,

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I Jefferson W. Tester I Mich ael Mod ell

Th erm od yn am ics
an d Its Ap pli cat ion s
3rd Edition

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Prentice Hall Internat ional Serles
In the Physical and Chemic al
Enginee ring Sdence s

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Thermodynamics and Its Applications. a classic text in its field, is now fully updated
and expanded to include: · ·
•Advanced treatment of graduate-level chemical thermodynamics
• Many diverse and challenging examples and problems
• New coverage of the molecular underpinnings of constitutive property models
Now in its third edition. Thermodynamics and Its Applications provides a comprehensive.
rigorous treatment of chemical thermodynamics at an advanced level.
Based on extensive classroom testing, this graduate-level text 1inks the fundamental
concepts of thermodynamics to their applications in engineering practice. It connects
theory with applications at every opportunity, using extensive examples and illustrations.
sample problems, and homework exercises.
Part I develops the theoretical basis of classical thermodynamics. including the 1st and
2nd Laws. the Fundamental Equation. Legendre transformations, and general equilibrium
and stability criteria. Part II contains an extensive description of how thermodynamic
properties are correlated, modeled, manipulated, and estimated .. Both macroscopic,
empirically-based and molecular-level approaches are discussed in depth for pure
components and mixture. Part lfl presents applications of classical thermodynamics
with phase and chemical equilibria emphasized in detail.
This new edition responds to the growing need for practicing chemical engineers to
understand how traditional empirically-based constitutive property models are
cor:inected to their roots at the molecular level. Using the formalism of statistical
mechanics. students can appreciate how intermolecular interactions cause deviations
from ideal behavior.
Other new coverage includes a unified development of combined phase and chemical
equilibria in multicomponent systems, using a vectorized framework and a new section
on availability/energy analysis cf UNIVERs1oAiiE DAccoiluriA·· -~sses involving heat-to-
work conversions. i Servifio de Biblio.tecas
Both molecular theory and pra/
in a single chapter, which inc!udw- ___ _!2~308744
:ectrolytes are discussed
ortant constitutive models
/111111111111/llj
for electrolyte solutions, from Debye-Huckel theory to today's advanced semi-empirical
models.
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Thermodynamics and Its Applications
3rd Edition
 PRENTICE HAl.L INTERNATIONAL SERIES
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Thermodynamics
and Its Applications
3rd Edition

Jefferson W. Tester
Michael Model/
Chemical Engineering Department
Massachusetts Institute of Technology
Cambridge, Massachusetts

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 Contents
Preface
xi
Nomenclature
xv

Part I Fundamental Principles

Chapter 1 The Scope of Classical Thermodynamics

1.1 An Engineering Perspective, 1
1.2 Preclassical Thermodynamics, 3
1.3 The Postulatory Approach, 7

Chapter 2 Basic Concepts and Definitions 11

2.1 The System and Its Environment, 1I
2.2 Primitive Properties, I I
2.3 Classification of Boundaries, 12
2.4 The Adiabatic Wall, 13
2.5 Simple and Composite Systems, 14
2.6 States of a System, 15
2.7 Stable Equilibrium States, 16
2.8 Thermodynamic Processes, 18
2.9 Derived Properties, 19
2.10 An Import.ant Note About Nomenclature and Units, 19
2.11 Summary, 21

Chapter 3 Energy and the First Law 22

3.1 Work Interactions, 22
3.2 Adiabatic Work rn'teractions, 26
3.3 Energy, 31
3 .4 Heat Interactions, 33
3.5 The Ideal Gas, 37
3.6 The First Law for Closed Systems, 39
3.7 Applications of the First Law for Closed Systems, 41
3.8 The First Law for Open Systems, 46

v
vi Contents

3.9 Application of the First Law for Open Systems, 50

Chapter 4 Reversibility and the Second Law 68

4.1 Heat Engines, 68
4.2 Reversible Processes, 72
4.3 Thermodynamic Temperature, 74
4.4 The Theorem of Clausius, 78
4.5 Entropy, 80
4.6 Internal Reversibility, 84
4.7 The Combined First and Second Laws, 86
4.8 Reversible Work of Expansion or Compression in Flow Systems, 92
4.9 Summary, 98

Chapter 5 The Calculus of Thermodynamics 124

5.1 The Fundamental Equation in Gibbs Coordinates, 125
5.2 Intensive and Extensive Properties, 130
5.3 Methods for Transforming Derivatives, 133
5 .4 Jacobian Transformations, 137
5.5 Reconstruction of the Fundamental Equation, 141
5.6 Legendre Transformations, 142
5.7 Graphical Representations of Thermodynamic Functions
and Their Transforms, 149
5 .8 Modifications to the Fundamental Equation for Non-simple Systems, J52
5.9 Relationships Between Partial Derivatives of Legendre Transforms, 155
5.10 Summary, 165

Chapter 6 Equilibrium Criteria 176

6. 1 Classification of Equilibrium States, 176
6.2 Extrema Principles, 178
6.3 Use of Other Potential Functions to Define Equilibrium States, 185
6.4 Membrane Equilibrium, 188
6.5 Phase Equilibria, 190
6.6 Chemical Reaction Equilibria, 191
6.7 Summary, 196

Chapter 7 Stability Criteria 201

7 .1 Criteria of Stability, 202
7 .2 Applications to Thennodynamic Systems, 209
Contents vii

7.3 Critical States, 225

7.4 Indeterminacy, 229
7.5 Use of Mole Fractions in the~ and~ Determinants, 231
7.6 Suounary, 234

Part II Thermodynamic Properties

Chapter 8 Properties of Pure Materials 239

8.1 Gibbs Energy Formulation of the Fundamental Equation, 239
8.2 PVI Behavior of Fluids and the Theorem of Corresponding States, 243
8.3 PyrN Equations of State for Fluids, 251
8.4 Ideal-Gas State Heat Capacities, 265
8.5 Evaluating Changes in Properties Using Departure Functions, 270
8.6 Compressibility and Heat Capacities of Solids, 283
8.7 Derived Property Representations, 286
8.8 Standard Enthalpy and Gibbs Free Energy of Formation, 291
8.9 Summary, 293

Chapter 9 Property Relationships for Mixtures 318

9.1 General Approach and Conventions, 318
9.2 PyrN Relations for Mixtures, 323
9 .3 Partial Molar Properties, 329
9.4 Generalized Gibbs-Duhem Relation for Mixtures, 333
9.5 Mixing Functions, 337
9.6 Ideal Gas Mixtures and Ideal Solutions, 340
9.7 Fugacity and Fugacity Coefficients, 344
9 .8 Activity, Excess Functioos and Activity Coefficients, 353
9.9 Reversible Work of Mixing and Separation, 365
9.10 Summary, 368

Chapter 10 Statistical Mechanical Approach for Property Models 388

10. l Basic Concepts of Statistical Mechanics, 388
10.2 Intermolecular Forces, 407
10.3 Intermolecular Potential Energy Functions, 410
10.4 The Virial Equation of State, 415
10.5 Molecular Theory of Corresponding States, 420
10.6 Generalized van der Waals Theory, 427
10.7 Radial Distribution Functions, 431
viii Conlents

10.8 Hard-Sphere Fluids, 435

10.9 Molecular Simulation Applications, 437
10.10 Summary, 447

Chapter 11 Models for Non-Jdeal, Non-Electrolyte Solutions 456

11.1 PYJN EOS - Fugacity Coefficient Approach, 457
11.2 D.Gex -Activity Coefficient Approach, 458
11.3 Ideal Entropy of Mixing and the Third Law, 460
I I .4 Regular and A thermal Solution Behavior, 464
11.5 Lattice Models with Configurational and Energetic Effects, 465
11.6 McMillan-Mayer Theory, 469
11.7 Activity Coefficient Models for Condensed Fluid Phases, 474
11.8 Activity Coefficient Models for Solid Phases, 490
11.9 Summary and Recommendations, 494

Chapter 12 Models for Electrolyte Solutions 503

12.1 Conventions and SU\ndard States, 503
12.2 Experimental Measurements of Ionic Activity, 512
12.3 Debye-Hiickel Model (theoretical), 516
12.4 Beyond Debye-Hiickel Theory, 527
12.5 Pitzer Ion Interaction Model, 528
12.6 Meissner Corresponding States Model, 535
12.7 Chen Local Composition Model, 541
12.8 Performance of Electtolyte Models in Engineering Practice, 544
12.9 Modeling Multisolvent Mixed Electrolyte Systems, 548
12.10 Summary and Recommendations, 549

Chapter 13 Estimating Physical Properties 555

13 .1 Approaches for Property Prediction and Estimation, 555
13.2 Sources of Physical Property Data, 560
13 .3 Group Contnbution Methods for Estimating Pure Component Properties, 56 I
13.4 Group Contribution Methods for Estimating Mixture Properties, 576
13.5 Applications to Modem Process Analysis and Simulation, 579
Contents ix

Part Ill Applications

Chapter 14 Practical Heat Engines and Power Cycles 586

14.J Availability, Lost Work, and Exergy Concepts, 587
14.2 Carnot, Cycle, and Utilization Efficiencies, 593
14.3 Heat Integration and Pinch Technology, 597
14.4 Turbine and Compressor Performance, 600
14.5 Power Cycle Analysis, 606
14.6 Summary, 618

Chapter 15 Phase Equilibrium and Stabilit}' 642

15.l The Phase Rule, 643
15.2 Phase Diagrams, 647
15.3 The Differential Approach for Phase Equilibrium Relationships, 667
15 .4 Pressure-Temperature Relations, 681
15.5 The Integral Approach to Phase Equilibrium Relationships, 688
15 .6 Equilibrium in Systems with Supercritical Components, 699
15.7 Phase Stability Applications, 704
15.8 Summary, 712

Chapter 16 Chemical Equilibria 749

16.l Problem Formulation and General Approach, 749
16.2 Conservation of Atoms, 752
16.3 Nonstoichiometric Formulation, 753
16.4 Stoichiometric Formulation, 756
16.5 Equilibrium Constants, 761
16.6 The Phase Rule for Chemically Reacting Systems, 770
16.7 Effect of Chemical Equilibrium on Thermodynamic Properties, 775
16.8 Le Chatelier' s Principle in Chemical Equilibria, 780
16.9 Summary, 787

Chapter 17 Generalized Treatment of Phase and Chemical Equilibria 825

17.1 Phase Rule Constrained Parameter Variability, 825
17 .2 Matrix!Detenninant Formalism Applied to Generalized
Gibbs-Duhem and Reaction Equilibrium Expressions, 826
17.3 Invariant Systems(:!= 0), 828
17 .4 Monovariant Systems .'.t=l: Pressure-Temperature Variations, 833
17 .5 Mono variant Systems: Temperature-Composition Variations, 842
x Contents

17.6 Indifferent States and Azeotropic Behavior !f?. 2, 848

17.7 Summary, 850

Chapter 18 Systems under Stress, in Electromagnetic or Potential Fields 858

18. l Electromagnetic Work, 858
18.2 Electrostatic Systems, 861
18.3 Magnetic Systems, 867
18.4 Thermodynamics of Systems under Stress, 872
18.5 Systems in Body-Force Fields or under Acceleration Forces, 876

Chapter 19 Thermodynamics of Surfaces 891

19.1 Surface Tension, 891
19.2 Equilibrium Considerations, 892
19.3 Effects of Pressure Differences across Curved Interfaces, 897
19.4 Pure-Component Relations, 903
19.5 Multicomponent Relations, 905
19.6 Surface Tension-Composition Relationships, 906
19.7 Nucleation, 910

Appendixes

A Summary of the Postulates 919

B Mathematical Relations of Functions of State 919
C Derivation of Euler's Theorem 921
D Cramer's Rule and Determinant Properties 923
E Generalized Cubic EDS Solver 925
F General Mixture Relationships for Extensive and Intensive Properties 929
G Pure Component Property Data 934
H Conversion Factors and Physical Constants inside back cover
Preface xi

Preface
Authors' Note. Robert C. Reid was a co-author of the first and second editions of
Themwdynamics a.nd Its Applications. His contributions to this book and to the field of
thermodynamics in general are widely known and respected. Even though Bob Reid is
not listed formally as an author of this edition, his impact on us and on the contents of
the third edition has been significant and is deeply appreciated.

General approach. For over 50 years, the M.I.T. Chemical Engineering Department has
offered a one-semester, graduate-level subject in classical thermodynamics. Traditionally,
this course has been applications oriented, with one of its primary objectives to develop
problem solving skills in applying fundamentals to applications in new and sometimes
unusual situations. About half of our classroom contact hours are now devoted to discussing
approaches to solving problems. Today, there is an increasing need for practicing chemical
engineers to connect traditional macroscopic and empirically-based property models to their
roots at the molecular-level where intermolecular interactions responsible for deviations
from ideal behavior are characterized in detail. Consequently, since the last edition was
published in 1983, we have expanded our core graduate curriculum in thermodynamics to
formally link molecular effects to constitutive property models using the principles of
statistical mechanics. The text material required to achieve these enhancements evolved
over time, leading to a plan for a comprehensive revision. In designing our approach, we
wanted to preserve the integrity of the theoretical and conceptual treatment of classical
thermodynamics contained in the earlier editions while introducing a molecular-level
perspective on a comparably rigorous basis. To do so, we restructured the second edition
somewhat, and added substantial new material. The third edition now is intended for a
two-semester subject in graduate-level chemical thermodynamics.
About this editWn. Those familiar with the first and second editions of ThemwdyrnJmics
and Its Applications, will see that we have retained many features including the postulatory
approach, the challenging homework problems, and the trealrnent of external fields and
surfuces. Enhancements in the third edition include six new chapters that provide; (1) in-depth
coverage of constitutive property models for non-ideal fluids, including a statistical mechanics
basis, a discussion of van der Waals and McMillan-Mayer theories, treatments of local
composition concepts and electrolyte solutions, and coverage of volumetric equations of state
and activity coefficient models fot non-electrolyte mixtures; (2) a unified development of
combined phase and chemical equilibria using a vectorized framework; and (3) a new section
on availability/exergy analysis of power cycles and other processes involving heat-to-work
conversions. The book now has 19 chapters and has been divided into: Part I, Fund.ameotal
Principles; Part IL Thermodynamic Properties; and Part ill, Applications.
While the subject matter has been updated to include the latest constitutive property
models that practicing chemical engineers and chemists employ, we have tried to keep the
coverage sufficiently general to be of lasting value both as a textbook and as a professional
reference. Example problems illustrate important concepts and problem solution methods.
xii Preface

Part I provides the theoretical basis of classical thermodynamics. Chapters 1-6 cover the
same topics as before, including the 1st and 2nd Laws, the Fundamental Equation, Legendre
transfonnations, and general equilibrium criteria. Several enhancements were added as well,
specifically more example problems, new homework problems, and revisions in notation
and coverage to provide better compatibility with the traditional undergraduate chemical
engineering textbooks in thermodynamics. Major changes were made in Chapter 5 to
incorporate the use of enhanced graphics into the fonnal treatment of the Fundamental
Equation to illustrate the geometric features of the USV Gibbs surface. In addition, Chapter
5 now contains a better derivation of Legendre transformations, and descriptions of other
mathematical methods for manipulating thermodynamic properties and their derivatives.
Chapter 7 covers only stability criteria, with stability applications moved to Chapter 15.
Part II contains an extensive description of how thermodynamic properties are correlated,
modeled, manipulated, and esti.mat.ed. Both macroscopic empirically-based and molecuJar-
level approaches are discussed in-depth for pure components and mixtures. Formal treat-
ments of fugacity and fugacity coefficients and activity and activity coefficients are related
to appropriate PVIN equations of state and tiGEX models. Chapter 8 on pure materials and
Chapter 9 on miXtures have been extensively revised. Completely new chapters include:
Chapter 10 on modeling properties using statistical mechanics; Chapter 11 on non-elec-
trolyte solution models; Chapter 12 on electrolyte models; and Chapter l3 on physical
property estimation.
In Part Ill, applications of classical thermodynamics are~ in detail Chapter 14 on
practical heat engines and power cycles is new, emphasizing the use of availability andexergy
concepts for assessing performance. Chapter 15 on phase equilibria and stability applications
combines appropriate material from Chapters 9 and 10 of the second edition. Chapter 16 covers
chemical equilibria with several enhancements. Chapter 17 is new, treating combined phase
and chemical equilibria problems using a robust vectoriz.ed approach that is completely general.
Chapter 18 covers the material on electromagnetic and other potential fields that was in Chapter
12 of the second edition. Major changes were introduced in Chapter 18 to the section on
electromagnetic fields to fix some earlier problems. Chapter 19 on surface thermodynamics is
essentially the same as Chapter 13 of the second edition.
In a typical two-semester subject sequence, all of Part I (Chapters 1-7) and Chapters 8,
9, 14, 15, 16,and 17 of Partsllandillarenormallycovered in the first semester, emphasizing
the fundamentaJs of classical thermodynamics and their primary applications to chemical
engineering, particularly to phase and chemical equilibria. In the second semester, emphasis
is placed on property models and specialized applications to external field effects and
surfaces, with Chapters 10, 11, 12, 13, 18, and 19 covered. To obtain a betterunderstanding
of how molecular-level effects lead to non-ideal behavior, macroscopicconstirutive property
models are connected to molecular theory in Chapters l l and 12, using the concepts of
statistical mechanics developed in Chapter 10. For further information please consult our
web page at http://web.mit.edu/testerelJthermo/
Jefferson Tester
Michael Modell
Cambridge, Massachusetts
Preface xiii

Acknowledgments and Credits The revisions necessary to complete this edition were
done by one of us (JWT) over the past four years. Recognizing that it is absolutely
impossible to thank all contributors for their support and suggestions and at the risk of
offending someone we inadvertently omit, I would like to extend special thanks to
several individuals who had major impact on the contents of the third edition.
Professor Kenneth Jolls of Iowa State provided major enhancements with his
numerous suggestions and contributions to Part r of the book. Of particular significance
were his graphical representations of the Fundamental Equation. Professors Kenneth
Smith and William Deen and Howard Herzog at MIT, Professors Dudley Herschbach
at Harvard and Keith Johnston at the University of Texas provided important suggestions
to the sections on departure functions and constitutive equations of state. Several other
colleagues including Doros Theodorou (University of Patras), Jonathan Harris (MIT),
Thanassis Panagiotopoulos (Cornell), Pablo Debenedetti (Princeton), William Peters
(MIT), and James Ely (Colorado School of Mines) provided substantive input to Chapter
10 on statistical thermodynamics. In addition, important course content discussions and
numerous homework problems were contributed by Professor Daniel Blankschtein of
MIT. Professors Greg Rutledge of MIT and Doros Theodorou also provided homework
problems. Contributions from Professors Erdogan Kiran (University of Maine), Steven
Penoncello (University of Idaho), and Edith Sevick (University of Colorado), and from
Raymond Thorpe, Keith Gubbins, Peter Harriott, Brad Anton, and Michael Duncan
(Cornell) are appreciated. Ronald Rosensweig's review of electromagnetic field effects
made an important contribution to Chapter 18. I am especially grateful for the stimulating
discussions on polymer thermodynamics provided by Professors Edward Merrill and
Robert Cohen of MIT, by Andrew Zydney of the University of Delaware and by
Ferdinand Rodriguez and Claude Cohen of Cornell.
Eliz.abeth Drake, Bill Peters, and other colleagues at the MIT Energy Lab unselfishly
provided me with the time needed to complete the revision. In addition, during the final
stages, while I was on sabbatical from MIT, colleagues at Los Alamos National
Laboratory, Cornell University and the University of Colorado afforded me welcome
sanctuary and encouragement. I would also like to acknowledge Professor Robert
Brown, MIT's current Dean of Engineering and former Department Head of Chemical
Engineering, and Professor David Litster, Vice-President for Research at MIT, for their
encouragement and support of this project.
I want to acknowledge the major effort expended by Susan Robson designing and
electronically typesetting tbe manuscript. Without her creative efforts and hard work,
we would not have been able to produce such a profes'sional document. Special thanks
also go to Michael Kutney for his conscientious assistance in proofreading and preparing
the figures for this edition, and to Tetsuo Maejima for his original artwork, which was
electronically transferred from the earlier editions. Bonnie Caputo and Anne Carbone
also provided valuable support in preparing early drafts and in the implementation of
the Beta-test program.
Over the years, many students assisted us in developing problems and in proofreading
and preparing charts and tables of data and parts of the appendix. For the third edition
specifically, I am especially grateful to A. Cano-Ruiz, M. DiPippo, J. DiNaro,
xiv Preface

P. Marrone, B. Phenix, R. Weinstein, M. Reagan, K. Sparks, M. Wilkinson, F. Armellini,

C.0. Grigsby, P. Webley, R. Helling, R. Holgate, C. Nagel, W.G. Worley, B. Kumnick,
J. Champion, and J. C]jne. In addition, I would like to thank all the students who
participated in the Beta-test program at MIT during the 1995-1996 academic year.
I have been blessed with the opportunity to have interacted with many great teachers
of thermodynamics who have shared their enthusiasm, knowledge, and insights for this
subject with me. Of these, Robert Reid, Herman P. Meissner, John Prausnitz, Raymond
Thorpe, Herbert Wiegandt, Irwin Oppenheim, John Heywood, Hank Van Ness, Robert
von Berg, and Jean P. Leinroth had an enonnous impact on me personally and
professionally.
And most of all, I am deeply thankful fortheencouragementgiven tome by my family
and friends throughout all of this. In particular, my daughter Kelsey's sensitivity and
spirit and my wife Sue's steadfast love, support and good advice have enriched my life
and these pages. I especially want to thank my Mother for teaching me to aim high and
assuring me that "this takes care of that!"

Jefferson W. Tester
 Nomenclnture

Symbols [units in SI]

a.a Specific and total surface area E Electric field slrength

[m 2/mol, m 2] [m2kg/s 3A or volt/m]
A Total Helmholtz free energy, E Total energy, extensive [J]
extensive [J) E Specific energy, intensive [J/mol, J/kg]
A Specific Helmholtz free energy, F Faraday constant [96,500
intensive [J/mol, J/kg] couJombs/mol or sA/mol]
a; Activity of component i Fugacity of pure i
ft
Qjj Activity of ionic electrolyte ij
ft" Fugacity of component i in a
a+ Mean ionic activity of electrolyte ij mixture
a Acceleration [m/s 2] F General force vector [N]
bt Number of moles of element 1. ]{ Force component vector magnitude [N]
8(1) Second virial coefficient 1" Number of intensive degrees of
freedom
!!. Availability, extensive [J]
B Specific availability [J/mol, J/kg] G Total Gibbs free energy, extensive [J]

B General extensive property G Specific Gibbs free energy, intensive

[J/mol, J/kg]
B General intensive property
g,g Acceleration of gravity [mls2J
B Magnetic induction [kgls2 A or tesla]
H Total enthalpy, extensive (J]
C, C Concentration [mol/L, etc.}
H Specific enthalpy, intensive
Cp Constant pressure heat capacity
[J/mol, J/kg)
[I/mo! K, J/kg K]
H Magnetic field strength [A/m]
Cv Constant volume heat capacity
[J/mol K, J/kg K) H Hamiltonian [J]

D Electric displacement [sA/m 2 or I Ionic strength [mol/kg]

coulombs/m 2] k Boltzmann constant
Elemental atom balance matrix {1.381x10-23 J/K]
'I>
"" Static dielectric constant Ka Equilibrium constant
Ds
dm Dipole moment, Debyes K~ Equilibrium ratio of fugacity
coefficients ($;)
dij ~ matrix element, number of atoms
i in component} Kp Equilibrium constant based on
partial pressures (p;)
e Elementary electron charge
[1.6021773 x 10-19 coulomb (C)] Ky Equilibrium ratio of mole fractions (yi}
K-y Equilibrium ratio of activity
co~fficients
(y.)
xvi Nomenclature

P. Number of elements Radial position coordinate

M Molarity [moU!iter or mol/L] I' Configuration space vector for
m,M Mass [kg] N particles or molecules
m Molality [moJ/kg of solvent] s Total entropy, extensive [JJK]

m Mass flow rate [kg/s] s Specific entropy fJ/mol K, J/kg KJ

m; Molecular weight of component i Time [s]

[g/moll T Absolute temperature [K]
M Magnetization [ampere/m or Alm) To Dead state or ambient temperature [Kl
N Number of moles [moll or molecules u Total internal energy, extensive [J}
NA Avogadro's number u Specific internal energy [J/mol, J/kg]
[6.022137 x 1023 mor 1) v Total volume, extensive [m 3 or LI
n Number of components v Specific volume [m 3/mol. m3/kg]
ne Moles of electrons transferred v Velocity vector [mis]
per mole
lvl. v Velocity vector magnitude [m/s]
nm, nout Entering or leaving mass or moles
Ve Sonic velocity [mis]
[kg or mo!]
n Normal unit vector
w Work [J]

p Pressure {Pa or bar]

w Work rate or power [J/s or W]
We Electrical work [J]
Pvp, P saJ Equilibrium vapor pressure
(Pa or bar] Wnu:u, Maximum or minimum work [J]
Dead state or ambient pressure
Wmin
Po
[Pa or bar] w,.,.. Reversible work [J]

P;, Pi Partial pressure of mixture component w.. Shaft work [J]

i [Pa er bar] Ws Shaft work rate or power [J/s or W1
p Polarization (A s/m2 or coulornb/m 2] x. z General displacement vector
p1V Momentum vector space for N xfsl Mole fraction of component i in
particles or molecules phases
PN@_;) Probability distribution of energy Xi Liquid mole fraction of component i
states Vapor mole fraction of component i
Yi
Q Heat [J] z Compressibility factor
Q,q Heat tTansfer rate [J/s] z• Configurational integral [Eq. (10-76)]
q Heat flux: vector [J/m 2s] z Elevation [m]
2. Electric charge (see Table 3.1) General canonical variable
Zi
R Gas law constant [J/mol K or (z;, ~i) Conjugate coordinates
Pam 3/mol KJ
z+, Z- Electrical charge or valance
r Nwnber of independent chemical
reactions and/or additional constraints
on a system
re Critical pressure ratio
Nomenclature xvii

Greek Symbols Charge density [coulombs/m3]

P±
rl.p Isobaric thennal coefficient of 0 Surface tension (N/m]
expansion [K-1] Ox Unidirectiooal stress (/5:/l!:_) [Pa]
Yi Activity coefficient cf component i $; Fugacity coefficient of pure i
A

Y± Mean ionic activity coefficient 4>; Fugacity coefficient of com po-

fij Reduced activity coefficient nent i in a mixture
of electrolyte ij 4>; Practical (molality based)
E..3 Blecrromotive force(emO (volts] osmotic coefficient
f.o Vacuum permittivity 4>;.x Rational (mole-fraction based)
£ Pennittivity of a medium osmotic coefficient

Tl General thermodynamic efficiency 4>MM Rational (McMillan-Mayer

based) osmotic coefficient
Tic, TlQznui1 Carnot efficiency
tt>i Volume fraction of component i
llcyc/.e Cycle efficiency
(~;, Zi) Conjugate coordinates in the
llr Turbine efficiency Fundamental Equation
'l')p Pump or compressor efficiency
l;. Si Extent of reaction [Eq. (6-51)]
a Thermometric or empirical or (ayCO>1a4) [Eq. (5-88))
temperature [°C, ~ • ...] cJ> Intermolecular potential energy
1( Heat capacity ratio= Cp/Cv co Acentric factor
Kr Isothermal compressibility .Q Surface area per mole (~/ N) or
[Pa' 1 or bar- 1)
one-dimensional strain (~Ix)
).. Lagrangian multiplier
)..;(1) Temperature dependent term in Operators
Eq. (9-81) equal toµ~ (T, P == l bar)
5 Denotes a path dependent variation
A;(T, P) Temperature and pressure
dependent term in Eq. (9-83) ll Finite change in a stllte property

A Thermal deBroglie wavelength d Total differential

[Eq. (10-64)] a Partial differential
µ1 Chemical potentjal of component i J Integral
YI Stoichiometric coefficient of ~ Closed path integral
component i In Natural logarithm (base e)
v+or v_ Stoichiometric coefficients for log or log10Common logarithm (base 10)

v
an electrolyte ij
Total number of ions produced
rr Cumulative product

per mole of electrolyte ij :L Cumulative summation

[v= v++ v_]
1t Number of phases
TI Osmotic pressure [Pa or bar]
p Density [mol/m3, kg/m3)
xviii Nomenclature

Subscripts Superscripts

aq Aqueous phase component ex Excess property (e.g., AHfX)

b Body force component (e.g., lf2,) ID Ideal solution or mixture (e.g., t.Gf!1)
c Critical point property (e.g. Pc} ig Ideal gas (e.g., Vig =RTIP)
f Formation (e.g., Mfj) (s) Phase identification (e.g., xis)= x?)
fus Fusion (solid to liquid) (e.g., AHtus) Infinitely dilute condition
in Incoming stream 0 Ideal gas or single pure component state
mix Mixing property (e.g., Aflmix) + General reference state
0 Ambient or dead state (e.g., T<" P0 ) ± Mean ionic conditions
out Exiting stream 0 Hypothetical reference state at unit
p lsobaric, constant pressure conditions molality

r Reduced property (e.g., Pr= PIP c) ** Hypothetical pure component

reference state
rx Chemical reaction (e.g., Mfrx)
* Attenuated condition where ideal gas
ref Reference component or conditions
behavior prevails
s Boundary (or surface) component or
solvent
sat Saturated condition at phase
equilibrium (e.g., Psat)
T Isothermal, constant temperature
conditions
vap Vaporization (liquid to vapor)
(e.g., Mfvap)
vp Vapor pressure (e.g., Pvp)
± Mean ionic property (e.g., Y±)

Special Notation

circwnflex A Denotes property of a

(as in/;) component in a mixture

overbar - Denotes partial molar property

(as in H;)

underbar Denotes extensive property

(as in Ji)