould be expected with the wide variety of different types of polar compounds.

Temperature Limitations The tabulated temperature functions weredeveloped for temperatures from TR = 0.56 to the critical temperature. The program willnot calculate properties outside of this range.

Bhirud30,31 This method actually consists of two correlations, one for "normal"fluids and one for polar compounds. The object of the correlation30 for nonpolar fluids isto have a correlation that gives high accuracy (comparable to the Gunn and Yamada orRackett) with only the "Pitzer" three parameters, TC, PC and ω, and not requiring areference density. As a result this correlation looks very much like Pitzer's but has betteraccuracy.

The Bhirud polar31 correlation uses the concept of a fourth parameter, as iscommon. However, different from Halm and Stiel Bhirud's fourth parameter is developedfrom liquid density, which seems to give this correlation an edge. Granted the Halm-Stielpolarity parameter, x, could be calculated from liquid density data, but it must then not beused in other correlations, such as vapor pressure. As would be expected the form ofthis correlation resembles that of Halm and Stiel.Bhirud, Liquid Density

ρ =P

UR TC

C

(95)

NonPolar



ln( ) ( ) ( )U U UNP NP= +0 1ω (96)

where, U andUNP NP( ) ( )0 1 are Tabulated functions of TR, see Appendix Table 17.

Polar

ln( ) ( ) ( ) ( )U U U UP NP P= + +0 1 2ω ψ (97)

where, U U andUP NP P( ) ( ) ( ),0 1 2 are Tabulated functions of TR, see Appendix Table 17.

ψω

=− −ln( ) ( ) ( )

( )

U U U

U

REF P REF NP REF

P REF

0 1

2 (98)

UP

R TREFC

REF C

=ρ

(99)

where, U U andUP NP P( ) ( ) ( ),0 0 2 are Tabulated functions of TR, see Appendix Table 17.

As indicated above tabulated functions were used for both correlations. Howeverthe original Bhirud also gives the following analytical functions that might be useful for aquick calculation.

U T T T T

T T

NP R R R R

R R

( ) . . . . .

. .

0 2 3 4

5 6

139644 24076 102615 255719 355895

256671 751088

= − + − + −

+ (100)

U T T T T

T T

NP R R R R

R R

( ) . . . . .

. .

1 2 3 4

5 6

134412 1357437 533380 1091435 123143

728 227 176737

= − + − + −

+(101)

U T T T T

T T

P R R R R

R R

( ) . . . . .

. .

0 2 3 4

5 6

040062 80006 493780 1706616 2876989

2325608 7303299

= − − + − + −

+(102)

U T T T T

T for T

P R R R R

R R

( ) . / . / . / . /

. / , .

2 2 3 4

5

330929 411794 237746 0628621

0062072 082

= − + − +

<(103)



U for TP R( ) . , .2 10 0 82= ≥ (104)

Expected Error The original author examined the error in the prediction ofliquid densities of 24 nonpolar compounds using equation 95. He found an average errorof ≈0.8%. He also predicted the same data using the Gunn and Yamada correlation andfound that equation to give an error of ≈ 1.1%. This would indicate that for nonpolarcompounds this formulation is a little better than the Gunn and Yamada and does notrequire a reference data point.

Again the original author gives the average error of data from 42 polarcompounds predicted by equation 81 to be ≈ 0.5%. However, it appears that the polarparameter, ψ was fit by regression technique to the liquid density data that was thenused in the error analysis. This is a little different situation than is normally present inestimation and in this program. In this program only one liquid density reference pointwill be used to calculate the polar parameter, ψ. Therefore, the error expected from thismethod will be somewhat higher.

II.11 Surface Tension

Surface tension is generally predicted either by the well known "parachor"method or by corresponding states methods. The "parachor" method requires thedifference between the saturated liquid and vapor densities. The corresponding statesmethods have similar accuracy, while not requiring any densities.

Two corresponding states methods are included here. The first, that of Brockand Bird32 used an idea originally proposed by Van derWaals33 to model surface tensionof nonpolar compounds. The method uses the Riedel parameter as the third factor in thecorresponding states theory. The Riedel factor can either be entered, calculated as anormal point property or estimated using a reference surface tension. If the Riedel factoris estimated by a surface tension data point, it will not be stored as a point property foruse anywhere else in the program.BROCK & BIRD, Surface Tension

σ α= − −P T TC C C R2 3 1 3 11 90 133 0 281 1/ / /( . . ) ( ) (105)

ασ

CREF

C C RP T TREF

=−

+

2 3 1 3 11 91

0 281 0 133/ / /( ). / . (106)



Expected Error Brock & Bird found a correlation fit of data on eighty foursubstances of 3%. This type of error can be expected for nonpolar compounds, if thecritical temperature and pressure are well known. The use of a reference data point willhelp assure this accuracy.

Temperature Limitation No temperature limitation is expressed by the originalauthors. Obviously the surface tension is not defined at temperatures greater than thecritical, so the program will not calculate any points in this region.

Hakim et al.34 the second method for surface tension included is an extension ofthe Brock and Bird equation. Hakim has extended the earlier relationship to include polarcompounds. This extension uses the same polarity factor of Halm and Stiel15 that wasseen earlier. The polarity factor like the acentric factor must be entered or calculatedfrom vapor pressure or heat of vaporization data.HAKIM ET AL., Surface Tension

[ ]= −P T Q TC C P RM2 3 1 3 1 0 4/ / ( ) / . (107)

Q x x xP = + − − − +0 1574 0 359 1769 13 69 0 510 12982 2. . . . . .ω ω ω (108)

M x x x= + − − − +1210 0 535 14 61 32 07 1656 22 032 2. . . . . .ω ω ω (109)

Expected Error The error for this method should be similar to that given for theBrock and Bird method. Additionally this method will also give similar results for polarcompounds.

Temperature Limitations As for the Brock and Bird the only temperaturelimitation imposed on the method is the critical temperature, above which the surfacetension has no meaning. The program will not calculate the surface tension above thecritical temperature.

II.12 Liquid Viscosity

Prediction of the liquid viscosity is very difficult. None of the current methods arevery accurate. The most common methods are group contribution methods, none ofwhich stand out as being of high accuracy.

Morris35 This group contribution method is generally applicable to many types oforganics and only requires the critical temperature as an additional parameter.Unfortunately this method is limited to temperatures less than 0.8 times the criticaltemperature. The method incorporates a pseudocritical viscosity which is dependent onthe compound class. This value is then scaled to the proper temperature using a group



contribution term and the reduced temperature. Most compound families and groups arerepresented.MORRIS, Liquid Viscosity

log101

1µµ

L

R

JT+ = −

(110)

( )JM

= +0 5771 2

./

Σ∆ µ (111)

where, ∆ µM: Group Contributions from Appendix Table 18B.

µ+ : Compound class group contribution from Appendix Table 18A.Expected Error The original author reports testing this method with data from

70 compounds with an average error of 12%. Reid et al.1 found that the errors varywidely and is higher for more complex molecules.

Temperature Limitations This method is limited to temperatures of TR < 0.8.The program will not allow calculation of properties at temperatures higher than this.

Letsou and Stiel For higher temperatures (TR > 0.76) the corresponding statesmethod of Letsou and Stiel36 is recommended. This method is based on the theory forlow pressure gases that is well established and applicable to liquids at high temperatures.This is the best method for estimating liquid viscosity. It's major limitation is that it is onlygood at high temperatures.LETSOU & STIEL, Liquid Viscosity

µµ ξ ω µ ξ

ξLL L=

+( ) ( )( ) ( )0 1

(112)

ξ =T

MW PC

C

1 6

1 2 2 3

/

/ / (113)

( ) . . .( )µ ξL R RT T0 20 015174 0 02135 0 0075= − + (114)

( ) . . .( )µ ξL R RT T1 20 042552 0 07674 0 0340= − + (115)

Expected Error The original authors reported a very low error of only about 3%for 14 compounds tested. These compounds were hydrocarbons, nitrogen, argon and



carbon dioxide. Higher errors can be expected with more complex compounds. Theyalso found that the errors increased as the critical temperature was approached.

Temperature Limitations This method is restricted to temperatures in therange, 0.76 < TR < 0.98. The program will not allow calculations outside of this range.

Gambill Another method of estimating the liquid viscosity is to fit a minimum ofdata to a temperature correlating equation. A very common equation of this type for liquidviscosity is the Andrade correlation37,

µLTe= Ω Λ( / ) (116)

This equation requires at least two experimental liquid viscosity/temperaturedata points to allow determination of the parameters. Usually if one is attempting topredict liquid viscosity, two data points will not be available. However, if only one datapoint is available the correlation of Gambill38 can be used. Originally published as agraphical method it was converted to an analytical form by VanSickle39. This method isbased on the empirical fact that the temperature dependence of the liquid viscosity isdependent on the value of the viscosity. That is, a viscosity of 1 cp at 100° C for onecompound will have the same relative temperature viscosity change (around 100° C) asanother compound that had 1 cp viscosity at 200° C would have around 200° C. Thetemperature variation is very similar to that of the Andrade correlation.GAMBILL, Liquid Viscosity

log ..

.10 2 32417758 56

53 698µ

υL T= − +

+ +(117)

υµ

=− − +

+

TREF

LREF

53 698 758 56

2 3241710

. .

log .(118)

Expected Errors Gambill claims that the correlation estimates the liquidviscosity within 20%. This author has found lower error when the correlation was usedwith small nonpolar compounds at moderate temperatures. The correlation should notbe used with highly polar fluids, emulsions, suspensions or highly polymeric materials.

Temperature Limitations No temperature limitations are enforced on thiscorrelation by the program except an upper limit at 0.8 times the critical point. Even thatrequirement will not be enforced if the critical temperature was not entered for someother property calculation. The expression really should not be used much above thecompound's normal boiling point as errors will be come quite high.

Joback65 This is a simple method that relates the log of viscosity to the



inverse of temperature. The slope and intercept are determined from groupcontributions. The set of groups are not as complete as the set Joback uses for otherpoint property calculations.

ln [( . ) / ( . )]L

MWa T b

J J= − + −Σ∆ Σ∆597 82 4 294 (119)

where ∆ ∆a and bJ J

are group contributions from Appendix Table 19.

Expected Errors In a comparison by Joback65 this method shows an averageerror of 18% with a standard deviation of 20% for 36 compounds at 3 to 5 differenttemperatures each. This compares with an average error using the Morris method aboveof 15% (standard deviation 15%) for the same compounds. This method has the singularadvantage of not requiring the critical temperature, as the Morris method does.

Temperature Limitations No temperature limitations are specified for thismethod other than as for all liquid property, the temperature must be less than thecritical.

II.13 Gas Viscosity

Gas viscosity can be described quite well by statistical mechanics using variousintermolecular force models. Several prediction models for this property are based onthese methods. However, in this program only corresponding states methods will beincluded. These methods are generally more applicable to the more complex organicmolecules of general chemical engineering use.

Thodos and Stiel The first of those methods is actually the group of methodsof Thodos and Stiel40 and Yoon and Thodos41. Their methods appear to be superior toearlier methods and work for a large number of compounds. As with earliercorresponding states methods, three parameter equations are satisfactory for nonpolarcompounds. In this case critical temperature, critical pressure and molecular weight areused. To extend the correlation to polar compounds the additional parameter criticalcompressibility is used.THODOS ET AL., Gas ViscosityNonPolar

µξG

RT TT e eR R

=− + +− −4 610 4 04 194 0 10 618 0 449 4 058. . . .. . .

(120)

ξ, see equation 113



Polar Hydrogen-Bonded

µξG

R CT Z=

− −( . . ) /0 755 0 055 5 4

(121)

Polar, non-Hydrogen-Bonded

µξG

R CT Z=

− −( . . ) / /190 0 29 4 5 2 3

(122)

Expected Error Yoon and Thodos41 developed the nonpolar correlation atnormal pressures using fifty different compounds. These included monatomic, diatomicand polyatomic substances. The average deviation was less than 1.75%.

Stiel and Thodos40 compared 129 experimental points of eleven differentcompounds with hydrogen bonding and found an average deviation of 1.47%. Using 197data points of compounds without hydrogen bonding the average deviation was 2.59%.

As always the error will depend on the quality of the input parameters.Temperature Limitations Being a gas property there is no inherent

temperature limitation, and the program allows calculation of this property at anytemperature for the nonpolar correlation. The polar correlation is limited to temperaturesbelow two times the critical and the hydrogen bonded correlation is bounded at TR = 2.5.The user should take care that the predictions from this method are only used atmoderate pressures, up to about two atmospheres. Pressures higher than that will beginto influence the results.

Reichenberg42 The second method presented here is a corresponding statesmethod with a group contribution term included. For low pressure gas viscosity thismethod is good for both polar and nonpolar gases, with a wide variety of groupcontributions available.REICHENBERG, Gas Viscosity

( )GR

R R

a T

T T=

+ −

*

. ( )/

1 0 36 11 6 (123)

aMW TC

R

*/

=1 2

Σ∆ µ

(124)



where, ∆ µR: Group Contributions from Appendix Table 20.

II.14 Liquid Heat Capacity

Liquid heat capacity is not a very strong function of temperature and as a result itis very easy to predict with reasonable error. There are two common liquid heatcapacities, the first CPL is the enthalpy change with temperature at constant pressure.Another common value, CσL, is the variation in enthalpy of a saturated liquid withtemperature. These two quantities can be assumed equal at temperatures less than TR= 0.8. At temperatures above TR = 0.8 the following relation relates the two,

C C R ePL LT TR R− = + − − +( ) . ( . . . )1 0 35 0 7074 31014 34 361 2

(125)

For a ω value of 0.5 this difference is 0.03 cal/gmole K at TR = 0.8 and 2.5 cal/gmole Kat TR = 0.95. Clearly not a problem at low temperature and only a few percentagedifference at high temperatures. The Yuan and Stiel correlation calculates CσL, while theother two methods calculate CPL.

All of the corresponding states methods require that the ideal gas heat capacitybe known at every temperature. This is not a problem here as this program includesgood ideal gas heat capacity methods. The user also has the option of entering apolynomial expression for the ideal gas heat capacity if known.

Included in this program are two corresponding states routines, one for polar ornonpolar compounds and one only for nonpolar compounds. The corresponding statesmethods are generally more applicable but they also require the ideal gas heat capacityand critical properties. Therefore, a group contribution method is also included for use ifgood critical properties or other inputs are not available.

Bondi The first method selected for use here is that of Bondi43 and Rowlinson44.As mentioned earlier this three parameter corresponding states method calculates CPL.This method gives good results, but is only applicable to nonpolar compounds.BONDI & ROWLINSON, Liquid Heat Capacity

C C RT

T

T TPL PR

R

R R

− = +−

+ +−

+−

° 2 560 436

12 91

4 28 1 0 296

1

1 3

..

.. ( ) .

( )

/

ω (126)

Expected Error Reid et al.1 have indicated that based on a large data set theerror should be between 5% and 10%. The correlation is not good for polar compoundsat low temperatures.



Temperature Limitations Reid and San Jose45 recommend that thiscorrelation not be used below a temperature of TR = 0.4 and like all liquid properties, theyare not defined at temperatures higher than the critical, and therefore the program willnot allow calculations in this area.

Yuan and Stiel46 This method predicts the CσL liquid heat capacity for polar ornonpolar compounds using a corresponding states method. It utilizes the Halm and Stielpolarity factor as a fourth parameter and while it is possible to calculate this parameterfrom liquid heat capacity data it must be entered or calculated from vapor pressure data.It is more common to have vapor pressure data available than liquid heat capacity data.

There are actually two different correlations, one for polar compounds andanother for nonpolar.YUAN & STIEL, Liquid Heat CapacityNonpolar

C C C CL Pσ ω− = +° ( ) ( )0 1 (127)

where, C(0) and C(1) are Tabulated functions of TR, see Appendix Table 22.Polar

C C C C x C x C C x CL PP P P P P P

σ ω ω ω− = + + + + +° ( ) ( ) ( ) ( ) ( ) ( )0 1 2 2 3 2 4 5 (128)

where, C(0P) , C(1P) , C(2P) , C(3P) , C(4P) and C(5P) are Tabulated functions of TR, seeAppendix Table 22.

Expected Error Reid et al.1 confirm the original authors claim that this methodgives errors usually less than 5%.

Temperature Limitations The tabulated functions for the nonpolar correlationare given from TR = 0.40 to TR = 0.96. For the polar correlation the functions aretabulated from TR = 0.44 to TR = 0.94. The program will not calculate properties outsideof this limitation. A further temperature limitation is exerted on this correlation by it'sdependence on the Ideal Gas Heat Capacity. The correlations given for that propertyhave a lower limit of 275 K, if this is higher than the above temperature limits it willoverride.

Missenard47 This group contribution method includes both polar and nonpolarcompounds and can be used over a range of temperatures. It is limited to a maximumtemperature of TR = 0.8 but avoids the need for any of the corresponding statesproperties.MISSENARD, Liquid Heat Capacity



C a b T c TPL CM CM CM= + +Σ ∆ Σ ∆ Σ ∆ 2 (129)

where, ∆ ∆ ∆a b and cCM CM CM, are Group Contributions from Appendix Table 21.Expected Error Reid et al.1 claim that the errors for this method rarely exceed

5%.Temperature Limitations This method is limited to a maximum temperature of

TR = 0.8. There is no lower temperature limit imposed by the program.

II.15 Ideal Gas Heat Capacity

Real gas heat capacity can be represented as the ideal gas heat capacity plus aresidual quantity. In the case of gases at low pressures, far from their critical point theresidual quantity will be small. In this program a method is provided for the predictiononly of the ideal gas heat capacity. For many engineering applications this will servesatisfactorily as the gas heat capacity.

There are several good group contribution methods available for ideal gas heatcapacity. The three chosen here are that of Rihani and Doraiswamy48, Benson49,55,67 ,and Joback65. In addition a method by Harrison and Seaton69 is included. This methoduses only atomic contributions and can accommodate any compound.

The Rihani and Doraiswamy and Joback methods are group contributionmethods that result in a cubic equation in temperature. That is, groups contributions aresummed-up for each coefficient in the equation. The other two methods sum up groupsor atomic contributions and determine the ideal gas heat capacity at specifictemperatures. In PREDICT these specific temperature-heat capacity values arereported, but they are also regressed to a cubic equation in temperature. A table oftemperatures and properties as requested by the user for all temperature correlatedproperties is then calculated and displayed. This equation is then saved in memory forlater use by other methods, such as liquid heat capacity and gas thermal conductivity,that require calculation of the ideal gas heat capacity.RIHANI & DORAISWAMY, Ideal Gas Heat Capacity

C a b T c T d TP CR CR CR CR° = + + +Σ ∆ Σ ∆ Σ ∆ Σ ∆2 3 (130)

where, ∆ ∆ ∆ ∆a b c and dCR CR CR CR, , are group contributions from Appendix Table 23.Expected Errors The original authors found that for a wide variety of organic

compounds the errors were about 3% at 300 K and 2% at 1500 K. Joback65 tested 28compounds and indicates the error for this method is 3.2% with a standard deviation of4.6% for the same compounds.

Temperature Limitations The error is expected to increase at temperatures



below 300 K. Therefore the correlation has been cut off at 275 K and the program willnot calculate properties below that point.BENSON, Ideal Gas Heat Capacity

Benson et al’s49,55,67 method for ideal gas heat capacity is a group contributionmethod, but deviates from most other similar method as it takes into account not only themolecular groups of the molecule but also the group's next nearest neighbor. Molecularinfluences beyond the next nearest neighbor were shown by Benson to be insignificant.The Benson method is the most accurate of all tested by Reid et al.66. It usescontributions in the following areas,

Hydrocarbon Groups & Ring CorrectionsOxygen Containing GroupsStrain and Ring Corrections for Oxygen-containing CompoundsNitrogen Groups & Ring CorrectionsHalogen Groups & Ring CorrectionsOrganosulfur Groups & Ring Corrections

Benson method does not generate heat capacity as a continuous function oftemperature, but tabulates these group contributions for specific temperatures, 300, 400,500, 600, 800 and 1000 K. The fundamental equation used by the Benson method is,

C TT

Po CB( )

( )

.=

Σ∆

41868(131)

where, ∆CB(T) are group contributions at specific temperatures, see Appendix 25.The individual heat capacity vs. temperature points calculated from this group

contribution method are then automatically regressed to the following polynomial intemperature,

C A B T C T D TP C C C CP P P P

° = + + +2 3 (132)

where, A B C and DC C C CP P P P, , are regression coefficients.

Expected Errors - Joback65 in his study of Ideal Gas Heat Capacity showedthe average error of the Benson method to be 1.1% with a standard deviation of 1.6% for28 compounds compared. In the original work by Benson et al.67 they identified absoluteerrors associated with some classes of compounds. They found the following errors forheat capacities at 300 and 800 K.

Benson Ideal Gas Heat Capacity ErrorsCompound Class Number of Compounds Error (cal/mol K)



Alkane 13 0.1Alkene 22 0.4Alkyne 7 0.1Aromatic 28 0.3Ring Compounds 24 0.6Alcohols & Phenols 10 0.2Aldehydes & Ketones 6 0.1Haloalkanes 22 0.2Haloalkenes & alkynes 32 0.1Sulfur containing 38 0.3

Temperature Limitations Benson calculates the heat capacity at specifictemperatures from 300 to 1000 K. PREDICT stretches the range of the regressedpolynomial (eq. 132) to include 275 to 1050 K.JOBACK, Ideal Gas Heat Capacity

This method, like Rihani and Doraiswamy, is a first order group contribution methodthat estimates the parameters of a third order polynomial in temperature directly. Thesame set of groups are used for this property as are used for the various point propertiesestimated by Joback65 methods.

C a b T c T d TP CJ CJ CJ CJ° = + + +Σ ∆ Σ ∆ Σ ∆ Σ ∆2 3 (133)

where, ∆ ∆ ∆ ∆a b c and dCJ CJ CJ CJ, , are group contributions from Appendix Table 24.Expected Errors Joback65 tested this method on 28 compounds, 8 of which

were not included in the development. The average error was 1.4% with a standarddeviation of 2%.

Temperature Limitations The temperature limitations suggested by Joback65

are 298 to 1000 K.HARRISON and SEATON, Ideal Gas Heat Capacity

Harrison and Seaton69 developed a method to supplement the Benson methodfor any compound not included in the Benson groups. This method uses contributionsfrom atomic species, including C, H, O, N, S, F, Cl, I, Br, Si, Al, B, P and veryimportantly, Any Other. This, Any Other, category allows the method to estimate theheat capacity of any compound.

C T T n T n T n T n T n T n

T n T n T n T n T n T n

T n T n

Po

C C H H O o N N S S F F

Cl Cl I I Br Br Si Si Al Al B B

P P OTH OTH CNST

( ) ( ( ) ( ) ( ) ( ) ( ) ( )

( ) ( ) ( ) ( ) ( ) ( )

( ) ( ) ) / .

= + + + + + ++ + + + + +

+ +

Φ Φ Φ Φ Φ ΦΦ Φ Φ Φ Φ ΦΦ Φ Φ 41868

(134)



where ΦC, ΦH, ΦO, ΦN, ΦS, ΦF, ΦCl, ΦI, ΦBr, ΦSi, ΦAl, ΦB, ΦP, ΦOTH are the atomiccontribution for each respective element and all others (OTH), ΦCONST is a constant. Allcontributions are tabulated at 300, 400, 500, 600, 800, 1000 and 1500 K, see AppendixTable 26.

This method, like the Benson ideal gas heat capacity method tabulates theproperty at specific temperatures. PREDICT as with Benson’s, automatically regressesthe tabulated results to a cubic polynomial in temperature (eq. 132) and uses thepolynomial to interpolate the data points requested by the user. The original data pointscalculated by the method are also given.

Expected Error The authors tested the method on 2500 data points, the errorfor all compounds ranged from 6% at low temperatures to 2.3% at 1500 K. For onlycompounds not included in the regression of the parameters, the errors were similar atlow temperatures and about 3.5% at high temperatures. For the same list of compoundsused by Joback in comparing the other methods listed above this method had a 3.2%error, slightly higher than Benson and Joback and about the same as Rihani andDoraiswamy.

Temperature Limitations This method determines heat capacity at specifictemperatures ranging from 300 K to 1500K. The regressed polynomial expands thisrange slightly to 275 K to 1550 K.

II.16 Liquid Thermal Conductivity

Experimental data for liquid thermal conductivity is very hard to come by.Therefore, the current attempts at estimation are not generally very good.

The primary method used here for the temperature dependence of the liquidthermal conductivity is the equation of Riedel50,

( )k k TL R= +

−

'

/1

20

31

2 3(135)

This equation allows one thermal conductivity point to be extended to othertemperatures. For the calculation of one thermal conductivity point either the method ofSato51 or Missenard47,52 can be used. The method of Sato calculates the thermalconductivity at the normal boiling point while the method of Missenard will calculate apoint at 0° C. The errors to be expected from the two methods are about the same withthe Missenard method being better for highly polar or complex compounds.SATO & RIEDEL, Liquid Thermal Conductivity



k xT

MW TLR

R

=+ −

+ −−2 64 10

3 20 1

3 20 13

2 3

1 2 2 3.( )

( ( ) )

/

/ / (136)

Expected Errors In a small review Reid et al.1 found an average error usingthis method of about 10%.

Temperature Limitations There is no lower limit imposed by the program.However, as with all liquid properties the upper temperature limit is the critical point andproperties will not be calculated at temperatures above this.MISSENARD & RIEDEL, Liquid Thermal Conductivity

k kT

T

L LoR

C

=+ −

+ −

3 20 1

3 20 1273 15

2 3

2 3

( )

.

/

/(137)

kx T C

MW nLoB PL

A

=−

° °84 10 6 1 2

1 2 1 4

( ) /

/ /(138)

The program allows complete flexibility in the calculation of the liquid density andliquid heat capacity required for this estimation. These values can be entered directly, ifknown, or estimated from any of the methods in the program. A polynomial as a functionof temperature could also be entered for either. The program will also allow entry of areference thermal conductivity data point. It's value would then be substituted intoequation 138 in place of the kLo with the appropriate temperature (in Kelvins) replacingthe 273.15 in that equation.

Expected Errors The errors with this method (without a reference data point)will be on the same order as those with the Sato method, but this method will work forthe more complex molecules.

Temperature Limitations The upper temperature limit of the critical point isthe only limitation.

II.17 Gas Thermal Conductivity

Two different types of estimations methods for the gas thermal conductivity aregiven here. First a method derived from the kinetic theory of gases and a second fromdimensional analysis.

Eucken53 This method was developed from the kinetic theory of gases.



Originally for monoatomic gases, the following proportionality between thermalconductivity and viscosity can be shown.

k MW CG G v= 2 5. µ (139)

For more complex systems Eucken proposed to separate the translationalenergy contributions from the internal energy contributions. The result was the modifiedEucken correlation for gases. Several others have expanded on this concept, breakingthe energy contributions up and separately modeling them. However, within theaccuracy of the models the more complex ones are no better.EUCKEN, Gas Thermal Conductivity

kC

MWGP G=

+− °10 0 8972 1326 ( . . ) µ(140)

Expected Error A small error analysis by Reid et al.1 showed this method togive approximately 10% error for various compound types.

Temperature Limitations This method has no temperature limitations.However, the methods chosen to calculate the ideal gas heat capacity and the gasviscosity could have temperature limitation associated with them. If that is the casethose limitations would set the temperature range for the correlation.

As with other methods in this program that require other temperature correlatedproperties in their calculation these other properties can be manually entered as apolynomial. If they are not available in that form they can be estimated using any of theschemes in the program.

Misic and Thodos54 This method was developed with dimensional analysis,using generally different quantities than those above. It should be pointed out, however,that the main parameter, ξ* is similar to the gas viscosity parameter, ξ. The method wasdeveloped in two different forms, depending on the class of compound. While both ofthese forms are for hydrocarbons and the accuracy of this method with other organics isunknown, this author has had very good success using this method for the prediction ofsome inorganic compound properties.Misic and Thodos, Gas Thermal ConductivityFor methane, naphthenes and aromatic hydrocarbons below TR = 1,

kx Co T

GP R=

−4 45 10 6.

*(141)



For all hydrocarbons,

kT Co

GR P=

−−10 14 52 5 146 2 3( . . )

*

/

(142)

ξ*/ /

/=T MW

PC

C

1 4 1 2

2 3 (143)

Expected Error Again Reid et al.1 did a short error analysis and found the errorof this method to be in the range of 2-10%.

Temperature Limitations The only temperature limitations associated withthis method will be that of the ideal gas heat capacity. If the heat capacity is entered asa polynomial, there will be no temperature limit.

II.18 Important Nomenclature

StandardCPL Constant pres. Liquid Heat Capacity, cal/gmoleKCPLo CPL at 0o C, cal/gmole KCσL Saturated Liquid Heat Capacity, cal/gmole KCP

° Ideal Gas Heat Capacity, cal/gmole KCV Constant Volume Gas Heat Capacity, cal/gmole K∆GF

o298 Ideal Gas Free Energy of Formation at 298 K, kcal/gmol

∆HFo

298 Ideal Gas Heat of Formation at 298 K, kcal/gmol

SFo

298 Ideal Gas Entropy at 298 K, kcal/gmol KHVAP Heat of Vaporization, cal/gmoleHVAP@TB Heat of Vaporization at TB, cal/gmole KMW Molecular WeightnA Number of atoms in moleculePC Critical Pressure, atmospheresPV Vapor Pressure, atmospheresPVR Reduced Vapor Pressure, PV/PCR Gas Constant, 82.05 atmospheres cc / gmole KT Temperature, KelvinsTB Normal Boiling Point, KelvinsTBR Reduced Normal Boiling Point, TB/TC



TC Critical Temperature, KelvinsTR Reduced Temperature, T/TCU Bhirud Liquid Density FunctionVC Critical Volume, cc/gmoleZC Critical Compressibility FactorZRA Rackett Liquid Density Parameterk’ Reference Liquid Thermal Conductivity, cal/cm sec KkL Liquid Thermal Conductivity, cal/cm secKkLo Liquid Thermal Conductivity at 0o C, cal/cm sec Kx Halm-Stiel Polarity parameter

GreekαC Riedel FactorµG Gas Viscosity, micropoiseµL Liquid Viscosity, centipoiseω Pitzer's Acentric FactorΩ, Λ Correlating Parameters in Andraes Liquid Viscosity Equationψ Bhirud's Liquid Density Polar Parameterρ Liquid Density, gmole/ccρo Liquid Density at 0o C, gmole/ccσ Surface Tension, dynes/cm

SubscriptsREF Reference data, a property, temperature pairEST Initial guess for iterative property calculationDATA Experimental dataCALC Calculated data from another equation1, 2 Used to distinguish between two reference states used in the

same equation.

PREDICT Version 4.0 Page III-1


III. REGRESSION

III.1 Regression System

The data regression system in PREDICT is designed to easily and rapidlyregress data estimated using PREDICT to one of many common temperature correlatingequations. Any of following ten equations, including a polynomial to the nth degree, canbe selected for any property type, except equation 8 which is for liquid density only. Theten equations were selected because they are commonly used for correlating physicalproperties.

ln ln( )Y AB

TC T D T E T= + + + + 2 (1)

ln Y AB

T C= +

+(2)

log Y AB

T C= −

+(3)

Y AT T

T TC

C B

B

=−

−

(4)

Y A B T C T D T E T F T= + + + + +2 3 4 5 (5)

ln ln( )Y AB

TC T= + + (6)

Y A B

T

TC=− −

1

2 7/

(7)

YP T

RA

C C

T

TC=

− + −

1 1

2 7/

(8)

Page III-2 PREDICT Version 4.0


Y A B TC

T= + + (9)

Y A B TC

T= + + 2 (10)

PREDICT will recommend which equation should be used with each physicalproperty. This is done with a star (*) in the equation selection menu. The user can eitherselect one of the recommended forms or any of the other equations. Therecommendations, based on the physical property being estimated, are as follows:

Physical Property Recommended Equation(s)

Vapor Pressure 1, 2 or 3Heat of Vaporization 4 or 5Liquid Density 5, 7 or 8Surface Tension 4 or 5Liquid Viscosity 2, 3 or 6Gas Viscosity 5Liquid Heat Capacity 5, 9 or 10Ideal Gas Heat Capacity 5Liquid Thermal Conductivity 5Gas Thermal Conductivity 5

Several of the equations (4, 7 and 8) require additional point properties,specifically, critical temperature (TC), critical pressure (PC) or normal boiling point (TB).When the regression option is called, PREDICT will create a file of these properties ifthey have been calculated or previously entered. If the necessary property is notavailable to the regression system, the user will be prompted for it. Critical pressure (PC)will always be used with units of atmospheres and critical temperature (TC) will be in unitsof either Kelvin or Rankine, matching the units of the temperature data. For theseequations, input temperature units of C or F will automatically be converted to K or R,respectively. The gas law constant R is required in equation 8. This is a liquid densityregression equation only. PREDICT will verify that the input data are in one of thefollowing liquid density units. Depending on the input units the gas constant, R, will havethe following value and units.



Density Units Temperature Units Gas Constant (R) - Value and Unitsgmole/cc K 82.05 cc atm/gmole Kkmole/m3 K 0.08205 m3 atm/kmole Klbmole/ft3 K 1.3143 ft3 atm/lbmole Kcc/g K 82.05/MW cc atm/g Km3/kg K 0.08205/MW m3 atm/kg Kft3/lb K 1.3143/MW ft3 atm/lb Kgmole/cc R 45.583 cc atm/gmole Rkmole/m3 R 0.045583 m3 atm/kmole Rlbmole/ft3 R 0.730 ft3 atm/lbmole Rcc/g R 45.583/MW cc atm/g Rm3/kg R 0.045583/MW m3 atm/kg Rft3/lb R 0.730/MW ft3 atm/lb R

The regression option is selected from the Main Selection Screen by typing REor <CNTL> F5. When selected the regression option will automatically use the mostrecently calculated temperature correlated property in the current output units. If noproperty has been selected, the regression option will allow the selection of previouslystored data.

The units used in the regression are the current output units selected inPREDICT.

Several of the equations were non-linear and were linearized in order to facilitateleast squares regression. The following equations were linearized:

ln Y AB

T C= +

+(2)

was linearized to the following equation for regression,Z p X q r W= + + (2a)where,Z = T lnY (2b)X = T (2c)W = -lnY (2d)and the regressed parameters are relate to the parameters in equation 2 as,A = p (2e)B = r (2f)C = q - p r (2g)



log Y AB

T C= −

+(3)

was linearized to the following equation for regression,Z p X q r W= + + (3a)where,Z = T logY (3b)X = T (3c)W = -logY (3d)and the regressed parameters are relate to the parameters in equation 3 as,A = p (3e)B = r (3f)C = p r - q (3g)

Y AT T

T TC

C B

B

=−

−

(4)

was linearized to the following equation for regression,Z = r + p W (4a)whereZ = ln Y (4b)

WT T

T TC

C B

=−

−

(4c)

and the regressed parameters are relate to the parameters in equation 4 as,A = er (4d)B = p (4e)

Y A B

T

TC=− −

1

2 7/

(7)was linearized to the following equation for regression,Z = r - p Wwhere, (7a)Z = ln Y (7b)

W = 1

2 7

−

T

TC

/

(7c)



and the regressed parameters are relate to the parameters in equation 7 as,A = er (7d)B = ep (7e)

YP T

RA

C C

T

TC=

− + −

1 1

2 7/

(8)

was linearized to the following equation for regression,Z = p Wwhere, (8a)

Z YP T

RC C= −

ln ln (8b)

WT

TC

= − + −

1 1

2 7/

(8c)

and the regressed parameters are relate to the parameters in equation 8 as,A = ep (8d)

All equations, either originally linear or made linear by rearrangement areregressed by standard least squares techniques. For originally linear equations, anestimate of error in the parameters is calculated along with the parameters. For all of theequations a complete listing is given for each data point showing the original value,calculated value from the regression, absolute error, percent error and root mean squareerror. In addition the standard deviation of fit, average percent and error average rootmean square error (for all points) are calculated.

Graphs of the results can also be plotted, they are:Regression & PREDICT Data vs. TemperaturePercent Error vs. TemperatureRegression vs. PREDICT Data

III.2 Using the Regression System

To fit predicted data to a temperature correlating equation, immediately afterpredicting the data in PREDICT, select Regress Data from the main PREDICT menu.PREDICT will automatically send the predicted data to a file and display the menu ofequations. On this menu one or more equations will be marked with a "*". These are therecommended equations for regression of the physical property of interest. Also on thescreen will be the type of data that you are attempting to regress (i.e. Liquid Density,



Vapor Pressure, etc.). At this point, move the cursor to the equation you wish to use andpress <ENTER>. The least squares regression will be performed. The equationcoefficients and a table of residuals will be displayed.

After viewing the table of residuals, you will be asked if you wish to graph thedata. If so, a menu of three graph options will appear. After selecting a graph andviewing it, a menu of previously stored data will be displayed. This menu will include thedata set just regressed. The user can now select either a different set of data to regressor re-regress the same set of data to a different equation.

Each set of data that has been predicted or regressed during the current sessionof PREDICT is saved temporarily in a file named PHYGPH##.TMP, where ## is asequential number, incremented each time the regression option is called. These filesare saved until there are 99 of them. Some of the regression equations require other point properties. These includenormal boiling point, critical temperature and critical pressure. If these properties wereused (either as inputs or predicted) in PREDICT they will automatically be available to theregression section. They are saved in the file PNTPRP##.TMP. If they are not presentwhen the regression program needs them, they can be entered directly from thekeyboard, or the user could return to the main program and predict them. If the databeing regressed is from a file, one not named PHYGPH##.TMP without an associatedPHYPRP##.TMP, the user must enter the point properties directly.

The user can enter their own data into a file and regress it by selecting the <F3>Enter File Name command. The format for information in the PHYGPH##.TMP file is asfollows:

Line 1: Method, Property and Compound Name, 80 Characters MaximumLine 2: Temperature, Units, 15th character should be C, K, F, or RLine 3: Property (10 characters), Property Units (10 characters)Line 4 to n+3: N data points, one on each line, temperature, property, free format,

separated by a space.

An example PHYGPH##.TMP file of liquid density data for “test” is given below:

GunnYamada Liquid Density test Temperature, C Liq. Den gmol/cm^3 0.000000 0.689245E-02 10.0000 0.682414E-02 20.0000 0.675567E-02

The first three lines are optional, but need to be present as blank lines. To have thetemperature units verified for equations 4, 7 and 8 a valid temperature unit specification



(C,F,K,R) should be given on line 2, space 15. If equation 8 is going to be used for liquiddensity, then the temperature units must be specified on line 2 and proper units for liquiddensity, see above description of gas constant and density units, must be given inspaces 11 to 20 on line 3. You can manually input the name of another file (with orwithout the TMP extension. Only those named as PHYGPH##.TMP will appear in themenu. The data input file must be exactly as shown above.

The data file PNTPRP##.TMP will also be prompted for if it is needed. This filerequires “flags” indicating which point properties are present in the file. The file musthave 18 flags with values of 1 or 0. A 1 indicates a property is given, 0 indicates it is not.Only the first 6 are important to the regression. The first 6 flags and the required inputunits are follows:

Flag Property Required Units1 MW None2 TC K3 PC atmospheres4 VC cc/gmole5 Acentric Fact. None6 TB K

If a property is present (flag = 1) then it is just listed in order of the flags, starting on line4. No line is skipped. If TC and TB were the only properties given, TC would be on line 4and TB on line 5. The format is:

PNTPRP##.TMP fileLine 1: 18 flags indicating if property is present, separated by at least one spaceLine 2: Continuation of flagsLine 3: Continuation of flagsLine 4: First property with a flag = 1Line 5: Second property with a flag = 1Line n: Continue until all properties are given



An example file, with point properties, TC (flag 2), PC (flag 3) and Acentric Factor (flag 5)

0 1 1 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 623.150 30.0000 0.300000

If this file is used the format of the file and the units must be exactly as indicatedabove. If these properties are needed but they are not in a file in the proper units, theycan be entered directly into PREDICT when prompted for in any valid PREDICT unit.

III.3 ASPEN Simulator Output

The main program has the ability to output results directly into a file compatiblewith the ASPEN PROP-DATA statements. To use this option, estimate the desiredproperty using PREDICT and then select the ASPEN option from the main menu. Theprogram will prompt you for a file name or ask if the current file open should be used.The rest of the unit conversion and file writing is automatic.

Any point properties that have been entered or estimated when the call toASPEN/SP is made will be stored in the file. If additional properties are calculated,select the ASPEN option after each property calculation and it will be appended to thePROP-DATA file. If the property is already in the PROP-DATA file you will be asked ifthe existing data should be overwritten or not.

III.4 Data Regression Files

PREDICT generates two files, PHYGPH##.TMP and PNTPRP##.TMP. The filesare available for reuse, e.g. to regress to a different equation. These TMP files are notdeleted until they reach 99. Once 99 files have been stored the next TMP file generatedwil cause the system to delete files numbered 90 through 99 and reuse 90.

When the system displays files for reuse, PREDICT will show the last 22. Anyfile in the system can be selected by number, even though it is not displayed. Also, ifone file is deleted, PREDICT will interpret that as the maximum and not display any fileswith higher numbers. It is recommended that files be periodically renamed to some otherdescriptor, e.g. *.TST. This will ensure that PREDICT never deletes data that waswanted.

PREDICT Version 4.0 Page IV-1


IV. References

1. Reid, Robert C., John M. Prausnitz, Thomas K. Sherwood, The Properties ofGases and Liquids, 3rd ed., New York: McGraw-Hill, 1977.

2. Danner, R. P., T. E. Daubert, Manual for Predicting Chemical Process DesignData, Data Prediction Manual, Design Institute for Physical Property Data,American Institute of Chemical Engineers, New York, 1982.

3. Lydersen, A. L.: "Estimation of Critical Properties of Organic Compounds", Univ.Wisconsin Coll. Eng., Eng. Exp. Stn. 3, Madison, Wis., April, 1955.

4. Ambrose, D., "Correlation and Estimation of Vapour-Liquid Critical Properties: I.Critical Temperatures of Organic Compounds", NPL Report Chem 92,September 1978, Teddington, UK.

5. Klincewicz, K. M., R. C. Reid, "Estimation of Critical Properties with GroupContribution Methods", AIChE J., 30(1): 137 (1984).

6. Fedors, R. F., "A Relationship Between Chemical Structure and the CriticalTemperature", Chem. Eng. Commum., 16: 149 (1982).

7. Gold, P. I., and G. J. Ogle, "Estimating Thermophysical Properties of LiquidsPart 2-Critical Properties", Chem. Eng., 75(21): 185 (1968).

8. Spencer, C. F., and T. E. Daubert, "A Critical Evaluation of Methods for thePrediction of Critical Properties of Hydrocarbons", AIChE J., 19: 482 (1973).

9. Ambrose, D., "Vapour-Liquid Critical Properties", NPL Report Chem 107,February 1980, Teddington, UK.

10. Ambrose, D., "Correlation and Estimation of Vapour-Liquid Critical Properties: II.Critical Pressures and Critical Volumes of Organic Compounds", NPL ReportChem 98, May 1979, Teddington, UK.

11. R. C. Reid, Personal Communication, September 1985.

12. Fedors, R. F., "A Method to Estimate Critical Volumes", AIChE J., 25(1): 202(1979).

Page IV-2 PREDICT Version 4.0


13. Halm, R. L., L. I. Stiel, "Saturated Liquid and Vapor Densities for Polar Fluids",AIChE J., 16(1): 3 (1970).

14. Pitzer, K. S., D. Z. Lippman, R. F. Curl, C. M. Huggins, and D. E. Petersen, "TheVolumetric and Thermodynamic Properties of Fluids. II. Compressibility Factor,Vapor Pressure and Entropy of Vaporization", J. Am. Chem. Soc., 77: 3433(1955).

15. Halm, R. L., L. I. Stiel, "A Fourth Parameter for the Vapor Pressure and Entropyof Vaporization of Polar Fluids, AIChE J., 13(2): 351 (1967).

16. Riedel, L., "Eine neue universelle Dampfdruckformel", Chemie-Ing.-Techn., 26:83 (1954).

17. Carruth, G. F., R. Kobayashi, "Extension to Low Reduced Temperatures ofThree-Parameter Corresponding States: Vapor Pressure, Enthalpies andEntropies of Vaporization and Liquid Fugacity Coefficients, Ind. Eng. Chem.Fundam., 11(4): 509 (1972).

18. Miller, C. O. M., Private Communication to E. Buck, Author of Physical PropertySection Perry's Chemical Engineers Handbook, 6th Edition, 1984.

19. Rackett, H. G., "Equation of State for Saturated Liquids", J. Chem. Eng. Data,15(4): 514 (1970).

20. Tyn, M. T., W. F. Calus, "Estimating liquid molal volume", Processing, 21(4), 16(1975).

21. Perrys Chemical Engineers Handbook 6th Ed., McGraw-Hill,New York, 1984, p.3-267.

22. Gomez-Nieto, M., G. Thodos, "A New Vapor Pressure Equation and ItsApplication to Normal Alkanes", Ind. Eng. Chem., Fundam., 16(2): 254 (1977).

23. Gomez-Nieto, M., G. Thodos, "Generalized Vapor Pressure Equation forNonpolar Substances", Ind. Eng. Chem., Fundam., 17(1): 45 (1978).

24. Gomez-Nieto, M., G. Thodos, "Generalized Treatment for the Vapor PressureBehavior of Polar and Hydrogrn Bonded Compounds", Can. J. Chem. Eng., 55:445 (1977).



25. Watson, K. M., "Thermodynamics of the Liquid State, Generalized Prediction ofProperties", Ind. Eng. Chem., 35: 398 (1943).

26. Gunn, R. D., T. Yamada, "A Corresponding States Correlation of SaturatedLiquid Volumes", AIChE J., 17(6): 1341 (1971).

27. Spencer C. F., R. P. Danner, "Improved Equation for Prediction of SaturatedLiquid Density", J. Chem. Eng. Data, 17(2): 236 (1972).

28. Spencer C. F., S. B. Adler, "A Critical Review of Equations for PredictingSaturated Liquid Density", J. Chem. Eng. Data, 23(1): 82 (1978).

29. Joffe, J., D. Zudkevitch, "Correlation of Liquid Densities of Polar and NonpolarCompounds", Chem. Eng. Prog. Symp. Ser., 70(140): 22 (1974).

30. Bhirud, V. L., "Saturated Liquid Densities of Normal Fluids", AIChE J., 24(6):1127 (1978).

31. Bhirud, V. L., "A Four-Parameter Corresponding States Theory: Saturated LiquidDensities of Abnormal Fluids", AIChE J., 24(5): 880 (1978).

32. Brock, J. R., R. B. Bird, "Surface Tension and the Principle of CorrespondingStates", AIChE J., 1(2): 174 (1955).

33. van der Waals, J. D.: Z. Phys. Chem., 13: 716 (1894).

34. Hakim, D. I., D. Steinberg, and L. I. Stiel, "Generalized Relationship for SurfaceTension of Polar Fluids", Ind. Eng.Chem. Fundam., 10: 174 (1971).

35. Morris, P. S.: M. S. Thesis, Polytechnic Institute of Brooklyn, Brooklyn, N. Y.,1964.

36. Letsou, A., L. I. Stiel, "Viscosity of Saturated Nonpolar Liquids at ElevatedPressures", AIChE J., 19(2): 409 (1973).

37. Andrade, E. N. da C.: Nature, 125: 309 (1930).Andrade, E. N. da C.: Phil. Mag., 17: 497, 698 (1934).



38. Gambill, W. R., "How P&T Change Liquid Viscosity", Chem. Eng., 66(3): 123(1959).

39. E. John Vansickle, Personal Communication, 1981.

40. Stiel, L. I., G. Thodos, "The Viscosity of Polar Gases at Normal Pressures",AIChE J., 8(2): 229 (1962).

41. Yoon, P., G. Thodos, "Viscosity of Nonpolar Gaseous Mixtures at NormalPressures, AIChE J., 16(2): 300 (1970).

42. Reichenberg, D., "New Method for the Estimation of the Viscosity Coefficients ofPure Gases at Moderate Pressures (With Particular Reference to OrganicVapors)", AIChE J., 21(1): 181 (1975).

43. Bondi, A., "Estimation of the Heat Capacities of Liquids", Ind. Eng. Chem.Fundam., 5(4): 443 (1966).

44. Rowlinson, J. S.: Liquids and Liquid Mixtures, 2nd ed., Butterworth, London,1969.

45. Reid, R. C., J. L. San Jose, "Estimating Liquid Heat Capacities-Part I", Chem.Eng., 83(26): 161 (1976). "Estimating Liquid Heat Capacities-Part II", Chem.Eng., 83(27): 67 (1976).

46. Yuan, T.-F., L. I. Stiel, "Heat Capacity of Saturated Nonpolar and Polar Liquids",Ind. Eng. Chem., Fundam., 9(3): 393 (1970).

47. Missenard, F. A., Comp. Rend., 260: 5521 (1965).

48. Rihani, O. N., L. K. Doraiswamy, "Estimation of Heat Capacity of OrganicCompounds from Group Contributions", Ind. Eng. Chem. Fundam., 4(1): 17(1965).

49. Benson, S. W.: "Thermochemical Kinetics," Chap. 2, Wiley, New York, 1968.

50. Riedel, L., "Neue Warmeleitfahigkeitsmessungen an organischen Flussigkeiten",Chemie-Ing.-Tech, 23: 321 (1951).



51. Reid, Robert C., John M. Prausnitz, Thomas K. Sherwood, The Properties ofGases and Liquids, 3rd ed., New York: McGraw-Hill, 1977, p. 519.



54. Misic, D., G. Thodos, "The Thermal Conductivity of Hydrocarbon Gases atNormal Pressures", AIChE J., 7(2): 264 (1961)., "Atmospheric ThermalConductivity for Gases of Simple Molecular Structure', J. Chem Eng. Data, 8(4):540 (1963).

55. Benson, S. W., J. H. Buss, "Additivity Rules for the Estimation of MolecularProperties. Thermodynamic Properties", J. Chem. Phys., 29(3): 546 (1958).

56. Franklin, J. L., Ind. Eng. Chem., 41: 1070 (1949).

57. Franklin, J. L., "Calculation of the Heats of Formation of Gaseous Free Radicalsand Ions", J. Chem. Phys., 21(11): 2029 (1953).

58. Verma, K. K., L. K. Doraiswamy, "Estimation of Heats of Formation of OrganicCompounds", Ind. Eng. Chem., Fundam., 4(4): 389 1965.

59. van Krevelen, D. W., H. A. G. Chermin, "Estimation of the free enthalpy (Gibbsfree energy) of formation of organic compounds from group contributions",Chem. Eng. Sci., 1(2): 66 (1951).

60. van Krevelen, D. W., H. A. G. Chermin, "Erratum: Estimation of the free enthalpy(Gibbs free energy) of formation of organic compounds from groupcontributions"Chem. Eng. Sci., 1(5): 238 (1952).

61. Riedel L., Chem Ing. Tech., 26: 679 (1954).

62. Chen, N. H., "Generalized Correlation for Latent Heat of Vaporization", J. Chem.Eng. Data, 10(2): 207 (1965).

63. Thompson, W. H., W. G. Braun, 29th Midyear Meet., Am. Pet. Inst.,Div.Refining, St. Louis, Mo., May 11, 1964, prepr. 06-64.



64. Silverberg, P. M., L. A. Wenzel, "The Variation of Latent Heat with Temperature",J. Chem. Eng. Data, 10(4): 363 (1965).

65. Joback, Kevin G., "A Unified Approach to Physical Property Estimation UsingMultivariate Statistical Techniques", MS Thesis, MIT, June 1982.

66. Ried, Robert C., John M. Prausnitz and Bruce E. Poling, The Properties ofGases & Liquids, 4th ed., New York: McGraw-Hill, 1987.

67. Benson, S. W., F. R. Cruickshank, D. M. Golden, G. R. Haugen, H.E. O'Neal,A.S. Rodgers, R. Shaw and R. Walsh, "Additivity Rules for the Estimation ofThermochemical Properties", Chem. Rev., 69(3): 279 (1969).

68. Myers, Kenneth H., “Thermodynamic and Transport Property Prediction Methodsfor Organometallic Compounds” MS Thesis, Pennsylvania State University,August 1990. Myers, K. H., R. P. Danner, “Documentation of the Basis forSelection of Prediction Methods for Organometallic Compounds in Manual forPrediction Chemical Process Design Data”, Documentation Report 802-90,Design Institute for Physical Property Data, AIChE, New York, 1990.

69. Harrison, B. K., W. H. Seaton, “Solution to Missing Group Problem for Estimationof Ideal Gas Heat Capacities”, Ind. Eng. Chem., Res., 27(8): 1536 (1988).

PREDICT Version 4.0 Page V-1


V. PROGRAM OPERATION

PREDICT has been design to be a very "user friendly" program. That is, onlyminimal instruction is required to enable an engineer to begin calculating properties.Therefore, no detailed instructions will be given, but rather, after a few general commentson some of the features several typical example calculations will be given.

V.1 Help

PREDICT currently has 184 help pages stored on-line. These will bedemonstrated in the examples. Prediction method help pages are intended to giveinformation on the reference of the prediction method, input parameters required,equations used, errors and other important information. Other pages describe therequested inputs and allowable units. Additional help screens are available explaininggroup contribution menus and giving examples. To access any of the HELP screens,press the function key <F1>.

V.2 Group Contribution Screens

There are useful HELP screens that can be accessed by pressing <F1> while atthe group contribution screen. But, simply, the user moves the cursor with the arrows toeach group in the compound. At each group, enter the number of that group in themolecule being modeled. In the case of methyl ethyl ether there are 2, -CH3's, 1 >CH2and 1 -OH groups. If you press the wrong number, you can clear all with <F10> and startagain, or you can move away from the group and return, indicating zero for the group youwish to remove. When you are satisfied that you have indicated all the groups that arepresent in the molecule to be estimated, press <END>. If the groups that you need arenot present, <ESC> will allow you to quit this method (even if you have already indicatedsome groups) and return to the previous menu. Additional keys that will help are the<HOME> key that will move the cursor to the upper left corner, <PgUp> will move thecursor to the upper right and <PgDn> will move the cursor to the lower right.

There are some special characters that will appear on the menus, these indicatefillers or comments and therefore cannot be selected. The double arrow indicates acomment. This cell can be entered but a number cannot be pressed. The bell will soundif an illegal operation such as that is attempted. The other, a solid block, is a filler at theend of the last column. This cell cannot be entered as a bell will sound. In some menusthis block will effect the <PgDn> key as it attempts to move the cursor to an illegal cell. Ifthat occurs, simply use the arrow keys to move the cursor.

Page V-2 PREDICT Version 4.0


V.3 Exiting and Quitting

To quit the program from the main menu, simply press the <ESC> key followedby any key. During various operations of the program the user can quit, returning to aprevious menu, by pressing <ESC>. The program will indicate when quitting is possible.Generally the user can quit from any group contribution screen, from the temperaturelimits input screen and from any property methods selection screen. The only time thatquiting is not allowed all the way back to the main menu is during the calculation of asecondary property. If a property is needed in the calculation of another, it must beentered or calculated itself. Therefore, when calculating such a secondary property theuser can only escape back to a point to manually enter the secondary property. In theevent that the wrong property is selected, QUIT <ESC> can be selected from theproperty menu. This will take you to the Main menu, from which you can start over, orquit the program.

V.4 Error Recovery

The most common errors will be in temperature inputs. Many of the routineshave temperature limitations. If the limits are exceeded so that no data can becalculated within the legal temperature limits of the method the program will announcethat fact and give the user an opportunity to reenter the limits, or quit. If the user makesan illegal entry of alpha characters when numbers are expected or if units that are notallowable for this entry an error message with an explanation of the error and examplesof valid entries are displayed. The user is then given another chance to make a validentry.

V.5 Yes/No Questions and selections from Menus

Throughout the program there are many yes/no questions, all of these can beanswered by y or n, or upper case answers. The default will be indicated by a letter inbrackets, such as <N>. If <N> is indicated as the default and the user simply pressesreturn, or any other character except y or Y, the answer of no will be used. For Y/Nquestions, there is no need to press return after the Y or N entry, (see the examplesincluded here). Similarly for the Menus, the user indicates a choice by pressing the initialif the desired property, method or option and the program goes. The initials are indicatedin red. For most menus the abbreviation is a one letter initial, usually the option's firstletter. However, in the main menu and the Halm-Stiel Polarity Factor menu, two lettersmust be selected. In all cases there is a function key that also corresponds to theselection. In most cases these are the function keys, F1 through F10, but on the mainmenu <ALT> function keys and <CNTL> function keys are also used. To access these



function keys, hold down the <ALT> or <CNTL> key while pressing the appropriatefunction key.

V.6 Output Units

There are four sets of output units included in PREDICT. They are, cgs, SI,English and a modified English set, see Table 1. The default units are cgs, with molesand centigrade for temperature. Weight units and other temperature units can also beselected. Just before the tabulated results are given the user will need to make adecision on units. Either the default set or any of the other three sets can be chosen.The units on each property used in each set are displayed to aid in selection. Oncechanged, the output units will remain in effect until changed again.

After a temperature correlated property has been displayed or printed it can beredisplayed, either to the screen or printer in any of the available units. This is done byselecting the Units option from the main menu. Some of the reference data entered, thatis displayed in the original report, will not be duplicated in the redisplay.

Table 1Available Output Units in PREDICT

Property Default,cgs S.I. Std. English Mod. EnglishPc, Pv atmosphere Pa (N/m2) psi psiVc cc/gmole[g] m3/Kmole[Kg] ft3/lbmole[lb] ft3/lbmole[lb]∆Hvap cal/gmole[g] J/Kmole[Kg] BTU/lbmole[lb] BTU/lbmole[lb]ρL gmole[g]/cc Kmole[Kg]/m3 lbmole[lb]/ft3 lbmole[lb]/ft3

σ dyne/cm N/m poundal/inch dyne/cmµL cpoise Pa s lb/ft hr cpoiseµG µpoise Pa s lb/ft hr µpoiseCPL,CP° cal/gmole[g] K J/Kmole[Kg] K BTU/lbmole[lb] F BTU/lbmole[lb] FkL, kG cal/sec cm K W/m K (J/s m K) BTU/ft hr F BTU/ft hr FNote: Terms in [ ] are for mass rather than mole units.

V.7 User Specified Input Units

The user has complete control of the units used on all requested inputs. Theserequested inputs are used by many methods and may include reference points,temperature correlations of supporting properties or point properties. In all cases anyinput (except temperature range) can be by-passed and estimated by one method oranother.

Each requested input has a default set of units, clearly indicated on each inputscreen. The user can enter other valid units in brackets [ ] to the right of the number



being entered. To find out what units are valid for each input, refer to Table 1 or simplypress the HELP key, F1. The HELP available for each input, clearly illustrates theallowable units for that input.

Table 2Allowable Units for User Inputs

Property Requested Default Unit Other Units AllowedTemperature C R, K, FPressure atm psi, Pa, barEnthalpy (Heat of Vap) cal/gmole BTU/lbmole, J/Kgmole,

cal/g, BTU/lb, J/KgHeat Capacity cal/gmole K BTU/lbmole F,

J/Kgmole K, cal/g K, BTU/lb F, J/Kg K

Density gmole/cc lbmole/cf, Kgmole/m^3g/cc, lb/cf, Kg/m^3

Volume cc/gmole cf/lbmole, m^3/Kgmolecc/g, cf/lb, m^3/Kg

Liquid Viscosity cp (centipoise) lb/ft hr, mp, Pa sVapor Viscosity mp (micropoise) lb/ft hr, cp, Pa sSurface Tension dyne/cm poundal/inch, N/mThermal Conductivity cal/cm s K BTU/ft hr F, W/m K

J/s m KIf no units are specified, PREDICT assumes the default units. If an improper unit

for that property is entered an appropriate error message will be displayed along with thehelp screen indicating the allowable units for the property being entered. Upper/lowercase in the unit name is unimportant. However the order and spacing is important (i.e.,BTU/ft hr F is allowable for thermal conductivity, but BTU/hr ft F will not be recognized).The proper way to enter an alternative set of units for a heat of vaporization requestwould be:Correct: 8600.5 [BTU/lbmole]Correct: 8600.5 [BTU/LBMOLE]Incorrect: 8600.5 [Btu]Incorrect: 8600.5 BTU/lbmoleIncorrect: 8600.5 btu

If either of the last two incorrect entries are made, PREDICT will not be able todistinguish the numeric portion of the entry from the units and will respond with a errorindicating an invalid entry.

Alternative units can also be specified for temperature correlations thatPREDICT may request. If the user would like to enter a correlation for ideal gas heat



capacity the default units are; heat capacity in cal/gmole K and temperature in K.However, if parameters were known for the heat capacity polynomial with units of heatcapacity in BTU/lb F (or any of the allowable units for heat capacity) and temperature inR (temperature must be absolute for temperature correlations, i.e. R or K, not C or F)they could be entered. The proper way to enter alternative units for a polynomial is toindicate the property units with the first parameter and the temperature units with thesecond parameter and no units with the additional parameters. The following would bean example of entering units for the ideal gas heat capacity,

Cp = A + B T + C T2 + DT3

Enter Value for A: 0.004941 [BTU/lb F]Enter Value for B: 2.711E-3 [R]Enter Value for C: -7.21E-6Enter Value for D: 7.649E-9

If the user has data correlated to a second order or first order equation, or even aconstant it can be entered in the above format with the remaining constants entered as0.0.

V.8 Extensive Error Checking On User Inputs

When the user responds to a request by PREDICT for data, PREDICT checks tosee that the input is of the type requested. These tests include; is a character string (i.e.,word) entered when a number is required or are improper elements listed in a chemicalformula. If an illegal input (or unit) is detected PREDICT will respond with an descriptiveerror message indicating what is wrong with the user input and offer suggestions forcorrecting it.

Many of the correlations used by PREDICT have specific temperature ranges ofapplicability. PREDICT checks these limits both as they apply to user entered referencepoints and to the calculation of final results. If PREDICT detects a condition for which itcannot use the user input or cannot calculate properties because of temperature rangelimitations a detailed error message will be displayed. This message is complete with thelimits of the correlation (in degrees C) and the violating input temperatures. This willallow the user to adjust the output temperature limits, enter a new reference point or quit.In the case of reference points, there are usually other methods for calculating theproperty of interest that may be applicable.

V.9 Internal Property Storage

The point properties are used in many other prediction methods. For this reasonall are retained in memory. One of these properties, which is calculated exactly,



molecular weight, cannot be changed. All other point properties can be changed or leftthe same every time they are called for. The retained properties that can be changedinclude, critical temperature, pressure and volume, acentric factor and the polarity factor.Currently the constants to the vapor heat capacity are stored once they have beencalculated, as are parameters from liquid density and gas viscosity. Further any of thesetemperature correlated properties that are called by other property methods can beentered and retained as polynomials.

Some reference properties are not stored and will have to be reentered eachtime they are used. All point properties, stored constants, names and unit specificationsincluding the molecular weight and normal boiling point, are reset by selecting the optionto calculate properties of a New Compound.

V.10 Property DATABASE and Empirical Formula Entry

PREDICT has its own physical property database as well as a user createddatabase. This database has been pre-loaded with point properties of over 1000chemicals. The point properties include all those that PREDICT calculates. Not allproperties are specified for all compounds, but these can be supplemented and updatedby PREDICT.

The availability of the database is immediately apparent when PREDICT isstarted, the initial screen asks if the user would like to retrieve a compound from thedatabase. If the response is Y for yes the user is prompted for an empirical formula. Alldatabase searching is accomplished initially by empirical formula. This is the quickestway to identify a group of chemicals to choose from. An empirical formula is simply thenumber of each element in the compound. Examples of valid and invalid empiricalformulas are as follows:



1. C4H10 Valid2. C4h10 Invalid element name "h"3. CH3CH2CH3 Invalid, C and H are listed more than once.4. H10C4 Valid5. C2H6O Valid6. OH4C Valid7. Lr4H8 Invalid, Lr is not currently supported as an element.8. C6H5Cl Valid9. C6H5CL Invalid element named "CL"

Currently the supported elements include: C, H, Ag, Al, As, Au, B, Ba, Be, Bi,Br, Ca, Cd, Cl, Co, Cr, Cs, Cu, F, Fe, Ga, Ge, Hg, I, In, Ir, K, Li, Mg, Mn, Mo, N, Na, Nb,Ni, O, Os, P, Pb, Pd, Pt, Rb, Re, Rh, Ru, S, Sb, Sc, Se, Si, Sn, Sr, Ta, Te, Ti, Tl, V, W,Y, Zn, Zr.

The upper/lowercase of each element must be supplied correctly. If an invalidelement, either one that is currently not supported or something that is spelled wrong (orwrong upper/lowercase) is entered, PREDICT will display an informative error message.If elements are used twice, as in example 3 above, a search will be conducted, butnothing will be found. The order in which elements are listed in the user enteredempirical formula makes no difference as PREDICT will reorder the formula to C, Hfollowed by other elements in alphabetical order. This same method is used wheneverPREDICT asks for an Empirical Formula, such as in the calculation of molecular weight.

After entry of a valid empirical formula, PREDICT will do a complete search ofthe database and return all compounds matching the empirical formula entered. Thereturned compounds are listed with their complete name. To select one, simply movethe cursor to the compound name of interest and press <RETURN>. The compound willbe selected and its database properties displayed. At this point the user can eitheraccept this compound, print the data or return and search for another. If no matches tothe entered empirical formula are found in the database, the user is given the option ofentering a new formula or by-passing the database and going directly to PREDICT with anew compound for property estimation.

When a compound is selected out of the database the properties are loaded intoPREDICT and are treated as any other property that has either been entered by the useror estimated by PREDICT. The PREDICT "method" listed for properties coming from thedatabase is either a database reference number "Ref: 1", if it is an original databaseproperty or a PREDICT method, e.g., "LYDERSEN" if it is coming from the userdatabase.



The user can calculate additional properties with PREDICT for a databasecompound and add that compound to the user database. The user cannot changeproperties of compounds in the system database.

V.10.1 Saving Data to the PREDICT User DATABASE

The user can save calculated point properties for a new compound or for acompound that has be retrieved from the database to the user database. To save datato the user database, select 'Save Data - File or DB' from the main PREDICT menu(press the letters FD or <CNTL> F3, followed by P or <F3>). If an empirical formula hasnot yet been entered for the compound, one will be requested. PREDICT will thensearch the user database for other compounds with exactly the same empirical formulaand compound name. If a match is found the user will be asked whether or not toREPLACE the current user database values or to ENTER a NEW NAME for thecompound and store it as a different entry. An example of a new name might be"propanol-a", which will differentiate it from an existing database compound "propanol".User stored compounds will be differentiated from the system database compounds byan asterisk when listed for selection after an empirical formula search.

V.10.2 References to Data Supplied with PREDICT

All data stored in the PREDICT system database are identified by a literaturereference number. To retrieve the complete reference, run Database Utilities &References (press the letters DA or <CNTL> F7 from the main menu) followed byDisplay System Database Reference (D or <F2>). This option will prompt you for thenumber of a reference. You can then view the reference or send them to a printer.Please note that other database utilities are not yet implemented.

V.11 Saving Data to ASCII Data Files

Any of the temperature correlated properties calculated in PREDICT can bestored in a disk file. From the main menu, select 'Save Data - File or DB' (press theletters FD or <CNTL> F3, followed by T or <F2>). Any combination of drive name andsubdirectory can be included in the name, up to a maximum of 40 characters. Theformat in this file is:Line 1: Method, Property name, Compound nameLine 2: Temperature UnitsLine 3: Property Name and UnitsLine 4 to n+3: temperature, property value

The data will be stored using the currently selected output units.



V.12 Displaying and Printing Graphs

Graphs of the predicted temperature correlated properties can be obtained usingthe Graph & Plotting option on the main menu. The most recently calculatedtemperature correlated property will be plotted on the screen. Before the graph is shown,the user is given the choice of linear or semi-log axises. The x-axis will be temperaturein the current set of output units. The y-axis will be the calculated physical property inthe current output units. For the linear y-axis the maximum and minimum values willrounded to even values outside the calculated range. For a semi-log plot the y-axis willbe plotted from one power of 10 less than the lowest value to one power of 10 greaterthan the highest value.

After showing the graph on the screen, press any key and you will be promptedto print the graph. For installing the printer or video graphics see the installation section.

V.13 Executing Under MS Windows

PREDICT can be run from within MS-Windows, please see the section underInstallation regarding setting up PREDICT under MS-Windows. In general PREDICTworks well in full screen mode.

To copy data or other information from PREDICT to the MS-Windows clipboardfor pasting into other program, you must first put PREDICT in a “window”. To do this,press <ALT><ENTER>. This will put PREDICT into a window (note that the propertyplots will only work when PREDICT is full screen). Once in a “window”, click on the“dash” in the upper left corner, select Edit, Mark. Then select the area to be copied withthe mouse. Finally, click on the “dash” again, followed by Edit, Copy. The markedinformation is then in the MS-Windows clipboard and can be pasted to other MS-Windows programs.

V.14 EXAMPLE CALCULATIONS

The following pages include sample calculations that have been carried out withPREDICT. It is suggested that the user follow through some of the sample calculationswith the program to get the best understanding of how PREDICT operates.

For each sample, all data and the purpose is given at the beginning of thecalculation.

PREDICT Version 4.0 Page VI-1


Appendix Table 1Lydersen Critical Constants Group Contribution

Group ∆TL ∆PL ∆VL Group ∆TL ∆PL ∆VL

-CH3 (non-ring) 0.020 0.227 55 -O- (ring) 0.014 0.120 8 >CH2 (non-ring) 0.020 0.227 55 >C=O (non-ring) 0.040 0.290 60 >CH- (non-ring) 0.012 0.210 51 >C=O (ring) 0.033 0.200 50 >C< (non-ring) 0.000 0.210 41 -HC=O (aldehyde) 0.048 0.330 73

=CH2 (non-ring) 0.018 0.198 45 -COOH (acid) 0.085 0.400 80 =CH- (non-ring) 0.018 0.198 45 -COO- (ester) 0.047 0.470 80>C= (non-ring) 0.000 0.198 36 =O (any other) 0.020 0.120 11 =C= (non-ring) 0.000 0.198 36 -NH2 0.031 0.095 28

≡CH (non-ring) 0.005 0.153 36 >NH (non-ring) 0.031 0.135 37

≡C- (non-ring) 0.005 0.153 36 >NH (ring) 0.024 0.090 27 >CH2 (ring) 0.013 0.184 45 >N- (non-ring) 0.014 0.170 42 >CH- (ring) 0.012 0.192 46 >N- (ring) 0.007 0.130 32 >C< (ring) -0.007 0.154 31 -CN 0.060 0.360 80 =CH- (ring) 0.011 0.154 37 -NO2 0.055 0.420 78 >C= (ring) 0.011 0.154 36 -SH 0.015 0.270 55 =C= (ring) 0.011 0.154 36 -S- (non-ring) 0.015 0.270 55

-F 0.018 0.224 18 -S- (ring) 0.008 0.240 45 -Cl 0.017 0.320 49 =S 0.003 0.240 47 -Br 0.010 0.500 70 >Si< 0.026 0.468 94 -I 0.012 0.830 95 >SiH- 0.040 0.513 94

-OH (alcohol) 0.082 0.060 18 -SiH3 0.027 0.468 94 -OH (phenols) 0.031 -0.020 3 >(-)Si-O- 0.025 0.730 157 -O- (non-ring) 0.021 0.160 20 [>(-)Si-O-] cyclic 0.027 0.668 116

Note: (-) indicates additional bonds on main element.Reprinted from A. L. Lydersen, Univ. Wisconsin Coll. Eng., Eng. Expt. Stn. 3, Madison, WI, April, 1955

Page VI-2 PREDICT Version 4.0


Appendix Table 2Ambrose Critical Constant Group Contributions

Groups ∆TA ∆PA ∆VA Groups ∆TA ∆PA ∆VA

Alkyl Groups Subsequent Halogens C atoms [Totall] 0.138 0.226 55.1 -F (subsequent) 0.055 0.223 14

>CH- -0.043 -0.006 -8 -Br (subsequent) 0.055 0.5 67 >C< -0.12 -0.03 -17 -Cl (subsequent) 0.055 0.318 45

double bond -0.05 -0.065 -20 Rings if Different triple bond -0.2 -0.17 -40 -CH2 0.09 0.182 44.5

Aliphatic Groups >CH (fused ring) 0.03 0.182 44.5 -O- 0.138 0.16 20 double bond -0.03 0.387 -15

>CO 0.22 0.282 60 -O- 0.09 0.16 10 -CHO 0.22 0.22 55 -NH- 0.09 0.135 30

-COOH 0.578 0.45 80 -S- 0.09 0.27 30 -COOOC- 1.156 0.9 160 Aromatics

-COO- 0.33 0.47 80 benzene 0.448 0.924 286 -NO2 0.37 0.42 78 pyridine 0.448 0.85 260 -NH2 0.208 0.095 30 C4H4(fused) 0.22 0.515 178 -NH- 0.208 0.135 30 -F 0.08 0.183 14 -OH * ** 15 -Cl 0.08 0.318 45 >N- 0.088 0.17 30 -Br 0.08 0.6 67 -CN 0.423 0.36 80 -I 0.08 0.85 90 -S- 0.105 0.27 55 -OH 0.198 -0.025 15 -SH 0.09 0.27 55 Non-Halogen Substitutions on Aromatics >Si< 0.138 0.461 102.2 1st Subst 0.01 0 0

>SiH(-) 0.371 0.507 102.2 Add'l Subst 0.03 0.02 0 -SiH3 0.195 0.461 102.2 Ortho Pairs -0.04 -0.05 0

>Si(-)-O- 0.159 0.725 168.2 Ortho Pairs with -OH -0.08 -0.05 0 >Si(-)-O- cycl 0.131 0.663 125.8 Highly Fluorinated, Perfluorocarbons

-F (first) 0.18 0.223 14 -CF3,>CF2,>CF- 0.2 0.55 83 -Br (first) 0.11 0.5 67 >CF2,>CF-(rng) 0.14 0.42 83 -Cl (first) 0.11 0.318 45 mono H- -0.05 -0.35 0

-Br (first) with -F 0.18 0.5 67 double bond -0.15 -0.5 0 -Cl (first) with -F 0.18 0.318 45 double bond ring -0.03 -0.5 0

* ∆TA (-OH) = 0.87 - 0.11x n + 0.003 x n 2 , **∆PA (-OH) = 0.10 - 0.013 x n, n = (T B - 314.1) / 19.2

∆TA (Platt #) = -0.023 x PLATT, ∆PA (Platt #) = -0.026 x PLATTReprinted with Permission from Ambrose, D., NPL Report Chem. 92, September 1978, Teddington, UK, and

Ambrose, D., NPL Report Chem. 98, May 1979, Teddington, UK



Appendix Table 3Klincewicz & Reid Critical Constant Group Contributions

Group ∆TK ∆PK ∆VK Group ∆TK ∆PK ∆VK

-CH3 -2.433 0.026 16.2 -CHO- 4.332 -0.196 -6.7 >CH2 (non-ring) 0.353 -0.015 16.1 -COOH -25.09 -0.251 -37

>CH2 (ring) 4.253 -0.046 8.2 -COO- (non-ring) 8.89 -0.277 -28.2 >CH- (non-ring) 6.266 -0.083 12.1 -NH2 -4.153 -0.127 -0.1

>CH- (ring) -0.335 -0.027 7.4 >NH (non-ring) 2.005 -0.18 53.7 >C< (non-ring) 16.416 -0.136 8.95 >NH (ring) 2.773 -0.172 -8

>C< (ring) 12.435 -0.111 -6.6 >N- 12.253 -0.163 -0.7 =CH2 -0.991 -0.015 13.9 =N- (ring) 8.239 -0.104 -18.4

=CH- (non-ring) 3.786 -0.05 9.8 -CN -10.38 -0.064 12 =CH- (ring) 3.373 -0.066 5.1 -SH 28.529 -0.303 -27.7

>C= (non-ring) 7.169 -0.067 2.7 -S- (non-ring) 23.905 -0.311 -27.3 >C= (ring) 5.623 -0.089 0.2 -S- (ring) 31.537 -0.208 -61.9

=C= 7.169 -0.067 2.7 -F 5.191 -0.067 -34.1

≡CH -4.561 -0.056 7.5 -Cl 18.353 -0.244 -47.4

≡C- 7.341 -0.112 3 -Br 53.456 -0.692 -148.1 -OH -28.93 -0.19 -24 -I 94.186 -1.051 -270.6

-O- (non-ring) 5.389 -0.143 -26.1 -XCX [X=halogen] -1.77 0.032 0.8 -O- (ring) 7.127 -0.116 -36.6 -NO2 11.709 -0.325 -39.2

>CO 4.332 -0.196 -6.7

NOTE: in -XCX, count all pairs, i.e. CF 2 has 1 -XCX, CCl 3 has 2 XCX

Reproduced by permission of the American Institute of Chemical EngineersKlincewicz, K.M., R. C. Reid, AIChE J., 30(1): 137 (1984).



Appendix Table 4Joback Critical Constant Group Contributions

Group ∆TJ ∆PJ ∆VJ nA Group ∆TJ ∆PJ ∆VJ nA

-CH3 (non-ring) 0.0141 -0.0012 65 4 -OH (phenols) 0.024 0.0184 -25 2 >CH2 (non-ring) 0.0189 0 56 3 -O- (non-ring) 0.0168 0.0015 18 1 >CH- (non-ring) 0.0164 0.002 41 2 -O- (ring) 0.0098 0.0048 13 1 >C< (non-ring) 0.0067 0.0043 27 1 >C=O (non-ring) 0.038 0.0031 62 2

=CH2 (non-ring) 0.0113 -0.0028 56 3 >C=O (ring) 0.0284 0.0028 55 2 =CH- (non-ring) 0.0129 -0.0006 46 2 -HC=O (aldehyde) 0.0379 0.003 82 3 >C= (non-ring) 0.0117 0.0011 38 1 -COOH (acid) 0.0791 0.0077 89 4 =C= (non-ring) 0.0026 0.0028 36 1 -COO- (ester) 0.0481 0.0005 82 3

≡CH (non-ring) 0.0027 -0.0008 46 2 =O (any other) 0.0143 0.0101 36 1

≡C- (non-ring) 0.002 0.0016 37 1 -NH2 0.0243 0.0109 38 3 >CH2 (ring) 0.01 0.0025 48 3 >NH (non-ring) 0.0295 0.0077 35 2 >CH- (ring) 0.0122 0.0004 38 2 >NH (ring) 0.013 0.0114 29 2 >C< (ring) 0.0042 0.0061 27 1 >N- (non-ring) 0.0169 0.0074 9 1 =CH- (ring) 0.0082 0.0011 41 2 -N=, HN= (non-ring) 0.0225 -0.01 0 1 >C= (ring) 0.0143 0.0008 32 1 -N= (ring) 0.0085 0.0076 34 1

-F 0.0111 -0.0057 27 1 -CN 0.0496 0.0101 91 2 -Cl 0.0105 -0.0049 58 1 -NO2 0.0437 0.0064 91 3 -Br 0.0133 0.0057 71 1 -SH 0.0031 0.0084 63 2 -I 0.0068 -0.0034 97 1 -S- (non-ring) 0.0119 0.0049 54 1

-OH (alcohol) 0.0741 0.0112 28 2 -S- (ring) 0.0019 0.0051 38 1Reprinted from Joback, Kevin G., “A Unified Approach to Physical Property Estimation Using Multivariate

Statistical Techniques”, MS Thesis, MIT, June 1982.



Appendix Table 5Fedors Critical Temperature Group Contributions

Group ∆TF Group ∆TF

-CH3 1.79 -NH- 3.04 -CH2- 1.34 -NH- (aromatic) 7.64

>CH- (alone) 0.45 >N- 0.89 >CH- (adjacent) 0.76 >N- (aromatic) 4.74

>C< -0.22 -N= 4.51 =CH2 1.59 -S-S- 9.83 =CH- 1.4 -S- 4.91 >C= 0.89 -SH 5.36

≡CH- 1.79 -F 2.1

≡C- 2.46 -F (aromatic) 0.45 =C= 1.03 -F (perfluoro) 0.54

-COOH 10.72 -Cl 4.2 -COOOC-(anhydride) 7.95 -Cl (disubstituted) 3.71

-COO- 5.32 -Cl (trisubstituted) 3.17 -OOCCOO- (oxalate) 6.25 -Br 5.58

-CO- 5.36 -I 8.04 -O- (non-aromatic) 1.56 -I (aromatic) 10.77

-O- (aromatic) 2.68 3-membered ring 0.45 -OH 5.63 5-membered ring 2.23

-OH (aromatic) 9.65 6-membered ring 2.68 -CHO 5.49 hetro (N,O,S) in ring 0.45

-C≡N 8.49 sub on C= (non arom) 0.58

-C≡N (aromatic) 9.38 ortho sub in bz ring 1.16 -NH2 4.56 conjugation, per = 0.13

-NH2 (aromatic) 9.2Reprinted with permission from Fedors, R. F., Chem. Eng. Commun., 16: 149 (1982)

Copyright 1982 Gordon and Breach, Science Publishers, Inc.



Appendix Table 6Fedors Critical Volume Group Contributions

Group ∆VF Group ∆VF

C 34.426 Si (siloxane) 126.483H 9.172 Si (cyclic siloxane) 126.483O 20.291 3-Membered Ring -15.824

O (alcohols) 18 4-Membered Ring -17.247N 48.855 5-Membered Ring -39.126

N (amines) 47.422 6-Membered Ring -39.508F 22.242 Double Bond 5.028Cl 52.801 Triple Bond 0.7973Br 71.774 Additional Ring 35.524I 96.402 attached directlyS 50.866 to another, i.e.Si 86.174 biphenyl,naphtalene

Reproduced by permission of the American Institute of Chemical EngineersFedors, R. F., AIChE J., 25(1): 202 (1979)



Appendix Table 7Joback Point Property Group Contributions

Group ∆BJ ∆HJ ∆GJ ∆HVJ Group ∆BJ ∆HJ ∆GJ ∆HVJ

-CH3 (non-ring) 23.58 -76.45 -43.96 567 -OH (phenols) 76.34 -221.7 -197.4 2987 >CH2 (non-ring) 22.88 -20.64 8.42 532 -O- (non-ring) 22.42 -132.2 -105 576 >CH- (non-ring) 21.74 29.89 58.36 404 -O- (ring) 31.22 -138.2 -98.22 1119 >C< (non-ring) 18.25 82.23 116.02 152 >C=O (non-ring) 76.75 -133.2 -120.5 2144

=CH2 (non-ring) 18.18 -9.63 3.77 412 >C=O (ring) 94.97 -164.5 -126.3 1588 =CH- (non-ring) 24.96 37.97 48.53 527 -HC=O (aldehyde) 72.24 -162 -143.5 2173 >C= (non-ring) 24.14 83.99 92.36 511 -COOH (acid) 169.09 -426.7 -387.9 4669 =C= (non-ring) 26.15 142.14 136.7 636 -COO- (ester) 81.1 -337.9 -302 2302

≡CH (non-ring) 9.2 79.3 77.71 276 =O (any other) -10.5 -247.6 -250.8 1412

≡C- (non-ring) 27.38 115.51 109.82 789 -NH2 73.23 -22.02 14.07 2578 >CH2 (ring) 27.15 -26.8 -3.68 573 >NH (non-ring) 50.17 53.47 89.39 1538 >CH- (ring) 21.78 8.67 40.99 464 >NH (ring) 52.82 31.65 75.61 1656 >C< (ring) 21.32 79.72 87.88 154 >N- (non-ring) 11.74 123.34 163.16 453 =CH- (ring) 26.73 2.09 11.3 608 -N=, HN= (non-ring) 74.6 23.61 0 797 >C= (ring) 31.01 46.43 54.05 731 -N= (ring) 57.55 55.52 79.93 1560

-F -0.03 -251.9 -247.2 -160 -CN 125.66 88.43 89.22 3071 -Cl 38.13 -71.55 -64.31 1083 -NO2 152.54 -66.57 -16.83 4000 -Br 66.86 -29.48 -38.06 1573 -SH 63.56 -17.33 -22.99 1645 -I 93.84 21.06 5.74 2275 -S- (non-ring) 68.78 41.87 33.12 1629

-OH (alcohol) 92.88 -208 -189.2 4021 -S- (ring) 52.1 39.1 27.76 1430Reprinted from Joback, Kevin G., “A Unified Approach to Physical Property Estimation Using Multivariate




Appendix Table 8Ideal Gas Heat of Formation Bond Contributions

Bond ∆SBC ∆HBC Bond ∆SBC ∆HBC

C-H 12.9 -3.83 O-H 24 -27 C-D 13.6 -4.73 O-D 24.8 -27.9 C-C -16.4 2.73 O-Cl 32.5 9.1

C(d)-H 13.8 3.2 O-O 9.1 21.5 C(d)-C -14.3 6.7 H-CO* 26.8 -13.9 Bz-H 11.7 3.25 C-CO -0.6 -14.4 Bz-C -17.4 7.25 O-CO 9.8 -50.5 C-Cl 19.7 -7.4 Cl-CO 35.2 -27

C(d)-Cl 21.2 -0.7 C-N -12.8 9.3 C-Br 22.65 2.2 N-H 17.7 -2.6

C(d)-Br 24.1 9.7 C-S -1.5 6.7 C-I 24.65 14.1 S-H 27 -0.8

C(d)-I 26.1 21.7 (NO2)- 43.1 -3 C-O -4 -12 (NO)-O 35.5 9

Bz ≡ Benzene Ring,C(d) ≡ tetravalent group >C=C<,* H-CO hydrogen-carbonyl bondReprinted from, Benson, S. W., “Thermochemical Kinetics”, Chap. 2, Wiley, New York, 1968.



Appendix Table 9Franklin Ideal Gas Heat of Formation Group Contributions

Group ∆HF Group ∆HF

-CH3 -10.12 -COOOC- -102.6 >CH2 -4.93 -C≡N 29.5 >CH- -1.09 -NO2 -8.5 >C< 0.8 -ONO -10.9

=CH2 6.25 -ONO2 -18.4 =C= 33.42 -N=C 44.4

≡C- 27.34 -NH2 (aromatic) -6.4

≡CH 27.1 -SH 3.1 -HC=CH2 15 -S- 10.6 >C=CH2 16.89 ⇔S⇔ 7.8 >C=C< 24.57 Ring Corrections >C=CH- 20.19 C3 cycloparaffin ring 24.22

-HC=CH- (cis) 18.88 C4 cycloparaffin ring 18.4 -CH=CH- (trans) 17.83 C5 cycloparaffin ring 4.94

⇔CH2 10.08 C6 cycloparaffin ring -0.45

⇔CH- 12.04 Paraffin Branching

⇔⇔CH 3.3 Side Chain with 2 or

⇔⇔C- 5.57 more C atoms 0.8

⇔⇔C⇔ 4.28 3 adjacent >CH- grps 2.3 -OH (primary alc) -41.9 adjacent >C<&>CH-grp 2.5

-OH (secondary alc) -44.9 adjacent >C<&>C< grp 5.4 -OH (tert alc) -49.2 >C< not adjacent to

-OH (aromatic) -46.9 terminal C 1.7 -CHO (aldehyde) -33.9 Aromatic Branching

>C=O (ketone) -31.6 1,2 Dimethyl 0.6 -COOH (acid) -94.6 1,3 methyl ethyl 0.6 -COO- (ester) -79.8 1,2-methyl ethyl 1.4

-O- (ether) -27.2 1,2,3-trimethyl 1.4

** ⇔ resonating bond **

Reprinted from, Franklin, J. L., Ind. Eng. Chem., 41: 1070 (1949) andFranklin, J. L., J. Chem. Phys., 21: 2029 (1953).



Appendix Table 10vanKrevelen Charmin Ideal Gas Free Energy of Formation Group Contributions

Group ∆GKC Group ∆GKC Group ∆GKC Group ∆GKC

-CH3 -4.3423 -C⇔⇔ 8.102 >C=C=O -7.4744 -F -45.696 >CH2 2.0484 ⇔C⇔⇔ 5.20564 -C≡N 28.6044 -Cl -8.25 >CH- 7.9668 3-mem ring 14.3839 -N=C 43.6678 -Br -2.3948 >C< 13.0883 4-mem ring 2.833 -NH2 10.8958 -I 7.8

H2C=CH- 18.6689 5-mem ring -2.728 >NH 22.3468 Six Member Ring H2C=C< 22.1737 6-mem ring -6.0003 >N- 30.8436 Single Br. -0.93

-CH=CH-(trns) 22.8937 Pentene ring -10.7941 ⇔N⇔ 14.6278 1,1 Position -0.25866 -CH=CH-(cis) 23.5187 Hexene ring -15.1961 -NO2 2.026 Cis 1,2 -0.19

-HC=C< 27.0561 Side Chain 2 C 1.31 -SH 7.4914 Trans 1,2 -2.41 >C=C< 32.80254 3 adj >CH- 2.12 -S- 0.9116 Cis 1,3 -2.7

H2C=C=CH2 48.31046 >CHC<(-) 1.8 ⇔S⇔ 0.5498 Trans 1,3 -1.6 H2C=C=CH- 52.4613 adj >C< 2.58 >SO -20.0878 Cis 1,4 -1.11 H2C=C=C< 55.47652 -OH -37.7456 >SO2 -65.9516 Trans 1,4 -2.8

-HC=C=CH- 56.87934 -O- -18.323 Five Member Ring Aromatic Ring

H2C⇔ 7.4485 ⇔O⇔ -15.986 Sngl Br. -1.04 1,2 position 1.02

-HC⇔ 10.4913 -CHO -26.9854 1,1 position -1.85 1,3 position -0.31

>C⇔ 13.6369 >CO -25.3682 Cis 1,2 -0.38 1,4 position 0.93

HC≡ 24.7683 -COOH -89.8672 Trans 1,2 -2.55 1,2,3 posit. 1.91

-C≡ 25.3735 -COO- -84.8422 Cis 1,3 -1.2 1,2,4 posit. 1.1

HC⇔⇔ 4.8797 -CH=C=O -11.4892 Trans 1,3 -2.35 1,3,5 posit. 0

⇔ conjugated bonds; (-) additional bonds on base atomReprinted from, van Krevelen, D. W. and H. A. G. Chermin, Chem. Eng. Sci., 1: 66 (1951), 1: 238 (1952)



Appendix Table 11ABenson Ideal Gas Heat of Formation Hydrocarbons Groups

Group ∆HB Group ∆HB Group ∆HB

C-(C)(H)3 -42.2 C-(C=)(H)3 -42.2 C-(Cφ)2(C)2 -4.86C-(C)2(H)2 -20.72 C-(C=)2(H)2 -17.96 C-

(Cφ)(C=)(H)2-17.96

C-(C)3(H) -7.95 C-(C=)2(C)2 4.86 C≡-(H) 112.75C-(C)4 2.09 C-(C=)(C)3 7.03 C≡-(C) 115.35

C=-(H)2 26.21 C-(C=)(C)(H)2 -19.93 C≡-(C=) 122.25C=-(C)(H) 35.96 C-(C=)(C)2(H) -6.2 C≡-(Cφ) 122.25C=-(C)2 43.29 C-(C=)2(C)(H) -5.19 C≡-(H) 13.82

C=-(C=)(H) 28.39 C-(C≡)(H)3 -42.2 C≡-(C) 23.07C=-(C=)(C) 37.18 C-(C≡)(C)(H)2 -19.8 Cφ-(C=) 23.78C=-(C=)2 19.26 C-(C≡)(C)2(H) -7.2 Cφ-(C≡) 23.86

C=-(Cφ)(H) 28.39 C-(Cφ)(H)3 -42.2 Cφ-(Cφ) 20.77

C=-(Cφ)(C) 36.17 C-(Cφ)(C)(H)2 -20.35 =C=(C)(C) 143.19

C=-(Cφ)2 33.49 C-(Cφ)(C)2(H) -4.1 Cφf-(Cφ)2(Cφf) 20.1

C=-(C≡)(H) 28.39 C-(Cφ)(C)3 11.76 Cφf-(Cφ)(Cφf)2 15.49

C=-(C≡)(C) 35.71 C-(Cφ)2(C)(H) -5.19 Cφf-(Cφf)3 6.07

Cφ, Indicates a carbon atom in a benzene ringReprinted from Benson, S. W., et al., Chem. Rev., 69(3): 279 (1969)

Appendix Table 11B Appendix Table 11CBenson Ideal Gas Heat of Formation Benson Ideal Gas Heat of FormationHydrocarbon Next Nearest Neighbors Hydrocarbon Ring Corrections

Group ∆HB Group ∆HB

Alkane gauche 3.35 Cyclopropane 115.56Alkene gauche 2.09 Cyclopropene 224.83

Cis 4.19 Cyclobutane 109.69Ortho 2.39 Cyclobutene 124.77

Cyclopentane 26.38Cyclopentene 24.7

Cyclopentadiene 25.12Cyclohexene 5.86Cycloheptane 26.8Cyclooctane 41.45

Reprinted from Benson, S. W., et al., Chem. Rev., 69(3): 279 (1969)



Appendix Table 11DBenson Ideal Gas Heat of Formation Halogen Groups


C-(F)3(C) -663.2 C-(Br)(C)3 -1.7 C=-(I)(H) 102.6C-(F)2(H)(C) -457.6 C-(I)(H)2(C) 33.5 C=-(C)(Cl) -8.8C-(F)(H)2(C) -215.6 C-(I)(H)(C)2 44 C=-(C)(I) 98.8C-(F)2(C)2 -406.1 C-(I)(C)(C=)(H) 55.77 C=-(C=)(Cl) -14.91

C-(F)(H)(C)2 -205.2 C-(I)(C=)(H)2 34.29 C=-(C=)(I) 92.7 C-(F)(C)3 -203.1 C-(I)(C)3 54.4 Cφ-(F) -179.2

C-(F)2(Cl)(C) -445.1 N-(F)2(C) -32.7 Cφ-(Cl) -15.9 C-(Cl)3(C) -86.7 C-

(Cl)(C)(O)(H)-90.4 Cφ-(Br) 44.8

C-(Cl)2(H)(C) -79.1 C-(I)2(C)(H) 108.9 Cφ-(I) 100.5 C-(Cl)(H)2(C) -69.1 C-(I)(O)(H)2 15.9 C-(Cφ)(F)3 -681.2 C-(Cl)2(C)2 -92.1 C=-(F)2 -324.5 C-(Cφ)(Br)(H)2 -28.9

C-(Cl)(H)(C)2 -62 C=-(Cl)2 -7.5 C-(Cφ)(I)(H)2 35.2 C-(Cl)(C)3 -53.6 C=-(F)(H) -157.4 C-(Cl)2(CO)(H) -74.5

C-(Br)(H)2(C) -22.6 C=-(Cl)(H) -5 C-(Cl)3(CO) -82.1 C-(Br)(H)(C)2 -14.2 C=-(Br)(H) 46.1 CO-(Cl)(C) -126.4


Appendix Table 11EBenson Ideal Gas Heat of Formation

Halogen Next Nearest NeighborsGroup ∆HB

Ortho (F)(F) 20.9Ortho (Cl)(Cl) 9.2

Ortho (Alkane)(Halogen) 2.5Cis (Halogen)(Halogen) 1.3Cis (Halogen)(Alkane) -3.3




Appendix Table 11FBenson Ideal Gas Heat of Formation Nitrogen Groups


C-(N)(H)3 -42.2 N[a]=-(C) 136.1 N-(CO)(Cφ) -2.1C-(N)(C)(H)2 -27.6 N-(Cφ)(H)2 20.1 C-(CN)(C)(H)2 94.2C-(N)(C)2(H) -21.8 N-(Cφ)(C)(H) 62.4 C-(CN)(C)2(H) 108

C-(N)(C)3 -13.4 N-(Cφ)(C)2 109.7 C-(CN)(C)3 121.4N-(C)(H)2 20.1 N-(Cφ)2(H) 68.2 C=-(CN)(H) 156.6N-(C)2(H) 64.5 Cφ-(N) -2.1 C=-(CN)(C) 163.91

N-(C)3 102.2 N[a]=-(N) 96.3 C=-(CN)2 352.1N-(N)(H)2 47.7 CO-(N)(H) -123.9 Cφ-(CN) 149.9

N-(N)(C)(H) 87.5 CO-(N)(C) -137.3 C≡-(CN) 267.1N-(N)(C)2 122.3 N-(CO)(H)2 -62.4 C-(NO2)(C)(H)2 -63.2

N-(N)(Cφ)(H) 92.5 N-(CO)(C)(H) -18.4 C-(NO2)(C)2(H) -66.2N[i]=-(H) 68.2 N-(CO)(C)2 19.7 C-(NO2)2(C)(H) -62.4N[i]=-(C) 89.2 N-(CO)(Cφ)(H) 1.7 O-(NO)(C) -24.7

N[i]=-(Cφ) 69.9 N-(CO)2(H) -77.5 O-(NO2)(C) -81.2N[a]=-(H) 105.1 N-(CO)2(C) -24.7

N[i], imine (N=C), N[a], azo (N=N), C φ, carbon atom in a benzene ringReprinted from Benson, S. W. et al., Chem. Rev., 69(3): 279 (1969)

Appendix Table 11GBenson Ideal Gas Heat of FormationNitrogen Containing Ring Corrections

Group ∆HB

Ethyleneimine 116Azetidine 109.7

Pyrrolidine 28.5Piperidine 4.2

Succinimide 35.6Reprinted from Benson, S. W. et al., Chem. Rev., 69(3): 279 (1969)



Appendix Table 11HBenson Ideal Gas Heat of Formation Oxygen Groups


CO-(CO)(H) -108.9 O-(CO)(H) -243.3 Cφ-(O) -3.77CO-(CO)(C) -122.3 O-(O)(C) -18.84 C-(CO)2(H)2 -31.82CO-(O)(C=) -136.1 O-(O)2 -79.55 C-(CO)(C)2(H) -7.54

CO-(O)(Cφ) -136.1 O-(O)(H) -68.12 C-(CO)(C)(H)2 -21.77CO-(O)(C) -147 O-(C=)2 -137.3 C-(CO)(C)3 6.7CO-(O)(H) -134.4 O-(C=)(C) -133.6 C-(CO)(H)3 -42.29

CO-(C=)(H) -132.7 O-(Cφ)2 -88.34 C-(O)2(C)2 -77.87

CO-(Cφ)2 -159.5 O-(Cφ)(C) -94.62 C-(O)2(C)(H) -68.24

CO-(Cφ)(C) -129.4 O-(Cφ)(H) -158.7 C-(O)2(H)2 -63.22

CO-(Cφ)(H) -144.9 O-(C)2 -99.23 C-(O)(Cφ)(H)2 -33.91CO-(C)2 -131.5 O-(C)(H) -158.7 C-(O)(Cφ)(C)(H) -25.46

CO-(C)(H) -121.8 C=-(CO)(O) 37.68 C-(O)(C=)(H)2 -28.89CO-(H)2 -108.9 C=-(CO)(C) 39.36 C-(O)(C)3 -27.63

O-(Cφ)(CO) -136.1 C=-(CO)(H) 35.59 C-(O)(C)2(H) -30.14O-(CO)2 -213.1 C=-(O)(C=) 37.26 C-(O)(C)(H)2 -33.91

O-(CO)(O) -79.55 C=-(O)(C) 43.12 C-(O)(H)3 -42.29

O-(CO)(C=) -196.4 C=-(O)(H) 36.01

O-(CO)(C) -185.5 Cφ-(CO) 40.61


Appendix Table 11IBenson Ideal Gas Heat of Formation Oxygen Ring & Stain Contributions

Group ∆HB Group ∆HB

Ether oxygen, gauche 1.3 1,3,5-Trioxane 21.4Dithertiary ethers 32.7 Furan -24.3Ethylene Oxide 115.7 Dihydropyran 5

Trimethylene Oxide 110.5 Cyclopentanone 21.8Tetrahydrofuran 28.1 Cyclohexanone 9.2Tetrahydropyran 9.2 Succinic Anhydride 18.8

1,3-Dioxane 3.8 Glutaric Anhydride 3.31,4-Dioxane 22.6 Maleic Anhydride 15.1




Appendix Table 11JBenson Ideal Gas Heat of Formation Sulphur Groups


C-(H)3(S) -42.2 S-(S)(Cφ) 60.7 C=-(C)(SO2) 60.58 C-(C)(H)2(S) -23.66 S-(S)2 12.73 SO2-(C=)(Cφ) -287.1 C-(C)2(H)(S) -11.05 C-(SO)(H)3 -42.2 SO2-(C=)2 -308.1

C-(C)3(S) -2.3 C-(C)(SO)(H)2 -32.32 SO2-(C)2 -292

C-(Cφ)(H)2(S) -19.8 C-(C)3(SO) -12.77 SO2-(C)(Cφ) -302.7 C-(C=)(H)2(S) -27 C-(C=)(SO)(H)2 -30.77 SO2-(Cφ)2 -287.1

Cφ-(S) -7.5 Cφ-(SO) 9.6 SO2-(SO2)(Cφ) -319.2 C=-(H)(S) 35.84 SO-(C)2 -60.33 CO-(S)(C) -132.1 C=-(C)(S) 45.76 SO-(Cφ)2 -50.2 S-(H)(CO) -5.9 S-(C)(H) 19.34 C-(SO2)(H)3 -42.2 CS-(N)2 -132.1

S-(Cφ)(H) 50.07 C-(C)(SO2)(H)2 -32.15 N-(CS)(H)2 53.51 S-(C)2 48.19 C-(C)2(SO2)(H) -10.97 S-(S)(N) -20.52

S-(C)(C=) 41.74 C-(C)3(SO2) -2.55 N-(S)(C)2 125.19 S-(C=)2 -19.01 C-

(C=)(SO2)(H)2-29.89 SO-(N)2 -132.1

S-(Cφ)(C) 80.22 C-(Cφ)(SO2)(H)2 -23.19 N-(SO)(C)2 66.99

S-(Cφ)2 108.44 Cφ-(SO2) 9.6 SO2-(N)2 -132.1

S-(S)(C) 29.52 C=-(H)(SO2) 52.46 N-(SO2)(C)2 -85.41


Appendix Table 11KBenson Ideal Gas Heat of FormationSulphur Containing Ring Corrections

Group ∆HB

Thiirane 74.11Trimethylene sulfide 81.1Tetrahydrothiophene 7.24

Thiacycloheptane 16.293-Thiocyclopentene 21.232-Thiocyclopentene 21.23

Thiophene 7.24Reprinted from Benson, S. W., et al., Chem. Rev., 69(3): 279 (1969)



Appendix Table 11LBenson Ideal Gas Heat of Formation Silicon Groups


Si-(C)(H)3 -39.4 Si-(C)(F)3 -1191 Si-(O)4 -256.3 Si-(C)2(H)2 -21.7 Si-(C)3(Br) -166.7 O-(Si)(O) -91.4 Si-(C)3(H) -38.6 Si-(C)3(I) -80.4 O-(Si)2 -357

Si-(C)4 -60.4 Si-(C)(H)(Cl)2 -359.8 O-(Si)(C) -190.8 Si-(Si)(H)3 40 Si-(C)2(H)(Cl) -208.3 O-(Si)(H) -283.1 Si-(Si)2(H)2 40.9 Si-(O)(F)3 -1274 Si-(Si)(C)(O)2 -494.8 Si-(Si)2(C)2 -18.3 Si-(O)3(Cl) -656.8 C-(Si)(O)(H)2 -7.8 Si-(Si)(C)3 -55.8 Si-(Si)(F)3 -1183 Si-(Cφ)4 -57.1

Si-(Si)4 169.9 Si-(Si)2(F)2 -795.7 Si-(Cφ)2(Cl)2 -404.3 C-(Si)(C)(H)2 -17.3 Si-(Si)(Cl)3 -493.2 Si-(Cφ)(O)3 -196.2 C-(Si)(C)2(H) -2.2 Si-(Si)(O)3 -238.3 Si-(Cφ)2(C)(H) -38.6

C-(Si)(H)3 -42.2 Si-(O)3(H) -98.3 Cφ-(Si) 28.7 Si-(C)(Cl)3 -487.2 Si-(C)(O)3 -196 O-(Si)(Cφ) -217.6 Si-(C)2(Cl)2 -364 Si-(C)2(O)2 -144.1 Ring Correc SiC3 62.9 Si-(C)3(Cl) -227.3 Si-(C)3(O) -95.5 Ring Correc SiC4 41.2


Appendix Table 11MBenson Ideal Gas Heat of Formation Boron Groups


B-(C)3 3.7 B-(C)2(O) -52.7 B-(N)2(Cl) -357.5 C-(B)(C)(H)2 -13.2 B-(Cφ)O)2 -218.5 B-(N)(Cl)2 -412.7 C-(B)(C)2(H) 4.7 B-(S)3 -279.5 B-(B)(Cl)2 -244.6

C-(B)(H)3 -42.2 S-(B)(C) 67.2 B-(O)2(Cl) -321.4

B-(Cφ)3 3.7 S-(B)(Cφ) 88.1 B-(O)(Cl)2 -374.7

Cφ-(B) 25.8 B-(N)3 -279.5 B-(C)2(Cl) -175.2 B-(O)3 -279.5 B-(C)2(N) -131.3 B-(Cφ)2(Cl) -283.2

B-(O)2(H) -150.4 B-(C)(N)(O) -199.5 B-(Cφ)(Cl)2 -343.5 B-(O)(H)2 -34.7 N-(B)(C)2 95.7 B-(C)2(Br) -111.6 B-(B)2(O)2 -142.2 N-(B)(C)(H) -126 B-(Cφ)2(Br) -199.1 O-(B)(C) -170.9 B-(O)(F)2 -834.9 B-(Cφ)(Br)2 -224.2 O-(B)(H) -255.7 B-(O)2(F) -531.3 B-(C)2(I) -35.8

O-(B)(Cφ) -173.6 B-(B)(F)2 -715.9 O-(B)(O) -54.1 B-(C)(F)2 -806.2




Appendix Table 11NBenson Ideal Gas Heat of Formation Phosphorous, Lead & Zinc Groups


C-(P)(H)3 -42.17 PO-(C)3 -304.6 N-(P)(C)2 134.72 C-(P)(C)(H)2 -10.33 PO-(C)(Cl)2 -514.6 N-(PO)(C)2 74.48 C-(PO)(H)3 -42.17 PO-(C)(O)(Cl) -471.1 P:N-(C)3(C) 2.09

C-(PO)(C)(H)2 -14.23 PO-(C)(O)2 -416.3 P:N-(Cφ)3(C) -107.5 C-(P:N)(H)3 -42.17 PO-(O)3 -437.7 P:N-(N:P)(C)2(P:N) -64.85

C-(N:P)(C)(H)2 81.17 PO-(O)2(F) -701.7 P:N-(N:P)(Cφ)2(P:N) -95.81

Cφ-(P) -7.53 PO-(Cφ)3 -221.3 P:N-(N:P)(Cl)2(P:N) -243.5

Cφ-(PO) 9.62 PO-(N)3 -437.7 P:N-(N:P)(O)2(P:N) -181.6

Cφ-(P:N) 9.62 O-(C)(P) -98.32 C-(Pb)(H)3 -42.17 P-(C)3 29.29 O-(H)(P) -245.6 C-(Pb)(C)(H)2 -7.11

P-(C)(Cl)2 -210.5 O-(C)(PO) -170.3 Pb-(C)4 305.01

P-(Cφ)3 118.41 O-(H)(PO) -272 C-(Zn)(H)3 -42.17 P-(O)3 -279.5 O-(PO)2 -228 C-(Zn)(C)(H)2 -7.45 P-(N)3 -279.5 O-(P:N)(C) -170.3 Zn-(C)2 139.33




Appendix Table 11OBenson Ideal Gas Heat of Formation Sn, Cr, Ti, V, Cd, Al, Ge & Hg Groups


C-(Sn)(H)3 -42.17 Sn-(C=)(C)3 157.32 Al-(C)2(Cl) -265.2 C-(Sn)(C)(H)2 -9.12 Sn-(Cφ)4 109.87 C-(Al)(H)3 -42.2 C-(Sn)(C)2(H) 14.14 Sn-(C)3(Cφ) 146.15 Al-(Al)(Cl)2 -405.9

C-(Sn)(C)3 34.14 Sn-(C)3(Sn) 110.46 C-(Ge)(C)(H)2 -32.22

C-(Sn)(Cφ)(H)2 -32.51 O-(Cr)(C) -98.32 Ge-(C)4 151.46

Cφ-(Sn) 23.05 Cr-(O)4 -267.78 Ge-(Ge)(C)3 65.27 C=-(Sn)(H) 36.69 O-(Ti)(C) -98.32 C-(Hg)(H)3 -42.17

Sn-(C)4 151.46 Ti-(O)4 -656.89 C-(Hg)(C)(H)2 -11.21 Sn-(C)3(Cl) -41 N-(Ti)(C)2 163.59 C-(Hg)(C)2(H) 15.15 Sn-(C)2(Cl)2 -205.9 Ti-(N)4 -514.63 Cφ-(Hg) -7.53 Sn-(C)(Cl)3 -374.5 O-(V)(C) -98.32 Hg-(C)2 177.82 Sn-(C)3(Br) -7.53 V-(O)4 -364.01 Hg-(C)(Cl) -11.8 Sn-(C)3(I) 41.42 C-(Cd)(H)3 -42.17 Hg-(C)(Br) 20.42 Sn-(C)3(H) 145.6 C-(Cd)(C)(H)2 -1.26 Hg-(C)(I) 66.02 Sn-(C=)4 151.46 Cd-(C)2 194.14 Hg-(Cφ)2 269.45

Sn-(C=)3(Cl) -34.31 Al-(C)3 45.3 Hg-(Cφ)(Cl) 41.42

Sn-(C=)2(Cl)2 -212.1 C-(Al)(C)(H)2 -28.4 Hg-(Cφ)(Br) 75.73

Sn-(C=)(Cl)3 -343.9 Al-(C)2(H) -9 Hg-(Cφ)(I) 116.73




Appendix Table 12Pitzer Vapor Pressure Parameters

TR -P(0) -P(1) TR -P(0) -P(1)

1 0 0 0.56 1.818 2.120.99 0.025 0.021 0.55 1.89 2.2420.98 0.05 0.042 0.54 1.965 2.370.97 0.076 0.064 0.53 2.04 2.5020.96 0.102 0.086 0.52 2.13 2.660.95 0.129 0.109 0.51 2.218 2.8120.94 0.156 0.133 0.5 2.315 2.9620.92 0.212 0.18 0.49 2.413 3.13

0.9 0.27 0.23 0.48 2.515 3.310.88 0.33 0.285 0.47 2.62 3.550.86 0.391 0.345 0.46 2.73 3.6950.84 0.455 0.405 0.45 2.85 3.90.82 0.522 0.475 0.44 2.97 4.1

0.8 0.592 0.545 0.43 3.1 4.320.78 0.665 0.62 0.42 3.24 4.540.76 0.742 0.705 0.41 3.385 4.770.74 0.823 0.8 0.4 3.54 5.010.72 0.909 0.895 0.39 3.7 5.28

0.7 1 1 0.38 3.87 5.560.69 1.047 1.06 0.37 4.04 5.880.68 1.096 1.12 0.36 4.22 6.240.67 1.145 1.185 0.35 4.41 6.640.66 1.198 1.25 0.34 4.6 7.080.65 1.25 1.32 0.33 4.8 7.650.64 1.308 1.39 0.32 5.005 8.30.63 1.368 1.463 0.31 5.22 8.980.62 1.424 1.545 0.3 5.45 9.940.61 1.485 1.628 0.29 5.68 10.92

0.6 1.544 1.71 0.28 5.91 11.960.59 1.61 1.81 0.27 6.14 13.10.58 1.68 1.908 0.26 6.38 14.250.57 1.747 2.02 0.25 6.65 15.9

Reprinted with permission from Pitzer, K. S., D. Z. Lippman,R. F. Curl, C. M. Huggins and D. E. Petersen, J. Am. Chem. Soc.,

7: 3433 (1955) and Carruth, G. F., R. Kobayashi , Ind. Eng.Chem. Fundam., 11(4): 509 (1972)



Appendix Table 13Halm Stiel Vapor Pressure Parameters

TR -P(0) -P(1) -P(2)

1 0 0 00.99 0.025 0.021 00.98 0.05 0.042 00.97 0.076 0.064 00.96 0.102 0.086 00.95 0.129 0.109 00.94 0.156 0.133 00.92 0.212 0.18 0

0.9 0.27 0.23 00.88 0.33 0.285 00.86 0.391 0.345 00.84 0.455 0.405 00.82 0.522 0.475 0

0.8 0.592 0.545 00.78 0.665 0.62 00.76 0.742 0.705 00.74 0.823 0.8 00.72 0.909 0.895 0

0.7 1 1 00.68 1.096 1.12 0.1560.66 1.198 1.25 0.3240.64 1.308 1.39 0.520.62 1.426 1.54 0.745

0.6 1.552 1.7 10.58 1.688 1.88 1.310.56 1.834 2.08 1.670.54 1.974 2.34 2.110.52 2.141 2.61 2.41

0.5 2.321 2.9 2.870.48 2.516 3.25 3.440.46 2.745 3.54 3.780.44 3.011 3.81 4.6

Reproduced by permission of the American Institute ofChemical Engineers, Halm, R. L., L. I. Stiel, AIChE J.,

13(2): 351 (1967).



Appendix Table 14Pitzer Heat of Vaporization Parameters

TR S(0) S(1) TR S(0) S(1)

1 0 0 0.66 14.62 20.50.99 2.57 2.83 0.64 15.36 21.80.98 3.38 3.91 0.62 16.12 23.20.97 4 4.72 0.6 16.92 24.60.96 4.52 5.39 0.58 17.74 26.20.95 5 5.96 0.56 18.64 27.80.94 5.44 6.51 0.54 19.56 29.840.92 6.23 7.54 0.52 20.55 32

0.9 6.95 8.53 0.5 21.6 34.220.88 7.58 9.39 0.48 22.7 36.480.86 8.19 10.3 0.46 24.05 38.80.84 8.79 11.2 0.44 25.5 41.140.82 9.37 12.1 0.42 27.05 43.5

0.8 9.97 13 0.4 28.83 460.78 10.57 13.9 0.38 30.7 49.20.76 11.2 14.9 0.36 32.8 530.74 11.84 16 0.34 35.1 57.40.72 12.49 17 0.32 37.55 63.6

0.7 13.19 18.1 0.3 40.2 71.50.68 13.89 19.3

Reprinted with permission from Pitzer, K. S.,. D. Z. Lippman, R. F. Curl, C. M. Hugginsand D. E. Petersen, J. Am. Chem. Soc., 7: 3433 (1955)

Copyright 1955 American Chemical Society



Appendix Table 15Halm Stiel Heat of Vaporization ParametersTR S(0) S(1) S(2)

0.72 12.49 17 24.80.7 13.19 18.1 28.6

0.68 13.89 19.3 31.80.66 14.62 20.5 34.50.64 15.36 21.8 36.90.62 16.12 23.2 39.1

0.6 16.92 24.6 41.10.58 17.74 26.2 42.90.56 18.64 27.8 44.7

Reproduced by permission of the American Institute ofChemical Engineers, Halm, R. L., L. I. Stiel, AIChE J.,

13(2): 351 (1967).



Appendix Table 16Halm Stiel Liquid Density Parameters

TR V(0) V(1) V(2) V(3) V(4) V(5)

1 0.291 -0.114 -1.42 0.069 -7.05 1.510.98 0.1968 -0.112 -1.39 0.078 -6.22 1.610.96 0.1799 -0.109 -1.36 0.079 -5.54 1.650.94 0.1696 -0.105 -1.33 0.076 -5.01 1.650.92 0.1614 -0.1 -1.31 0.071 -4.48 1.64

0.9 0.1547 -0.096 -1.29 0.066 -4.25 1.620.88 0.149 -0.092 -1.27 0.062 -3.99 1.610.86 0.1443 -0.089 -1.25 0.059 -3.78 1.60.84 0.1401 -0.086 -1.23 0.057 -3.61 1.590.82 0.1366 -0.084 -1.22 0.056 -3.47 1.58

0.8 0.1335 -0.082 -1.21 0.056 -3.35 1.580.78 0.1307 -0.081 -1.19 0.056 -3.25 1.580.76 0.1281 -0.081 -1.18 0.057 -3.15 1.580.74 0.1257 -0.08 -1.17 0.057 -3.05 1.570.72 0.1235 -0.079 -1.16 0.057 -2.95 1.56

0.7 0.1215 -0.079 -1.14 0.057 -2.85 1.550.68 0.1195 -0.078 -1.13 0.057 -2.76 1.530.66 0.1176 -0.078 -1.11 0.058 -2.66 1.510.64 0.1159 -0.078 -1.1 0.059 -2.58 1.490.62 0.1143 -0.078 -1.08 0.061 -2.5 1.47

0.6 0.1129 -0.079 -1.06 0.064 -2.44 1.450.58 0.1116 -0.08 -1.04 0.067 -2.41 1.420.56 0.1102 -0.081 -1.02 0.069 -2.41 1.39

Reproduced by permission of the American Institute of Chemical EngineersHalm, R. L., L. I. Stiel, AIChE J., 16(1): 3 (1970)



Appendix Table 17Bhirud Liquid Density Parameters

TR UNP(0) UNP

(1) UP(0) UP

(2) TR UNP(0) UNP

(1) UP(0) UP

(2)

1 -1.243 -0.2629 -1.248 0.7 0.74 -1.7797 -0.5222 -1.7797 1.00240.999 -1.425 -0.283 -1.3 0.905 0.72 -1.7708 -0.524 -1.7709 1.0040.998 -1.454 -0.302 -1.35 0.935 0.7 -1.7605 -0.5254 -1.7605 1.00610.996 -1.489 -0.337 -1.457 0.955 0.68 -1.7487 -0.5265 -1.7483 1.0090.994 -1.515 -0.367 -1.502 0.97 0.66 -1.7355 -0.5273 -1.7343 1.01280.992 -1.533 -0.392 -1.531 0.98 0.64 -1.7205 -0.528 -1.7181 1.0177

0.99 -1.548 -0.412 -1.547 0.987 0.62 -1.7038 -0.5288 -1.6995 1.02380.988 -1.564 -0.428 -1.562 0.993 0.6 -1.6852 -0.5298 -1.6785 1.03130.986 -1.578 -0.441 -1.573 0.995 0.58 -1.6646 -0.5315 -1.6549 1.04040.984 -1.59 -0.451 -1.584 0.997 0.56 -1.642 -0.534 -1.6286 1.05120.982 -1.604 -0.459 -1.594 0.999 0.54 -1.6174 -0.5376 -1.5997 1.0638

0.98 -1.6198 -0.4626 -1.6004 1 0.52 -1.5908 -0.5425 -1.5682 1.07840.96 -1.6791 -0.4805 -1.6654 1 0.5 -1.5623 -0.5485 -1.5343 1.09490.94 -1.7227 -0.492 -1.713 1 0.48 -1.5319 -0.5555 -1.4983 1.1130.92 -1.7538 -0.4991 -1.7469 1 0.46 -1.4997 -0.563 -1.4604 1.1325

0.9 -1.7751 -0.5036 -1.7701 1 0.44 -1.4659 -0.57 -1.4211 1.15260.88 -1.7888 -0.5067 -1.7852 1 0.42 -1.4305 -0.5753 -1.3807 1.17220.86 -1.7966 -0.509 -1.794 1 0.4 -1.3936 -0.577

0.84 -1.8001 -0.5112 -1.7981 1 0.38 -1.3552 -0.5725

0.82 -1.8002 -0.5133 -1.7988 1 0.36 -1.3152 -0.55860.8 -1.7978 -0.5156 -1.7968 1.0005 0.34 -1.2733 -0.5311

0.78 -1.7933 -0.5179 -1.7928 1.0008 0.32 -1.2292 -0.48470.76 -1.7872 -0.5201 -1.787 1.0014 0.3 -1.1824 -0.4131

Reproduced by permission of the American Institute of Chemical EngineersBhirud, V. L., AIChE J., 24(6): 1127 (1978), 24(5): 880 (1978).



Appendix Table 18AMorris Liquid Viscosity, Compound Class Group Contributions

Group µ+

Hydrocarbons 0.0875Halogenated Hydrocarbons 0.148Benzene Derivatives 0.0895Halogenated Benzene Derivatives 0.123Alcohols 0.0819Organic Acids 0.117Ethers, Ketones, Aldehydes, Acetates 0.096Phenols 0.0126Miscellaneous 0.1

Reprinted from Morris, P. S.: M.S. Thesis, Polytechnic Instituteof Brooklyn, NY, 1964.

Appendix Table 18BMorris Liquid Viscosity, J Group Contributions

Group ∆M Group ∆

M

-CH3, >CH2, >CH- 0.0825 >CH2 (ring member) 0.1707 Halogen Sub. -CH3 0 -CH3, >CH2, >CH 0.052 Halogen Sub. >CH2 0.0893 (adjoining ring) Halogen Sub. >CH- 0.0667 NO2 (adjoining ring) 0.417 Halogen Sub. >C< 0 NH2 (adjoining ring) 0.7645

-Br 0.2058 F, Cl (adjoining ring) 0 -Cl 0.147 -OH (alcohols) 2.0446 -F 0.1344 -COOH (acids) 0.8896 -I 0.1908 -C=O (ketones) 0.3217

Double Bond -0.0742 O=C-O (acetates) 0.4369 C6H4 (Benzene Ring) 0.3558 -OH (phenols) 3.442

Additional H in ring 0.1446 -O- (ethers) 0.109Reprinted from Morris, P. S.: M.S. Thesis, Polytechnic Instituteof Brooklyn, NY, 1964.



Appendix Table 19Joback Liquid Viscosity Group Contributions

Group ∆aJ

∆bJ Group ∆a

J∆b

J

-CH3 (non-ring) 548.29 -1.719 -Br 738.91 -2.038 >CH2 (non-ring) 94.16 -0.199 -I 809.55 -2.224 >CH- (non-ring) -322.15 1.187 -OH (alcohol) 2173.72 -5.057 >C< (non-ring) -573.56 2.307 -OH (phenols) 3018.17 -7.314

=CH2 (non-ring) 495.01 -1.593 -O- (non-ring) 122.09 -0.386 =CH- (non-ring) 82.28 -0.242 -O- (ring) 440.24 -0.953

>CH2 (ring) 307.53 -0.798 >C=O (non-ring) 340.35 -0.35 >CH- (ring) -394.29 1.251 -HC=O (aldehyde) 740.92 -1.731 =CH- (ring) 259.65 -0.702 -COOH (acid) 1317.23 -2.578 >C= (ring) -245.74 0.912 -COO- (ester) 483.88 -0.966

-Cl 625.45 -1.814 =O (any other) 675.24 -1.34Reprinted from Joback, Kevin G., “A Unified Approach to Physical Property Estimation Using Multivariate




Appendix Table 20Reichenburg Gas Viscosity Group Contributions

Group ∆R Group ∆

R

-CH3 9.04 -F 4.46 >CH2 (nonring) 6.47 -Cl 10.06 >CH- (nonring) 2.67 -Br 12.83 >C< (nonring) -1.53 -OH (alcohols) 7.96

=CH2 7.68 -O- (nonring) 3.59 =CH- (nonring) 5.53 >C=O(nonring) 12.02 >C= (nonring) 1.78 -CHO (aldehydes) 14.02

ðCH 7.41 -COOH (acids) 18.65

≡C- (nonring) 5.24 -COO-(ester) or HCOO- 13.41 >CH2 (ring) 6.91 -NH2 9.71 >CH- (ring) 1.16 >NH (nonring) 3.68 >C< (ring) 0.23 =N- (ring) 4.97 =CH- (ring) 5.9 -CN 18.13 >C= (ring) 3.59 >S (ring) 8.86

Reprinted by permission of the American Institute of Chemical EngineersReichenburg, D., AIChE J., 21(1): 181 (1975).



Appendix Table 21Missenard Liquid Heat Capacity Group Contributions

Group ∆aCM ∆bCM ∆cCM

-H 4.12 -0.0151 4.30E-05 -CH3 9.45 -0.0141 5.30E-05 >CH2 7.21 -0.0096 2.70E-05 >CH- -3.1 0.0468 -5.60E-05 >C< 2 0 0

-CðC- 11 0 0 -O- 5.91 0.004 0

-CO- 8.016 0.008 0 -OH -7.55 0.0366 7.90E-05

-COO- (ester) 9.32 0.0165 0 -COOH 5.35 0.0458 0 -NH2 39.05 -0.2004 4.00E-04 >NH 12.2 0 0 >N- 2 0 0 -CN 12.4 0.004 0

-NO2 13.04 0.0092 0 -NH-NH- 19 0 0

C6H5- (phenyl) 12.68 0.0526 0 C10H7- (naphthyl) 50.6 -0.0945 2.57E-04

-F 8.31 -0.0223 4.90E-05 -Cl 5.7 0.0047 0 -Br 7 0.0055 0 -I 8.05 0.0054 0

-S- 7.18 0.0068 0Reprinted from Missenard, F. A., Comp. Rend. 260: 5521 (1965)



Appendix Table 22Yuan & Stiel Liquid Heat Capacity Parameters

TR C(0) C(1) C(0p) C(1p) C(2p) C(3p) C(4p) C(5p)

0.96 14.87 370.94 12.27 29.2 12.3 29.2 -1260.92 10.6 27.2 10.68 27.4 -123

0.9 9.46 26.1 9.54 25.9 -1210.88 8.61 25.4 8.67 24.9 -117.50.86 7.93 24.8 8 24.2 -1150.84 7.45 24.2 7.6 23.5 -112.50.82 7.1 23.7 7.26 23 -110

0.8 6.81 23.3 7.07 22.6 -1080.78 6.57 22.8 6.8 22.2 -1070.76 6.38 22.5 6.62 21.9 -1060.74 6.23 22.2 6.41 22.5 -105 -69 -4.22 -29.50.72 6.11 21.9 6.08 23.6 -107 15 -7.2 -30

0.7 6.01 21.7 6.01 24.5 -110 131 -10.9 -29.10.68 5.91 21.6 5.94 25.7 -113 236 -15.2 -22.80.66 5.83 21.8 5.79 27.2 -118 306 -20 -7.940.64 5.74 22.2 5.57 29.3 -124 324 -25.1 14.80.62 5.64 22.8 5.33 31.8 -132 287 -30.5 43

0.6 5.54 23.5 5.12 34.5 -141 194 -36.3 73.10.58 5.42 24.5 4.92 37.6 -151 50.5 -42.5 1020.56 5.3 25.6 4.69 41.1 -161 -137 -49.2 1280.54 5.17 26.9 4.33 45.5 -172 -358 -56.3 1490.52 5.03 28.4 3.74 50.9 -184 -602 -64 165

0.5 4.88 30 2.87 57.5 -198 -856 -72.1 1790.48 4.73 31.7 1.76 65 -213 -1110 -80.6 1920.46 4.58 33.5 0.68 72.6 -229 -1330 -89.4 2060.44 4.42 35.4 0.19 78.5 -244 -1500 -98.2 2210.42 4.26 37.4

0.4 4.08 39.4Reprinted with permission from Yuan, T. -F., L. I. Stiel, Ind. Eng. Chem., Fundam., 9(3): 393 (1970).

Copyright 1970 American Chemical Society



Appendix Table 23Rihani-Doraiswamy Ideal Gas Heat Capacity Group Contributions

Group ∆aCR ∆bCR ∆cCR ∆dCR Group ∆aCR ∆bCR ∆cCR ∆dCR

x 102 x 105 x 108 x 102 x 105 x 108 -C⇔(⇔) -1.388 1.5159 -1.069 0.2659 -S- 4.2256 0.1127 -0.026 -0.007

⇔C⇔(⇔) 0.1219 1.217 -0.855 0.2122 ⇔S⇔ 4.0824 -0.03 0.731 -0.608

3-membered ring -3.532 -0.03 0.747 -0.551 -SO3H 6.9218 2.4735 1.776 -2.245

4-membered ring -8.655 1.078 0.425 -0.025 -CH3 0.6087 2.1433 -0.852 0.1135

5-mem ring(pentane) -12.29 1.8609 -1.037 0.2145 >CH2 0.3945 2.1363 -1.197 0.2596

5-mem ring(pentene) -6.881 0.7818 -0.345 0.0591 =CH2 0.5266 1.8357 -0.954 0.195

6-mem ring(hexane) -13.39 2.1392 -0.429 -0.187 >CH- -3.523 3.4158 -2.816 0.8015

6-mem ring(hexene) -8.024 2.2239 -1.915 0.5473 >C< -5.831 4.4541 -4.208 1.263

-OH 6.5128 -0.135 0.414 -0.162 -CH=CH2 0.2773 3.458 -1.918 0.413

-O- 2.8461 -0.01 0.454 -0.273 >C=CH2 -0.417 3.8857 -2.783 0.7364

-CH(=O) 3.5184 0.9437 0.614 -0.698 -CH=HC- trans -3.121 3.806 -2.359 0.5504

>C=O 1.0016 2.0763 -1.636 0.4494 -CH=HC- cis 0.9377 2.9904 -1.749 0.3918

-C=O(-OH) 1.4055 3.4632 -2.557 0.6886 >C=HC- -1.471 3.3842 -2.371 0.6063

-C=O(-O-) 2.735 1.0751 0.667 -0.923 >C=C< 0.4736 3.5183 -3.15 0.9205

⇔O⇔ -3.734 1.3727 -1.265 0.3789 -CH=C=CH2 2.24 4.2896 -2.566 0.5908

-C≡N 4.5104 0.5461 0.269 -0.379 >C=C=CH2 2.6308 4.1658 -2.845 0.7277

-NC 5.086 0.3492 0.259 -0.244 -CH=C=CH- -3.125 6.6843 -5.766 1.743

-NH2 4.1783 0.7378 0.679 -0.731 ≡CH 2.8443 1.0172 -0.69 0.1866

>NH -1.253 2.1932 -1.604 0.4237 HC⇔(⇔)arom -1.457 1.9147 -1.233 0.2985

>N- -3.468 2.9433 -2.673 0.7828 -F 1.4382 0.3452 -0.106 -0.003

⇔N⇔ 2.4458 0.3436 0.171 -0.272 -Cl 3.066 0.2122 -0.128 0.0276

-NO2 1.0898 2.6401 -1.871 0.475 -Br 2.7605 0.4731 -0.455 0.142

-SH 2.5597 1.3347 -1.189 0.382 -I 3.2651 0.4901 -0.539 0.1782

Reprinted with permission from D. N. Rihani and L. K. Doraiswamy, Ind. Eng. Chem. Fundam., 4: 17 (1965).Copyright 1965 American Chemical Society



Appendix Table 24Joback Ideal Gas Heat Capacity Group Contributions

Group ∆aCJ ∆bCJ ∆cCJ ∆dCJ Group ∆aCJ ∆bCJ ∆cCJ ∆dCJ

x 102 x 105 x 108 x 102 x 105 x 108

-CH3 (non-ring) 4.66 -0.193 3.66 -2.31 -OH (phenols) -0.672 2.66 -2.76 1.18

>CH2 (non-ring) -0.217 2.27 -1.3 0.285 -O- (non-ring) 6.1 -1.51 2.65 -1.31

>CH- (non-ring) -5.49 4.88 -6.34 2.86 -O- (ring) 2.92 -0.3 1.44 -0.922

>C< (non-ring) -15.80 10.2 -153 71.9 >C=O (non-ring) 1.54 1.6 -0.852 0.068

=CH2 (non-ring) 5.64 -9.11 41 -24.6 >C=O (ring) 7.26 -1.98 5.63 -3.14

=CH- (non-ring) -1.91 2.5 -2.3 8.5 -HC=O (aldehyde) 7.37 -0.803 3.81 -2.36

>C= (non-ring) -6.72 4.97 -7.32 34.8 -COOH (acid) 5.75 1.02 1.92 -1.64

=C= (non-ring) 6.55 -1.33 2.42 -12 -COO- (ester) 5.86 0.959 0.959 -1.08

≡CH (non-ring) 5.84 -0.647 2.64 -16.2 =O (any other) 1.63 0.469 0.304 -0.426

≡C- (non-ring) 1.88 0.481 -0.199 0.033 -NH2 6.42 -0.983 3.91 -2.33

>CH2 (ring) -1.44 2.04 -0.191 -0.429 >NH (non-ring) -0.290 1.82 -1.16 0.251

>CH- (ring) -4.9 3.86 -3.83 1.49 >NH (ring) 2.83 -0.549 2.56 -1.5

>C< (ring) -21.7 13.3 -21.5 11.2 >N- (non-ring) -7.43 5.42 -7.65 3.49

=CH- (ring) -0.51 1.37 -0.039 -3.8 -N=,HN=(non-ring) 1.36 -0.099 3.05 -2.12

>C= (ring) -1.97 2.42 -3.38 1.62 -N= (ring) 2.11 -0.092 1.04 -0.622

-F 6.34 -2.18 4.56 -2.47 -CN 8.71 -1.75 4.4 -2.47

-Cl 7.95 -2.3 4.46 -2.38 -NO2 6.18 -0.089 3.09 -2.12

-Br 6.82 -1.55 3.24 -1.78 -SH 8.43 -1.81 4.42 -2.45

-I 7.67 -1.53 3.02 -1.64 -S- (non-ring) 4.67 -0.134 0.96 -0.66

-OH (alcohol) 6.13 -1.65 4.22 -2.36 -S- (ring) 4 0.115 0.661 -0.503

Reprinted from Joback, Kevin G., “A Unified Approach to Physical Property Estimation Using MultivariateStatistical Techniques”, MS Thesis, MIT, June 1982.



Appendix Table 25ABenson Gas-Heat Capacity Hydrocarbon Group Contributions

Hydrocarbons Groups ∆CB ∆CB ∆CB ∆CB ∆CB ∆CB300 400 500 600 800 1000

C-(C)(H)3 25.92 32.82 39.36 45.18 54.51 61.84C-(C)2(H)2 23.03 29.1 34.54 39.15 46.35 51.67C-(C)3(H) 19.01 25.12 30.02 33.7 38.98 42.08

C-(C)4 18.3 25.67 30.81 34 36.72 36.68C=-(H)2 21.35 26.63 31.44 35.59 42.16 47.19

C=-(C)(H) 17.42 21.06 24.33 27.21 32.03 35.38C=-(C)2 17.17 19.3 20.89 22.02 24.28 25.46

C=-(C=)(H) 18.67 24.24 28.26 31.07 34.96 37.64C=-(C=)(C) 18.42 22.48 24.83 25.87 27.21 27.72C=-(Cφ)(H) 18.67 24.24 28.26 31.07 34.96 37.64C=-(Cφ)(C) 18.42 22.48 24.83 25.87 27.21 27.72C=-(C≡)(H) 18.67 24.24 28.26 31.07 34.96 37.64C=-(C≡)(C) 18.42 22.48 24.83 25.87 27.21 27.72C-(C=)(H)3 25.92 32.82 39.36 45.18 54.51 61.84

C-(C=)2(H)2 19.68 28.47 35.17 40.14 47.31 52.75C-(C=)2(C)2 14.95 25.04 31.44 35.04 37.68 37.76C-(C=)(C)3 16.71 25.29 31.11 34.58 37.35 37.51

C-(C=)(C)(H)2 22.69 28.72 34.83 39.73 46.98 52.25C-(C=)(C)2(H) 17.42 24.74 30.73 34.29 39.61 42.66C-(C=)2(C)(H) 15.66 24.49 30.65 34.75 39.94 43.17

C-(C≡)(H)3 25.92 32.82 39.36 45.18 54.51 61.84C-(C≡)(C)(H)2 20.72 27.47 33.2 38.02 45.47 51.04C-(C≡)(C)2(H) 16.71 23.49 28.68 32.57 38.1 41.45

C-(Cφ)(H)3 25.92 32.82 39.36 45.18 54.51 61.84C-(Cφ)(C)(H)2 24.45 31.86 37.6 41.91 48.11 52.5C-(Cφ)(C)2(H) 20.43 27.88 33.08 36.63 40.74 42.91

C-(Cφ)(C)3 18.3 28.43 33.87 36.76 38.48 37.51C-(Cφ)2(C)(H) 15.66 24.49 30.65 34.75 39.94 43.17C-(Cφ)2(C)2 14.95 25.04 31.44 35.04 37.68 37.76

C-(Cφ)(C≡)(H)2 19.68 28.47 35.17 40.19 47.31 52.75C≡-(H) 22.06 25.08 27.17 28.76 31.28 33.33C≡-(C) 13.1 14.57 15.95 17.12 19.26 20.6



Appendix Table 25A - Cont.Benson Gas-Heat Capacity Hydrocarbon Group Contributions

Hydrocarbons Groups ∆CB ∆CB ∆CB ∆CB ∆CB ∆CB300 400 500 600 800 1000

C≡-(C=) 10.76 14.82 14.65 20.6 22.36 23.03C≡-(Cí) 10.76 14.82 14.65 20.6 22.36 23.03Cφ-(H) 13.57 18.59 22.86 26.38 31.57 35.21Cφ-(C) 11.18 13.15 15.41 17.38 20.77 22.78

Cφ-(C=) 15.03 16.62 18.34 19.76 22.11 23.49Cφ-(C≡) 15.03 16.62 18.34 19.76 22.11 23.49Cφ-(Cφ) 13.94 17.67 20.47 22.06 24.12 24.91

Cα 16.33 18.42 19.68 20.93 22.19 23.03Cφf-(Cφ)2(Cφf) 12.52 15.32 17.67 19.43 21.9 23.24Cφf-(Cφ)(Cφf)2 12.52 15.32 17.67 19.43 21.9 23.24

Cφf-(Cφf)3 8.71 11.93 14.65 16.87 19.89 21.52Cφ, Indicates a carbon atom in a benzene ring


Appendix Table 25BBenson Heat Capacity Hydrocarbon Next Nearest Neighbor Contributions

Hydrocarbons ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBNext Nearest Neighbors 300 400 500 600 800 1000

Cis -5.61 -4.56 -3.39 -2.55 -1.63 -1.09Ortho 4.69 5.65 5.44 4.9 3.68 2.76


Appendix Table 25CBenson Heat Capacity Hydrocarbon Ring Correction Contributions

Hydrocarbons ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBCorrections for Ring 300 400 500 600 800 1000

Cyclopropane -12.77 -10.59 -8.79 -7.95 -7.41 -6.78Cyclobutane -19.3 -16.29 -13.15 -11.05 -7.87 -5.78Cyclobutene -10.59 -9.17 -7.91 -7.03 -6.2 -5.57Cyclopentane -27.21 -23.03 -18.84 -15.91 -11.72 -7.95Cyclopentene -25.04 -22.4 -20.47 -17.33 -12.27 -9.46Cyclohexane -24.28 -17.17 -12.14 -5.44 4.61 9.21Cyclohexene -17.92 -12.73 -8.29 -5.99 -1.21 0.33




Appendix Table 25DBenson Gas Heat Capacity Oxygen Containing Group Contributions

∆CB ∆CB ∆CB ∆CB ∆CB ∆CBGroups 300 400 500 600 800 1000

CO-(CO)(H) 28.14 32.78 37.26 41.41 47.86 50.74CO-(C))(C) 22.86 26.46 29.98 32.95 37.68 40.86CO-(O)(C=) 25 28.05 31.02 33.58 37.14 39.19CO-(O)(Cφ) 9.13 11.51 16.66 21.06 26.33 29.56CO-(O)(C) 25 28.05 30.98 33.58 37.14 39.19CO-(O)(H) 29.43 32.95 36.93 40.53 46.72 51.08

CO-(C=)(H) 29.43 32.95 36.93 40.53 46.72 51.08CO-(Cφ)2 22.02 28.34 32.11 35.5 40.28 41.24

CO-(Cφ)(C) 23.78 28.97 32.24 35 39.31 40.86CO-(Cφ)(H) 26.8 32.32 37.3 41.24 48.11 50.62

CO-(C)2 23.4 26.46 29.68 32.49 37.22 40.24CO-(C)(H) 29.43 32.95 36.93 40.53 46.72 51.08CO-(H)2 35.46 39.27 43.79 48.23 55.98 62.01

O-(Cφ)(CO) 8.62 11.3 13.02 14.32 16.24 17.5O-(CO)2 -1.72 7.45 13.4 16.75 21.48 24.49

O-(CO)(O) 15.49 15.49 15.49 15.49 17.58 17.58O-(CO)(C=) 6.03 12.48 16.66 18.8 20.81 21.77O-(CO)(C) 16.33 15.11 17.54 19.34 20.89 20.18O-(CO)(H) 15.95 20.85 24.28 26.54 30.1 32.45O-(O)(C) 15.49 15.49 15.49 15.49 17.58 17.58O-(O)2 15.49 15.49 15.49 15.49 17.58 17.58

O-(O)(H) 21.65 24.24 26.29 27.88 29.94 31.44O-(C=)2 14.24 15.49 15.49 15.91 18.42 19.26

O-(C=)(C) 14.24 15.49 15.49 15.91 18.42 19.26O-(Cφ)2 4.56 5.11 6.28 8.33 11.93 14.7

O-(Cφ)(C) 14.24 15.49 15.49 15.91 18.42 19.26O-(Cφ)(H) 17.58 18.84 20.1 21.77 25.12 27.63

O-(C)2 14.24 15.49 15.49 15.91 18.42 19.26O-(C)(H) 18.13 18.63 20.18 21.9 25.2 27.67

C=-(CO)(O) 23.4 29.31 31.32 32.45 33.58 34.04C=-(CO)(C) 15.62 18.76 21.02 22.61 24.91 26.67C=-(CO)(H) 15.87 20.52 24.45 27.8 32.66 36.59C=-(O)(C=) 18.42 22.48 24.83 25.87 27.21 27.72C=-(O)(C) 17.17 19.3 20.89 22.02 24.28 25.46C=-(O)(H) 17.42 21.06 24.33 27.21 32.03 35.38Cφ-(CO) 11.18 13.15 15.41 17.38 20.77 22.78Cφ-(O) 16.33 22.19 25.96 27.63 28.89 28.89

C-(CO)2(H)2 23.45 29.52 35.13 40.53 48.48 53.88C-(CO)(C)2(H) 26 31.65 33.49 34.37 38.43 40.32C-(CO)(C)(H)2 25.96 32.24 36.43 39.77 46.47 51.08



Appendix Table25D Cont.Benson Gas Heat Capacity Oxygen Containing Group Contributions

Oxygen Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBGroups 300 400 500 600 800 1000

C-(CO)(C)3 21.23 28.81 32.7 34.62 36.84 36.09C-(CO)(H)3 25.92 32.82 39.36 45.18 54.51 61.84C-(O)2(C)2 6.66 16.54 25.96 30.94 31.9 35.5

C-(O)2(C)(H) 21.19 30.48 37.81 39.4 43.17 45.01C-(O)2(H)2 11.85 21.19 31.48 38.18 43.21 47.27

C-(O)(Cφ)(H)2 15.53 26.25 34.67 40.99 49.36 55.27C-(O)(Cφ)(C)(H) 21.52 30.56 36.97 39.48 42.83 44.38C-(O)(C=)(H)2 19.51 29.18 36.22 41.37 48.32 53.3

C-(O)(C)3 18.13 25.92 30.35 32.24 34.33 34.5C-(O)(C)2(H) 20.1 27.8 33.91 36.55 41.07 43.54C-(O)(C)(H)2 20.89 28.68 34.75 39.48 46.52 51.62

C-(O)(H)3 25.92 32.82 39.36 45.18 54.55 61.84Cφ, Indicates a carbon atom in a benzene ring


Appendix Table 25EBenson Gas Heat Capacity Oxygen Containing Ring & Strain Contributions

Oxygen Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBStrain & Ring Groups 300 400 500 600 800 1000Ether oxygen, gauche -0.42 -3.73 -4.61 -3.06 -2.51 -0.96

Dithertiary ethers -16.5 -23.61 -29.94 -36.97 -50.41 -62.38Ethylene Oxide -8.4 -11.7 -12.6 -10.9 -9.6 -9.6

Trimethylene Oxide -19.3 -20.9 -17.6 -14.7 -10.9 0.8Tetrahydrofuran -17.8 -19.01 -17.04 -14.86 -12.94 -10.93Tetrahydropyran -17.92 -12.73 -8.29 -5.99 -1.21 0.33

1,3-Dioxane -10.51 -12.06 -9.55 -6.24 -1.09 2.341,4-Dioxane -17.42 -19.13 -13.02 -7.87 -4.56 -1.97

1,3,5-Trioxane 7.49 2.34 -2.55 -2.72 -5.02 -10.17Furan -17.54 -15.2 -12.23 -10.01 -8.33 -7.2

Dihydropyran -18.59 -13.4 -6.53 -1.88 1.76 2.76Cyclopentanone -35.71 -30.1 -22.23 -15.57 -9.46 -5.11Cyclohexanone -33.91 -27.51 -17.75 -8 2.93 8.25

Succinic Anhydride -33.08 -25.2 -18.8 -14.99 -14.03 -12.81Glutaric Anhydride -33.2 -25.29 -18.84 -15.03 -14.03 -12.85Maleic Anhydride -21.44 -14.15 -8.46 -9.17 -1.55 -0.04




Appendix Table 25FBenson Gas Heat Capacity Nitrogen Containing Group Contributions

Nitrogen Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBGroups 300 400 500 600 800 1000

C-(N)(H)3 25.92 32.82 39.36 45.18 54.51 61.84C-(N)(C)(H)2 21.98 28.89 34.57 39.31 46.43 51.67C-(N)(C)2(H) 19.55 26.46 31.99 35.13 40.03 42.83

C-(N)(C)3 18.21 25.79 30.61 33.12 35.55 35.59N-(C)(H)2 23.95 27.26 30.65 33.79 39.4 43.84N-(C)2(H) 17.58 21.81 25.67 28.6 33.08 36.22

N-(C)3 14.57 19.09 22.73 25 27.47 27.93N-(N)(H)2 25.54 30.9 35.29 38.81 44.13 48.23

N-(N)(C)(H) 20.18 24.28 27.21 29.31 32.66 34.75N-(N)(C)2 6.53 10.47 13.86 16.2 19.34 20.89

N-(N)(Cφ)(H) 13.73 16.96 19.89 22.23 26.29 28.93N[i]=-(H) 12.35 19.18 27 32.28 38.23 41.53N[i]=-(C) 10.38 13.98 16.54 17.96 19.22 19.26N[i]=-(Cφ) 10.89 13.48 15.95 17.67 20.05 21.44N[a]=-(H) 18.34 20.47 22.78 24.87 28.34 31.07N[a]=-(C) 11.3 17.17 20.6 22.36 23.82 23.91

N-(Cφ)(H)2 23.95 27.26 30.65 33.79 39.4 43.84N-(Cφ)(C)(H) 15.99 20.47 23.91 26.29 30.1 32.36N-(Cφ)(C)2 2.6 8.46 13.69 17.29 21.9 23.4N-(Cφ)2(H) 9.04 13.06 17.29 21.35 28.3 32.99

Cφ-(N) 16.54 21.81 24.87 26.46 27.34 27.47N[a]=-(N) 8.88 17.5 23.07 28.34 28.72 29.52CO-(N)(H) 29.43 32.95 36.93 40.53 46.72 51.08CO-(N)(C) 22.48 25.83 29.6 32.07 40.28 46.85

N-(CO)(H)2 17.04 24.03 29.85 34.71 41.7 46.98N-(CO)(C)(H) 16.2 21.27 24.91 28.3 28.76 27.38N-(CO)(C)2 7.66 15.87 21.94 25.92 29.77 31.07

N-(CO)(Cφ)(H) 12.69 16.37 19.26 23.36 26.08 26.46N-(CO)2(H) 15.03 23.19 28.05 30.94 33.29 34.29N-(CO)2(C) 4.48 12.98 18.05 20.93 22.94 27.09N-(CO)(Cφ) 4.1 12.81 17.71 20.31 22.11 22.15

C-(CN)(C)(H)2 46.47 56.1 64.9 72.01 82.5 89.18C-(CN)(C)2(H) 46.05 53.17 59.03 64.48 72.43 77.87

C-(CN)(C)3 36.22 46.72 53.97 58.82 64.94 67.78C-(CN)2(C)2 61.63 74.78 83.74 90.48 99.56 104.5 C=-(CN)(H) 41.03 48.89 55.68 60.71 68.24 72.43C=-(CN)(C) 40.78 47.23 52.25 55.52 60.5 62.51C=-(CN)2 56.94 69.29 78.21 84.78 93.53 98.77

C=-(NO)2(H) 51.5 63.2 72.9 80.4 90.4 97.1Cφ-(CN) 41 46.9 51.5 54.9 59.5 62.4



Appendix Table 25F Cont.Benson Gas Heat Capacity Nitrogen Containing Group Contributions

Nitrogen Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBGroups 300 400 500 600 800 1000C≡-(CN) 43.12 47.31 50.66 53.17 56.94 59.87

C-(NO2)(C)(H)2 52.71 66.24 77.54 86.5 99.6 108.44C-(NO2)(C)2(H) 50.2 63.68 74.19 82.1 92.86 99.23

C-(NO2)(C)3 41.41 55.85 66.4 73.77 81.27 87.34C-(NO2)2(C)(H) 72.52 95.54 113.34 126.48 143.82 154.2

O-(NO)(C) 38.1 43.12 46.9 50.2 55.7 58.2O-(NO2)(C) 39.94 48.32 55.52 65.31 68.62 72.77


Appendix Table 25GBenson Gas Heat Capacity Nitrogen Containing Ring Corrections

Nitrogen Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBRing Groups 300 400 500 600 800 1000

Ethyleneimine -8.67 -9.13 -9.09 -8.58 -8.12 -7.87Azetidine -19.8 -18.92 -17.08 -15.11 -11.14 0.04

Pyrrolidine -25.83 -23.36 -20.1 -16.75 -12.02 -9.09Piperidine -2.34 1.55 4.52 6.53 7.16 -1.93

Succinimide 9.04 17.08 25.71 33.54 38.14 40.91Reprinted from Benson, S. W., et al., Chem. Rev., 69(3): 279 (1969)

Appendix Table 25HBenson Gas Heat Capacity Halogen Containing Group Contributions

Halogen Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBGroups 300 400 500 600 800 1000

C-(F)3(C) 53.2 62.8 68.7 74.9 80.8 83.7C-(F)2(H)(C) 41.4 50.2 57.4 63.2 69.9 74.5C-(F)(H)2(C) 33.9 41.87 50.2 54.43 63.6 69.5C-(F)2(C)2 41.4 49.4 56.5 60.3 67.4 69.5

C-(F)(H)(C)2 30.56 37.85 43.84 48.4 54.85 58.66C-(F)(C)3 28.47 37.1 42.71 46.72 52.04 53.26

C-(F)2(Cl)(C) 57.4 67.4 73.3 77.9 82.9 85.4C-(Cl)3(C) 68.2 75.4 80 82.9 86.2 87.9

C-(Cl)2(H)(C) 50.7 58.6 64.5 69.1 74.9 78.3C-(Cl)(H)2(C) 37.3 44.8 51.5 56.1 64.1 69.9C-(Cl)2(C)2 51.1 62.3 66.78 69 71.01 71.26

C-(Cl)(H)(C)2 37.7 41.4 44 46.9 58.2 61.1C-(Cl)(C)3 38.9 44 46.1 47.3 51.9 53.2C-(Br)3(C) 69.9 75.4 78.7 81.2 83.3 85

C-(Br)(H)2(C) 38.1 46.1 52.8 57.4 64.9 70.3C-(Br)(H)(C)2 37.39 44.63 50.07 53.76 58.82 61.63C-(I)(H)(C)2 38.5 45.6 51.1 54.4 59.5 62



Appendix Table 25H Cont.Benson Gas Heat Capacity Halogen Containing Group Contributions

Halogen Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBGroups 300 400 500 600 800 1000

C-(Br)(C)3 38.9 46.1 48.1 51.5 55.7 55.7C-(I)(H)2(C) 38.5 46.1 54 58.2 66.2 72

C-(I)(C)(C=)(H) 34.04 41.95 44.49 52.8 58.6 62.4C-(I)(C=)(H)2 36.93 45.68 54.3 58.78 66.78 72.6

C-(I)(C)3 41.16 49.19 54.09 56.31 57.74 56.94C-(Cl)(Br)(H)(C) 51.9 58.6 65.3 68.2 74.9 79.5

N-(F)2(C) 34.54 42.41 48.23 53.59 60.16 62.72C-(Cl)(C)(O)(H) 41.24 43.5 46.26 48.44 52.13 55.01

C-(I)2(C)(H) 53.13 61.88 67.87 71.68 76.66 79.67C-(I)(O)(H)2 34.42 43.92 51.2 56.73 64.27 69.38

C=-(F)2 40.6 46.1 50.2 53.2 57.8 60.7C=-(Cl)2 47.7 52.3 55.7 58.2 61.1 62.8C=-(Br)2 51.5 55.3 58.2 59.9 62.4 63.6

C=-(F)(Cl) 43.1 49 52.8 55.7 59.5 61.5C=-(F)(Br) 45.2 50.2 53.6 56.5 59.9 61.5C=-(Cl)(Br) 50.7 53.2 56.5 59 61.5 61.5C=-(F)(H) 28.5 35.2 39.8 44 49.4 53.2C=-(Cl)(H) 33.1 38.5 43.1 46.9 51.5 54.8C=-(Br)(H) 33.9 39.8 44.4 47.7 51.9 55.3C=-(I)(H) 36.8 41.9 45.6 48.6 52.8 55.7

C=-(C)(Cl) 33.5 35.2 35.6 37.7 38.5 39.4C=-(C)(I) 37.3 38.5 38.1 39.4 39.8 40.2

C=-(C=)(Cl) 34.8 38.5 39.4 41.4 41.4 41.4C=-(C=)(I) 38.5 41.4 41.9 43.1 43.1 42.3

C≡-(Cl) 33.1 35.2 36.4 37.7 39.4 40.2C≡-(Br) 34.8 36.4 37.7 38.5 39.8 40.6C≡-(I) 35.2 36.8 38.1 38.9 40.2 41Cφ-(F) 26.4 31.8 35.6 38.1 41 42.7Cφ-(Cl) 31 35.2 38.5 40.6 42.7 43.5Cφ-(Br) 32.7 36.4 39.4 41.4 43.1 44Cφ-(I) 33.5 37.3 40.2 41.4 43.1 44

C-(Cφ)(F)3 52.3 64.1 72 77.5 84.2 87.9C-(Cφ)(Br)(H)2 38.9 46.47 52.51 57.32 65.27 69.96C-(Cφ)(I)(H)2 40.95 48.4 54.01 58.95 66.49 70.8

C-(Cl)2(CO)(H) 53.6 61.76 66.36 69.71 75.07 77.71C-(Cl)3(CO) 71.2 78.5 81.85 83.53 86.37 87.34CO-(Cl)(C) 37.14 39.52 42.87 46.39 52.46 56.9




Appendix Table 25IBenson Gas Heat Capacity Halogen Next Nearest Group Corrections

Halogen Next ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBNearest Groups 300 400 500 600 800 1000

Ortho (F)(F) 0 0 0 0 0 0Ortho (Cl)(Cl) -2.09 -1.84 -2.3 -2.22 -1.17 -0.08

Ortho (Alkane)(Halogen) 1.76 1.84 1.17 0.8 0.5 0.59Cis (Halogen)(Halogen) -0.75 -0.04 -0.13 -0.71 0 -0.13Cis (Halogen)(Alkane) -4.06 -2.93 -2.22 -1.97 -1 -0.54


Appendix Table 25JBenson Gas Heat Capacity Sulfur Containing Group Contributions

Sulfur Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBGroups 300 400 500 600 800 1000

C-(H)3(S) 25.92 32.82 39.36 45.18 54.51 61.84C-(C)(H)2(S) 22.52 29.64 36.01 41.74 51.33 59.24C-(C)2(H)(S) 20.31 27.26 32.57 36.38 41.45 44.25

C-(C)3(S) 19.13 26.25 31.19 34.12 36.51 33.91C-(Cφ)(H)2(S) 17.21 28.26 36.43 42.5 49.95 54.85C-(C=)(H)2(S) 20.93 29.27 36.3 42.16 51.98 59.83

Cφ-(S) 16.33 22.19 25.96 27.63 28.89 28.89C=-(H)(S) 17.42 21.06 24.33 27.21 32.03 35.38C=-(C)(S) 14.65 14.95 16.04 17.12 18.46 20.93S-(C)(H) 24.53 25.96 27.26 28.39 30.56 32.28S-(Cφ)(H) 21.44 22.02 23.32 25.25 29.27 32.82

S-(C)2 20.89 20.77 21.02 21.23 22.65 23.99S-(C)(C=) 17.67 21.27 23.28 24.16 24.58 24.58S-(C=)2 20.05 23.36 23.15 26.33 33.24 40.74

S-(Cφ)(C) 12.64 14.19 15.53 16.91 19.34 20.93S-(Cφ)2 8.37 8.42 9.38 11.47 15.91 19.72S-(S)(C) 21.9 22.69 23.07 23.07 22.52 21.44S-(S)(Cφ) 12.1 14.19 15.57 17.38 20.01 21.35

S-(S)2 19.7 20.9 21.4 21.8 22.2 22.6C-(SO)(H)3 25.92 32.82 39.36 45.18 54.51 61.84

C-(C)(SO)(H)2 19.05 26.88 33.29 38.35 48.85 51.16C-(C)3(SO) 12.81 19.18 20.26 27.63 31.57 33.33

C-(C=)(SO)(H)2 18.42 26.63 29.06 38.73 45.93 51.29Cφ-(SO) 11.18 13.15 15.41 17.38 20.77 22.78SO-(C)2 37.18 41.99 43.96 45.18 45.97 46.77SO-(Cφ)2 23.95 38.06 40.61 47.94 47.98 47.1

C-(SO2)(H)3 25.92 32.82 39.36 45.18 54.51 61.84C-(C)(SO2)(H)2 22.52 29.64 36.01 41.74 51.33 35.65C-(C)2(SO2)(H) 18.51 26.17 31.65 35.5 40.36 43.12



Appendix Table 25J Cont.Benson Gas Heat Capacity Sulfur Containing Group Contributions

Sulfur Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBGroups 300 400 500 600 800 1000

C-(C)3(SO2) 9.71 18.34 23.86 27.17 30.44 31.23C-(C=)(SO2)(H)2 20.93 29.27 36.3 42.16 51.96 59.83C-(Cφ)(SO2)(H)2 15.53 27.51 34.57 40.99 49.78 55.27

Cφ-(SO2) 11.18 13.15 15.41 17.38 20.77 22.78C=-(H)(SO2) 12.73 19.55 24.83 28.64 32.95 36.3C=-(C)(SO2) 7.75 13.02 16.66 19.26 22.32 23.74SO2-(C=)(Cφ) 41.41 48.15 55.89 61.17 65.82 66.65

SO2-(C=)2 48.23 50.12 55.89 59.79 64.39 66.49SO2-(C)2 42.62 49.15 54.09 57.65 63.35 66.99

SO2-(C)(Cφ) 41.62 48.15 56.31 60.75 65.4 66.65SO2-(Cφ)2 35 46.18 56.73 62.55 66.4 66.82

SO2-(SO2)(Cí) 41.07 48.15 56.61 61.67 65.77 67.11CO-(S)(C) 23.4 26.46 29.68 32.49 37.22 40.24S-(H)(CO) 31.95 33.87 34 34.21 35.59 34.5C-(S)(F)3 41.37 54.47 62.09 68.54 76.07 80.01CS-(N)2 23.4 26.46 29.68 32.49 37.22 40.24

N-(CS)(H)2 25.41 30.48 34.25 37.3 42.24 45.97S-(S)(N) 15.5 15.5 15.5 15.5 17.6 17.6

N-(S)(C)2 16.62 21.65 26 29.06 30.94 38.69SO-(N)2 23.4 26.46 29.68 32.49 37.22 40.24

N-(SO)(C)2 17.58 24.62 25.62 27.34 28.6 34.92SO2-(N)2 23.4 26.46 29.68 32.49 37.22 40.24

N-(SO2)(C)2 25.2 26.59 31.57 34.46 37.81 38.48Cφ, Indicates a carbon atom in a benzene ring


Appendix Table 25KBenson Gas Heat Capacity Sulfur Containing Ring Corrections

Sulfur Containing ∆CB ∆CB ∆CB ∆CB ∆CB ∆CBRing Groups 300 400 500 600 800 1000

Thiirane -11.93 -10.84 -11.14 -12.64 -18.09 -24.37Trimethylene sulfide -19.22 -17.5 -16.37 -16.37 -19.26 -23.86Tetrahydrothiophene -20.52 -19.55 -15.41 -15.32 -18.46 -23.32

Thiacyclohexane -26.04 -17.84 -9.38 -2.89 3.6 5.4Thiacycloheptane -32.45 -20.6 -5.11 10.84 20.05 19.3

3-Thiocyclopentene -26.96 -17.75 -17.71 -17.5 -20.1 -24.952-Thiocyclopentene -26.96 -17.75 -17.71 -17.5 -10.1 -24.45

Thiophene -20.52 -19.55 -15.41 -15.32 -18.46 -23.32Reprinted from Benson, S. W., et al., Chem. Rev., 69(3): 279 (1969)



Appendix Table 26Harrison Seaton Ideal Gas Heat Capacity Parameters

TR ΦC ΦH ΦO ΦN ΦS ΦF ΦCl ΦI

300 9.04 5.69 16.6 10.5 17.8 16.8 12.7 18.7400 12.6 7.37 19.1 13.7 19.9 18.9 16.2 20.5500 15.5 8.89 21 16.1 21.2 20.2 17.9 22.1600 17.5 10.5 22.5 17.8 22.4 21.4 20.1 23.3800 20.1 13.1 24 20.5 23.4 22.4 21.5 25

1000 21.6 15.2 24.5 21.6 23.8 22.8 22.4 25.41500 23.9 17.9 25 22.7 23 22.6 22.1 24.6

TR ΦBr ΦSi ΦAl ΦB ΦP ΦOTH ΦCONST

300 11.9 11.4 18 15.3 17.5 19.5 4.86400 14 13.9 20.9 17 19.8 20.8 0.864500 16 15.7 21.6 19.4 22.3 21.7 -1.85600 17.3 17.5 22.8 20.3 22.1 22.1 -4.61800 19.4 19.4 23 22.3 24.5 23 -7.49

1000 20.4 20.4 23.4 22.9 24.6 23.3 -8.531500 21.1 20.6 24.2 22.5 24 23.3 -7.37

Reprinted from Harrison, B. K., W. H. Seaton, Ind. Eng. Chem. Res., 27(8): 1536 (1988)

PREDICT - MW Softwaremwsoftware.com/dragon/manual.pdf · PREDICT can execute compatibly with most...

Documents

Transcript of PREDICT - MW Softwaremwsoftware.com/dragon/manual.pdf · PREDICT can execute compatibly with most...