THE PROPERTIES OF
`GASES AND LIQUIDS
`
`Bruce E. Poling
`Professor of Chemical Engineering
`
`University of Toledo
`
`John M. Prausnitz
`Professor of Chemical Engineering
`
`University of California at Berkeley
`
`John P. O’Connell
`Professor of Chemical Engineering
`
`University of Virginia
`
`Fifth Edition
`
`McGRAW-HILL
`
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`
`Arkema Exhibit 1127
`
`1 of 13
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`

`
`Library of Congress Cataloging-in-Publication Data
`
`Poling, Bmce E.
`The properties of gases and liquids / Bruce E. Poling, John M. Prausnitz, John P.
`O'Connell.-5th ed.
`
`cm.
`p.
`Includes bibliographical references and index.
`ISBN 0-07-011682-2
`
`1. Gases.
`III. Title.
`
`2. Liquids.
`
`I. Prausnitz, J. M.
`
`II. O'Connell. John P. (John Paul)
`
`TP242.P62
`660’ .042—dc2l
`
`2000
`
`McGraw-Hill
`
`00-061622
`
`A Division of The McGraw-Hill Companies
`
`Copyright © 2001, 1987, 1977, 1966, 1958 by The McGraw-Hill Companies.
`Inc. All rights reserved. Printed in the United States of America. Except as
`permitted under the United States Copyright Act of 1976. no part of this
`publication may be reproduced or distributed in any form or by any means,
`or stored in a data base or retrieval system, without the prior written per-
`mission of the publisher.
`
`67890IBT/IBT0l0987
`
`ISBN 0-07-01 1682-2
`
`The sponsoring editor for this book was Kenneth R McCombs and the
`production supervisor was Sherri Souflrance. It was set in Times Roman
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`
`2of13
`
`

`
`CONTENTS
`
`Preface
`
`vii
`
`Chapter 1 The Estimation of Physical Properties
`
`1.1
`
`1-1 Introduction / 1.1
`/ 1.3
`1-2 Estimation of Properties
`1-3 Types of Estimation / 1.3
`1-4 Organization of the Book / 1.6
`
`Chapter 2 Pure Component Constants
`
`2.1
`
`2-1 Scope / 2.1
`2-2 Vapor-Liquid Critical Properties
`2-3 Acentric Factor
`/ 2.23
`/ 2.26
`2-4 Boiling and Freezing Points
`2-5 Discussion of Estimation Methods for Pure Component Constants
`2-6 Dipole Moments
`/ 2.34
`2-7 Availability of Data and Computer Software / 2.35
`
`/ 2.2
`
`/ 2.33
`
`Chapter 3 Thermodynamic Properties of Ideal Gases
`
`3.1
`
`/ 3.1
`3-1 Scope and Definitions
`3-2 Estimation Methods
`/ 3.5
`3-3 Method of Joback / 3.6
`3-4 Method of Constantinou and Gani (CG)
`3-5 Method of Benson [1968; 1969]
`/ 3.14
`3-6 Discussion and Recommendations
`/ 3.46
`3-7 Heat of Combustion / 3.47
`
`/ 3.8
`
`Chapter 4 Pressure-Volume-Temperature Relationships of Pure
`Gases and Liquids
`
`4.1
`
`/ 4.1
`
`4-1 Scope / 4.1
`4-2 Introduction to Volumetric Properties
`4-3 Corresponding States Principle / 4.5
`4-4 Equations of State / 4.8
`4-5 Virial Equation of State / 4.11
`4-6 Analytical Equations of State / 4.17
`4-7 Nonanalytic Equations of State / 4.25
`4-8 Discussion of Equations of State / 4.31
`4-9 PVT Properties of Liquids—General Considerations
`
`/ 4.32
`
`iii
`
`3 of 13
`
`

`
`iv
`
`CONTENTS
`
`4-10 Estimation of the Liquid Molar Volume at the Normal Boiling Point
`4-11 Saturated Liquid Densities as a Function of Temperature / 4.35
`4-12 Compressed Liquid Densities
`/ 4.43
`
`/ 4.33
`
`Chapter 5 Pressure-Volume-Temperature Relationships of Mixtures
`
`5.1
`
`5-1 Scope / 5.1
`5-2 Mixture Properties—General Discussion / 5.2
`5-3 Corresponding States Principle (CSP): The Pseudocritical Method / 5.5
`5-4 Virial Equations of State for Mixtures
`/ 5.8
`5-5 Analytical Equations of State for Mixtures
`/ 5.12
`5-6 Nonanalytic Equations of State for Mixtures
`/ 5.18
`5-7 Discussion of Mixture Equations of State / 5.22
`5-8 Densities of Liquid Mixtures at Their Bubble Point
`5-9 Densities of Compressed Liquid Mixtures
`/ 5.26
`
`/ 5.23
`
`Chapter 6 Thermodynamic Properties of Pure Components
`and Mixtures
`
`6.1
`
`6-1 Scope / 6.1
`6-2 Fundamental Thermodynamic Relationships for Pure Components
`6-3 Departure Functions for Thermodynamic Properties
`/ 6.4
`6-4 Evaluation of Departure Functions for Equations of State / 6.6
`6-5 Heat Capacities of Real Gases
`/ 6.16
`6-6 Heat Capacities of Liquids
`/ 6.17
`6-7 Partial Properties and Fugacities of Components in Mixtures
`6-8 True Critical Points of Mixtures
`/ 6.30
`
`/ 6.26
`
`/ 6.1
`
`Chapter 7 Vapor Pressures and Enthalpies of Vaporization of
`Pure Fluids
`
`7.1
`
`7-1 Scope / 7.1
`7-2 Theory / 7.1
`7-3 Correlation and Extrapolation of Vapor-Pressure Data / 7.3
`7-4 Ambrose-Walton Corresponding-States Method / 7.7
`7-5 Riedel Corresponding-States Method / 7.9
`7-6 Discussion and Recommendations for Vapor-Pressure Estimation and
`Correlation / 7.11
`/ 7.13
`7-7 Enthalpy of Vaporization of Pure Compounds
`7-8 Estimation of ⌬Hv from Vapor-Pressure Equations
`/ 7.14
`7-9 Estimation of ⌬Hv from the Law of Corresponding States
`7-10 ⌬Hv at the Normal Boiling Point
`/ 7.19
`7-11 Variation of ⌬Hv with Temperature / 7.23
`7-12 Discussion and Recommendations for Enthalpy of Vaporization / 7.24
`7-13 Enthalpy of Fusion / 7.25
`7-14 Enthalpy of Sublimation; Vapor Pressures of Solids
`
`/ 7.16
`
`/ 7.28
`
`Chapter 8 Fluid Phase Equilibria in Multicomponent Systems
`
`8.1
`
`8-1 Scope / 8.1
`8-2 Thermodynamics of Vapor-Liquid Equilibria / 8.9
`
`4 of 13
`
`

`
`CONTENTS
`
`v
`
`8-3 Fugacity of a Pure Liquid / 8.11
`8-4 Simplifications in the Vapor-Liquid Equilibrium Relation / 8.12
`8-5 Activity Coefficients; Gibbs-Duham Equation and Excess Gibbs Energy / 8.12
`8-6 Calculation of Low-Pressure Binary Vapor-Liquid Equilibria with Activity
`Coefficients
`/ 8.19
`8-7 Effect of Temperature on Low-Pressure Vapor-Liquid Equilibria / 8.22
`8-8 Binary Vapor-Liquid Equilibria: Low-Pressure Examples
`/ 8.23
`8-9 Multicomponent Vapor-Liquid Equilibria at Low Pressure / 8.32
`8-10 Determination of Activity Coefficients
`/ 8.42
`8-11 Phase Equilibrium with Henry’s Law / 8.111
`8-12 Vapor-Liquid Equilibria with Equations of State / 8.120
`8-13 Solubilities of Solids in High-Pressure Gases
`/ 8.158
`8-14 Liquid-Liquid Equilibria / 8.159
`/ 8.177
`8-15 Phase Equilibria in Polymer Solutions
`8-16 Solubilities of Solids in Liquids
`/ 8.180
`8-17 Aqueous Solutions of Electrolytes
`/ 8.191
`8-18 Concluding Remarks
`/ 8.193
`
`Chapter 9 Viscosity
`
`9.1
`
`9-1 Scope / 9.1
`9-2 Definitions of Units of Viscosity / 9.1
`9-3 Theory of Gas Transport Properties
`/ 9.2
`9-4 Estimation of Low-Pressure Gas Viscosity / 9.4
`9-5 Viscosities of Gas Mixtures at Low Pressures
`/ 9.15
`9-6 Effect of Pressure on the Viscosity of Pure Gases
`/ 9.29
`9-7 Viscosity of Gas Mixtures at High Pressures
`/ 9.47
`9-8 Liquid Viscosity / 9.51
`9-9 Effect of High Pressure on Liquid Viscosity / 9.55
`9-10 Effect of Temperature on Liquid Viscosity / 9.56
`9-11 Estimation of Low-Temperature Liquid Viscosity / 9.59
`9-12 Estimation of Liquid Viscosity at High Temperatures
`/ 9.75
`9-13 Liquid Mixture Viscosity / 9.77
`
`Chapter 10 Thermal Conductivity
`
`10-1 Scope / 10.1
`10-2 Theory of Thermal Conductivity / 10.1
`/ 10.2
`10-3 Thermal Conductivities of Polyatomic Gases
`10-4 Effect of Temperature on the Low-Pressure Thermal Conductivities of Gases
`10-5 Effect of Pressure on the Thermal Conductivities of Gases
`/ 10.18
`10-6 Thermal Conductivities of Low-Pressure Gas Mixtures
`/ 10.29
`10-7 Thermal Conductivities of Gas Mixtures at High Pressures
`/ 10.35
`10-8 Thermal Conductivities of Liquids
`/ 10.42
`/ 10.44
`10-9 Estimation of the Thermal Conductivities of Pure Liquids
`10-10 Effect of Temperature on the Thermal Conductivities of Liquids
`/ 10.51
`10-11 Effect of Pressure on the Thermal Conductivities of Liquids
`/ 10.52
`10-12 Thermal Conductivities of Liquid Mixtures
`/ 10.56
`
`10.1
`
`/ 10.18
`
`Chapter 11 Diffusion Coefficients
`
`11.1
`
`11-1 Scope / 11.1
`
`5 of 13
`
`

`
`vi
`
`CONTENTS
`
`/ 11.1
`11-2 Basic Concepts and Definitions
`11-3 Diffusion Coefficients for Binary Gas Systems at Low Pressures: Prediction from
`Theory / 11.5
`11-4 Diffusion Coefficients for Binary Gas Systems at Low Pressures: Empirical
`Correlations
`/ 11.9
`11-5 The Effect of Pressure on the Binary Diffusion Coefficients of Gases
`11-6 The Effect of Temperature on Diffusion in Gases
`/ 11.19
`11-7 Diffusion in Multicomponent Gas Mixtures
`/ 11.19
`11-8 Diffusion in Liquids: Theory / 11.20
`11-9 Estimation of Binary Liquid Diffusion Coefficients at Infinite Dilution / 11.21
`11-10 Concentration Dependence of Binary Liquid Diffusion Coefficients
`/ 11.33
`11-11 The Effects of Temperature and Pressure on Diffusion in Liquids
`/ 11.38
`11-12 Diffusion in Multicomponent Liquid Mixtures
`/ 11.41
`11-13 Diffusion in Electrolyte Solutions
`/ 11.43
`
`/ 11.12
`
`Chapter 12 Surface Tension
`
`12.1
`
`12-1 Scope / 12.1
`12-2 Introduction / 12.1
`12-3 Estimation of Pure-Liquid Surface Tension / 12.2
`12-4 Variation of Pure-Liquid Surface Tension with Temperature / 12.11
`12-5 Surface Tensions of Mixtures
`/ 12.12
`
`A.1
`Appendix A Property Data Bank
`Appendix B Lennard-Jones Potentials as Determined from Viscosity Data
`Appendix C Group Contributions for Multiproperty Methods
`C.1
`Index follows Appendix C
`
`B.1
`
`6 of 13
`
`

`
`3.6
`
`CHAPTER THREE
`
`Yoneda (1979), Thinh, et al. (1971), Thinh and Trong (1976) and Cardozo (1983;
`1986), for these properties but they are not repeated here. All methods of this
`chapter are evaluated and discussed in Sec. 3-6 while their application to computing
`heats of combustion is described in Sec. 3-7.
`Comparisons with data in Appendix A are made where experimental property
`values are available and all of the group contribution values have been determined.
`The substances which have been compared are generally organic in nature, but the
`details depend on the method and the limitations of the data base. Where available
`in the literature, discussion from other comparisons is included. In general, the
`results here are typical of what others have found.
`
`3(cid:173)3 METHOD OF JOBACK
`
`Choosing the same atomic and molecular groups as for the properties in Chap. 2,
`Joback (1984; 1987) used the values given in Stull, et al. (1956; 1969) to obtain
`group contributions for
`and polynomial coefficients
`⌬G ⬚(298.15 K), ⌬H ⬚(298.15 K)
`ƒ
`ƒ
`for
`His group values are shown in Appendix Table C-1, and they are to be
`C ⬚(T ).
`p
`used in Eqs. (3-3.1) to (3-3.3). Distinctions are made among nonring, nonaromatic
`ring and aromatic ring groups as well as different atoms and bonding.
`
`⌬G ⬚(298.15 K) ⫽ 53.88 ⫹
`ƒ
`
`⌬H ⬚(298.15 K) ⫽ 68.29 ⫹
`ƒ
`
`k
`
`冘
`冘
`
`k
`
`N ⌬gƒk
`k
`
`⫺1
`(kJ mol
`
`)
`
`(3-3.1)
`
`N ⌬hƒk
`k
`
`⫺1
`(kJ mol
`
`)
`
`(3-3.2)
`
`N CpAk ⫺ 37.93 ⫹
`k
`
`冎
`
`N CpBk ⫹ 0.210 T ⫹
`k
`
`冎
`
`k
`
`C ⬚(T ) ⫽
`p
`
`k
`
`再
`冘
`冘再
`冘再
`
`k
`
`k
`
`再
`冘
`冎
`冎
`
`2
`N CpCk ⫺ 3.91E ⫺ 04 T ⫹
`k
`
`⫺1
`⫺1
`(J mol K )
`
`(3-3.3)
`
`N CpDk ⫹ 2.06E ⫺ 07 T
`k
`
`3
`
`where Nk is the number of groups of type k in the molecule, FK is the contribution
`for the group labeled k to the specified property, F, and T is the temperature in
`kelvins.
`
`Example 3-1 Estimate
`⌬H ⬚(298.15 K), ⌬G ⬚(298.15 K),
`ƒ
`ƒ
`ethylphenol by using Joback’s group method.
`
`and
`
`C ⬚(700 K)
`p
`
`for 2-
`
`solution 2-ethylphenol contains one —CH3 , one
`CH(ds), twofour—CH —, ⫽
`
`2
`C(ds),
`and one —ACOH (phenol). From Appendix Table C-1
`
`
`
`⫽
`
`7 of 13
`
`

`
`THERMODYNAMIC PROPERTIES OF IDEAL GASES
`
`3.7
`
`Group k
`
`
`
`Nk Ni⌬hƒk
`
`
`
`Ni⌬gƒk
`
`NiCpAk
`
`NiCpBk
`
`NiCpCk
`
`NiCpDk
`
`—CH3
`—CH2—
`CH(ds)⫽
`C(ds)⫽
`—ACOH(phenol)
`
`1.53E-04 ⫺9.70E-08
`19.500 ⫺0.00808
`⫺76.45 ⫺43.96
`1
`⫺20.64
`8.42 ⫺0.909
`0.09500 ⫺0.54E-04
`1.19E-08
`1
`8.36
`45.20 ⫺8.560
`0.22960 ⫺0.06E-04 ⫺6.36E-08
`4
`92.86
`108.10 ⫺16.500
`0.20200 ⫺2.80E-04
`13.56E-08
`2
`1 ⫺221.65 ⫺197.37 ⫺2.810
`0.11100 ⫺1.16E-04
`4.94E-08
`
`N F冘 k
`
`5
`
`k⫽1
`
`k
`
`⫺217.52 ⫺79.61 ⫺9.279
`
`0.62952 ⫺3.07E-04
`
`3.59E-08
`
`⌬H ⬚(298.15 K) ⫽ 68.29 ⫹
`ƒ
`
`⌬G ⬚(298.15 K) ⫽ 53.88 ⫹
`ƒ
`
`5
`
`冘
`
`k⫽1
`
`5
`
`冘
`
`k⫽1
`
`⫺1
`N ⌬H ⫽ ⫺149.23 kJ mol
`k
`ƒk
`
`⫺1
`N ⌬G ⫽ ⫺25.73 kJ mol
`k
`ƒk
`
`C ⬚(700) ⫽
`p
`
`N C ⫺ 37.93 ⫹
`k
`pAk
`
`冎
`
`再
`冘
`
`k
`
`N C ⫹ 0.210 T
`k
`pBk
`
`冎
`
`再
`冘
`冘再
`冘再
`
`k
`
`⫹
`
`⫹
`
`k
`
`k
`
`N C ⫺ 3.91E ⫺ 04 T
`k
`pCk
`
`N C ⫹ 2.06E ⫺ 07 T
`k
`pDk
`
`冎
`冎
`
`2
`
`3
`
`⫽ {⫺9.279 ⫺ 37.93} ⫹ {0.62952 ⫹ .210}(700)
`
`2
`3
`⫹ {⫺3.074 ⫺ 3.91}(700 / 100) ⫹ {0.0359 ⫹ 0.206}(700 / 100)
`
`⫺1
`⫺1
`⫽ 281.21 J mol K
`
`The Appendix A values for the formation properties are ⫺145.23 and ⫺23.15 kJ mol⫺1,
`respectively, while the heat capacity calculated from the coefficients of Appendix A is
`283.14 J mol⫺1 K⫺1. Thus the differences, are
`
`⫺1
`⌬H ⬚(298.15 K) Difference ⫽ ⫺145.23 ⫺ (⫺149.23) ⫽ 4.00 kJ mol
`ƒ
`
`or 2.75%
`
`⫺1
`⌬G ⬚(298.15 K) Difference ⫽ ⫺23.15 ⫺ (⫺25.73) ⫽ 2.58 kJ mol
`ƒ
`
`or 11.14%.
`
`However, since
`only 10.97%.
`
`⌬G ⬚ / RT
`ƒ
`
`is small (0.934), the error in the equilibrium constant is
`
`⫺1
`⫺1
`C ⬚(700 K) Difference ⫽ 283.14 ⫺ 281.21 ⫽ 1.93 J mol K or 0.68%
`p
`
`A summary of the comparisons between estimations from the Joback method
`and experimental Appendix A values for
`⌬H ⬚(298.15 K), ⌬G ⬚(298.15 K),
`and
`C ⬚
`ƒ
`ƒ
`p
`at various temperatures are shown in Table 3-1.
`The information in Table 3-1 indicates that the Joback method is marginally
`accurate for the formation properties of all substances regardless of size and good
`for ideal gas heat capacities for temperatures at ambient and above. The substances
`with major errors are halogenated species, suggesting that the group contributions
`for —F, —Cl, —Br, and —I might be revised in light of the greater abundance of
`data available now than when the correlation was developed. The terms in the heat
`capacity correlation are usually of opposite sign so there is no consistent error at
`
`8 of 13
`
`

`
`3.8
`
`CHAPTER THREE
`
`TABLE 3-1 Summary of Comparisons of Joback Method with Appendix A Data Base
`
`Property
`
`(298.15 K)
`⌬G ⬚
`ƒ
`kJ mol⫺1
`
`(298.15 K)
`⌬H ⬚
`ƒ
`kJ mol⫺1
`
`(100 K)
`C ⬚
`p
`J mol⫺1 K⫺1
`
`(298 K)
`C ⬚
`p
`J mol⫺1 K⫺1
`
`(700 K)
`C ⬚
`p
`J mol⫺1 K⫺1
`
`(1000 K)
`C ⬚
`p
`J mol⫺1 K⫺1
`
`#
`Substances
`
`AAEc
`
`A%Ec
`
`# Err ⬎ 10%d
`
`# Err ⬍ 5%e
`
`291a
`234b
`
`307a
`246b
`
`121a
`78b
`
`248a
`193b
`
`248a
`193b
`
`248a
`193b
`
`11.9
`9.9
`
`17.7
`10.2
`
`20.2
`25.7
`
`4.0
`4.4
`
`5.9
`6.5
`
`9.7
`10.6
`
`13.3
`13.4
`
`11.3
`9.2
`
`43.4
`53.4
`
`3.2
`3.0
`
`2.3
`2.0
`
`3.3
`2.7
`
`86
`69
`
`59
`42
`
`111
`74
`
`10
`7
`
`4
`1
`
`18
`10
`
`141
`113
`
`200
`171
`
`2
`1
`
`195
`152
`
`225
`179
`
`201
`168
`
`a The number of substances in Appendix A with data that could be tested with the method.
`b The number of substances in Appendix A having 3 or more carbon atoms with data that could be
`tested with the method.
`c AAE is average absolute error in the property; A%E is average absolute percent error. For
`(298.15
`⌬G ⬚
`ƒ
`K), the 21 substances with absolute values less than 10 kJ mol⫺1 were not counted in the A%E. Note the
`discussion of Fig. 3-1 about errors in
`(298.15 K) and the reaction equilibrium constant. Thus, the average
`⌬G ⬚
`ƒ
`absolute percent errors in K were more than 50%, mainly due to the species with errors greater than 25 kJ
`mol⫺1.
`d The number of substances for which the absolute percent error was greater than 10%.
`e The number of substances for which the absolute percent error was less than 5%. The number of
`substances with errors between 5% and 10% can be determined from the table information.
`
`low and high temperatures that might be easily corrected. Abildskov (1994) studied
`Joback results for properties of formation while Nielsen (1998) studied the method
`for formation properties and for heat capacities. Both did a much more limited
`examination than for the properties of Chap. 2 but found absolute percent errors
`that were similar to those of Table 3-1.
`Discussion comparing the Joback technique with other methods for the proper-
`ties of this chapter is presented in Sec. 3-6.
`
`3(cid:173)4 METHOD OF CONSTANTINOU AND
`GANI (CG )
`
`Choosing the same first and second order atomic and molecular groups as for the
`properties in Chap. 2, Constantinou and Gani (1994) obtained group contributions
`⌬G ⬚(298.15 K)
`⌬H ⬚(298.15 K).
`for
`and
`Following this approach and the initial
`ƒ
`ƒ
`developments of Coniglio and Daridon (1997) for hydrocarbons, Nielsen (1998)
`C ⬚(T )
`developed correlations for polynomial coefficients to obtain
`for all classes
`p
`of organic substances. The group values are shown in Appendix Tables C-2 and
`C-3 with sample assignments in Table C-4. These values are to be used in Eqs.
`(3-4.1) to (3-4.3).
`
`9 of 13
`
`

`
`APPENDIX C
`GROUP CONTRIBUTIONS FOR
`MULTIPROPERTY METHODS
`
`This appendix contains the group definitions, correlating equations and parameter
`values of group contribution methods for pure component property estimation that
`are found in more than one chapter. Specifically, basic equations, tables of group
`identities, example molecules and values for contributions to properties are given
`for the Constantinou and Gani (1994; 1995) Nielsen (1998) and Joback (1984,
`1987) methods. The Constantinou / Gani table has been assembled with additional
`assistance of Dr. Jens Abildskov, Department of Chemical Engineering, Technical
`University of Denmark, Lyngby, DK-2800, including use of the computer software
`of ProPred in the ICAS suite of the Computer Aided Process Engineering Center
`(CAPEC) jointly led by Drs. Rafiqul Gani and Sten Bay Jørgensen of the Technical
`University of Denmark (http: / / www.capec.kt.dtu.dk). The Joback table was assem-
`bled with the assistance of Dr. K. G. Joback, especially using the computer software
`of CRANIUM provided by Molecular Knowledge Systems, Inc. Bedford, NH,
`03110 (http: / / www.molknow.com). The authors are grateful to all of these individ-
`uals and organizations for their help.
`The symbol * has been included with the group formula if it is not present in
`the substances of the data base in Appendix A and therefore has not been directly
`tested in the methods of Chaps. 2, 3, and 4. Results using such groups are included
`in summaries of original and later sources. Many small molecules with two or fewer
`carbon atoms are treated as single groups. It is possible to form some of them from
`the groups listed; comparisons have been made when this was possible, but the
`results were often poor. However, since property values for most small molecules
`are in Appendix A, it is not recommended that they be predicted anyway. If no
`contribution was assigned for a group in a method, the symbol X is used in this
`appendix.
`
`C(cid:173)1 JOBACK PROPERTY FUNCTIONS FROM
`GROUP CONTRIBUTIONS
`
`For a molecule with Ni groups, a property denoted as in the main text and Appendix
`A is given by the equation below with values of the individual parameters in Table
`C-1. Tb is the normal boiling temperature in Kelvins; accuracy is much greater if
`the experimental value is used instead of an estimation (See Chap. 2). Natoms is the
`total number of atoms in the molecule.
`
`C.1
`
`
`
`
`
`10 of 13
`
`

`
`1.36E-04⫺7.45E-08
`1.87E-04⫺9.96E-08
`1.91E-04⫺1.03E-07
`1.01E-01⫺1.42E-04
`6.78E-08
`5.74E-02⫺1.64E-06⫺1.59E-08
`5.57E-01⫺9.00E-04
`4.69E-07
`1.62E-01⫺1.60E-04
`6.24E-08
`8.54E-02⫺8.00E-06⫺1.80E-08
`1.39E-09
`2.01E-02⫺8.33E-06
`1.11E-04⫺6.78E-08
`1.01E-04⫺5.02E-08
`1.46E-07
`3.56E-08
`1.72E-04⫺1.03E-07
`3.01E-07
`1.20E⫺07
`1.19E-08
`1.53E-04⫺9.67E-08
`
`2.08E-01⫺3.06E-04
`1.05E-01⫺9.63E-05
`
`⫺28.100
`⫺8.000
`
`4.27E-01⫺6.41E-04
`2.04E-01⫺2.65E-04
`9.50E-02⫺5.44E-05
`
`⫺23.600⫺3.81E-02
`⫺66.200
`⫺23.000
`⫺0.909
`19.500⫺8.08E-03
`
`28.600⫺6.49E-02
`33.300⫺9.63E-02
`26.500⫺9.13E-02
`⫺8.250
`⫺2.140
`⫺90.900
`8.670
`⫺6.030
`7.870
`
`24.500⫺2.71E-02
`27.400⫺5.57E-02
`
`1573
`861
`1083
`601
`⫺160
`334
`731
`572
`608
`263
`154⫺328
`464
`775
`573
`117
`789
`992
`276
`555
`636
`1128
`511
`732
`527
`643
`412⫺113
`152⫺349
`179
`404
`619
`532
`217
`567
`
`71⫺29.48⫺38.06
`58⫺71.55⫺64.31
`27⫺251.92⫺247.19
`32
`46.43
`54.05
`41
`2.09
`11.30
`27
`79.72
`87.88
`38
`8.67
`40.99
`48⫺26.80
`⫺3.68
`37
`115.51
`109.82
`46
`79.30
`77.71
`36
`142.14
`136.70
`38
`83.99
`92.36
`46
`37.97
`48.53
`56
`⫺9.63
`3.77
`27
`82.23
`116.02
`41
`29.89
`58.36
`56⫺20.64
`8.42
`65⫺76.45⫺43.96
`
`66.860.0133
`0.0057
`38.130.0105⫺0.0049
`⫺15.78⫺0.030.0111⫺0.0057
`0.0008
`0.0011
`0.0061
`0.0004
`0.0025
`0.0016
`9.200.0027⫺0.0008
`26.150.0026
`0.0028
`24.140.0117
`0.0011
`24.960.0129⫺0.0006
`18.180.0113⫺0.0028
`18.250.0067
`0.0043
`21.740.0164
`0.0020
`22.880.0189
`0.0000
`23.580.0141⫺0.0012
`
`43.43
`13.55
`
`37.02
`8.13
`60.15
`19.88
`7.75
`64.32
`⫺11.18
`17.78
`11.14
`8.73
`⫺4.32
`46.43
`12.64
`11.27
`⫺5.10
`
`31.010.0143
`26.730.0082
`21.320.0042
`21.780.0122
`27.150.0100
`27.380.0020
`
`Br(1)
`Cl(1)
`F(1)
`⫽C(ds)(3)
`⫽CH(ds)(2)
`C(ss)(4)
`CH(ss)(3)
`CH2(ss)(2)
`⬅C(2)
`⬅CH(1)
`⫽C⫽(2)
`⫽C(3)
`⫽CH(2)
`⫽CH2(1)
`C(4)
`CH(3)
`CH2(2)
`CH3(1)
`Groupk
`
`C.2
`
`mol⫺1K⫺1
`
`mol⫺1K⫺1
`
`mol⫺1K⫺1
`
`mol⫺1K⫺1
`
`mol⫺1
`
`mol⫺1
`
`mol⫺1
`
`kJmol⫺1
`
`J
`
`J
`
`J
`
`J
`
`CpDk
`
`CpCk
`
`CpBk
`
`CpAk
`
`cal
`
`hmk
`
`cal
`
`hvk
`
`cal
`
`gƒk
`
`hƒk
`
`mol⫺1
`cm3
`
`vck
`
`bar
`
`pck
`
`K
`
`tck
`
`K
`
`tbk
`
`K
`
`tƒpk
`
`Units
`
`Property
`
`TABLEC-1JobackGroupContributionsforVariousProperties
`
`11 of 13
`
`

`
`1.46E-07
`1.07E-04⫺6.28E-08
`1.05E-08
`1.64E-04⫺9.76E-08
`1.27E-05⫺1.78E-08
`4.02E-05⫺4.52E-08
`8.04E-05⫺6.87E-08
`1.60E-04⫺9.88E-08
`2.36E-04⫺1.31E-07
`2.86E-09
`6.03E-05⫺3.86E-08
`1.11E-04⫺5.48E-08
`4.94E-08
`1.77E-04⫺9.88E-08
`1.26E-04⫺6.87E-08
`
`7.62E-02⫺4.86E-05
`
`11.800⫺2.30E-02
`⫺1.210
`26.900⫺4.12E-02
`6.820
`1.96E-02
`24.500
`4.02E-02
`24.100
`4.27E-02
`30.900⫺3.36E-02
`30.400⫺8.29E-02
`
`6.70E-02⫺3.57E-05
`
`6.450
`
`1.11E-01⫺1.16E-04
`
`12.200⫺1.26E-02
`25.500⫺6.32E-02
`⫺2.810
`25.700⫺6.91E-02
`32.100⫺6.41E-02
`
`2.77E-05⫺2.11E-08
`4.02E-05⫺2.76E-08
`1.85E-04⫺1.03E-07
`1.29E-04⫺8.88E-08
`1.84E-04⫺1.03E-07
`1.28E-04⫺8.88E-08
`4.35E-05⫺2.60E-08
`
`16.700
`4.81E-03
`19.600⫺5.61E-03
`35.300⫺7.58E-02
`25.900⫺3.74E-03
`36.500⫺7.33E-02
`5.690⫺4.12E-03
`8.830⫺3.84E-03
`
`X
`
`X
`
`X
`
`2.27E-01⫺3.20E-04
`
`X
`
`⫺31.100
`
`372
`987
`564
`2313
`577
`
`X
`
`872
`
`X
`
`1124
`1790
`1197
`840
`866
`1663
`2641
`764
`
`X
`
`1001
`1405
`284
`1073
`575
`651
`
`1430
`1629
`1645
`4000
`3071
`2908
`1560
`797
`453
`1656
`1538
`2578
`1412
`2302
`4669
`2173
`1588
`2144
`1119
`576
`2987
`4021
`2275
`
`*GroupcouldnotbetestedwithsubstancesavailableinApp.A.
`
`88.43
`93.70
`57.550.0085
`0.0076
`55.52
`74.600.0255⫺0.0099
`23.61
`11.740.0169
`0.0074
`123.34
`163.16
`52.820.0130
`0.0114
`29
`31.65
`75.61
`50.170.0295
`0.0077
`35
`53.47
`89.39
`73.230.0243
`0.0109
`38⫺22.02
`14.07
`2.08⫺10.500.0143
`0.0101
`36⫺247.61⫺250.83
`82⫺337.92⫺301.95
`81.100.0481
`0.0005
`89⫺426.72⫺387.87
`169.090.0791
`0.0077
`72.200.0379
`0.0030
`82⫺162.03⫺143.48
`94.970.0284
`0.0028
`55⫺164.50⫺126.27
`76.750.0380
`0.0031
`62⫺133.22⫺120.50
`31.220.0098
`0.0048
`13⫺138.16⫺98.22
`22.420.0168
`0.0015
`18⫺132.22⫺105.00
`76.340.0240
`0.0184⫺25⫺221.65⫺197.37
`28⫺208.04⫺189.20
`92.880.0741
`0.0112
`5.74
`97
`93.840.0068⫺0.0034
`
`38
`27.76
`54
`33.12
`63⫺17.33⫺22.99
`91⫺66.57⫺16.83
`89.22
`91
`119.66
`79.93
`
`39.10
`41.87
`
`X
`
`34
`
`X
`
`9
`
`X
`
`21.06
`
`52.100.0019
`0.0051
`68.780.0119
`0.0049
`63.560.0031
`0.0084
`152.540.0437
`0.0064
`125.660.0496⫺0.0101
`
`X
`
`X
`
`X
`
`79.93
`34.40
`20.09
`127.24
`59.89
`
`X
`
`68.40
`
`X
`
`48.84
`101.51
`52.66
`66.89
`
`53.60
`155.50
`36.90
`75.97
`61.20
`23.05
`22.23
`82.83
`44.45
`41.69
`
`S(ss)(2)
`S(2)
`SH(1)
`NO2(1)
`CN(1)*
`⫽NH(1)*
`⫽N⫺(ds)(2)
`⫽N⫺(2)
`N(3)
`NH(ss)(2)
`NH(2)
`NH2(1)
`⫽O(1)*
`COO(2)
`COOH(1)
`CH⫽O(1)*
`C⫽O(ss)(2)
`C⫽O(2)
`O(ss)(2)
`O(2)
`ACOH(1)
`OH(1)
`I(1)*
`
`C.3
`
`12 of 13
`
`

`
`C.4
`
`APPENDIX C
`
`Property
`
`Function
`
`T ⫽ 122 ⫹
`ƒp
`
`N (tƒpk)
`k
`
`T ⫽ 198 ⫹
`b
`
`N (tbk)
`k
`
`k
`
`k
`
`冘
`冘
`
`Tƒp
`
`Tb
`
`Tc
`
`Pc
`
`Vc
`
`⌬H ⬚
`ƒ
`
`⌬G ⬚
`ƒ
`
`⌬Hv
`
`⌬Hm
`
`C ⬚
`p
`
`T ⫽ T
`c
`b
`
`冋
`
`0.584 ⫹ 0.965
`
`再
`冘
`
`k
`
`N (tck) ⫺
`k
`
`冎
`
`N (tck)
`k
`
`2 ⫺1
`
`冎 册
`
`再
`冘
`册
`
`k
`
`⫺2
`
`N ( pck)
`k
`
`P ⫽ 0.113 ⫹ 0.0032N
`c
`atoms
`
`冋
`
`⫺
`
`冘
`
`k
`
`V ⫽ 17.5 ⫹
`c
`
`冘
`
`k
`
`N (vck)
`k
`
`⌬H ⬚ ⫽ 68.29 ⫹
`ƒ
`
`N (hƒk)
`k
`
`⌬G ⬚ ⫽ 53.88 ⫹
`ƒ
`
`N (gƒk)
`k
`
`⌬H ⫽ 15.30 ⫹
`
`v
`
`N (hvk) ⫻ 0.004184
`k
`
`⌬H ⫽ ⫺0.88 ⫹
`m
`
`N (hmk) ⫻ 0.004184
`k
`
`k
`
`k
`
`k
`
`k
`
`k
`
`冘
`冘
`冘
`冘
`冘冋
`冘冋
`冘冋
`冘冋
`
`C ⬚ ⫽
`p
`
`N (CpAk) ⫺ 37.93
`k
`
`册
`册
`
`N (CpBk) ⫹ 0.21 T
`k
`
`N (CpCk) ⫺ 3.91E⫺04 T
`k
`
`N (CpDk) ⫹ 2.06E⫺07 T
`k
`
`册
`册
`
`2
`
`3
`
`⫹
`
`⫹
`
`⫹
`
`k
`
`k
`
`k
`
`The headings of Table C-1 are quantities in the summations of the above for-
`mulae. The number of other groups that each group is bonded to is given in pa-
`renthesis. Thus, ⫽CH2 is bonded to 1 other group (which must be ⫽CH2 , ⫽CH
`or ⫽C), ⫽CH is bonded to 2 groups (one of which must be ⫽CH2 , ⫽CH or
`⫽C) , and ⫽C is bonded to 3 groups (one of which must be ⫽CH2 , ⫽CH
`or ⫽C). The symbol (ss) indicates a group in a nonaromatic ring; (ds) indicates a
`group in an aromatic ring. Note that particular units have been included for most
`are at 298.15 K and 1 atm. ⌬Hv and ⌬Hm are at Tb and
`properties.
`and
`⌬H ⬚
`⌬G ⬚
`ƒ
`ƒ
`Tm.
`
`C(cid:173)2 CONSTANTINOU / GANI PROPERTY
`FUNCTIONS FROM GROUP
`CONTRIBUTIONS
`
`First-Order groups are indicated by k, Second-Order groups by j. For a molecule
`with Ni First-Order groups and Mj Second-Order groups, a property is given by the
`
`13 of 13