Activity Coefficients

in
Electrolyte Solutions
2nd Edition

Editor

Kenneth S. Pitzer, Ph.D.

Professor
Department of Chemistry
University of California
Berkeley, California

Boca Raton London New York

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Activity coefficients in electrolyte solutions/editor Kenneth S.

Pitzer. — 2nd ed.
p. cm.
Includes bibliographical references and index.
ISBN 0-8493-5415-3
1. Electrolytes—Handbooks, manuals, etc. 2. Activity
coefficients—Handbooks, manuals, etc. I. Pitzer, Kenneth S.
(Kenneth Sanborn), 1914-
QD565.A27 1991
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 PREFACE
The progress toward a second edition of "Activity Coefficients in Electrolyte Solutions"
was well advanced by Dr. R. M. Pytkowicz, the editor of the first edition, when he resigned
in early 1989 for health reasons. After a substantial hiatus, I was asked to take over the
editorship. Most of the chapters and authors remain as were planned by Dr. Pytkowicz, but
a few changes in authorship or coauthorship were necessary and one new chapter (8) was
added. I am responsible for the present organization of the book but am happy to acknowledge
the role of Dr. Pytkowicz.
My evaluation concerning the general state of knowledge in this field and the oppor-
tunities for advances as well as certain specific comments concerning points of possible
misunderstanding are given in the Introduction. At this point, I wish to thank all of the
authors for the prompt completion of their chapters and my secretary, Peggy Southard, for
assistance on various aspects of this project.

Kenneth S. Pitzer
 INTRODUCTION

It has been eight decades since activity coefficients came into use in the representation
of the solute chemical potential in electrolyte solutions, together with the osmotic coefficient
for the solvent chemical potential. While ionic solutions in other polar solvents have been
and continue to be investigated, aqueous solutions dominate the electrolyte scene with respect
to their importance in biological, geological, and industrial systems as well as in the range
and intensity of scientific study. Although all of the concepts and theories are equally
applicable to nonaqueous electrolytes, almost all of the particular systems that are considered
here are aqueous.
In the earlier years, most research concerned pure, single-solute electrolytes at or near
room temperature and at low and moderate concentration. Only a few systems were measured
over the full molality range available. Subsequently, Robinson and Stokes and others through
isopiestic measurements greatly extended the knowledge of a large number of electrolytes
at 25°C. In their book Robinson and Stokes1 summarize this information as well as presenting
an excellent account of the principles and the methods of measurement for electrolytes.
While a few measurements of mixed electrolytes were made in very early years, it was
Harned2 and his associates that measured quite a number of mixed systems and stated the
rules bearing his name concerning their behavior. Again, this work was confined to tem-
peratures near 25°C and to moderate molalities. Many others made substantial contributions
to experimental research on electrolytes prior to the first edition of this book published in
1979. It is impractical to list here all of the important contributors of that period; their names
are cited in various chapters.
Even by 1910 it was recognized that the behavior of electrolytes in the dilute range
differed from that of nonionic solutions. In 1912, Milner3 explained theoretically the cause
of this difference in terms of the long-range nature of ionic forces, but his mathematical
expression was so complex that it received little attention. In 1923, however, Debye and
Hiickel4 presented a simple expression that captured the essential consequence of the ionic
forces. Subsequently, various theorists investigated the difficult problem of an electrolyte
with greater rigor and confirmed the correctness of the limiting law of Debye and Hiickel.
As is described in certain chapters of this book, several of these later theories also contributed
expressions for the behavior of more concentrated electrolytes.
The major advances in this field over the last fifteen years have been, first, in the area
of mixed aqueous electrolytes of relatively high concentration extending to the limits of
solid solubility, and second, for high temperatures up to 300°C and to pressures of hundreds
of bars. Both of these advances are recognized in major additions to Chapter 3, a largely
new chapter on natural waters, and new chapters on mineral solubilities and ion association
at high temperatures and pressures.
With the ion-interaction (Pitzer) equations, including the theoretical terms for unsym-
metrical mixing of ions of the same sign, together with ion-association equilibria where
significant, it is now possible to predict activity coefficients and water activities accurately
for mixtures of unlimited complexity and to the limits of solid solubility in most cases,
provided, of course, that the solid properties are also accurately known. Computer programs
are now available for such calculations.5 Special recognition is due to Harvie and Weare6
for their pioneering calculations of mineral solubility by these methods including the key
case of CaSO4 solubility in aqueous NaCl where this method gave good results, whereas
older ion-association methods gave a qualitatively incorrect trend with NaCl molality. Also
important are the numerous treatments extending to solid solubility by Filippov and asso-
ciates.7
In past years, ion-interaction and ion-association methods have been regarded as com-
petitive. The first edition of this book gives a good account of the status and viewpoints of
1979. Clegg and Whitfield discuss both the history and current status of these methods in
Section II of Chapter 6. While the title of Chapter 6 is "Activity Coefficients in Natural
Waters," this discussion is comprehensive and not limited to "Natural Waters".
For systems with little or no ion association, specific interionic effects are still significant
at substantial molality and the ion-interaction method has proven to be excellent. Even where
there is unquestioned association to a moderate degree, such as to MgSO4 in seawater and
similar solutions, the inclusion of a special term in the ion-interaction equations has been
found to be a better method at moderate temperatures than the inclusion of a formal association
reaction. For H2SO4, however, the explicit inclusion of the association reaction to HSO4~
is essential. Thus, when HSO4~ or HCO3 ~ or similar species are formed by strong association
reactions, one requires a combination of ion-interaction and ion-association methods to obtain
accurate results. Also, the tendency toward ion association increases at high temperature
where the dielectric constant of water becomes small (see Chapter 8).
For pure electrolytes at room temperature, there has been a good database since the
1955 book of Robinson and Stokes,1 although significant improvements have been made as
well as extensions to additional solutes. The appearance of accurate values at high temper-
atures to 300°C and at high pressures is the second area of major recent advance. Particularly
notable are the solvent vapor pressure measurements of Liu and Lindsay8 for NaCl(aq) and
the isopiestic measurements of Holmes and Mesmer for several other salt solutions. Heat
capacity, heat of dilution, and volumetric measurements have also been made extending to
300°C or above. This has allowed comprehensive thermodynamic treatments; many of these
are listed in Chapters 3 , 7 , and 8.
There have been a number of interesting theoretical advances including those allowing
statistical calculations for more realistic physical models; these are reported in Chapter 2.
Nevertheless, it remains necessary to use semi-empirical methods to represent data to the
full experimental accuracy.
As described in Chapter 1, various measures of composition can be used for electrolytes:
mole fraction, molality (moles per kg of solvent), molarity (moles per liter of solution),
weight fraction, etc. Most electrolytes have a range of solubility limited to about 15 mol * kg" 1
or less, and for such solutions molality has been found to be by far the most convenient
measurement system. Thus, molality is used very generally in this book, but for exceptional
cases of extremely wide solubility range, mole fraction is used. Indeed, for a pure ionic
liquid the molality is infinite; hence, the change to mole fraction is necessary.
The words ' 'ideal" or "ideality'' are ordinarily associated with behavior that corresponds
to unit activity coefficients on the mole fraction basis. The behavior given by unit activity
and osmotic coefficients on the molality basis is similar, has the same limiting property at
infinite dilution, but is quantitatively different at other compositions. It is very convenient
in either system to use expressions for an excess Gibbs energy defined as the difference of
the actual Gibbs energy from that of the ideal or another simple reference pattern. In each
system, mole fraction or molality, it is most convenient and useful to use, as the reference
pattern, that of unit activity coefficients in the same system. Thus, two slightly different
"excess Gibbs energies" are now used. No confusion need arise provided each system is
used self-consistently and with clear statements and definitions.
That the advances of the last decade are important to geochemistry and chemical ocean-
ography is clear from the results presented in various chapters, especially in Chapters 6 and
7. The application to aerosols which comprise aqueous electrolytes is less obvious but
important; at low humidity these aerosol solutions become highly concentrated. This is
recognized in Chapter 6.
There are many biologically important aqueous fluids where chemical thermodynamics
has been applied and has been essential to an understanding of the complex array of processes
taking place. Ions are present in most of these fluids; indeed, it is the activity of a particular
ion that is related to a biological function in many cases.9'16 The ionic strength is rather
low, however, so that a simple approximation for activity coefficients may suffice.
Thus, the numerous reactions involving adenosine mono-, di-, and triphosphates with
various ions present and with varying pH constitute a very interesting system subject to
treatment by the methods of chemical thermodynamics with equilibrium quotients for various
reactions.9"11 Some of the early treatments were for constant ionic strength. They omitted
activity coefficients and used equilibrium quotients assumed to be valid for that fixed ionic
strength. Other treatments consider data for different ionic strengths but assume that an
activity coefficient depends only on the ion charge and the ionic strength and is independent
of the specific ions present.
As the precision of thermodynamic measurements for biologically important systems
increases, it will be necessary to recognize the specific effects of other ions on the activity
coefficient of a given ion. Since these effects are now accurately known for many ions, this
information can be included without introducing unknown parameters. There may be other
interactions in a particular case which are not known independently, but it will be a better
approximation to include the known ion-interaction terms than to ignore all interionic in-
teractions and use only the ionic strength.
There is one area with a biological connection where highly concentrated electrolytes
are involved. This is the use of concentrated solutions of NaCl or other salts to control the
moisture content of foods in storage and its relationship to microbiological growth. Kitic et
al.17 have used the ion interaction equations and reported their methods in the literature for
food science.
Some biologically oriented investigations are now using the ion-interaction equations
(Chapter 7 of the 1st edition, Chapter 3 of this edition) in the treatment of their data. Indeed,
Baumgarten18 has published in a biological journal a simple computer program for this
method. It seems probable that the more precise and complete treatments described in this
volume will find increasing application in biological systems in the near future.
Finally, I note that in the geological area and in engineering there is great interest in
aqueous electrolytes at still higher temperatures, far above 300°C, and this range requires
a different theoretical approach from that used in this book. There is the phase separation
of water and an appreciable salt solubility in the steam phase. Also, the compressibility of
the solvent becomes infinite at its critical point. These aspects require the use of the Helmholtz
energy rather than the Gibbs energy as the basic function. While several research contributions
have been made, which are related to this higher temperature range, many aspects are still
to be investigated. It will be an interesting field both theoretically and in applications in the
near future.
 REFERENCES
1. Robinson, R. A. and Stokes, R. H., Electrolyte Solutions, revised, Butterworths, London, 1st ed,, 1955;
2nded., revised 1965.
2. Harned, H. S. and Owen, B. B., The Physical Chemistry of Electrolyte Solutions, Reinhold Publishing,
New York, 1958.
3. Milner, S. R., The virial of a mixture of ions, Phil. Mag., 23, 551, 1912; 25, 742, 1913.
4. Debye, P. and Hiickel, E., Zur theorie der electrolyte, I and II, Phys. Z., 24, 185 and 305, 1923.
5. Plummet, L. N., Parkhurst, D. L., Fleming, G. W., and Dunkle, S. A., A computer program incor-
porating Pitzer's equations for calculation of geochemical reactions in brines, U.S. Geological Survey,
Water-Resources Investigations Report 88-4153, Reston, VA, 1988. Also, see Chapters 3, 6, and 7.
6. Harvie, C. E. and Weare, J. H., The predication of mineral solubilities in natural waters: the Na-K-Mg-
Ca-Cl-SO4-H2O system from zero to high concentration at 25°C, Geochim. Cosmochim, Acta, 44, 981,
1980.
7. Filippov, V. K., Dmitriev, G. V., and Yakovleva, S. I., Use of the Pitzer method for calculating the
activity of components in mixed solutions of electrolytes according to data on solubility, Dokl. Akad. Nauk.
SSSR, Fiz. Khim., 252, 156, 1980; Engl. transl., 252, 359, 1980; and subsequent papers.
8. Liu, C. and Lindsay, W. T., Jr., Thermodynamics of sodium chloride solutions at high temperatures, J,
Solution Chem., 1, 45, 1972.
9. Alberty, R. A., Standard Gibbs free energy, enthalpy, and entropy changes as a function of pH and pMg
for several reactions involving adenosine phosphates, J. BioL Chem., 244, 3290, 1969.
10. Phillips, R, C., George, P., and Rutman, R. J., Thermodynamic data for the hydrolysis of adenosine
triphosphate as a function of pH, Mg 2+ ion concentration, and ionic strength, J. BioL Chem., 244, 3330,
1969.
1 1 . Goldberg, R. N. and Tewari, Y. B., Thermodynamics of the disproportionation of adenosine 5'-diphos-
phate to adenosine 5'-triphosphate and adenosine 5'-monophosphate, Biophys. Chem., 40, 241, 1991.
12. Guyrin, R. W., Gelberg, H. J., and Veech, R. L., Equilibrium constants of the malate dehydrogenase,
citrate synthase, citrate lyase, and acetyl coenzyme A hydrolysis reactions under physiological conditions,
J. BioL Chem.r 248, 6957, 1973.
13. Cohen, C. J., Fozzard, H. A., and Sheu, S.-S., Increase in intracellular sodium ion activity during
stimulation in mammalian cardiac muscle, Circ. Res., 50, 651, 1982.
14. Shorofsky, S. R., Field, M., and Fozzard, H. A., Mechanism of Cl secretion in canine trachea; changes
in intracellular chloride activity with secretion, /. Membrane BioL, 81, 1, 1984.
15. Biber, T. U. L., Drewnowska, K., Baumgarten, C. M., and Fisher, R. S., Intracellular Cl activity
changes of frog skin, Am. J. PhysioL, 249, F432, 1985.
16. Gam bale, F., Menini, A., and Rauch, G., Effects of calcium on the gramicidin A single channel in
phosphatidylserine membranes, Eur. Biophys. J., 14, 369, 1987.
17. Kitic, D., Pollio, M. L., Favetto, G. J., and Chirife, J., Mixed saturated salt solutions as standards for
water activity measurements in the microbiological growth range, J. FoodSci., 53, 578, 1988, and preceding
articles there cited.
18. Baumgarten, C. M., A program for calculation of activity coefficients at selected concentrations and
temperatures, Comput. BioL Med., 11, 189, 1981.
 THE EDITOR
Kenneth S. Pitzer was born in Pomona, California in 1914. He received his B.S. degree
from the California Institute of Technology in 1935, his Ph.D. from the University of
California, Berkeley in 1937, a [Link]. from Wesleyan University in 1962, and an LL.D.
from the University of California in 1963 and from Mills College in 1969. He was a member
of the faculty at Berkeley from 1937 to 1960, serving also as Dean of the College of Chemistry
from 1951 to 1960. On leave from the University of California, he was Technical Director
of the Maryland Research Laboratory, a World War II entity from 1943 to 1944, and was
Director of Research for the U.S. Atomic Energy Commission from 1949 to 1951. In 1961,
he became President and Professor of Chemistry at Rice University, serving until 1968 when
he became President of Stanford University until 1970. In 1971 he returned to the University
of California, Berkeley, as Professor until 1984 and thereafter as Professor Emeritus but
was recalled for continued service.
His advisory committee and other part-time service included the General Advisory
Committee to the AEC, 1958 to 1965 (Chairman 1960 to 1962); President's Science Advisory
Committee, 1965 to 1968; Commission on Chemical Thermodynamics of the International
Union of Pure and Applied Chemistry, 1953 to 1961; NASA Science and Technology
Advisory Committee, 1964 to 1965; Trustee, Harvey Mudd College, 1956 to 1961, Mills
College, 1958 to 1961, Pitzer College 1966 to the present, Rand Corporation, 1962 to 1972;
Member of the Board of Directors, Owens Illinois, Inc., 1967 to 1986; Federal Reserve
Bank of Dallas, 1965 to 1968, the American Council on Education, 1967 to 1971; and
Member of the Council of the National Academy of Sciences, 1964 to 1967 and 1973 to
1976.
His research has extended through many areas of physical chemistry and into topics of
importance including inorganic and organic chemistry, chemical engineering, and geochem-
istry. In addition to work on aqueous electrolytes reflected in this volume, his research has
included quantum theory and statistical mechanics as applied to chemical problems ranging
from the potential restricting rotation about single bonds, to the bonding in polyatomic
carbon molecules, and to the effects of relativity on chemical bonds involving very heavy
atoms. In addition to many journal articles and several book chapters, his books include
Quantum Chemistry, 1953; Selected Values of Physical and Chemical Properties of Hydro-
carbons and Related Compounds, with F. D. Rossini and others, 1947, 2nd edition, 1953;
Thermodynamics, 2nd edition with L. Brewer, 1961, and a revision of the 1st edition of
G. N. Lewis and M. Randall.
His honors and awards include the National Medal of Science, 1975, the Robert A.
Welch Award in Chemistry, 1984, the Alumnus of the Year Award, University of California,
Berkeley, 1951, and the Alumni Distinguished Service Award, California Institute of Tech-
nology, 1966. From the American Chemical Society he received the Award in Pure Chem-
istry, 1943, in Petroleum Chemistry, 1949, the Gilbert Newton Lewis Medal, 1965, the
Priestley Medal, 1969, and the Willard Gibbs Medal, 1976. Other recognitions include many
special lectureships, a Guggenheim Fellowship, 1951, and election to the National Academy
of Sciences in 1949.
 CONTRIBUTORS
James N. Butler, Ph.D. Kenneth S. Pitzer, Ph.D.
Professor Professor
Division of Applied Sciences Department of Chemistry
Harvard University University of California
Cambridge, Massachusetts Berkeley, California

Simon L. Clegg, Ph.D. Robert F. Platford, Ph.D.

Research Fellow Retired
School of Environmental Sciences Campbellville, Ontario
University of East Anglia Canada
Norwich, United Kingdom
Joseph A. Rard, Ph.D.
Robert M. Mazo, Ph.D. Chemist
Professor Earth Sciences Department
Department of Chemistry University of California
University of Oregon Lawrence Livermore National Laboratory
Eugene, Oregon Livermore, California
Robert E. Mesmer, Ph.D.
Rabindra N. Roy, Ph.D.
Section Head
Chairman and Professor
Chemistry Division
Department of Chemistry
Oak Ridge National Laboratory
Drury College
Oak Ridge, Tennessee
Springfield, Missouri
Chung Yuan Mou, Ph.D.
Professor J. M. Simon son, Ph.D.
Department of Chemistry Research Scientist
National Taiwan University Chemistry Division
Taipei, Taiwan Oak Ridge National Laboratory
Oak Ridge, Tennessee
Roberto T. Pabalan, Ph.D.
Research Scientist R. H. Stokes
CNWRA Professor Emeritus
Southwest Research Institute Department of Chemistry
San Antonio, Texas University of New England
Armidale, Australia
Donald A. Palmer, Ph.D.
Research Scientist Michael Whitfield, Ph.D.
Chemistry Division Deputy Director
Oak Ridge National Laboratory Plymouth Marine Laboratory
Oak Ridge, Tennessee Plymouth, United Kingdom
 TABLE OF CONTENTS
Chapter 1
Thermodynamics of Solutions 1
R. H. Stokes

Chapter 2
Introduction to the Statistical Mechanics of Solutions 29
Robert M. Mazo and Chung Yuan Mou

Chapter 3
Ion Interaction Approach: Theory and Data Correlation 75
Kenneth S. Pitzer

Chapter 4
Experimental Methods: Potentiometric 155
James N. Butler and Rabindra N. Roy

Chapter 5
Experimental Methods: Isopiestic 209
Joseph A. Rard and Robert F. Platford

Chapter 6
Activity Coefficients in Natural Waters 279
Simon L. Clegg and Michael Whitfield

Chapter 7
Mineral Solubilities in Electrolyte Solutions 435
Roberto T. Pabalan and Kenneth S. Pitzer

Chapter 8
Ion Association at High Temperatures and Pressures 491
Robert E. Mesmer, Donald A. Palmer, and J. M. Simonson

Index 531
 1
Chapter 1

THERMODYNAMICS OF SOLUTIONS

R. H. Stokes

TABLE OF CONTENTS

I. Basic Thermodynamic Functions U H V S G A and Their Physical

Significance; Differential Relations 2
A. Thermodynamic Functions 2
B. Equations of State 3
C. Conventional and Absolute Values of Thermodynamic
Properties 3
D. Physical Meaning of Thermodynamic Quantities 3
E. The Laws of Thermodynamics 4
F. Differential Relations between Thermodynamic Functions 5

II. Solutions: Partial Molar Quantities; Chemical Potentials 5

A. Open Phases: The Chemical Potential 5
B. Partial Molar Quantities 6
C. Additivity of Partial Molar Quantities 6

III. Chemical Potentials and Activity Coefficients; Standard States and

Composition Scales for Nonelectrolytes and Electrolytes 7
A. Activities of Components 7
B. Standard States 8
C. Chemical Potentials in Electrolyte Solutions 8
D. Activity, Activity Coefficients, and Standard States 9
E. Mean Activities and Activity Coefficients 10
F. Relations between Activity Coefficients on Different Scales 11
G. The Solvent Chemical Potential, Solvent Activity, and the
Osmotic Coefficient 12

IV. The Gibbs-Duhem Relation; Various Forms for Two- and

Multicomponent Systems 12
A. The Gibbs-Duhem Equation 12
B. Relation between Mean Activity Coefficient and Osmotic
Coefficient 13

V. Ideal Solutions; Entropy of Mixing on Various Statistics; Regular

Solutions; Athermal Solutions 15
A. Ideal Solutions 15
B. The Entropy of Mixing 15
C. Regular Solutions 17

VI. Colligative Properties 17

A. Freezing Point Depression 17
B. Boiling Point Elevation 19
C. Osmotic Pressure 19
2 Activity Coefficients in Electrolyte Solutions, 2nd Edition

D. Derivation of Thermodynamic Quantities for Electrolyte

Solutions from Electromotive Forces of Cells 20

VII. Enthalpy and Volume Properties; Apparent Molar Quantities 21

A. Temperature and Pressure Dependence of Activity Coefficients 21
B. Pressure Dependence of Activity Coefficients 22
C. Partial Molar Enthalpies and Volumes 22

VIII. Excess Thermodynamic Properties 24

IX. Multicomponent Systems — Thermodynamic Relations; Salting-Out

and Salting-In Effects 26
A. Thermodynamic Relations for Multicomponent Solutions 26
B. Salting-Out Effects 27

References 28

I. BASIC THERMODYNAMIC FUNCTIONS U H V S G A AND

THEIR PHYSICAL SIGNIFICANCE; DIFFERENTIAL RELATIONS
A. THERMODYNAMIC FUNCTIONS
The thermodynamic properties of a substance or system at equilibrium may be grouped
into (1) intensive properties, of which the most familiar are the temperature and pressure,
and (2) extensive quantities, of which the volume and mass are most familiar. The former
are independent of the size of the sample taken for measurement and are constant throughout
each phase of the system. The temperature, in fact, must be the same in all phases of the
system for true equilibrium to exist, though the pressure may be different in different phases,
as in osmotic equilibrium. Other intensive properties are the density, refractive index,
dielectric constant, percentage composition, and the various molar quantities (see Section
ILB).
Extensive quantities are directly proportional to the amount of the sample taken for
measurement. The various energy quantities and the entropy are also extensive quantities
when they refer to a phase or system as a whole, but their values per mole are intensive
quantities.
The most frequently encountered thermodynamic functions in work on solutions are

The total energy or intrinsic energy U

The enthalpy H = U + PV
The entropy S
The Gibbs free energy G = H - TS
The Helmholtz free energy A = U - TS
The heat capacities at constant pressure and at con-
stant volume
 3

The isothermal compressibility

The adiabatic compressibility

The thermal expansion coefficient

The last three properties above are intensives.

The thermodynamic properties and others defined in terms of them are functions of the
state, that is, their values depend only on the existing state of the system and not on the
route by which that state has been reached.

B. EQUATIONS OF STATE
If the nature and amounts of substances are specified, the volume, temperature, and
pressure are related by an equation of the form:

V = f(T,P)

known as the equation of state. Thus only two of V, T, and P can be varied independently,

C. CONVENTIONAL AND ABSOLUTE VALUES OF THERMODYNAMIC

PROPERTIES
The existence of a true zero pressure, that of a perfect vacuum, is obvious, and the
aboslute zero temperature is equally familiar. The entropy of a pure substance also has a
true zero, that of its pure crystalline solid form at zero (Kelvin) temperature, according to
the third law of thermodynamics. The energy quantities U, H, G, A, however, do not have
a natural zero, and are consequently measured relative to arbitrarily chosen standard states.
Thus the total energy U of a compound is usually referred to that of its constituent elements
either at absolute zero or at 25°C.

D. PHYSICAL MEANING OF THERMODYNAMIC QUANTITIES

Temperature, pressure, and volume need no discussion. The total energy U is defined
by the first law of thermodynamics

dU = q + w (1)

where q is the heat absorbed and w the work done on the system in an infinitesimal change.
Hence, AU is measurable as the heat absorbed at constant volume, e.g. , in bomb calorimetry .
Solution calorimetry, on the other hand, is usually carried out at constant (atmospheric)
pressure, and the heat absorbed in this case is identified as AH. The entropy, and the free
energies that involve it, are the least obvious of the thermodynamic functions, and textbooks
of general thermodynamics should be consulted for a full explanation.1'7 The Gibbs free
energy G is the most important function in dealing with chemical equilibria, being so defined
that it is a minimum for equilibrium at constant temperature and pressure. It may be thought
of as the chemical analogue of potential energy in a mechanical system, and, in particular,
as closely related to electrical energy through the equation for reversible electrical cells

AG = -nEF (2)
4 Activity Coefficients in Electrolyte Solutions, 2nd Edition

where n is the number of electrons transferred and E is the reversible potential for a cell
operating at constant temperature and pressure. The change AG in a process at constant
temperature and pressure is equal in magnitude to the maximum reversible work which can
be done by the process.

E. THE LAWS OF THERMODYNAMICS

The first law of thermodynamics, also known as the law of conservation of energy, says
that the quantity U defined by

dU = q + w

is a function of the state of a system. Here q is the heat absorbed by, and w is the work
done on, the system. The second law concerns the behavior of the entropy (S), stating that
in a natural or spontaneous process taking place at a Kelvin temperature T, in which the
system absorbs heat q from its surroundings,

and that in a reversible change

Processes in which dS < q/T cannot occur according to the second law, and are called
unnatural processes.
In measurements of the heat capacity CP of a pure substance at constant pressure, heat
is added at temperature T under reversible conditions, so that

q = cpdi
where

and

where I is an integration constant.

The third law of thermodynamics states that for a pure crystalline solid the integration
constant I is zero, i.e., the entropy itself is zero at the absolute zero. (In some cases allowance
has to be made for the existence of different states of nuclear spin, which persist at the
absolute zero.) This law arises from the statistical nature of entropy, expressed by Boltz-
mann's famous equation
 5

S = k in W (4)

where W is the number of complexions (distinguishable states) of the system.

In a perfect crystal, W = 1, so S = 0.
Some authorities refer to a zeroth principle of thermodynamics, which amounts to a
statement of the existence of temperature. Guggenheim3 formulates this as, "If two systems
are both in thermal equilibrium with a third system, then they are in thermal equilibrium
with each other."

F. DIFFERENTIAL RELATIONS BETWEEN THERMODYNAMIC FUNCTIONS

For a closed system, i.e., one which no matter enters or leaves, the first and second
laws are summed up by the equations

dU = TdS - PdV
dH = TdS + VdP
dA = -SdT - PdV
dG = -SdT + VdP (5)

The last of these is the most important in solution thermodynamics, giving the very
useful results

Equation 6 with G = H - TS yields the very important Gibbs-Helmholz equation:

which may also be expressed as

Equations 5 to 9 are used in treating change of equilibrium constants with temperature and
pressure.

II. SOLUTIONS: PARTIAL MOLAR QUANTITIES; CHEMICAL

POTENTIALS
A. OPEN PHASES: THE CHEMICAL POTENTIAL
An open phase is one which matter is able to enter or leave. When a chemical substance
is added to or removed from a phase (e.g., when water evaporates from a solution), the
thermodynamic properties of the phase are altered. These changes are described by adding
to Equation 5 terms representing the energy, enthalpy, or free energy associated with each
substance added. Each such term takes the form: chemical potential of substance x differ-
ential quantity added. Thus
6 Activity Coefficients in Electrolyte Solutions, 2nd Edition

where n> denotes the number of moles of species i present in the phase. The last of these
equations gives the clearest physical meaning to the chemical potential, since by considering
the addition of dnj mol of species j to a phase at constant temperature and pressure we find

The subscripts as usual denote which state variables are held constant during the partial
differentiation; i ^ j means that the amounts of all species other than j are held constant.

B. PARTIAL MOLAR QUANTITIES

For a phase such as a solution, any of the extensive thermodynamic properties (e.g.,
V, H, U, S, A, G) can be regarded as a function of the state variables P, T, and n^ Using
X to denote an extensive property in general, we can then define the partial molar value of
X for component j, denoted X, relation:

(The term partial molal is often used instead of partial molar. In this context, either molar
or molal means simply per mole, and has nothing to do with the molarity or molality
concentration scales.)
The chemical potential of species j in the solution is thus identical with its partial molar
Gibbs free energy:

A physical interpretation of the chemical potential of a substance is therefore that it is the

free energy change per mole of substance added to the phase when the amount added becomes
vanishingly small; or the Gibbs free energy change when 1 mol of the substance is added
to an infinite amount of the phase, the temperature and pressure being held constant in either
case.

C. ADDITIVITY OF PARTIAL MOLAR QUANTITIES

Equation 12 can be integrated at constant temperature and pressure, with respect to the
quantity of each component in turn. The components can be added in infinitesimal quantities,
each proportional to the final amount of that component in the phase. This process can be
described by

dn; = n^x

where dx is the same for all components, and x increases from 0 to 1 during the integration.
 7

Now the ni are constants during the integration (since they describe the final state, and the
relative amounts of the components remain unchanged as the additions proceed); hence, the
Xj are also constant since they depend on the temperature, pressure, and composition. The
integration therefore gives

Furthermore, Xinitial refers to the start of the process, when the amount of the phase is zero;
so clearly Xinitial is zero. The result is

showing that the value of the extensive property X for a phase is composed additively of
the partial molar values of its components, each weighted by the number of moles present.
In particular,

III. CHEMICAL POTENTIALS AND ACTIVITY COEFFICIENTS;

STANDARD STATES AND COMPOSITION SCALES FOR
NONELECTROLYTES AND ELECTROLYTES
A. ACTIVITIES OF COMPONENTS
The activity ^ of a component in a solution is a convenient alternative means of describing
its chemical potential:

Here the superscript ° denotes an arbitrarily chosen standard state for the component i.
fjL° is then called the standard chemical potential of i. It is conventional to choose the
corresponding standard activity a° as unity, giving the simpler relation:

The reason for the logarithmic form requires some comment. In the simplest case, that of
a single-component ideal gas phase containing i^ mol, Equations 14 and 7 give

hence
8 Activity Coefficients in Electrolyte Solutions, 2nd Edition

and

fjij = const 4- RT In P, (18)

This means that the chemical potential approaches minus infinity as the pressure goes
to zero, and the chemical potential is therefore an awkward quantity to discuss or tabulate
for low pressures. Similar problems occur with solutions; in this case the logarithmic term
involves the concentration instead of the pressure. However, when activities with appro-
priately chosen standard states are considered, no infinite values occur; they are always
positive, tending to zero at infinite dilution.
To avoid problems concerned with units, Equation 18 may be rewritten as

where JJL° is the chemical potential of the gas at the standard pressure P°.

B. STANDARD STATES
It must be emphasized that the choice of standard state is arbitrary; indeed, it is sometimes
convenient to use different standard states for the same substance in the same solution. There
is nothing arbitrary about the chemical potential itself: for a component of a given solution
at a given temperature and pressure, its value is uniquely defined. It follows from Equation
17 that if we change the standard state, we also change the value of the activity.
In some cases it is convenient to use an actual physically realizable state as the standard
state. In the thermodynamics of mixed liquid nonelectrolytes, the usual choice is the pure
liquid component at the same temperature and pressure as the solution. With this choice,
the activity of any component must lie between 0 and 1 at equilibrium. This standard state
is also almost invariably adopted for the solvent component of electrolyte solutions. Thus
the activity of pure water is defined as unity, and the water activity in any solution is

The starred pressure symbol denotes the fugacity, an idealized partial pressure, which can
be evaluated from the actual partial pressure P by the use of data on the nonideal gas behavior
of the vapor.3'5 The superscript zero refers to pure liquid solvent at the same temperature
and hydrostatic pressure as the solution.

C. CHEMICAL POTENTIALS IN ELECTROLYTE SOLUTIONS

For substances that are solids at the temperature of interest, the use of the pure liquid
as the standard state is inconvenient since it represents a metastable or unstable condition.
Nevertheless, if the enthalpy and free energy of fusion are known, it is possible to retain
this standard state for the solution, as is done, for example, in Hildebrand's8 treatment of
the solubility of solid nonelectrolytes.
For electrolytes, however, a standard state is required which recognizes the ionic char-
acter of the solution. This raises a problem peculiar to electrolyte solutions, which must
now be discussed. We may define the chemical potential of the ion of species i by

where j refers to all ionic species other than i and s to the solvent. However, the physical
operation represented by Equation 21 cannot be carried out: there is no way in which we
 9

can add to the solution ions of species i only, because only an electrolyte with equal amounts
of positive charge on its cations and negative charge on its anions can be handled. For the
electrolyte (formula B) as a whole there is no difficulty; the definition

represents a physically realizable process.

Equation 21 is actually incomplete in that it does not recognize that in adding charged
ions of one species only, we will build up a charge in the solution. The free energy required
to build up this charge from zero is in principle calculable from electrostatic theory, but
will depend on the shape of the body of solution involved. Guggenheim3 proposed the use
of the "electrochemical potential" for individual ionic species as a way of avoiding this
difficulty. The internal electrical potential i|iint of any phase, charged or not, may be defined
as the work done in bringing a unit of electrical charge from infinity to the interior of the
phase. Then the free energy of the phase is the electrochemical potential jx[.

where F is the faraday and z; is the (signed) charge number of the ion. This concept finds
its main application in the study of electrodes and other charged interfaces. For the present
problem, it suffices to note that provided the internal electrical potential is the same, dif-
ferences in electrochemical potential are equal to differences in chemical potential defined
by Equation 21. This overcomes the conceptual difficulty, but not the physical obstacle that
we cannot actually add one kind of ion only. The consequence of this fact of life is that
there is no rigorous method of measuring the chemical potential of a single ionic species;
all experimental methods lead, if fully analyzed, to values for the chemical potential of an
electrically neutral assemblage of ions, or else to differences between the chemical potentials
of electrically equivalent amounts of ions of the same sign. Theoretical treatments, on the
other hand, frequently lead to calculated values for the chemical potentials of single ionic
species. In order to compare these with experiment, they must be combined to give the
chemical potential of an electrically neutral assemblage,

D. ACTIVITY, ACTIVITY COEFFICIENTS, AND STANDARD STATES

Accepting the conventional use of chemical potentials of individual ionic species, we
may write

This places no restriction on the choice of standard state. Several different choices are in
common use for electrolytes.
First, when the composition of the solution is described in terms of the molality scale,
the standard state is the "hypothetical one-molal solution" of the ion. It is so chosen that
as the molality approaches zero, the ratio a/m; tends to unity. This ratio is defined as the
molal activity coefficient y(:

The additional subscript (m) has been added to |JL° to emphasize that the standard state
in question applies to the molality scale.
10 Activity Coefficients in Electrolyte Solutions, 2nd Edition

There is an awkward problem of dimensions concealed in Equations 24 and 25. The

activity coefficient y is a dimensionless quantity, tending to 1 at infinite dilution. The molality
irii, on the other hand, has dimensions mol kg" 1 . Strictly speaking, then, Equations 24 and
25 should be written

where m° is the unit molality, i.e., 1 mol kg *. The inconvenience of inserting the m° factor
in all expressions deriving from Equation 25, including equilibrium constants, is, however,
sufficient to deter all but the most rigorously minded from doing so, and we shall use the
handier form of Equation 25.
The standard state has the same composition as a real 1 molal solution, but its hypothetical
character involves the imagined absence of all interactions between ions due to their charge,
size, and other relevant properties. In this respect, the analogy between the ideal gas standard
state of 1 standard atmosphere pressure and an actual gas at the same pressure is useful. In
particular, the standard state must be such that Equations 24 and 25 hold at all temperatures
and pressures. It follows from Equations 7 and 9 that the partial molar enthalpy and partial
molar volume of the ion have the same values in the standard state as at infinite dilution.
Also, ^ must be unity in the standard state. We see that the standard state is an imaginary
one in which the molality of the ion is 1 mol kg~ ] , but all the partial molar functions not
involving the entropy have the same value as in the actual infinitely dilute solution.
Second, for the molarity scale (ci = moles of ion i per liter), a different standard state
and activity coefficient are used: the hypothetical 1 molar solution and the molar activity
coefficient (y^:

Again the standard state is chosen so that yi —> 1 as c —> 0.

Some care is needed in the use of thermodynamic relations derived from Equation 26
by differentiation with respect to temperature or pressure, e.g., from Equation 6 or 7. It
must be remembered that, unlike the molality, c varies with temperature and pressure.
Third, the mole fraction scale often appears in theoretical treatments, and very recently
has come into practical use for very concentrated electrolytes.9 The standard state is now
one that has unit mole fraction of the solute species concerned, but in other respects has the
properties of the solute in infinitely dilute solution. This is an even more theological concept
than the hypothetical molal and molar solutions.

where fi is the rational or mole-fraction scale activity coefficient.

E. MEAN ACTIVITIES AND ACTIVITY COEFFICIENTS

Thermodynamic measurements yield chemical properties not of individual ionic species,
but of electrolytes as a whole. Taking the general formula to be M y , X V2 where the cation
M has charge = z ( e and the anion X has charge z2e, we have

vl z, = — v2 z2 (28)

for electrical neutrality. The chemical potential of the electrolyte is

 11

Here the JUL° term is a combination of those for the separate ions.

More briefly, putting B for the formula of the electrolyte and denoting the cation by 1 and
the anion by 2:

The mean molality and mean activity coefficient are now defined as

where v = vv + v2, so that Equation 30 becomes

In single electrolytes, m ± is easily evaluated from the molality m and the formula, e.g.,
m ± = m for 1-1, 2-2, or 3-3 electrolytes, and nu = 41/3 m for 1-2 and 2-1 electrolytes.
In mixtures, m ± can be evaluated from Equation 31 for any arbitrary choice of the electrolyte
B, subject to the condition of electrical neutrality.
The mean activity coefficient is the commonly tabulated quantity, and the subscript ( ± )
is often omitted from tables and equations where no ambiguity is likely to arise.

F. RELATIONS BETWEEN ACTIVITY COEFFICIENTS ON DIFFERENT

SCALES
Occasionally it is necessary to convert activity coefficients for one concentration scale
to those for another, in particular to convert molal activity coefficients y to molar activity
coefficients y. The relationship can always be established by noting that the chemical potential
of a substance in a given solution is unaffected by the choice of composition scale, but the
standard states for different scales will differ by a constant amount (which may, however,
change with temperature). The amount of this constant difference is fixed by the requirement
that as the solution approaches infinite dilution of all components, all the solute activity
coefficients must approach unity. (This condition applies to all the concentration scales used
for electrolytes, but not to the case of liquid mixtures where the pure liquid component is
the standard state.)
The most often needed conversion is between the molality and molarity scales, for
which:

where d$ is the density of the pure solvent. Calculation of the ratio c/m of course requires
a knowledge of the density of the solution, or of the apparent or partial molar volumes of
the solute components.
12 Activity Coefficients in Electrolyte Solutions, 2nd Edition

G. THE SOLVENT CHEMICAL POTENTIAL, SOLVENT ACTIVITY, AND THE

OSMOTIC COEFFICIENT
For the solvent s

where the standard state is by convention the (real) pure solvent at the same temperature
and hydrostatic pressure as the solution. Hence, the activity of the pure solvent is unity. In
dilute solutions of electrolytes, the activity, and even the activity coefficient of the solvent
are very little different from unity, so that the reporting of solvent properties in these terms
requires a large number of significant figures. To overcome this problem and to simplify
many calculations the osmotic coefficient 4> is defined by

where Ms is the molar mass of the solvent, and the electrolyte k is present at molality mk;
1 mol of the electrolyte k gives vk mol of ions in solution.
The corresponding molar scale osmotic coefficient is seldom used. The osmotic coef-
ficient is so defined that it must tend to unity at infinite dilution of all solutes, i.e., it
recognizes the fact that Raoult's law for the solvent component becomes exact at infinite
dilution.

IV. THE GIBBS-DUHEM RELATION; VARIOUS FORMS FOR

TWO- AND MULTICOMPONENT SYSTEMS
A. THE GIBBS-DUHEM EQUATION
A general differentiation of Equation 14 at constant temperature and pressure gives

However, by Equation 13

Hence

gives a relation between the values of any partial molar extensive property for the components
of a solution. This trivial-seeming result is of enormous importance in solution thermody-
namics.
When X represents Gibbs free energy, it becomes

for any change of composition at constant T and P.

 13

B. RELATION BETWEEN MEAN ACTIVITY COEFFICIENT AND OSMOTIC

COEFFICIENT
Since the chemical potentials in the standard states are independent of composition,
Equations 40, 33, and 36 give for a single electrolyte solution

Integrating from m = 0 (where In y± = 1) we obtain

Another manipulation of Equation 41 yields

Equation 43 is used when vapor pressure measurements have been made on a solution,
yielding values of <J> via Equations 36 and 20. It is clear from Equation 43 that the mea-
surements must be made down to as low concentrations as possible, and must be spaced
closely enough to permit accurate evaluation of the integral. However, with electrolyte
solutes the limiting behavior of the osmotic coefficient at low concentrations makes Equation
43 impractical in the form shown. This is because

where A is the limiting Debye-Hiickel slope for the osmotic coefficient. Hence, the integral
in Equation 43 becomes

in which the integrand approaches — °o as m —> 0.

This difficulty is overcome by changing the independent variable from m to m172 when
Equation 44 becomes

in which the integrand now approaches the finite value — A as m —* 0. The fact that A is
calculable from interionic attraction theory assists in drawing the curve of (<j> — l)/m 1/2 vs.
m1'2 in the region where experimental results become inaccurate.
The vast majority of vapor pressure measurements on electrolyte solutions are made by
the isopiestic method (see Chapter 5). In this method, a known amount of the solute under
study is placed in a small silver or platinum dish, and another dish contains a known amount
of a reference solute such as sodium chloride; appropriate amounts of water are added (or
already present in the stock solutions if the solutes are used in this form), and the dishes
are placed in a desiccator on a copper or silver block to ensure good thermal contact between
them. The desiccator is evacuated of air as far as possible and held in a thermostat for a
14 Activity Coefficients in Electrolyte Solutions, 2nd Edition

day or two, with mechanical rocking to keep the solutions uniform. Under these conditions
water passes from one solution to the other through the vapor phase until the vapor pressures
(and hence the water activities) are equal. The equilibrium molalities m and m^ are then
determined by weighing the dishes, and are related to the osmotic coefficients by

The ratio (mref/m) is called the isopiestic ratio. In practice it is found that (J> can be measured
with —0.1% accuracy by this method at molalities down to about 0.1 mol kg" 1 . With 1-1,
1-2, and 2-1 electrolytes, this is low enough to permit a reasonably accurate estimate of the
integrand in Equation 45 between 0.1 m and zero concentration (where its value is —A),
and hence to determine true values of *y ± . For higher valency-type electrolytes, however,
the gap in the integrand between 0.1 m and zero concentration is usually too large for this
method to be applied. The activity coefficients above 0.1 m can then be evaluated only
relative to the value at 0.1:

and recourse must be had to EMF (see Chapter 4) or freezing point studies to determine In
•y ± (m = 0.1).
Equation 44 finds its main application in cases where *y± has been found by EMF
measurements, and osmotic coefficients are required. The integral may be evaluated graph-
ically or analytically. The results of measurements of activity coefficients are often given
in the form of a Debye-Hiickel expression plus a power series in m

for which Equation 47 becomes

where

F(x) = 3 [1 + x - 2 In (1 + x) - 1/(1 + x)]/x3 (50)

The function F(pm1/2) approaches unity as m —> 0. The factor a/3 in Equation 49 is the
constant A referred to in the discussion of the integration of Equation 45.
In a solution with several solutes besides the solvent S, the Gibbs-Duhem relation
becomes

where the summation is carried over all the solute electrolytes.

 15

V. IDEAL SOLUTIONS; ENTROPY OF MIXING ON VARIOUS

STATISTICS; REGULAR SOLUTIONS; ATHERMAL SOLUTIONS
A. IDEAL SOLUTIONS
The ideal solution is defined by the condition that the chemical potential of component
i at all compositions is given by

Hence the activity coefficients f> are unity at all concentrations. If there are only two
components, it is sufficient to specify that one of them obeys Equation 52; it can then be
proved by the Gibbs-Duhem equation that Equation 52 must hold for the other component,
also. It should be noted that though the mole fraction scale activity coefficient f; is unity,
this does not hold for the molal activity coefficient y or the molar activity coefficient y in
an ideal solution.* Consider a nonelectrolyte A, which forms an ideal solution in the solvent
S, at molality m, and let ns° denote the number of moles of S in 1 kg of pure solvent. Then

Hence, In y = B/(m -f ns°) where B is a constant to be fixed by the condition -yA —>
1 as m -> 0. Thus, B = ns°, and yA = 1/(1 4- m/ns°) for an ideal solution of a nonelectrolyte.
For an ideal solution of an electrolyte in water (an unrealizable case) we should obtain

where v is the ion number defined in Section III.E. This expression is found as a term in
some versions of the Debye-Hiickel equation, when it is argued that the solution would be
ideal but for the ion-ion interactions.
Ideal solutions have (as a necessary consequence of Equation 52) the property of mixing
without enthalpy or volume changes, i.e., the partial molar enthalpies and volumes of the
components in solution are the same as those of the pure liquids. One can probably say with
safety that no actual solution is known that conforms exactly to the ideal solution model,
but mixtures of substances differing only in isotopic composition come very close to it, and
Equation 52 can also be shown to hold for the solvent as a limiting case in very dilute
solutions.

B. THE ENTROPY OF MIXING

When r\l mol of substance 1 are mixed with n2 mol of 2 at constant temperature to form
a single phase, the entropy of mixing ASmix is defined by:

where the superscript zero refers to the pure substances.

If the solution is ideal, it follows from Equation 52 that

* One may define <|> = 1, y{ = 1 as an alternate reference pattern of solution behavior in the molality system;
see Chapter 3, Equations 25 through 33.
16 Activity Coefficients in Electrolyte Solutions, 2nd Edition

where the mole fraction x, = 1 - x2 = n 1 /(n 1 + n 2 ). Also, the partial molar entropies are

These equations clearly generalize for any number of ideal components.

The statistical mechanics of the entropy of mixing of molecules of differing shape and
size have been intensively studied.10 Flory and Huggins, dealing with the problem of long,
flexible, polymer molecules dissolved in normal small-molecular solvents such as benzene,
concluded that the entropy of mixing should be given more accurately by

where 3>, the volume fraction of the component, has replaced the mole fraction of Equation
57. __ _ _
Since <!>, = n^/OiiY, 4- n^), the Flory-Huggins equation reduces to the ideal mixing
Equation 57 only when V t = V 2 .
Solutions which obey Equation 59 as regards ASmix, but which also have the ideal
properties of no volume change or enthalpy change on isothermal mixing, are called athermal
solutions.
The expression Equation 59 is frequently and appropriately used in discussing polye-
lectrolyte solutions in regard to that part of the entropy of mixing that does not arise from
coulombic interactions. It has also been used with some success in the case of simple
electrolytes,11-12 where it was first proposed by Glueckauf1 for dealing with the entropy of
mixing of solvated ions with the solvent. Its theoretical foundation in this case is a good
deal more shaky, for the solute is now far different from the flexible chain model used for
polymers.
A question with obvious relevance to the simple electrolyte problem is what is the
observed behavior of the entropy of mixing of globular molecules of widely different sizes?
This has been studied particularly by Marsh13'14 and collaborators, who have measured free
energies and enthalpies of mixing of cyclo-paraffin solutions of other cyclo-paraffins and
of siloxanes such as octamethyl cyclo-tetrasiloxane. From these measurements, entropies of
mixing are derived by the relation

The general conclusion is that the entropy of mixing of these real molecules usually lies
between the ideal value (Equation 57) and the value given by the Flory-Huggins or "volume-
fraction statistics" (Equation 59) and somewhat nearer to the latter. To this extent, it supports
the use of Equation 59 in calculations on electrolyte solutions.
In this case, however, it must be understood that it refers only to a part of the entropy
of mixing, that part due to neither the coulombic forces between ions nor to the entropy
changes that occur as the result of solvation of the ions or their effects on the structure of
water, but due essentially to the differences of size between water molecules and (solvated)
ions.
In many models of electrolyte solutions, starting with that of Debye and Hiickel, the
ions are treated as charged hard spheres, and the solvent as a structureless continuum
separating them, characterized only by its dielectric constant; this is known as the primitive
model. With this model the above discussion of the entropy of mixing is scarcely relevant.
A more appropriate model would treat the water molecules as another collection of hard
spheres. The entropy of mixing of hard spheres of different sizes has been calculated by
 17

Lebowitz and Rowlinson,15 and differs from the ideal value by amounts depending on both
the ratio of diameters and the packing density. The complexity of the expressions is, however,
such that they are unlikely to find general use in electrolyte theory except for molten salts.

C. REGULAR SOLUTIONS
A "regular solution'* is defined as one for which the entropy of mixing is given by the
ideal expression Equation 52, but the enthalpy of mixing is nonzero, being given by

where W is a constant characterizing the interaction of the two species, and AHm is the
enthalpy increase when 1 mol of solution is made at constant temperature by mixing x} and
x2 mol of the components. From this definition, it follows that the mole-fraction activity
coefficients are

Further, it can be shown that when W > 2RT there will be a range of compositions for
which the solution will separate into two phases: the upper critical solution temperature is
given by Tc = W/2R.
This model is mainly used for mixtures of nonelectrolytes, sometimes in combination
with Equation 59 instead of Equation 56 for the entropy of mixing. The regular solution is
the next simplest approximation to the ideal solution. It is relevant to electrolyte solutions
in suggesting an appropriate form for the "nonelectrolyte" interaction terms to be added to
theoretical expressions for the coulombic contributions to the activity coefficient. The fl and
f 2 in the above equations are referred to unity in the standard state of the pure liquid
component. This is the standard state used for the solvent component in electrolytes, so
Equation 52 suggests that the nonelectrolyte interactions will contribute to In as, a term of
the form

The corresponding contribution to the osmotic coefficient <|> will be

where a and a' are constants.

By Equations 48 and 49, a similar term in the first power of m will appear in the
expression for In -y. This argument gives a qualitative justification for the inclusion of first-
order terms in m in the expressions for osmotic and activity coefficients. Higher integral
powers are sometimes necessary as well.

VI. COLLIGATIVE PROPERTIES

A. FREEZING POINT DEPRESSION
Freezing point depression measurements provide a useful means of studying activities
in electrolyte solutions and fill an important gap in the region below 0.1 m where the
isopiestic method is insufficiently accurate. The only other feasible method in this region
is the measurement of EMF of cells, and this is frequently impossible because no suitable
reversible electrodes are known.
18 Activity Coefficients in Electrolyte Solutions, 2nd Edition

At the freezing point Tf of a solution, the chemical potential of the solvent in the solution
is equal to the chemical potential of the pure solid solvent at Tf. The latter quantity can be
calculated from the freezing point of the solvent by the Gibbs-Helmholtz equation, provided
that the latent heat of fusion of the pure solvent and its temperature dependence are known.
For the solvent S in the solution we use unprimed symbols, and for the pure solid, primed
symbols. Then for equilibrium at temperature T

For an infinitesimal change of composition, while equilibrium between solid and solution
is maintained by a corresponding infinitesimal change in T:

where AHf is the molar enthalpy of fusion of the pure solvent. In general, AHf is not quite
constant but is a function of T

where T° is the freezing point of the pure solvent.

Integrating Equation 66, subject to Equation 67 with ACp assumed independent of T,
gives

where D is an integration constant.

To evaluate the integration constant, take the case of the pure solvent, where as = 1
and T = T°, finding

so that

This equation may be simplified by expansion in powers for AT/T°, where AT is the freezing
point depression AT = T° - T, but there is little point in this in the age of personal electronic
calculators. The left-hand side of Equation 69 reminds us that freezing point data give the
solvent activity at the temperature of the freezing point of the solution concerned.
For dilute solutions, where T is no more than a degree or so below T°, the difference
 19

between In as for the same solution at T and at T° is usually negligible. However, the freezing
point method can be used at higher concentrations; in that case the conversion from T to
T° requires the use of data on enthalpies of dilution, as discussed in Section VII. These data
are also needed in conversion from T° to higher temperatures.
Activity coefficients may be obtained from freezing point data via Equations 69, 36,
and 45. Alternative methods of calculating are available to give them more directly, but as
both osmotic and activity coefficients are of interest there is no particular advantage in doing
this.

B. BOILING POINT ELEVATION

Boiling point elevation measurements may also be used to determine solvent activities,
though they are not popular since the same information may be obtained more conveniently
by high-temperature isopiestic measurements. The freezing point method assumes that only
the pure solvent freezes out from a solution. With electrolyte solutes, this is generally true,
but a long-standing discrepancy in the activity coefficients of ammonium chloride was
resolved by the discovery that the solid phase in this case is a dilute solid solution. Similarly,
the boiling point method assumes that the solute is involatile.
Direct measurement of the vapor pressure is important chiefly as having provided some
of the standard osmotic coefficient data2 for the reference electrolytes used in isopiestic
measurements — e.g., NaCl, CaCl2, and H2SO4.

C. OSMOTIC PRESSURE
The osmotic pressure of electrolyte solutions is of great biological importance, but its
measurement is seldom used as a direct source of thermodynamic data on simple electrolytes
owing to the difficulty of making genuinely semipermeable membranes for small ions.
Because of the industrial importance of "reverse osmosis" in water purification, the basic
thermodynamic relation is shown below.
In osmotic equilibrium across a truly semipermeable membrane, the solution under a
pressure P = P° + II is in equilibrium with pure solvent at pressure P° and at the same
temperature. Hence, for the solvent component:

Now the pressure dependence of |xs is given by Equation 7:

where Vs is the partial molar volume of the solvent. Making the approximation of treating
this as independent of the pressure (i.e., depending on temperature and composition only),
we have for a given temperature and composition by integrating Equation 71

Hence, by Equation 70

from which follow various approximate forms, including the familiar equation for dilute
nonelectrolyte solutions
20 Activity Coefficients in Electrolyte Solutions, 2nd Edition

Equation 71 with 36 shows that the osmotic pressure is related to the osmotic coefficient <f>
and the molality

This is a case where a careful look at the units involved is required. If Equation 36 were
written with proper attention to units, it would read

where m° is unit molality (1 mol • kg *) and the 1000 in Equation 36 is recognized as really
meaning 1000 g.
Hence, Equation 74 should strictly be

e.g., for 0.1 m aqueous NaCl at 25°C, taking <}> = 0.932, Vs = 18.0 cm3 • mol- 1 , Ms =
18.016 g • mol"1, and v = 2, we obtain

n = 8.314 x 298.15 x 18.016 x 0.2 x 0.932/1000 x 18.0 J - cm~ 3

= 0.462 J • cm' 3
= 4.62 x 105 Pa = 4.62 bar

It should be noted that the basic osmotic pressure Equation 72 holds for any mixed
electrolyte or nonelectrolyte solution, since it involves directly only solvent properties as,
V s , and Ms. The first two of these are, of course, functions of the composition, though for
dilute solutions Vs is close to the pure solvent value. In a solution of a single solute at
concentration c, Vs is conveniently calculated from

where p is the density of the solution.

D. DERIVATION OF THERMODYNAMIC QUANTITIES FOR ELECTROLYTE

SOLUTIONS FROM ELECTROMOTIVE FORCES OF CELLS
The applications of electromotive force measurements are the subject of another chapter
in this volume. Here we give only some basic thermodynamic relations. If an electrical cell
with perfectly reversible electrodes is held at constant temperature and pressure, and its EMF
E is measured under conditions of zero current drain, the Gibbs free energy change for the
cell reaction is given by

where n is the number of electrons transferred in the equation for the cell reaction, and F
is the faraday. Equation 78 implies that E is counted as positive for the spontaneous cell
reaction, so that the spontaneous free energy change is negative. In other words, E is given
the sign of the electrode from which electrons are abstracted in the spontaneous cell reaction.
 21

For a particular cell, E depends on the chemical potentials of all the substances involved
in the cell reaction. If these are all taken to be in their standard states, the EMF is the
standard cell potential E°, and Equation 78 then gives the standard free energy charge for
the spontaneous reaction, AG°. Since the electrode constituents themselves are usually pure
substances (or are at least in states that do not alter with the solution composition), the
quantity E-E° can be expressed in terms of the activities of the components of the cell
solution. It should be noted that these may include the solvent as well as the electrolyte and
nonelectrolyte solutes, and it is essential to start the thermodynamic analysis of EMF data
by writing out the chemical equations for the electrode and cell reactions, to be sure that
no relevant component is overlooked.
From Equation 78, other thermodynamic quantities such as activity coefficients and
equilibrium constants can be derived. Also, by measuring the temperature dependence of
E, the entropy change and hence the enthalpy change can be obtained:

Some care must be taken in assessing the reliability of entropy and enthalpy data obtained
in this way.
For a cell reaction involving a one-electron transfer (n = 1), Equation 78 shows that
an error of 0.1 mV in E corresponds to approximately 10 J/mol uncertainty in AG for the
cell reaction. The same error in AE over a 10° temperature range, i.e., an error of 10~ 5
VK~' in dE/dT, corresponds to 1 J K ~ ] mol™ 1 in AS, and therefore to -300 J mor 1 in
AH. These are realistic limits for the best EMF data, and it follows that enthalpy changes
can often be obtained more reliably from direct calorimetric studies.

VII. ENTHALPY AND VOLUME PROPERTIES; APPARENT

MOLAR QUANTITIES
A. TEMPERATURE AND PRESSURE DEPENDENCE OF ACTIVITY
COEFFICIENTS
The chemical potential of component i of a solution may be written:

Applying the Gibbs-Helmholtz relation Equation 9 to Equation 80 gives, since m^ is inde-

pendent of T:

Because the standard state is so chosen that at all temperatures In y{ —> 1 as m —» 0, it

follows that

confirming an earlier remark that the partial molar enthalpy in the standard state is the same
as at infinite dilution. The term on the right of Equation 81 may therefore be written (R"
22 Activity Coefficients in Electrolyte Solutions, 2nd Edition

— HJ/RT2 for any solute component. For the solvent, the corresponding result is

where H° is the enthalpy of the pure solvent.

For an electrolyte B, applying Equation 81 to each ion, we find

where LB = HB - HB is the relative partial molar enthalpy of the electrolyte (i.e., relative
to infinite dilution).

B. PRESSURE DEPENDENCE OF ACTIVITY COEFFICIENTS

By a similar argument based on Equation 7, we find for the variation of activity coef-
ficients with pressure at constant temperature and composition

where VB is the partial molar volume of the solute, and also

C. PARTIAL MOLAR ENTHALPIES AND VOLUMES

Equations 82 to 85 involve the partial molar quantities corresponding to the extensives
Hand V.

For electrolytes, both these partials vary with composition, the variation of H being
more pronounced than that of V. It is possible in principle to approximate physically to the
operations implied by Equation 86, e.g., when i is the solvent, a small amount of it can be
added to the solution and AH or AV can be observed directly. This method is quite practical
with nonelectrolytes, using, respectively, the isothermal dilution calorimeter16 or the isoth-
ermal dilution dilatometer.17 For electrolytes, however, the Vc-dependence makes it difficult
to use such methods at low enough concentrations. Most experimental methods therefore
depend on measurement of apparent molar quantities and the analytical conversion of these
to partials.
The apparent molar value *XB of the extensive X for the solute component B of a solution
is defined by

where ns and nB are the numbers of moles of the components present, X is the value of the
extensive for the total quantity of solution (ns -f nB mol), and XI is the molar extensive
 23

for the pure solvent at the same temperature and pressure. Thus in the case of volume, *VB
= (volume of solution — volume of solvent before mixing)/moles of solute, or

This is to be compared with

where VB and Vs are the partial molar volumes.

By differentiating Equation 88 partially with respect to nB we find

and since the molality m is defined for constant ns, this becomes

Vs then follows from Equation 89.

The advantage of this method is that ^VB can be determined directly from the composition
of the solution and the densities of the solution and the pure solvent by Equation 87; the
differentiation is the carried out graphically or analytically using Equation 90.
For electrolytes, theory shows that the limiting behavior of *V in dilute solutions is
given by

where the limiting slope A is known from theory. Hence Equation 90 is transformed to

before calculating the differential.

The limiting value *V may be obtained by plotting *V against m 1/2 according to Equation
91, the extrapolation being guided by the requirement that the theoretical slope should be
approached as m1/2 —> 0,
The accuracy with which *V can be determined in this way depends essentially on the
uncertainty in the quantity (p - p°)/m. Pyknometrically determined densities have errors
of (at least) a few parts in a million, and the error in *V is therefore inversely proportional
to m. With higher valency types than 1-1 electrolytes, it is necessary to go to quite low
concentrations (<0.01 m) in order to reach the region of validity of Equation 91, and the
errors become unacceptably large. They may be reduced by using a dilatometric method17
for the dilute solutions. A stock solution is prepared of such concentration that ^V for it
may be obtained, within say 0.01 cm3 mol" 1 by density measurement. A known amount of
the stock solution, containing nB mol of solute, is then mixed isothermally with a much
larger volume of solvent in a dilatometer, in which the volume change AV on mixing can
be directly observed in a calibrated capillary. The apparent molar volume of the solute in
the solution after mixing is then given by

For example, if 0.5 cm3 of 2.0 M solution is mixed with water in a dilatomer of 1 1 volume,
24 Activity Coefficients in Electrolyte Solutions, 2nd Edition

nB « 0.001 mol, and AV may be measured within ~2 x 10™ 4 cm3, so that *V for the final
(0.001 M) solution is known within ±0.2 cm3 mol" 1 . The uncertainty in AV arises mainly
from variations in temperature before and after mixing; the figure quoted corresponds to a
change of — 0. 001 Konthe 1-1 volume, which is well within the capacity of a good thermostat.
To obtain the same accuracy in ^V by direct density measurements at 0.001 M would require
an accuracy of 1 x 10~ 7 g cm" 3 in both p and p°.
Enthalpy changes for electrolytes are measured in two main ways. First, the enthalpy
of solution of the solid electrolyte is measured in a calorimeter18 in which usually a known
quantity of the solute is contained in a thin-walled bulb that is broken under a known mass
of solvent, and the heat change is measured against an electrical heating standard. Second,
the enthalpy of dilution of various solutions is measured.19'20 This is frequently done19 in a
twin calorimeter. In one vessel, pure solvent is mixed with pure solvent; in the other, a
similar amount of a solution is mixed with the pure solvent. Stirring is necessary, and in
this method its heating effects are largely cancelled. The temperature difference between
the two vessels is followed and kept close to zero by heating one or the other liquid
electrically. Another technique uses an isothermal dilution calorimeter16 in which solution
is progressively added to the pure solvent, electrical heating (and cooling, if necessary)
being used to hold the temperature constant. Both these methods measure changes in the
apparent molar enthalpy, *H, and after extrapolation to infinite dilution one obtains values
of the relative apparent molar enthalpy *L. From these values the partial molar enthalpies
LB and Ls (Equation 83) relative to infinite dilution may be calculated by methods similar
to that discussed above for the volume.

VIII. EXCESS THERMODYNAMIC PROPERTIES

An ideal solution has the following thermodynamic functions of mixing at constant
temperature and pressure:

Molar excess functions, XE, are defined by the general equation (where X denotes any
extensive)

XE - X (actual) - X (ideal) (95)

and conveniently refer to 1 mol of the mixture. Hence, for example,

If we consider an electrolyte solution containing 1 kg of solvent (= s mol of solvent)

and Hi; mol of various ionic species i, its total free energy G is given by

For the corresponding ideal solution, where the activity coefficients fi and f s are unity:
 25

For the solvent, the standard states in Equations 97 and 98 are the same (the pure
solvent); but for the solute species \L°' is not identical with fi°. To establish the relation
between them, we note that jo^ is independent of the composition scale

Considering the special case when all m^ —> 0, and f4 and y{ —> 1, Equation 99 gives

From Equations 97, 98, and 100 we find

Applying this to the case of a single electrolyte at molality m, and using

we obtain for the excess free energy of the solution per mole of electrolyte present

Since s (in aqueous solutions at least, where s = 55.51) is typically large compared to vm,
we may expand the logarithm in the last term of Equation 102 to give

where

The approximate expression Equation 104 is treated in many papers as giving GE ex-
actly.* Certainly the error is usually small, and being a function of m only, it cancels when
comparing GE values for different electrolytes of the same valency type; also, it disappears
on taking derivatives of GE at constant composition, as, for example,

* With the alternate definition yl = 1, <f> = 1 as a reference pattern in the molaJity system, Equation 104 becomes
the exact expression for the excess quantity in that system; see Chapter 3, Equations 25 through 33.
26 Activity Coefficients in Electrolyte Solutions, 2nd Edition

From Equation 101, however, the exact expression for GE is

Here f s is the mole-fraction scale activity coefficient of the solvent: fs = as/xs where xs is
calculated counting each water molecule and ion as a separate particle.

IX. MULTICOMPONENT SYSTEMS — THERMODYNAMIC

RELATIONS; SALTING-OUT AND SALTING-IN EFFECTS

A. THERMODYNAMIC RELATIONS FOR MULTICOMPONENT SOLUTIONS

The total Gibbs free energy G of a solution containing nl9 n 2 , n3 mol of components
1,2,3, . . . , respectively, can be written in terms of the chemical potentials of the com-
ponents

One relation between the chemical potentials is the Gibbs-Duhem Equation 40. Another
may be obtained by using the cross-differentiation relation of partial differential calculus.
If W - f(x,y . . . ), then

This relation states that the order of two successive partial differentiations with respect
to different variables is immaterial. From Equation 107

Applying Equation 108 to these results

It is understood here that temperature, pressure, and all the n's except the one that appears
in the denominator of the partial are kept constant.
When using Equation 110 in solution thermodynamics, it is usual to express the com-
position in terms of the molality of each electrolyte present. In the case of a solvent S with
two solutes 1 and 2, this amounts to putting

ns = 1000 g/Ms
 27

n, - m t
n2 = m2

so that Equation 110 becomes

Equations 40 and 110 make it possible in principle to determine the changes in chemical
potentials of ail the components of a solution from measurements of the chemical potential
of any one component over the entire range of solution compositions. Thus isopiestic vapor
pressure measurements on mixtures of two electrolytes can be used to find the activity
coefficients of both electrolytes. For most electrolytes, however, solute solubility limits the
range of composition for the solution, and this restricts the possibility of calculation of other
activities from measurements of the activity of one solute (see Chapter 3, Section IV.C).
Equation 111 can be expressed in terms of the mean activity coefficients. If there is no
common ion,

where Q is a numerical factor calculable from the formula of the electrolyte. Hence

and Equation 108 becomes

For a nonelectrolyte solute, v is replaced by 1 and y is simply the molal activity coefficient
rather than the mean activity coefficient.

B. SALTING-OUT EFFECTS
Salting-out (or salting-in) is the phenomenon by which the solubility of one solute in a
solvent is altered by the presence of another solute. In a solution saturated with respect to
a solute 1, the chemical potential of 1 is constant at constant temperature and pressure,
because: ^(sat) = jui^solid) = f(T,P) only,
Hence

and from Equation 112

Thus, if the addition of solute 2 to the solution increases the activity coefficient of solute
1, the solubility of solute 1 is reduced, i.e., 1 is "salted-out" by 2. In dilute solutions of
28 Activity Coefficients in Electrolyte Solutions, 2nd Edition

electrolytes, yl decreases as the ionic strength increases, and the right-hand side of Equation
116 is therefore positive. The solubility of a sparingly soluble salt is therefore increased by
the presence of low concentrations of another salt. This argument implicitly assumes that
the added salt has no ion in common with the first salt.
When there is a common ion, Equations 1 1 1 and 40 still hold, but ^ does not take the
simple form of Equation 112. Considering the case of two electrolytes, say NaCl and KC1
at molalities ml and m2:

and the calculation of (6 m^sat)/^ m2)T,P follows.

The uses of solubility measurements in solution thermodynamics are discussed elsewhere
in this volume.

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Ion Interaction Approach: Theory and Data Correlation

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