-.-.

Lawrence Berkeley Laboratory

UNIVERSITY OF CALIFORNIA

EARTH SCIENCES DIVISION

LBL--23554

DE87 014072
To be presented at the Annual Meeting of the
Geological Society of America, Phoenix, AZ,
October 26-29, 1987, and to be published in
Reviews in Mineralogy

A THERMODYNAMIC MODEL FOR AQUEOUS

SOLUTIONS OF LIQUID-LIKE DeNSITY
K.S. Pitzer

June 1987

.,. ...i
,'t

DISCLAIMER
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- V

A THERMODYNAMIC MODEL FOR AQUEOUS SOLUTIONS OF LIQUID-LIKE DENSITY

Kenneth S. Pitzer

Lawrence Berkeley Laboratory

University of California
Berkeley, California 94720

June 1987

This work was supported by the U.S. Department of Energy under

Contract Number DE-AC03-76SF00098.

DlSTHiBljTlQN OF I HIS OilCI!MCYT

IS U@.ifd'satT

A THERYODYNWIC MODEL FOR AQUEOUS SOLUTIONS OF LIQUID-LIKE DENSITY

Kenneth

S.

Pitzer

INTRODUCTION
NOTATION
EXCESS GIBBS ENERGY; ACTIVITY AND OSMOTIC COEFFICIENTS
Basic Equation
Pure Electrolytes
Mixed Electrolytes
Neutral Solutes
Association Equilibria
TEMPERATURE AND PRESSURE EFFECTS ON STANDARD STATE PROPERTIES
DATA BASE
Standard-state Values f o r 25C
Standard-state Enthalpies, Entropies, Heat Capacities, and
Volumes
Pure-electrolyte Parameters for 25C
Pure-electrolyte Parameters for High Temperatures
Mixing Parameters
APPLICATIOXS
Solubilities of Solids
Complex Ion Equilibria
Vapor-phase Equilibria
Thermal Properties
SUPPLEMENTARY COmENTS
ACKNOWLEDGEMENTS
APPENDIX A:

THEORETICAL BACKGROUND

APPENDIX B:

KUNERICAL PARA!!ETERS
EXPRESSIONS

REFEREKCES

FOR TEMPERATURE DEPENDENCY

NOTATION

activity; also a negative ion; also parameter in eq. ( 4 6 )

Helmholtz energy

($

Debye-Hzckel parameter
second virial coefficient or binary ion interaction parameter
for interaction i-j (also B 0 .)
iJ
parameter in extended Debye-HGckel expression; also parameter

in eq. ( 4 6 )
positive ion; also parameter in eq. ( 4 6 )

(also 'C

) third virial coefficient

ij
density of water

electronic charge

ij

extended Debye-Hiickel function

F

collection of terms for the activity coefficient (eq. 3 2 , 3 3 )

defined function (eq. 19)
defined function (eq. 20)

Gex

excess Gibbs energy

enthalpy

ionic strength

ij

defined function (eq. All)

Boltzmann constant

equilibrium constant

electrostatic length (eq. A9)

positive ion

*O

molality of i

number of moles of water

Avogadro's number
pressure

vi
qij
r

defined function (eq. A12)

interparticle distance

gas constant

entropy

temperature in

absolute temperature

negative ion

charge on ion i

total charge molality (eq. 35)

2
U

O C

ij

ij

short range potential

interionic potential of mean force

Greek letters
parameter in second virial coefficient expression (also al, a2)
(also Bij

Bij
( 2 ) ) second virial coefficient for interaction i-j

activity coefficient of ion i

mean activity coefficient f o r electrolyte PX
second virial coefficient contribution from short-range forces
same but for long-range force
Debye length (eq. A3)
second virial coefficient for interaction i-j
standard chemical potential of species i
third virial coefficient for interaction i-j-k
number of ions of type i in the complete salt
total number of ions in salt MX
osmotic coefficient
total second virial coefficient for ions i-j of the same sign
third virial coefficient for mixing effects

INTRODUCTION
There are many geologically important natural systems involving
multicomponent aqueous solutions; other similar systems are important in
steam power generation, chemical processing, and other industrial operations.

Thus it is important to have an accurate and convenient model

for the prediction of the thermodynamic properties of such aqueous solutions since it would be very burdensome to make experimental measurements
for each composition at all of the temperatures and pressures of interest.
Aqueous solutions are also of theoretical interest, and existing theory
provides a general structure for the desired model as well as the precise
form of certain terms, but other terns are best evaluated empirically
from appropriate experiments.

The model and its applications are de-

scribed and discussed in the present chapter and the following one by
Weare.
This model was initially developed (Pitzer, 1973, 1975; Pitzer and
Kim, 1974) for solutions near room temperature, but it has been found to
be applicable to aqueous systems up to 300C or a little higher tempera-

ture.

A liquid-like density and relatively small compressibility are

assumed.

Thus the present model is not applicable close to the criti-

cal point of water at 374C.

The requirements for a theory applicable

to ionic solutions in the critical region were discussed by Levelt

Sengers et al.(1986).

Progress has been made toward models valid for

aqueous systems at above critical temperatures and pressures (Sverjensky,

a chapter in this volume; Pitzer and Li, 1983, 1984; Bischoff and Pitzer,
1985), but much more research is needed for these more extreme conditions.
A

typical application is the prediction of the equilibrium between

an aqueous phase (brine) and one or more solid phases (minerals).

are many published examples of solubility calculations; especially

There

2
pertinent are those of Harvie and Weare (19801, Krumgalz and Millero
(1983), and Harvie et a1.(1984)

for 25"C, and for high temperatures that

of Pabalan and Pitzer (1987b).

The following chapter by Weare emphasizes

solubility calculations.

The vapor phase may also be present and

important. A complete calculation of either type involves several steps

which can be considered separately as follows:

1. The standard state chemical potential or molar Gibbs energy of

formation of each substance involved.

For aqueous species the standard

state is a hypothetical state with ideal properties at one molal which

is actually evaluated in a limiting process at infinite dilution.

General

tables of standard state chemical potentials for solids, gases, and

solution species at the reference temperature, 25C = 298.15 K, and the
reference pressure of 1 bar are available from several sources (Robie
et ab, 1978; Wagman et ab, 1982).

Our interest is in accurate values

for particular differences, and the tables of Harvie and Weare (1980),
Harvie et a1.(1984),

and in the following chapter of this volume have

been prepared to best meet this need.

2.

The excess Gibbs energy for the solution, which yields the

activity coefficients of all solute species and the osmotic coefficient.

The model for these quantities is described below.

Additional informa-

tion concerning the theoretical basis for the model is given in Appendix
A.

This model was first tested at 25OC and the most extensive array of

parameters pertain to that temperature.

Also there have been a very

extensive array of successful applications at 25OC, some of which are

described below and others by Weare in the next chapter. Recently, this
model has been extended to 200C o r above for a number of the geologically important solutes and these results are also described below.
Appendix B gives numerical values for several solutes at elevated
temperatures.

3
3.

For h i g h t e m p e r a t u r e a p p l i c a t i o n s , t h e changes of s t a n d a r d -

s t a t e chemical p o t e n t i a l v a l u e s from 25" t o t h e t e m p e r a t u r e of i n t e r e s t .

T h i s c a l c u l a t i o n i s n o r m a l l y based on v a l u e s f o r t h e s t a n d a r d - s t a t e
e n t r o p y ( o r e n t h a l p y ) a t 25OC and f o r t h e s t a n d a r d - s t a t e h e a t c a p a c i t y
o v e r a r a n g e of t e m p e r a t u r e from 25C upward.

Sample c a l c u l a t i o n s of

t h i s t y p e a r e d i s c u s s e d and a summary of e n t r o p y v a l u e s and h e a t c a p a c i t y

e q u a t i o n s are g i v e n below.
S i n c e t h e model i s based on a g e n e r a l e q u a t i o n f o r . t h e Gibbs e n e r g y
of t h e aqueous f l u i d , any thermodynamic p r o p e r t y c a n be o b t a i n e d from
the appropriate derivative.

P h a s e e q u i l i b r i a w i t h several s o l i d

m i n e r a l s a r e e s p e c i a l l y i n t e r e s t i n g a p p l i c a t i o n s which are d i s c u s s e d by

Weare i n t h e f o l l o w i n g c h a p t e r .

Thermal p r o p e r t i e s of t h e b r i n e are

sometimes r e q u i r e d , and t h e s e are d i s c u s s e d below, a s are e q u i l i b r i a of

t h e aqueous f l u i d w i t h a v a p o r phase.
There a r e , of c o u r s e , o t h e r models which w i t h s i m i l a r a c c u r a c y

t r e a t some of t h e p r o p e r t i e s and s y s t e m s h e r e c o n s i d e r e d .

But none of

t h e o t h e r models h a s shown a comparably wide r a n g e of a p p l i c a b i l i t y and

accuracy.

Hence, w e s h a l l n o t burden t h i s p a p e r w i t h e x t e n s i v e d i s c u s -

s i o n s of o t h e r models and comparisons of r e s u l t s .

Such comparisons are

a v a i l a b l e e l s e w h e r e ; many p u b l i c a t i o n s h e r e c i t e d c o n t a i n s u c h
comparisons.
EXCESS GIBBS ENERGY; ACTIVITY AND OSMOTIC COEFFICIENTS
r

Basic Equation
I n c o n s t r u c t i n g a model f o r aqueous i o n i c s o l u t i o n s a l l v a l i d and
u s e f u l t h e o r y s h o u l d be i n c l u d e d .

The s t a t i s t i c s of i d e a l s o l u t i o n

b e h a v i o r a r e f i r s t i n c l u d e d i n t h e d e f i n i t i o n s of t h e e x c e s s Gibbs
e n e r g y and t h e a c t i v i t y and o s m o t i c c o e f f i c i e n t s .

Next i n i m p o r t a n c e

and now f u l l y confirmed i s t h e l i m i t i n g l a w of Debye and Huckel; t h i s i s

4
t h e l e a d i n g term f o r d e p a r t u r e from i d e a l i t y f o r any i o n i c s o l u t i o n .
It depends o n l y on t h e c o n c e n t r a t i o n s of t h e e l e c t r i c a l l y charged

s p e c i e s , t h e t e m p e r a t u r e , and t h e macroscopic p r o p e r t i e s of t h e s o l v e n t ,
T h i s t y p e of t e r m arises p u r e l y

t h e d e n s i t y and d i e l e c t r i c c o n s t a n t .
from long-range e l e c t r o s t a t i c f o r c e s .

There a r e h i g h e r o r d e r terms of

t h e same t y p e , depending o n l y on e l e c t r i c a l f o r c e s , b u t i n many c a s e s

t h e s e are i n d i s t i n g u i s h a b l e from terms a r i s i n g from s h o r t - r a n g e f o r c e s
between s o l u t e s p e c i e s .

These s h o r t - r a n g e f o r c e s a r e complex and n o t

p r a c t i c a l l y p r e d i c t a b l e a t p r e s e n t ; hence, t h e i r e f f e c t s are t r e a t e d
empirically.
There i s one h i g h e r - o r d e r e l e c t r o s t a t i c term t h a t y i e l d s e f f e c t s
q u i t e d i f f e r e n t from t h o s e from s h o r t - r a n g e f o r c e s .

It arises o n l y when

i o n s of d i f f e r e n t c h a r g e of t h e same s i g n are mixed, i . e . , Ca2+ and Na

o r SO4

2-

and C1-.

It c a n be c a l c u l a t e d from t h e o r y and t h e p r o p e r t i e s

of t h e s o l v e n t .
N e u t r a l s o l u t e s p e c i e s i n t e r a c t only through short-range f o r c e s .
These e f f e c t s are e a s i l y i n c l u d e d i n any g e n e r a l e q u a t i o n f o r t h e e x c e s s
Gibbs e n e r g y .

The remaining q u e s t i o n s r e l a t e t o t h e c h o i c e of v a r i a b l e s

f o r the basic equation.

The b a s i c t h e o r y i s developed i n terms of t h e

t o t a l volume and t h e c o n c e n t r a t i o n s of s o l u t e s p e c i e s as w e l l as t h e
temperature.

But f o r most p r a c t i c a l s y s t e m s p r e s s u r e i s a more appro-

p r i a t e v a r i a b l e t h a n t o t a l volume.

Also c o m p o s i t i o n v a r i a b l e s s u c h a s

m o l a l i t y or mole f r a c t i o n , which are independent of p r e s s u r e and temper-

a t u r e , are much more c o n v e n i e n t t h a n c o n c e n t r a t i o n .

For e l e c t r o l y t e s ,

m o l a l i t y i s s o w i d e l y used t h a t i t seems d e s i r a b l e t o adopt i t .

It i s

p o s s i b l e t o make r i g o r o u s t r a n s f o r m a t i o n s from volume t o p r e s s u r e and

from c o n c e n t r a t i o n t o m o l a l i t y , b u t t h e s e are v e r y cumbersome i n g e n e r a l .
Thus, i t i s c o n v e n i e n t and s a t i s f a c t o r y f o r most p u r p o s e s t o s e t up t h e
b a s i c e q u a t i o n w i t h t h e v a r i a b l e s T , P , mi and w i t h g u i d a n c e from t h e o r y .

for the details of certain terms and the general structure of the
equation. The empirical terms can be accepted as such o r can be related
to the corresponding theoretical terms in the T, V, c
desired.

equation, if

But, it must be remembered that the volume to pressure trans-

formation breaks down with the infinite compressibility at the solvent

critical point.

Hence, the present treatment has this limitation and

should not be used above 3 5 O o C , except at pressures far above critical.

Most of the applications of the present model have been at 300C or
lower temperatures, and in that range the pressure basis is fully
satisfactory.
There are alternate presentations of the basic statistical
mechanics of multicomponent Ionic fluids which suggest the basic equation adopted for the present model.

Appendix A describes the most

rigorous analysis which, however, is abstract.

In the original presen-

tation and an early summary of this model (Pitzer, 1973, 1979), a basic
but approximate treatment was presented which suggests the same form of
equation and gives an easier understanding of the general physical
picture.

The approximations of the latter treatment do not carry over

to the basic equation of the model, however.

The model

Is

postulated

for empirical use and I s to be justified by Its empirical success.

This equation (A7 in Appendix A) expresses the excess Glbbs energy as
f 01lows:

Here nW is the number of kg of water and m i' mj ,... are the molalities
of all solute species. The ionic strength is given by

I = 1/2

1 mizi

i
where z

i s t h e number of c h a r g e s on t h e iths o l u t e .

The f i r s t term on

t h e r i g h t i n e q u a t i o n (1) i n c l u d e s t h e Debye-Hiickel 1 m i t ng l a w , b u t i s an
extended form chosen f o r e m p i r i c a l e f f e c t i v e n e s s .

Note t h a t f ( 1 ) depends

o n l y on t h e i o n i c s t r e n g t h and n o t on i n d i v i d u a l i o n i c m o l a l i t i e s o r
other solute properties.
The q u a n t i t y X

ij

( I ) r e p r e s e n t s t h e s h o r t range i n t e r a c t i o n i n t h e

p r e s e n c e of t h e s o l v e n t between s o l u t e p a r t i c l e s i and j.

This binary

i n t e r a c t i o n p a r a m e t e r o r second v i r i a l c o e f f i c i e n t d o e s n o t i t s e l f have
any c o m p o s i t i o n dependence f o r n e u t r a l s p e c i e s , b u t f o r i o n s i t i s
dependent on t h e i o n i c s t r e n g t h ; i t d o e s depend, o f c o u r s e , on t h e
p a r t i c u l a r s o l u t e s p e c i e s i and j and t h e t e m p e r a t u r e and p r e s s u r e .

similar quantity f o r t r i p l e i n t e r a c t i o n is u

ijk;

The

i n p r i n c i p l e i t might

be i o n i c s t r e n g t h d e p e n d e n t , b u t w i t h a s i n g l e p o s s i b l e e x c e p t i o n
( P h u t e l a and P i t z e r , 1 9 8 6 a ) , t h e r e i s no i n d i c a t i o n of s u c h dependence.
Hence, w e s h a l l w r i t e o u r e q u a t i o n s w i t h o u t c o n s i d e r i n g any I-dependence
for

u.

Fourth o r higher o r d e r i n t e r a c t i o n s could be included, but w e

w i l l n o t do s o i n t h i s p r e s e n t a t i o n .

They are needed o n l y f o r e x t r e m e l y

c o n c e n t r a t e d s o l u t i o n s (Ananthaswany and A t k i n s o n , 1985), and

t h e n a l t e r n a t e methods may be p r e f e r a b l e ( P i t z e r and Simonson, 1986).
The s t a n d a r d d e f i n i t i o n s and thermodynamic t r a n s f o r m a t i o n s y i e l d
t h e e q u a t i o n s f o r t h e a c t i v i t y and o s m o t i c c o e f f i c i e n t s

LL

Here f ' and A ' are t h e i o n i c s t r e n g t h d e r i v a t i v e s of f and A .

= ni/nw

w i t h ni t h e number of moles of s p e c i e s i.

i n e q u a t i o n s (1, 2 , 3) a r e u n r e s t r i c t e d , i . e . ,

Also

The m u l t i p l e sums

e a c h sum c o v e r s a l l

A l s o , w e n o t e t h e d e f i n i t i o n of t h e e x c e s s Gibbs energy

solute species.

i n t h e m o l a l i t y system and a n o t h e r u s e f u l r e l a t i o n s h i p .

Here

E1 is

t h e molar Gibbs energy of water and

Ei

t h e p a r t i a l molar

Gibbs energy f o r s p e c i e s i , e a c h i n i t s s t a n d a r d s t a t e .
For s o l u t i o n s c o n t a i n i n g i o n s , t h e r e q u i r e m e n t of e l e c t r i c a l
n e u t r a l i t y makes i t i m p o s s i b l e t o e v a l u a t e c e r t a i n i n d i v i d u a l i o n i c
quantities.

T h i s becomes more e x p l i c i t as one d e r i v e s t h e working

e q u a t i o n f o r an e l e c t r o l y t e w i t h a s i n g l e s o l u t e .
Pure E l e c t r o l y t e s
I f t h e e l e c t r o l y t e MX h a s vM p o s i t i v e i o n s of c h a r g e zM i n i t s
formula and v

n e g a t i v e i o n s of c h a r g e z

zM v M = IzxIvx; a l s o w e t a k e v = v?I
m o l a l i t i e s are

= vMm and

= vxm.

X'

X;

neutrality requires
For a s a l t m o l a l i t y m , t h e i o n

The o s m o t i c c o e f f i c i e n t becomes

3
3
2VMUMMM
+ 2vxpxm)

'

*I

From t h e e x p e r i m e n t a l l y measured p r o p e r t i e s of t h e p u r e e l e c t r o l y t e ,
t o g e t h e r w i t h t h e Debye-Htickel

term ( I F l - f ) ,

one c a n e v a l u a t e o n l y t h e

b r a c k e t e d term i n A's, a f u n c t i o n o f i o n i c s t r e n g t h , and t h e f i n a l term

i n p a r e n t h e s e s i n v o l v i n g u's.

f'

Thus w e d e f i n e f',

B 0 ( I ) and C

'

as f o l l o w s

= (f'-f/I)/2

(7)

A t t h i s p o i n t w e c o u l d have i n c l u d e d t h e terms i n p

MMM

urn

and

in

t h e d e f i n i t i o n of C 4 , b u t w e s h a l l n e g l e c t them l a t e r s o omit them now.

These terms r e l a t e t o s h o r t - r a n g e i n t e r a c t i o n s of t h r e e i o n s a l l of t h e

same s i g n .

S i n c e e l e c t r i c a l r e p u l s i o n s make i t u n l i k e l y t h a t t h r e e i o n s

of t h e same sign are o f t e n c l o s e t o g e t h e r , t h e s e terms are e x p e c t e d t o

be v e r y small, and no i n d i c a t i o n h a s a r i s e n t h a t t h e y need t o b e
included.

E q u a t i o n ( 6 ) now r e d u c e s t o t h e s i m p l e form

For a 1-1 e l e c t r o l y t e a l l of t h e c o e f f i c i e n t s became u n i t y .

I n o r i g i n a l l y d e v e l o p i n g t h i s model ( P i t z e r , 1 9 7 3 ) , two c h o i c e s

were made a t this p o i n t :

t h e extended form of t h e Debye-Huckel

4
and t h e form f o r t h e i o n i c s t r e n g t h dependence of Bm.

term f Q

A l l combinations

of t h e most l i k e l y forms were t e s t e d w i t h an a r r a y of a c c u r a t e l y measured e x p e r i m e n t a l o s m o t i c c o e f f i c i e n t s f o r several 1-1, 2-1,

and 1-2

9
t y p e s a l t s a t 2 5 O C , and t h e b e s t r e s u l t s were o b t a i n e d f o r t h e forms:

The g e n e r a l p a t t e r n of i o n i c s t r e n g t h dependence w a s i n d i c a t e d t h e o r e t i c a l l y f o r e a c h f u n c t i o n , b u t a l t e r n a t e forms were e q u a l l y p l a u s i b l e ,

and t h e c h o i c e w a s made f o r e m p i r i c a l e f f e c t i v e n e s s .
u n i v e r s a l p a r a m e t e r w i t h t h e v a l u e 1.2 k
g'
2.0

k 2 - mol-'

mol-'

Here b i s a

and a h a s t h e v a l u e

f o r a l l of t h e s a l t s i n t h e t e s t s e t .

I t w i l l b e pos-

s i b l e t o u s e a d i f f e r e n t v a l u e of a f o r o t h e r s a l t s o r s a l t s of o t h e r
c h a r g e t y p e s ; t h i s w i l l b e d i s c u s s e d below.
$MX

a r e s p e c i f i c t o t h e s a l t MX.

The p a r a m e t e r s

$E)

and

It w a s e x p e c t e d t h a t t h e s e p a r a m e t e r s

r e p r e s e n t i n g s h o r t - r a n g e i n t e r a c t i o n s would b e s p e c i f i c t o t h e i n t e r acting ions.

A s s a l t s of o t h e r v a l e n c e t y p e s were s t u d i e d , i t w a s found t h a t

e q u a t i o n ( 1 2 ) w i t h a = 2.0 s e r v e d w e l l f o r 3-1 and even 4-1 s a l t s b u t

n o t f o r 2-2 s a l t s s u c h a s MgSO ( P i t z e r and Mayorga, 1973, 1974).
4

The

2-2 t y p e s a l t s show an e l e c t r o s t a t i c i o n p a i r i n g e f f e c t which h a s u s u a l l y

been r e p r e s e n t e d by c o n s i d e r i n g t h e i o n p a i r as a s e p a r a t e s o l u t e s p e c i e s .
I n t r o d u c t i o n of s u c h a s p e c i e s i n e q u i l i b r i u m w i t h o t h e r s p e c i e s complic a t e s t h e c a l c u l a t i o n s c o n s i d e r a b l y , however.

We found t h a t good a g r e e -

ment w i t h o b s e r v e d p r o p e r t i e s w a s o b t a i n e d f o r t h e 2-2 s a l t s if one

s i m p l y added a n o t h e r term t o Bo

Mx

as f o l l o w s :

The v a l u e s a

= 1.4 kg'

mol-'

and a

f o r a l l 2-2 e l e c t r o l y t e s a t 25C.

= 12 k$

The p a r a m e t e r

related t o the association equilibrium constant.

mol-'

were s a t i s f a c t o r y

$2)

i s n e g a t i v e and i s

10
In a very extensive investigation of aqueous HC1 Holmes et a1.(1987)
found that the B(2)

term was unnecessary below 250C.

375OC they obtained a good fit with a B(2)

a2 = 6.7 A
a

0'

From 250 to

term and with

ci

= 1.4 and

There is theoretical support for the proportionality of

to the Debye-Huckel parameter A

0'

Finally, we note the theoretical expression for the Debye-Huckel

parameter
A0

(1/3)(2aNodw/1000)

1/2( 2
3/2
e /ckT)

with N 0 Avogadro's number, dw the density of water, e the electronic

charge, k Boltzmann's constant, and E the dielectric constant or the
relative permittivity of water.

For SI units

with c0 the permittivity of free space.

used instead of

is multiplied by 4

7 ~ ~ ~

In many papers the symbol D is

for the dielectric constant.

Next we transform Bm6 and C&

as defined by equations (8) and (9)

to the corresponding forms for the excess Gibbs energy as follows:

These quantities are used for the equations for mixed electrolytes.
Introduction of the selected forms from equations (11) and (13) yields

Further manipulations yield the useful relationships

For the activity coefficient equation, it is useful to define the

following:

fY = -A [I'/(l+bI')

( 2 / b ) Z n ( l + b I %) I

Cm
Y

= 3Cm/2
@

The mean activity coefficient for a salt is defined as

Zr.y+
- = (wMZnyM

wxZnyx)/v

and for the present model with a single salt this becomes

Equations (10) and (27) were applied to the very extensive array of data
-1
for 25OC with excellent agreement to about 6 mol*kg for various types
of electrolytes (Pitzer and Mayorga, 1973, 1974).

The resulting para-

meters are discussed in a subsequent section.

Mixed Electrolytes
In order to treat mixed electrolytes it is desirable to rewrite
equation (1) in terms of the experimentally determinable quantities B
and C instead of the individual ion quantities

and

transformations yield for the excess Gibbs energy

IJ. Appropriate

12

cc

c<c'

mcmcl[2@cc'

rnaJlccIa

cc

a<a'

mama' W

aar

c m$Jcaal1

where the sums are over the various cations c,c' and over the anions a , a ' .
If neutral solute species n, n' are present, the terms from equation (1)
and uijk are retained; only those in X
are shown in the last
ij
ij
three sums. Difference combinations of X's and p's arise which are

in X

defined as follows:

Analogous expressions for @ aa ' and Jlcaa,

indices.

arise from permutation of the

These quantities account for interactions between ions of like

sign, which arise only for mixed solutions, and can best be determined
from simple common-ion mixtures.
In terms of various quantities defined above, the following
equations give the osmotic coefficient of the mixed electrolyte and the
activity coefficients of cation M and anion X , respectively.

13

The third virial terms for neutrals are omitted in equations (31)-(33).
The quantity F includes the Debye-Hiickel term and other terms as
follows:

-A [I35 /(1+b14)

(2/b) Zn(l+b14)]

1 1m

m B'
c
a ca
c a

Also, 9' is the ionic strength derivative of @, and

(35)

0 cc

'

= Q cc' + I@&

(36)

It should be remembered that single ion activity coefficients are

not measurable by ordinary thermodynamic methods because of space charge
limitations. Also in the transformation from equation (2) to (32) and
( 3 3 ) certain terms in A ' s and u's remain which cancel for any neutral

combination of ions; see Pitzer (1979) for more details.

Thus there is

no pretense that equations (32) and (33) yield absolute values of singleion activity coefficients; rather these are practical values for use in
all practical thermodynamic calculations. For complex mixed electrolytes,
the use of the single ion activity coefficients is much more convenient

14
t h a n t h e u s e of mean a c t i v i t y c o e f f i c i e n t s and e l e c t r i c a l l y n e u t r a l
d i f f e r e n c e s of a c t i v i t y C o e f f i c i e n t s , a l t h o u g h t h e f i n a l r e s u l t s are
identical.
Since l i k e charged i o n s r e p e l one a n o t h e r , w e e x p e c t t h e i r s h o r tr a n g e i n t e r a c t i o n s t o be s m a l l and t h a t X

We f u r t h e r n o t e t h a t Q

c c ' and 'cc'a

cc' Xcc'7

e t c . are a l l s m a l l .

are d i f f e r e n c e s between t h e s e small

q u a n t i t i e s ; hence, t h e y should c e r t a i n l y b e small.

Indeed b o t h Bronsted

(1922) and Guggenheim (1935) n e g l e c t e d t h e s e terms c o m p l e t e l y .

We do

n o t n e g l e c t t h e s e q u a n t i t i e s , b u t w e do f i n d them t o b e s m a l l i n most
cases.

T h e r e i s an e x c e p t i o n , n o t e d above, where t h e long-range elec-

t r i c a l f o r c e s y i e l d a term t h a t a p p e a r s I n 4

cc '

It a p p e a r s o n l y f o r unsymmetrical mixing, i . e . ,

and c '

( o r a and a ' ) d i f f e r .

1975, 1983).

where t h e c h a r g e s on c

T h i s term I s g i v e n by t h e o r y ( P i t z e r ,

The complete e x p r e s s i o n s f o r 4

where EO(I) and

i n t h i s formulation.

ij

are:

8 ' ( I ) a c c o u n t f o r t h e s e e l e c t r o s t a t i c unsymmetrical

mixing e f f e c t s and depend o n l y on t h e c h a r g e s of t h e i o n s i and j , t h e

t o t a l i o n i c s t r e n g t h , and on t h e s o l v e n t p r o p e r t i e s
t h e t e m p e r a t u r e and p r e s s u r e ) .

and dw ( h e n c e , on

The t h e o r y and e q u a t i o n s f o r c a l c u l a t i n g

t h e s e terns a r e g i v e n i n Appendix A , which a l s o d e s c r i b e s a method of

n u m e r i c a l c a l c u l a t i o n by Chebyshev a p p r o x i m a t i o n s d e v i s e d by

Harvie (1981).

The remaining term 8

ij

a r i s i n g from s h o r t - r a n g e f o r c e s

i s t a k e n as a c o n s t a n t f o r any p a r t i c u l a r c , c ' o r a , a ' a t a g i v e n T and

P.

Its i o n i c s t r e n g t h dependence i s v e r y small and i s u s u a l l y n e g l e c t e d

15
as

we have done here, but this effect may be significant in some cases

as shown by recent calculations of heats of mixing by Phutela and

Pitzer (1986a).
Thus starting from theoretical considerations, the ion-interaction
model gives an expression for the activity and osmotic coefficients of
electrolyte mixtures in terms of the empirical parameters,, B (0), Bm(1),
Provided that their temperature and pressure
dependencies are known, these coefficients permit the calculation of
solubilities in binary, ternary and more complex mixtures at different
temperatures and pressures.

It is important to recognize that the same equation for total excess

Gibbs energy yields other thermodynamic functions such as excess
volumes, enthalpies, entropies, and heat capacities by appropriate differentiation. These other functions are directly obtainable from experiment and their evaluation yields accurate data on the pressure o r
temperature-dependencies of the ion-interaction coefficients.

Also the

entropy o r enthalpy of the fluid is required for analysis of some

important processes,and it can be calculated from the temperature derivative of the Gibbs energy.

Since these relationships are standard

thermodynamics, we will not burden t h i s paper with the detailed equations

f o r mixtures.

The equations f o r pure electrolytes were given by Pitzer

et al. (1984).
There i s , therefore, a wide array of experimental data from which
the ion-interaction parameters and their temperature functions can be
determined. This includes measurements of
1)

freezing point depression

2)

boiling point elevation

*3 )
* 4)

vapor pressure
isopiestic concentrations

16

*
*

5)

E.M.F.

6)

e n t h a l p y of d i l u t i o n

7)

e n t h a l p y of mixing

8)

e n t h a l p y of s o l u t i o n

9)

heat capacity

10)

solubility

Those marked w i t h a n a s t e r i s k are t h o s e that so f a r have been most

u s e f u l a t t e m p e r a t u r e s g r e a t e r t h a n 100OC.

E n t h a l p i e s of d i l u t i o n

measured a t 25OC are a l s o i m p o r t a n t f o r t h e i r r e l a t i o n t o t h e temperat u r e dependency of t h e Gibbs e n e r g y .

Neutral Solutes
The s i t u a t i o n i s much s i m p l e r f o r uncharged s o l u t e s p e c i e s , and
t h e r e i s no need t o r e a r r a n g e t h e terms i n h
e q u a t i o n s ( l ) , (2), and (3).

iJ

and pijk

i n the basic

The terms for n e u t r a l s p e c i e s were

i n c l u d e d i n e q u a t i o n s (32) and (33) f o r t h e a c t i v i t y c o e f f i c i e n t s of i o n s .

The c o r r e s p o n d i n g e q u a t i o n f o r t h e a c t i v i t y c o e f f i c i e n t of a n e u t r a l
species is

:ryN

= 2(1C mcXNc

(40)

a maANa n mnAN,n)
+

T h i r d v i r i a l terms from e q u a t i o n (2) c a n be added t o e q u a t i o n ( 4 0 ) , if

needed.

Even f o r n e u t r a l m o l e c u l e s i n t e r a c t i n g w i t h i o n s , t h e f o r c e s

are s h o r t r a n g e d , and t h e r e i s no need t o modify t h e A's and v's.

E l e c t r i c a l n e u t r a l i t y l i m i t s t h e e v a l u a t i o n of X's and u's t o e l e c t r i c a l l y n e u t r a l sums and d i f f e r e n c e s , b u t i t does n o t seem w o r t h w h i l e t o
d e f i n e new q u a n t i t i e s .

S i n c e Setchenow i n 1892, t h e d e p a r t u r e of

n e u t r a l - s p e c i e s a c t i v i t y c o e f f i c i e n t s from u n i t y h a s t r a d i t i o n a l l y been
d e s c r i b e d i n terms e q u i v a l e n t t o t h e A's of t h e s e e q u a t i o n s .

An e x t e n -

s i v e review of n e u t r a l s o l u t e s i n aqueous s a l t s o l u t i o n s w a s p r e s e n t e d

17
by Long and McDevit ( 1 9 5 2 ) .
E m p i r i c a l l y t h e r e i s no e v i d e n c e f o r an i o n i c - s t r e n g t h dependence
I

f o r t h e A's f o r n e u t r a l s p e c i e s .

Thus a l l X

ij

and ( 3 ) c a n b e o m i t t e d f o r b o t h n e u t r a l - n e u t r a l
actions.

terms i n e q u a t i o n s ( 2 )
and n e u t r a l - i o n i n t e r -

T h e r e i s some t h e o r e t i c a l b a s i s f o r a small i o n i c s t r e n g t h

e f f e c t f o r i n t e r a c t i o n s of i o n s w i t h n e u t r a l s h a v i n g l a r g e d i p o l e
moments ( o r h i g h e r - o r d e r e l e c t r i c moments); t h i s i s d e s c r i b e d i n
But t h i s e f f e c t i s s o small t h a t t h e r e i s no r e a s o n t o

Appendix A.

complicate t h e equations a t present.

Also t h e q u e s t i o n may be asked w h e t h e r t h e d i e l e c t r i c c o n s t a n t
s h o u l d b e t h a t of a mixed s o l v e n t , i n c l u d i n g n e u t r a l s o l u t e s p e c i e s ,
i n s t e a d of t h e v a l u e f o r water.

I t i s p o s s i b l e t o s e t up e q u a t i o n s f o r

mixed s o l v e n t s , and t h i s i s n e c e s s a r y i f t h e s o l v e n t c o m p o s i t i o n v a r i e s
o v e r a wide r a n g e , e . g . ,

from p u r e water t o p u r e methanol.

But t h e

p r e s e n t e q u a t i o n s assume a p u r e s o l v e n t , and i t s d i e l e c t r i c c o n s t a n t
must be used.

The e f f e c t of n e u t r a l - m o l e c u l e s o l u t e s on i n t e r i o n i c

e f f e c t s v i a changes i n d i e l e c t r i c c o n s t a n t a r e i n c l u d e d a l o n g w i t h o t h e r
e f f e c t s i n t h e second and t h i r d v i r i a l c o e f f i c i e n t s i n c l u d i n g a poss i b l e i o n i c - s t r e n g t h dependence of t h e i o n - n e u t r a l
efficient.

second v i r i a l co-

Such an i o n i c - s t r e n g t h dependence h a s n o t been d e t e c t e d up

t o t h e p r e s e n t , b u t t h e p o s s i b i l i t y s h o u l d b e k e p t i n mind.
S i l i c a d i s s o l v e s i n water t o form a n e u t r a l s p e c i e s , presumably
Si(OH)4; t h i s is an i n t e r e s t i n g example t o d i s c u s s b r i e f l y .

Silica

s o l u b i l i t y , b o t h i n p u r e water and i n s a l t s o l u t i o n s , h a s been measured

by v a r i o u s i n v e s t i g a t o r s i n c l u d i n g Chen and M a r s h a l l (1981).

For t h e three-component system S i 0 2

salt

H20 w i t h s a l t m o l a l i t y

m , t h e y summarized t h e i r r e s u l t s w i t h t h e e q u a t i o n

log y = D m

E m

(41a)

18
where y is the activity coefficient of the silica.
silica and the salt MX has v

and v

If S represents

ions, respectively, our equation

( 2 ) reduces in this case to

ZnyS = Zm(vMASM

Evidently 2.303D = 2(vMXsN

+ vxXsx) + 3m2 (vMuSMM

2
+ vxusxx)
2

+ vXASX)

and 2.303E = 3(vMuSm

2

+ vxusxx).
2

Chen and Marshall fit their equation to their data both with and without
the term in E and then give equations for the parameters over the range
of temperature 25-300C.

Even for solutions extending to as high

molality as 7, the effect of the E term was rather small for the salts
NaC1, Na2S04, MgC12, and MgS04.
In an accompanying paper Marshall and Chen (1981) restated their
results (with E = 0) in terms of ion molalities.

Since all of the

Individual Ion parameters cannot be evaluated, they set the parameter

Their parameter D now becomes just (2/2.303) X

in
i
si
our equation ( 2 ) . Marshall and Chen also made solubility measurements
for Na

to zero.

for silica in mixed salt solutions and verified that the ionic effects
were additive as implied by equation

(2).

Association Equilibria
Up to this point we have assumed that the selection of solute
species was unambiguous and that electrical neutrality was the only
supplementary relationship between solute molalities.

But there may be

association equilibria such as H+ + HC03

= CO (aq)

one solute molality to other molalities.

The chemical thermodynamics

H20 which relate

of each suchequilibriumis straightforward with an equilibrium constant

relationship involving molalities and activity coefficients.
carbonic acid case this is

For the

hn +"
-y +y
assoc. = a
H2mC02YC02/ H HCO
H HC03
3

Each s u c h e q u i l i b r i u m adds one o r more r e l a t i o n s h i p s between t h e

m o l a l i t i e s and a n e q u i l i b r i u m - c o n s t a n t e q u a t i o n a l l of which must b e
s a t i s f i e d s i m u l t a n e o u s l y i n t h e complete s o l u t i o n of t h e problem.

For c a r b o n a t e s and many o t h e r cases t h e a s s o c i a t i o n c o n s t a n t s a r e

large (i.e.,

t h e d i s s o c i a t i o n c o n s t a n t s are v e r y s m a l l ) and t h e r e i s no

q u e s t i o n a b o u t t h e need t o r e c o g n i z e t h e a s s o c i a t e d s p e c i e s .
t r e a t e d u s i n g t h e p r e s e n t model i n c l u d e N a
C02

H 2 0 ( P e i p e r and P i t z e r , 1 9 8 2 ) , H+

e t a l a , 1 9 7 7 ) , and H+
1976).

K+

H PO
2 4

--H

PO

+-

--

HC03

--

HS04

SO4

2-

C03

2-

Examples

- c1- -

H20 ( P i t z e r

H20 ( P i t z e r and S i l v e s t e r ,

The l a s t example i s i n t e r e s t i n g i n t h a t i t models t h e p h o s p h o r i c

a c i d t o such high m o l a l i t y t h a t a t h i r d v i r i a l c o e f f i c i e n t f o r t r i p l e
i n t e r a c t i o n of t h e n e u t r a l s p e c i e s i s r e q u i r e d .
I n some cases t h e a s s o c i a t i o n , a l t h o u g h s i g n i f i c a n t , i s n o t s t r o n g ,
and t h e f r a c t i o n i n t h e a s s o c i a t e d form i s n e v e r l a r g e .

In the d i l u t e

r a n g e t h e d e g r e e of a s s o c i a t i o n i n c r e a s e s w i t h c o n c e n t r a t i o n .

But a t

h i g h e r c o n c e n t r a t i o n , t h e a c t i v i t y c o e f f i c i e n t s of t h e i o n s d e c r e a s e , a n d
t h e d e g r e e of a s s o c i a t i o n l e v e l s o f f and may even d e c r e a s e .

This last

e f f e c t i s p a r t i c u l a r l y s t r o n g f o r m u l t i p l y charged i o n s s u c h a s t h e
d i v a l e n t metal s u l f a t e s .

I n t h e case of t h e M

2+

SO4

2-

solutions i t

w a s found ( P i t z e r and Mayorga, 1974) t h a t t h e a s s o c i a t e d s p e c i e s c o u l d

b e o m i t t e d p r o v i d e d a n a d d i t i o n a l i o n i c - s t r e n g t h dependent t e r m w i t h a
l a r g e exponent a
e q u a t i o n (13).

w a s added t o t h e second v i r i a l c o e f f i c i e n t , see

The c o e f f i c i e n t i n t h i s term
) : 6

i s n e g a t i v e and, i n

t h e l i m i t of low m o l a l i t y , i s r e l a t e d t o t h e a s s o c i a t i o n c o n s t a n t K by
8(2) = -K/2.
meter A @ *

Also t h e exponent a

i s r e l a t e d t o t h e Debye-Huckel p a r a -

I n d e e d , t h e e q u a t i o n w i t h o u t t h e MSO 4 n e u t r a l s p e c i e s and

w i t h t h e f3(2). t e r m r e p r e s e n t e d t h e p r o p e r t i e s t o h i g h m o l a l i t y w i t h o u t

20

difficulty.

In contrast, association treatments with the simple

inclusion of the ion-pair association equilibrium constant are not successful at high molality; further terms are required

either virial

coefficients involving the MSO

triple or quadruple ions.

species or association equilibria to

4
Thus the treatment with the 6 ( 2 ) term and

without the association equilibrium has many advantages.

With increase in temperature the dielectric constant of water decreases rather rapidly and one expects ion pairing to become stronger.
Archer and Wood (1985) found this to be the case in a general treatment
of MgS04(aq).

They included not only the neutral ion pair but also the

+ , MX2 -

and a sextuplet M X with association constants at

3 3
6
2 5 O C of 126.4, 557.3, and 3.813 x 10 , respectively, and enthalpies of
triplets M2X

association of approximately 6, 6, and 27 kJ

mol-'.

They also adjusted

heat capacities of association for each reaction as well as a simple

pattern of temperature-dependent second and third virial coefficients to
account for repulsive interactions and obtained good agreement with the
available data up to 3 mol

kg-I and 150C.

Soon thereafter Phutela and

Pitzer (1986b) presented high-temperature heat capacity measurements

for MgSO (as) and a comprehensive treatment of that system without
4
association equilibria but with temperature-dependent 6 (01,
and C 9

p ,p

They found that - 8 ( 2 ) increased with temperature, as expected.

They also investigated the effect of change of the exponent a2 with

temperature proportionally to A 9'

The temperature-dependent CI 2 gave

-1
better agreement below 0.1 mol-kg , but there was no difference above
-1

0.1 mol-kg
molekg

Thus for mixed electrolytes at ionic strength above 0.4

-1 the simple treatment with constant a2 is fully satisfactory.

The general agreement for various properties for the two treatments was
comparable; the treatment without association equilibria gave agreement

21

for the osmotic coefficient at 110C to higher molality ( 5 mol-kg-l) and

better agreement at 140OC.

The association treatment gives a better fit

to the heats of dilution at high temperatures in the dilute range below

-1
0.03 mol-kg

The more recent heat capacity measurements were not

available at the time of Archer and Wood's treatment; as expected, the

Phutela and Pitzer treatment fits these data much more accurately.
In estimating the need to introduce associated species, these
results for MgS04 give the best guide for 2-2 electrolytes. For less
highly charged ions, the ion pairs must be recognized for somewhat
smaller values of the association constant because the activity coefficient for the ions decreases less rapidly with increase of molality.
The case of aqueous HC1 was investigated very thoroughly by Holmes et al.
(1987).

They found no need to include a 8(2) tern below 250OC.

For

higher temperatures up to 375"C, they obtained good agreement with an

equation including a 8 ( 2 ) term.

In the range of their data -B ( 2 ) is as

large as 32 corresponding to an association constant of 6 4 .

At room temperature most 1-1 electrolytes are either unambiguously
associated, such as acetic acid or ammonia, or are clearly strong electrolytes where the present equations are adequate without the

13(2)

term.

The situation for 2-1 or 1-2 electrolytes at 25C was studied carefully
by Harvie et a1,(1984);

they concluded that association should be

recognized for cases with association constants greater than 20 (or

dissociation constants less than 0.05).

This general topic is also

discussed by Weare in the following chapter.

TEMPERATURE AND PRESSURE EFFECTS ON STANDARD-STATE PROPERTIES
For the calculation of equilibria one requires the chemical potentials of all substances at the temperature and pressure of interest.

22

We first consider the change of the chemical potential from the reference
temperature, normally 25OC, to another temperature.

The entropy and

heat capacity determine this difference as follows:

0

or

T
Cp,idT'
0
Tr

-T

I'

.
(Ci,i/T')dT'

(44)

Tr

Here S represents the standard absolute entropy of component i, and

i
0

is the standard state heat capacity (at constant pressure) which

Psi
itself is expressed as a function of temperature. T and T represent
r
the reference temperature and temperature of interest, respectively. An

analogous but somewhat more complex expression f o r the temperature

dependence of the chemical potential can be written in terms of the
enthalpy and heat capacity.
For aqueous species the heat capacities become large as the critical temperature of water is approached; for ions the heat capacity
becomes negative but for neutral species it can be positive.

At the

critical pressure this trend becomes a divergence to plus or minus

infinity at the critical point.
For solids the heat capacities remain moderate in magnitude except
at certain solid phase transitions.

In the case of transitions, the

integration is divided into ranges and the entropy change for the transition is included explicitly.
The effect of pressure on the chemical potential is given by the
molar or partial molar volume and can be determined from density data.
At saturation pressure these effects are usually small, particularly for
the solids, but can be significant at higher pressures (Rogers and
Pitzer, 1982; Pitzer, 1986).

23
The b a s i c e q u a t i o n f o r p r e s s u r e dependency i s

P
0

1.I

i,P

%,P

O
0

where

Vi

=Ip

VidP

(45)

i s t h e p a r t i a l molar volume of s o l u t e s p e c i e s i i n i t s s t a n d a r d

s t a t e a t t h e t e m p e r a t u r e of i n t e r e s t .

The d a t a b a s e f o r volumes i s

d i s c u s s e d below.

DATA BASE

S t a n d a r d S t a t e Values f o r 25OC
There are many s o u r c e s of s t a n d a r d - s t a t e chemical p o t e n t i a l s (molar
Gibbs e n e r g i e s ) of f o r m a t i o n , e n t r o p i e s , h e a t c a p a c i t i e s , and volumes

a t 25C (298.15 K) and 1 b a r f o r s u b s t a n c e s of g e o l o g i c a l i n t e r e s t .

Wagman e t a1 (1982) g i v e v e r y e x t e n s i v e t a b l e s w h i l e Robie e t a1.(1978)
consider geological i n t e r e s t i n t h e i r selection.

For s o l u b i l i t y c a l c u -

l a t i o n s , t h e a c c u r a c y of p a r t i c u l a r d i f f e r e n c e s i s e s p e c i a l l y i m p o r t a n t
and t h e t a b l e s of Harvie and Weare ( 1 9 8 0 ) , of H a r v i e e t a 1 . ( 1 9 8 4 ) , and
of Weare i n t h e f o l l o w i n g c h a p t e r have been p r e p a r e d t o meet t h i s need.
T a b l e 1 c o n t a i n s , f o r convenience, an a b b r e v i a t e d l i s t of c h e m i c a l p o t e n -

t i a l s and e n t h a l p i e s of f o r m a t i o n , and of e n t r o p i e s and p a r a m e t e r s f o r

heat capacity equations.

The s o u r c e s of t h e e n t r o p i e s and h e a t c a p a c i t i e s

w i l l b e d i s c u s s e d below; t h e c h e m i c a l p o t e n t i a l s are from Harvie e t a l .

(1984).
S t a n d a r d - S t a t e E n t h a l p i e s , E n t r o p i e s , Heat C a p a c i t i e s , and Volumes
The c o n v e r s i o n of s t a n d a r d - s t a t e chemical p o t e n t i a l s t o o t h e r
t e m p e r a t u r e s r e q u i r e s e n t r o p y v a l u e s f o r t h e r e f e r e n c e t e m p e r a t u r e and
h e a t c a p a c i t i e s a s a f u n c t i o n of t e m p e r a t u r e .

The e n t r o p y v a l u e s a r e

g e n e r a l l y a v a i l a b l e from t h e t a b l e s of Wagman e t a1.(1982) or Robie e t a l .

24
(1978).

I n some cases t h e e n t r o p y w a s o b t a i n e d i n d i r e c t l y from t h e

e n t h a l p y and t h e Gibbs e n e r g y ( c h e m i c a l p o t e n t i a l ) , and i n s u c h cases

one s h o u l d r e v i s e t h e e n t r o p y t o b e c o n s i s t e n t w i t h any change i n t h e
Gibbs e n e r g y .

The p r o p e r t i e s of s o l i d s do n o t o r d i n a r i l y depend appre-

c i a b l y on c r y s t a l s i z e , b u t t h e r e are cases where e x t r e m e l y small

c r y s t a l s a r e o b t a i n e d w i t h s i g n i f i c a n t l y l a r g e r molar e n t r o p i e s and
chemical p o t e n t i a l s .

Kieserite (MgSO * H 0) i s a n example where t h e

d a t a of KO and Daut (1979) f o r t h e e n t h a l p y and F r o s t e t a1.(1957) f o r

t h e h e a t c a p a c i t y and e n t r o p y show s i g n i f i c a n t d i f f e r e n c e s w i t h c r y s t a l
size.
I n T a b l e 1 p a r a m e t e r s are g i v e n f o r t h e f o l l o w i n g e q u a t i o n f o r t h e
h e a t c a p a c i t y of a s o l i d :
Cp/R = a

+ bT +

The r a n g e of v a l i d i t y i s a l s o i n d i c a t e d .

w e r e t a k e n m o s t l y from K e l l e y (1960).

cT-~

(46)

These h e a t c a p a c i t y p a r a m e t e r s

The c o e f f i c i e n t s g i v e n by K e l l e y

(1960) f o r KCl(s) a r e i n c o r r e c t , and t h e v a l u e s l i s t e d a r e from Holmes

and Mesmer (1983).

The v a l u e s f o r N a SO -10 H20(s) and Na SO ( s ) were

2 4

2 4

f i t t e d by P a b a l a n and P i t z e r (1987b) t o d a t a from B r o d a l e and Giauque

(1958, 1 9 7 2 ) , w h i l e t h o s e f o r MgS04(s) were d e r i v e d from JANAF d a t a
( S t u l l and P r o p h e t , 1971).

The C

c o e f f i c i e n t s f o r MgS04*H20(s) and

MgS04*6H20(s) were d e r i v e d from l i n e a r f i t s t o t h e low t e m p e r a t u r e d a t a

of F r o s t e t a 1 . ( 1 9 5 7 ) and Cox e t a 1 . ( 1 9 5 5 ) , r e s p e c t i v e l y .

Heat c a p a c i t y d a t a f o r MgS04*4H20(s), MgS04*5H20(s), and

MgS04*7H20(s) a r e n o t a v a i l a b l e .

However, t h e c o n t r i b u t i o n of each
1

water m o l e c u l e t o t h e e n t r o p y o r h e a t c a p a c i t y of a h y d r a t e d s o l i d i s
e x p e c t e d t o be about t h e same.

P a b a l a n and P i t z e r (1987b) p r e s e n t

i s o t h e r m a l p l o t s of t h e measured e n t r o p i e s and h e a t c a p a c i t i e s of
MgCl2*nH20(s) and MgS04.nH O ( s ) v e r s u s t h e number of h y d r a t i o n waters
2

Table 1: The Chemical Potentials, Enthalpies of Formation, and Entropies at 298.15 K of the Species and
Minerals of the Na-K-Mg-C1-SO -0H-H20 System and the Temperature Functions of the Heat Capacity
4
of the Solids
Cp/R

+ bT + cT-2

Substance
Water
Hydroxide ion
Chloride ion
Sulfate ion
Magnesium ion
Calcium ion
Sodium ion
Potassium ion
Arcanit e
Bischof ite
Epsomite
Halite
Hexahydrite
Kieserite
Leonhardtite
Ma gnesi um
chloride
Magnesium
chloride
hydrate
Ma gnesium
chloride
dihydrate
Ma gnesi um
chloride
tetrahydrate
Magnesium
sulfate
Mirabilite
Pentahydrite
Sylvite
Thenardite

Formula

/RT

115.304
92.780
67.432
366.800
188.329
218.98
96.865
101.81
580.01
1008.11
(1 366.27)
165.88
(1244.79)
649.34
1007.13

8.409
-1.293
6.778
2.42
-16.64
-6.39
7.096
12.33
21.12
44.03
44.79
8.676
41.87
(14.99)
(30.64)

14.48
29.08
11.8
5.525
10.9
6.89
9.39

11.98
29.56
118
1. 963
104
31.05
74.8

-2. 144

238.74

258.71

10.78

9.511

0.7146

-1.037

MgCl2 H 2 0 (C )

347.66

389.94

16.505

10.95

9.788

298-650

NP;C12 2H2 0( c)

451.06

516.24

21.64

15.05

13.74

298

- 500

MgC12'4H20(~)

654.93

766.06

31.75

22.56

21.65

298

450

472.26
1471.15
965.13
164.84
512.39

518.33

11.02

6.71

16.30

298

700

1475.75
176.034
559.55

71.21
(35.7)
9.934
17.99

10.65
10.2
5.575
13.16

196.0
89.3
2.011
13.70

95.6635
63.452
52.955
300.386
183.468
223.30
105.651
11 3.957
532.39
853.1
1157.74
154.99
1061.37
579. 184
868.55

I
I
II

/RT

So/R

-11~

MgS04 (c)
Na2 SO4 10H20(c)
MgS04*5H20(~)
KCl(c)
Naz SOI, (c)

-A,HO

103b

1 0 - ~ ~ T(K)range

-1.666

298 - 8.56
298 - 385
-273 --473
298 -1073
-273 --473
-273 --473
-273 --473
298

- 987

-200 --450

-273 --473
-298 --7OO
270 - 700

hl

cn

26
which show a l i n e a r t r e n d .

Thus t h e unknown C

temperature functions
P
f o r MgS04*4H20(s), MgS04.5H20(s), and MgS04*7H20(s) were e s t i m a t e d on

t h i s basis.
The S"/R v a l u e s i n T a b l e 1 are m o s t l y from Wagman e t a 1 . ( 1 9 8 2 ) .
Values i n p a r e n t h e s e s were c a l c u l a t e d from u f " / R T and AHfo/RT.

For

p e n t a h y d r i t e , whose e n t r o p y i s n o t known i n d e p e n d e n t l y , i t s v a l u e w a s
e s t i m a t e d from t h e e n t r o p y v a l u e s of t h e o t h e r MgSO

hydrous s a l t s .

With t h e e x c e p t i o n of MgS04-H20(s), v a l u e s of AHfo/RT v a l u e s g i v e n i n

t h e t a b l e were c a l c u l a t e d from p O/RT and S"/R or were t a k e n from
f
Wagman e t a1.(1982) when t h e v a l u e of S"/R is i n p a r e n t h e s i s .
MgSO * H O ( s ) ,
4 2

For

t h e e n t h a l p y of f o r m a t i o n a t 25C w a s t a k e n from KO and

Daut (1979).

Numerical e q u a t i o n s f o r t h e aqueous s t a n d a r d s t a t e h e a t c a p a c i t i e s
as a f u n c t i o n of t e m p e r a t u r e are g i v e n a l o n g w i t h t h e s o l u t i o n p r o p e r t i e s f o r several s o l u t e s i n Appendix B.

Table 2 includes s e v e r a l other

s o l u t e s f o r which t h i s i n f o r m a t i o n is a v a i l a b l e (sometimes o v e r a more

l i m i t e d range) t o g e t h e r w i t h a p p r o p r i a t e r e f e r e n c e s .
The v o l u m e t r i c p r o p e r t i e s of many aqueous e l e c t r o l y t e s have been
measured t o h i g h p r e s s u r e a t 25C or o v e r t h e 0 - 5 0 C r a n g e .
information i s of oceanographic i n t e r e s t .
i n f o r m a t i o n is much more l i m i t e d .

This

Above 50C t h e v o l u m e t r i c

NaCl(aq) h a s been i n v e s t i g a t e d o v e r

a wide r a n g e of t e m p e r a t u r e and p r e s s u r e and g e n e r a l c o r r e l a t i o n s are

a v a i l a b l e (Rogers and P i t z e r , 1982).

measurements by an a d d i t i o n a l method.
e x t e n s i v e (Holmes e t a l , , 1 9 8 7 ) .

Gates (1985) h a s made f u r t h e r

I n f o r m a t i o n on aqueous H C 1 i s now

The d e n s i t i e s of a number of o t h e r

aqueous s y s t e m s have been measured a t moderate p r e s s u r e t o 200C and i n

a d d i t i o n a l cases t o 100C.

E q u a t i o n s have been f i t t e d t o t h e s e d a t a

y i e l d i n g s t a n d a r d s t a t e volumes; t h e p a r t i c u l a r s o l u t e s are l i s t e d i n
T a b l e 2 which i n c l u d e s t h e p e r t i n e n t r e f e r e n c e s .

27

T a b l e 2:

B i n a r y E l e c t r o l y t e S o l u t i o n s w i t h A v a i l a b l e High
Temperature Data
Range of T and P
T/OC

P/kbar

1:l E l e c t r o l y t e s
HC 1
LiC1
NaC1
NaI
NaOH
KC 1
CsF
CSCl
CSI

0
0
0
25
0
0
25
0
25

375
250
300
100
350
250
100
250
100

0-0.4

0-1.0
0-0.1
0-0.4

0-0.1
0-0.1
0-0.1

1:2 o r 2 : l E l e c t r o l y t e s

MgC5

25

CaC12

25

SrC12

25

Li2S04

Na2 SO4

K2S04
cs2s04

225
225
225
225

0-0.1

200

0-0.1

250

0-0.1

200

0-0.1

2:2 E l e c t r o l y t e s
25-200

a S a l u j a e t a l . (1986).
Holmes e t a l . (1987).
C

Holmes and Mesmer (1983)

P i t z e r e t a l . (1984).

P a b a l a n and P i t z e r (1987a).
Holmes and Mesmer (1986).
P h u t e l a e t a l . (1987).

0-0.1

Holmes e t a l . (1978)
P h u t e l a and P u t z e r (1986b).

j P h u t e l a and P i t z e r ( 1 9 8 6 ~ ) .
Ananthaswamy and
Atkinson (1985).

a. Mdller ( s u b m i t t e d ) .

28
S i n c e c o m p r e s s i b i l i t i e s of aqueous s o l u t i o n s d e c r e a s e w i t h i n c r e a s e
i n p r e s s u r e , t h e assumption of a c o n s t a n t molar volume i n e q u a t i o n (45) u s u a l l y
o v e r e s t i m a t e s t h e e f f e c t of p r e s s u r e on t h e c h e m i c a l p o t e n t i a l .

I n any

c a s e , t h e r e i s no d i v e r g e n c e of t h e p a r t i a l molar volume a t h i g h p r e s s u r e as t h e r e i s w i t h t e m p e r a t u r e f o r t h e h e a t c a p a c i t y as t h e c r i t i c a l
p o i n t i s approached.

Thus one c a n make r e a s o n a b l e estimates of p r e s s u r e

e f f e c t s t o h i g h e r p r e s s u r e s t h a n t h o s e l i s t e d i n T a b l e 2.
There have been s e v e r a l g e n e r a l c o r r e l a t i o n s of h i g h - t e m p e r a t u r e
v o l u m e t r i c d a t a w i t h u s e of approximate t h e o r y .

A v e r y recent s t u d y i s

by Tanger and Helgeson ( 1 9 8 7 ) , w h i l e an e a r l i e r p a p e r w a s p r e s e n t e d by

Zarembo and L'vov (1982); t h e s e p a p e r s g i v e r e f e r e n c e s t o a d d i t i o n a l
e x p e r i m e n t a l measurements.

Thus i t i s p o s s i b l e t o estimate t h e change

of chemical p o t e n t i a l w i t h p r e s s u r e even i n c a s e s where t h e r e are no

e x p e r i m e n t a l measurements f o r a p a r t i c u l a r s o l u t e .

P u r e E l e c t r o l y t e Parameters f o r 25OC
The a c t i v i t y and osmotic c o e f f i c i e n t s a t 25OC of many e l e c t r o l y t e s
a s w e l l as n e u t r a l s o l u t e s i n w a t e r were measured q u i t e a c c u r a t e l y many
y e a r s ago.

Robinson and S t o k e s w i t h t h e i r c o l l a b o r a t o r s made many of

t h e s e measurements, and t h e i r book (Robinson and S t o k e s , 1965) i n c l u d e s

e x c e l l e n t t a b l e s of s e l e c t e d v a l u e s o v e r wide r a n g e s of m o l a l i t y .

The

parameters f o r t h e p r e s e n t e q u a t i o n s were d e r i v e d by l e a s t s q u a r e s
r e g r e s s i o n f o r a v e r y wide r a n g e of e l e c t r o l y t e s by P i t z e r and Mayorga
(1973, 1974) u s i n g more r e c e n t measurements as w e l l as t h e s e l e c t e d
v a l u e s of Robinson and S t o k e s .

S u b s e q u e n t l y , P i t z e r e t a1.(1978)

o b t a i n e d v a l u e s for t h e p a r a m e t e r s f o r t h e rare e a r t h c h l o r i d e s ,
n i t r a t e s , and p e r c h l o r a t e s from t h e e x t e n s i v e measurements of Spedding
and a s s o c i a t e s .

O t h e r r e s e a r c h h a s c o n t r i b u t e d new o r improved v a l u e s

for particular solutes.

geological i n t e r e s t .

Table 3 c o n t a i n s values s e l e c t e d f o r p o s s i b l e

29

Table 3:
Cation

S i n g l e E l e c t r o l y t e S o l u t i o n Parameter Values f o r 25"Ca

Anion

(0)

Bca

H
H
H
Li
Na
Na
Na
Na
Na
Na
Na
Na
K
K
K
K
K

0.1775
0.0298
0.2065
0.1494
0.0765
0.0973
0.01958
0.0454
0.0864
0.0277
0.0399
0.043
0.04835
0.0569
0.04995
-0.0003
0.1298
0.0296
0.1488
0.0300
0.0522
0.35235
0.43268
0.2210
0.4746

K
K

cs
NH 4
Mg
Mg
Mg
Mg
Mg
Mg
MgOH
Ca
Ca
Ca
Ca
Ca
Ca

uo 2
uo 2
A1

La
Th
a

(1)
'ca
0.2945

0.5556
0.3074
0.2644
0.2791
1.113
0.398
0.253
0.0411
1.389
0.024
0.2122
0.2212
0.7793
0.1735
0.320
-0.013
1.043
0.0558
0.1918
1.6815
1.75275
3.343b
1.729

0.329

0.6072

-0.010
0.3159
0.3816
0.20
0.2145
-0.1747
0.004
0.4274
0.322
0.6993
0.5889
1.0138

1.658
1.614
1.61325
3. 1973b
2.53
-0.2303
2.977
1.644b
1.827
5.845
5.600
13.331

(2)
Bca

C@
ca

0.0008
0.9438

0.00359
0.00127
0.00116
0.00497

0.0044

0.0044
-0.0084
-0.00180

0.0041
-0.008
-0.0015
0.00038
-0.00301
0.00519
0.00312
0.0025

-0.00034
-0.00257

-0.03686
-0.0176
0.00273
-0.0238
-0.1034

From P i t z e r (1979) or Harvie e t a l . (1984) exce t Na(Si04H3) from

Hershey and Miller0 (1986); n o t e t h a t C ca = C ca
@ 127zcza(.
-1
b
a l = 1 . 4 kg*mol
(otherwise a 1 = 2.0 kg-mol-l).
C
-1
a 2 = 12 kg-mol

30

Very recently, Kodytek and Dolejs (1986) refitted the rare-earthsalt data including a f3(2)

term.

Their values of f3(2)

thus there is no indication of ion-pairing.

are positive;

But the extra flexibility

does give a better fit for the low molalities.

Their treatment emphasi-

sized the dilute range, and the older values may be preferable at high
molalities.
Pure Electrolyte Parameters for High Temperature
In an earlier section the various measurements were listed from
which the pure electrolyte parameters can be derived.

The isopiestic

method, which is so useful at 25"C, has provided valuable data up to

about 250C.

The reference solution is usually NaCl which has been

thoroughly studied by other methods including the vapor pressure relative to that of pure water.

Provided the heat of dilution as well as

the excess Gibbs energy are known at 25"C, measurements of the heat
capacity at higher temperatures provide the required information for
both the solution parameters and the standard state entropy and chemical
potential.

In practice two or more methods are usually used, and the

parameters determined from a least-squares optimization of the parameters to fit all of the accurate measurements.
There i s now an extensive array of data for the most important
aqueous solutes extending upward in temperature as indicated in Table 2.
But in many cases further work would be welcome to extend the temperature range further, to better account for the effect of pressure, and
to increase accuracy.

Appendix B gives a brief listing of the numerical

parameters in the temperature dependency expressions for both standardstate heat capacities and nonideality properties for several pure
electrolytes and includes remarks concerning the Debye-Huckel
parameter.

31
For NaCl(aq),

there is an extensive array of thermodynamic data as

reported by Pitzer, Peiper, and Busey (1984).

Their evaluation of these

data yield a complete set of parameters valid in the region 0-300C and
saturation pressure to 1 kbar.

Solubility data were not used in the

general regression; hence a comparison of calculated solubilities with

experimentally measured values is a check on a prediction. As shown in
figures 1, there is excellent agreement between calculated and experimentally determined values with a maximum deviation of 1.5% at 275OC.
This general equation is also consistent with the very recent heat
capacity measurements of Gates et al.(1987);
the uncertainty stated for the equation.

most values agree within

For KCl(aq),

Holmes and

Mesmer (1983a) combined their isopiestic vapor pressure measurements to

250C with other literature data to yield a thermodynamically consistent
set of parameters f o r KC1 solutions.
In the case of MgCl
ment.

there is no fully satisfactory general treat-

The ion-interaction parameters of de Lima and Pitzer (1983) were

based on isopiestic measurements of Holmes et a1.(1978) at high temperature and Rard and Miller (1981) at 25C.
adjusted the trend of '
C

Pabalan and Pitzer (1987b)

at the higher temperatures to better fit t h e

solubility of the various hydrates of MgC12 which rises to 14 molvkg-'

at 20OoC. This adjustment affects the agreement with the osmotic coefficients of Holmes et al, which extend only to 3.5 mol*kg-',

but the

agreement is still good with standard deviations less than 0.003.

The

standard state heat capacity is taken from Phutela et a1.(1987).

This

investigation also reported ion-interaction parameters, but their

validity is limited to about 2 rno1.kg-l; hence, they are not useful for
solubility calculations. The final comparison of calculated and
observed solubilities is shown on figure 2.

32

Halite
(NaCI)

Figure 1.

IO

I1

NaCl

Calculated h a l i t e (NaC1) s o l u b i l i t i e s i n t h e binary

NaC1-H 0 system compared to experiment. The s o l u b i l i t y
2
data from 75-300C a r e from Liu and Lindasy ( 1 9 7 2 ) , and
t h o s e below 75C a r e from Linke and S e i d e l l ( 1 9 6 5 ) .

33

Figure 2.

C a l c u l a t e d s o l u b i l i t i e s i n t h e MgC12-H20 b i n a r y
system compared t o e x p e r i m e n t a l d a t a from L i n k e and
S e i d e l l (1965). The t r i a n g l e s r e p r e s e n t e x p e r i m e n t a l
d a t a a t t h e t r i p l e p o i n t s . The Cb% f u n c t i o n above
100C was a d j u s t e d t o f i t t h e s o l u i l i t i e s .

34
For CaC12 Phutela and Pitzer (1983) gave equations valid to 200C
and 4.3 mol-kg-' based on osmotic-coefficient and heat-of-dilution data.
Above 5 mol-kg-' the usual form of equation terminating with the third
virial coefficient is inadequate, and Ananthaswamy and Atkinson (1985)
used a form extended through the sixth virial coefficient.
treatment is valid to 100C.

Their

Very recently Mdller (submitted) has

considered vapor pressure data f o r CaCl2(as) above 200C and derived

equations for the ion-interaction parameters valid to 250C.

Mdller

(submitted) also considered CaS04 and reported appropriate parameters.

Although it is not necessary to recognize the neutral CaS04 species at
25"C, Mdller found that the equilibrium forming this species should be
included at higher temperature.
For Na SO (aq) and K2S04(aq),

2 4

one has the equations of Holmes and

Mesmer (1986) which were fit to data up to 225C including heat capacities of Na2S04 to 200C from Rogers and Pitzer (1981).

Pabalan and

Pitzer (1987b) made solubility comparisons based on these equations and

found excellent agreement to 175C for Na 2SO4 but some deviation at
higher temperature.

For K SO the comparison showed some differences

2 4

in the 100-215C interval, but the agreement was reasonably good over
the entire range.
In the case of MgS04(aq)

solutions, a comprehensive regression of

heat capacity, enthalpy, and osmotic coefficient data by Phutela and

Pitzer (1986b) yielded parameters that are valid from 25-200C.

Figure

3 shows that calculated solubilities are in very good agreement with

experimental data to 200C.
Holmes et al. (1987) presented a comprehensive treatment for HCl(aq).
They gave three sets of parameters for the present model. The first,
-1
valid to 523 K and 7 mol-kg , involves only the usual terns for a 1-1
electrolyte and is summarized in Appendix B.

A second treatment adds a

35

5.0

.I

4.0

3.0

/
2 .o

I .c

C 1

\
I

50

IO0

Temperature
Figure 3 .

I50

200

O C

Calculated s o l u b i l i t i e s i n t h e system MgSO -H,O compared t o

Pvnerimental
data from Linke and S e l d e l l (t965).
---r - - -

36

-1

f o u r t h v i r i a l c o e f f i c i e n t and i s v a l i d to 1 6 m o l - k g

For t e m p e r a t u r e s

t h e y i n c l u d e a B(2) t e r m .

from 523 t o 6 4 8 K and from 0 t o 7 mol*kg-',

For NaOH(aq) t h e a v a i l a b l e v o l u m e t r i c and v a p o r p r e s s u r e d a t a t o

10 mol-kg-'

w e r e e v a l u a t e d by P a b a l a n and P i t z e r (1987a) who g i v e

e q u a t i o n s f o r t h e v i r i a l c o e f f i c i e n t s e x t e n d i n g t o 350OC.

Standard

s t a t e h e a t c a p a c i t i e s c o u l d n o t b e o b t a i n e d from t h e s e d a t a , b u t t h i s i s
not a deficiency f o r s o l u b i l i t y c a l c u l a t i o n s s i n c e t h e s o l u b i l i t y of
NaOH e x c e e d s t h e r a n g e of v a l i d i t y o f t h e s o l u t i o n model.

These p a r a -

meters a r e u s e f u l , however, f o r t h e c a l c u l a t i o n of t h e e f f e c t of NaOH

on mixed s o l u t i o n p r o p e r t i e s i n c l u d i n g t h e s o l u b i l i t y of o t h e r s a l t s .
V a r i o u s forms have been used t o d e s c r i b e t h e t e m p e r a t u r e dependency

No a t t e m p t h a s been made t o f i n d

of the ion-interaction c o e f f i c i e n t s .

a s i n g u l a r form t o d e s c r i b e t h i s dependency; t h e p a r a m e t e r s o b t a i n e d i n
t h e c i t e d s t u d i e s are l i s t e d i n Appendix B f o r t h e s o l u t e s d i s c u s s e d
above.

T h e r e are e q u a t i o n s c o v e r i n g less e x t e n s i v e t e m p e r a t u r e r a n g e s

f o r a f e w o t h e r s o l u t e s a s n o t e d I n T a b l e 2 where r e f e r e n c e s are l i s t e d .
The i n i t i a l change w i t h t e a p e r a t u r e above 25OC f o r an even w i d e r r a n g e
of s o l u t e s i s g i v e n by S i l v e s t e r and P i t z e r (1978).
.

Mixing P a r a m e t e r s
The mixing p a r a m e t e r s f3

il and

J,

ijk

f o r many s i m p l e i o n s a t 25OC

were d e r i v e d from t h e a v a i l a b l e measurements of a c t i v i t y and o s m o t i c

c o e f f i c i e n t s by P i t z e r and K i m (1974).

These p a r a m e t e r s are b e s t

e v a l u a t e d from d a t a f o r common-ion m i x t u r e s .
'Na ,K and ' N a , K , C 1

NaC1-KC1

may be determined from o s m o t i c c o e f f i c i e n t d a t a f o r

solutions.

charged i o n s .

For example, t h e v a l u e s of

The E!

ij

p a r a m e t e r s are independent of t h e o p p o s i t e l y

Thus, a l l t h e d a t a f o r N a +

s i m u l t a n e o u s l y (NaC1-KC1,
s i n g l e v a l u e of ONa,K

- K+ mixing

are c o n s i d e r e d

NaNO -KN03, e t c . ) t o d e t e r m i n e a
N a S O -K SO
2 4 2 4 '
3

and v a l u e s of $Na,K,C1,

'Na , K , SO4 ' e t c .

Solubility

37
measurements a l s o c o n t r i b u t e v a l u a b l e i n f o r m a t i o n c o n c e r n i n g t h e s e para-

meters, and t h e y w e r e n o t c o n s i d e r e d by P i t z e r and K i m .

Harvie and

Weare (1980) and Harvie e t a l . (1984) o b t a i n e d a d d i t i o n a l v a l u e s and

recommended some changes, p r i m a r i l y of t h e t h i r d v i r i a l $

..

b a s i s of s o l u b i l i t y d a t a .

ijk

S i n c e t h e e f f e c t of t h e t e r m i n $

on t h e

ijk

increases

w i t h t h e s q u a r e of t h e m o l a l i t y , t h i s q u a n t i t y i s b e s t determined from
measurements a t t h e h i g h e s t m o l a l i t i e s , i . e . , i n s a t u r a t e d s o l u t i o n s
where t h e s o l u b i l i t y of a s o l i d i s measured.
and JI
f o r 25OC f o r v a r i o u s i n t e r i o n i c
T a b l e 4 l i s t s v a l u e s of 8
ij
ijk
i n t e r a c t i o n s w h i l e T a b l e 5 l i s t s v a l u e s of X

ij

f o r ion-neutral inter-

+.

a c t i o n s on t h e b a s i s of z e r o f o r t h e i n t e r a c t i o n w i t h H

The v a l u e s

i n T a b l e s 4 and 5 are t h e same as t h o s e of H a r v i e e t a l . (1984), e x c e p t

f o r t h e p a r a m e t e r s i n v o l v i n g C1-SO4 i n t e r a c t i o n s , where s l i g h t l y d i f f e r e n t v a l u e s from Downes and P i t z e r (1976) and P a b a l a n and P i t z e r
(1987b) a r e l i s t e d .

I n t h e i r 1974 work P i t z e r and K i m o b t a i n e d r e a s o n a b l e r e s u l t s w i t h o u t t h e h i g h e r - o r d e r e l e c t r o s t a t i c terms f o r cases of unsymmetrical 2-1

mixing of i o n s of one s i g n and a common i o n of t h e o p p o s i t e s i g n .

But

t h e y concluded t h a t t h e m o r e extreme 3-1 m i x i n g showed c l e a r d e v i a t i o n ,

and t h i s w a s e x p l a i n e d by t h e h i g h e r - o r d e r terms ( P i t z e r , 1975).

Sub-

s e q u e n t l y , t h e case of CaS04 s o l u b i l i t y i n N a C 1 , w i t h 2-1 mixing of b o t h

c a t i o n s and a n i o n s , c l e a r l y r e q u i r e d t h e h i g h e r - o r d e r terms (Harvie and

Weare, 1980).
for 0
Eb

i -j

ij*

and

The r e s u l t i s t h a t two s e t s of v a l u e s a r e o f t e n g i v e n

one t o be used w i t h t h e h i g h e r - o r d e r e l e c t r o s t a t i c f u n c t i o n s
i -j

, and

t h e o t h e r t o b e used w i t h o u t t h e s e terms.

seems b e s t a l w a y s t o i n c l u d e t h e 0

and

E
0

I t now

terms f o r a l l cases of un-

symmetrical mixing, and a l l v a l u e s i n Table 4 a r e f o r t h a t b a s i s .

Once

a modern computer h a s a s u b r o u t i n e f o r t h e c a l c u l a t i o n of t h e s e terms,

38

Table 4:

Mixing Parameters for 25OC

Na
Na
Na
Na
Na

K
K
K
K
Ca
Ca
Ca
Mg
Mg

c1
c1
C1
c1
c1
so4

SO4

SOI,
so4

OH
HCO3

C'

K
Ca
Mg
MgOH
H
Ca
Mg
MgOH
H
Mg
MgOH
H
MgOH
H

a'

ecc'

k'C1

'cc'S0 4

-0.012
0.07
0.07

-0.0018
-0.007
-0.012

0.036
0.032
0.

-0.004
-0.025
-0.022

0.005
0.007

-0.011
-0.012

0.092
0.010

-0.015
0.028
-0.011

'aa'

'aa'Na

'aa'K

0.000
-0.006
-0.006
-0.015
0.0085
-0.0094
-0.009
-0.005
-0.005
-0.017
0.002

-0.005

sob 0.030
HSOI+-0.006
OH
-0.050
HCO3 0.003
co3
-0.002
HSOk
OH
-0.013
HCOj 0.001
co3
0.002
COS
0.010
C03 -0.004

-0.010
-0.055
-0.015

-0.048
-

0.0197
0.024

-0.006
0.004
-0.0677
-0.050

-0.009
-0.001
0.012

'cc'HS04

'cc 'OH 'cc

'HC03 'cc 'CO

-0.0129
-0.0265
-

-0.0178

'aa

Ca

-0.002

-0.025
-

'aa 'Mg

-0.008

-0.096

-0.425

-0.161
-

'

aa 'MgOH

'aa'H

39

Table 5:
i
H

Neutral-ion Parameter Values for 2 5 O C

xco2 ,i
0.0

Na

.loo

.051
.183
.183

Ca
Mg
MgOH

c1
so4

HS04
HC03

c03

-.005
.097
-.-003

lCaC03,i

'MgC03, i

40
the further complications are minimal.

Thus, it is easier and less

likely to lead to error if these terms are always included than if

choices are made in each case to include or exclude them.
Both 9ij and $ijk undoubtedly vary with temperature, and there are
heat of mixing data which give their temperature derivatives at 25OC
(Phutela and Pitzer, 1986a).

Until heat of mixing measurements become

generally available at higher temperature, however, we must depend

primarily on solubility data for the values of 0
temperatures.

and $ijk at high

ij
Pabalan and Pitzer (1987b) found that the mineral solu-

bilities in many systems could be fitted with constant 0 ' s at their

25OC values together with J l ' s either constant or varying with temperature in a simple manner.

Figures 4 and 5 show the results for the

systems NaC1-KC1-H20 and NaC1-MgC12-H20, respectively.

In each case

the parameter giving the temperature dependence of $

Na,K,Cl

Or

'Na,Mg,Cl

was determined to best fit the array of solubility measurements above

25C.

Mdller (submitted) obtained excellent agreement for the solu-

bility of NaCl in the NaC1-CaC12-H20 system with a temperature-inde'Na,Ca,Cl

Table 6 includes the 0 ' s and J l ' s valid at elevated

temperatures for several systems of interest.

APPLICATIONS
Solubilities of Solids
Since solubility calculations are discussed in detail by Weare in
his chapter, only brief comments are included here.

A multicomponent

example at high temperature is shown in Figure 6. Here the solubilities

of both NaCl and of KC1 at fixed MgC12 molality are indicated for the

four-component system NaC1-KC1-YgC12-H 20. Since all parameters were

evaluated in simpler systems, the curves on Figure 6 are independently

----

z
-I

1
-

Solid Phases :

8(

0 Holite ( N a C I )
0 Sylvite ( K C I )

A Holite

Sylvite

7
I

- 5
0
0

3 -

I -

,IO

II

mKCI
Figure 4.

C a l c u l a t e d s o l u b i l i t i e s i n t h e t e r n a r y m i x t u r e NaC1-KC1-H 0 compared w i t h
e x p e r i m e n t a l d a t a t a k e n from Linke and S e i d e l l (1965). T i e i n t e r s e c t i o n s of
i s o t h e r m a l c u r v e s r e p r e s e n t c a l c u l a t e d t r i p l e p o i n t s . One parameter i n t h e
f u n c t i o n was a d j u s t e d t o f i t t h e s o l u b i l i t i e s above 25C.
"Na ,K ,C 1

14

Solid Phases :
0

12

IO

A
A

Holite (NoCI)
Bischofite (MgCI2' 6 H 2 0 )

%-

MgC12'4H20
MgC12.2H20
Halite + Bisc hof tte
Halite + MgC12. 4 H 2 0

I
I
I

2
0

Figure 5.

C a l c u l a t e d and experimental s o l u b i l i t i e s i n t h e NaC1-MgC1 -H 0 system. Experimental d a t a

below 1 0 0 C are from Linke and S e i d e l l (1965), while thosg d o v e 100C a r e from Akhumov and
V a s l l ' e v (1932). The dashed curves are e x t r a p o l a t i o n s of t h e s o l u b i l i t i e s of e i t h e r
MgC12*nH 0 o r N a C l i n t o t h e s u p e r s a t u r a t e d s o l u t i o n c o n c e n t r a t i o n of t h e o t h e r s o l i d . The
i n t e r s e c i o n of t h e curves denotes t h e c a l c u l a t e d t r i p l e p o i n t . One parameter in t h e
'Na ,Mg,Cl f u n c t i o n was a d j u s t e d t o f i t t h e s o l u b i l i t i e s above 25C.

.P
N

43

Table 6:

Mixed Electrolyte Parameters f o r

High Temperatures

i
Na
Na
Na
K
c1

C1

Mg
Ca
Mg

C1

OH
OH

C1
C1
C1
Na
K
Mg
Na
Na

s04

'ijk

-0.012
0.07
0.05
0
0.030

-0.050
-0.013

-0.0068
0.0199
-0.003
0.0259
0.00
-0.005
-0.1175
0.0273
0.0302

1.68E-5T
9.51/T

14.27/T

32.63/T
9.93/T
11.69/T

..
I

'9

..
"

Solid Phases:
o Sylvite (KCI)
Halite (NaCI)
A Sylvite + Halite

E*

Figure 6.

Predicted and experimental solubilities of halite and/or sylvite in

the quaternary system NaC1-KC1-MgC12-H20 at 20, 55, and 90C and at
MgC12 molalities of approximately 1.1, 2.1, and 3.2. Experimental
data are from Kayser (1923).

45
determined p r e d i c t i o n s of t h e s o l u b i l i t i e s shovm.

While t h e agreement

i s n o t p e r f e c t , i t a p p r o a c h e s t h e a c c u r a c y of t h e s o l u b i l i t y measurements.

T h i s c a l c u l a t i o n w a s f i r s t p r e s e n t e d by P a b a l a n and P i t z e r

(1987b).
T h e r e a r e many c a l c u l a t i o n s f o r 25OC of m i n e r a l s o l u b i l i t i e s i n
complex, c o n c e n t r a t e d b r i n e s .

I n a d d i t i o n t o t h o s e of Harvie and Weare

(1980) and H a r v i e e t a l . (1982, 1 9 8 4 ) , o t h e r n o t a b l e examples i n c l u d e

Krumgalz and M i l l e r o (1982, 1 9 8 3 ) , Gueddari e t a l . ( 1 9 8 3 ) , Monnin and
S c h o t t ( 1 9 8 4 ) , and Langmuir and M e l c h i o r (1985).
Complex-Ion E q u i l i b r i a
Many heavy metals form a series of complex i o n s w i t h c h l o r i d e and
o t h e r anions.
w i t h hydroxide.

M u l t i p l y charged c a t i o n s a l s o form v a r i o u s complex i o n s

V a r i o u s o t h e r i o n s , i f p r e s e n t i n t h e s o l u t i o n , have

s p e c i f i c e f f e c t s on t h e s e complex-ion e q u i l i b r i a .

A good example of t h e

u s e of t h e p r e s e n t model i s t h e t r e a t m e n t of l e a d c h l o r i d e complexes
by M i l l e r o and Byrne (1984).

+ , N a+ ,

They c o n s i d e r t h e e f f e c t s of H

Mg2+, and Ca2+ on t h e e f f e c t i v e complexation c o n s t a n t s .

Vapor-Phase

Equilibria

Within t h e c r i t e r i o n of t h e p r e s e n t model, water of l i q u i d - l i k e

d e n s i t y as s o l v e n t , one c a n c a l c u l a t e t h e f u g a c i t i e s of v a p o r s p e c i e s
i n equilibrium.

The a c t i v i t y of water i s o b t a i n e d from t h e o s m o t i c

coefficient.

where M

species.

i s t h e m o l e c u l a r mass of water and t h e sum i s o v e r a l l s o l u t e

The a c t i v i t y of a v o l a t i l e s o l u t e s p e c i e s i s g i v e n by

46
provided t h a t s p e c i e s i s r e c o g n i z e d as a s o l u t e i n t h e l i q u i d phase.
I n some c a s e s a s o l u t e i s s o f u l l y d i s s o c i a t e d i n t h e l i q u i d t h a t one
c o n s i d e r s a d i r e c t r e l a t i o n s h i p between t h e v

c a t i o n s and v

a n i o n s of

t h e i o n i z e d s o l u t e and t h e a s s o c i a t e d v a p o r , whereupon

Zn ai

= v M Zn(%yM)

vx Zn(%yx).

(49)

Given t h e a c t i v i t i e s of t h e v o l a t i l e s p e c i e s , one c a n c a l c u l a t e t h e
vapor f u g a c i t i e s from t h e H e n r y ' s c o n s t a n t s ' a n d t h e v a p o r f u g a c i t y of

water.

Then t h e p r e s s u r e and c o m p o s i t i o n of t h e v a p o r p h a s e i s e a s i l y

c a l c u l a t e d on an i d e a l - g a s b a s i s .

For moderately imperfect g a s e s , t h e

f u g a c i t y c o e f f i c i e n t s a r e r e a d i l y o b t a i n e d i f t h e p e r t i n e n t gas-phase
second v i r i a l c o e f f i c i e n t s are known o r c a n b e e s t i m a t e d by a method
s u c h as t h a t of Tsonopoulos (1974).

More s u b s t a n t i a l d e p a r t u r e from

t h e i d e a l g a s r e q u i r e s t h e u s e of a more comprehensive e q u a t i o n of

s t a t e t o d e t e r m i n e t h e f u g a c i t i e s (see Holloway, 1977).

These methods

are s t e a d i l y improving and are o f t e n r e p o r t e d i n t h e c h e m i c a l e n g i n e e r ing journals.

An i n t e r e s t i n g a p p l i c a t i o n of t h e p r e s e n t s o l u t i o n model c o n c e r n s
t h e v a p o r i n e q u i l i b r i u m w i t h a t m o s p h e r i c a e r o s o l s where d r o p l e t s c o n t a i n
mixed e l e c t r o l y t e s .

When t h e r e l a t i v e h u m i d i t y d e c r e a s e s below 75%,

t h e s e s o l u t i o n s become v e r y c o n c e n t r a t e d w i t h i o n i c s t r e n g t h above

-1

10 mol*kg

s u c h as HNO
conditions.

.
3

Clegg and Brimblecomb ( s u b m i t t e d ) show t h a t s t r o n g a c i d s

and HC1 d e v e l o p a p p r e c i a b l e v a p o r p r e s s u r e under t h e s e
They have extended t h e s e s t u d i e s t o i n c l u d e t h e v a p o r

p r e s s u r e s of v a r i o u s a c i d s w i t h m a r i n e s e a s a l t a e r o s o l s (Brimblecomb
and C l e g g , s u b m i t t e d ) .

47-

Another set of interesting applications involving neutral as well as

ionized solutes and vapor equilibria were presented by Chen et al. (1979).
One example involves vapor-liquid equilibrium for the system

K+

C03

2-

HC03

C02

to 40 wt. % carbonate.

H 0 at temperatures to 14OOC and concentrations

2

48
Thermal P r o p e r t i e s
The e n t h a l p y , e n t r o p y , and h e a t c a p a c i t y of t h e l i q u i d are a l l g i v e n
by a p p r o p r i a t e t e m p e r a t u r e d e r i v a t i v e s of t h e Gibbs energy.
s t a n d a r d thermodynamic r e l a t i o n s h i p s .

These are

S i n c e t e m p e r a t u r e dependent

e x p r e s s i o n s a r e g i v e n i n Appendix B f o r v a r i o u s p a r a m e t e r s of t h e pres e n t model, t h e s e d e r i v a t i v e s a r e r e a d i l y t a k e n .

Indeed, i t i s the

s t a n d a r d - s t a t e h e a t c a p a c i t y t h a t i s g i v e n , and i t must b e i n t e g r a t e d
t o obtain t h e enthalpy o r entropy.

The t o t a l e n t r o p y of t h e l i q u i d as

a f u n c t i o n of t e m p e r a t u r e and p r e s s u r e i s r e q u i r e d f o r r e v e r s i b l e f l o w
p r o c e s s e s where e n t r o p y i s c o n s e r v e d .

S i m i l a r l y t h e e n t h a l p y i s re-

quired f o r i r r e v e r s i b l e , t h r o t t l e d processes.

I n o t h e r cases where

h e a t t r a n s f e r i s r e c o g n i z e d , t h e e n t h a l p y of t h e f l u i d i s a l s o needed.
The t o t a l f l u i d e n t r o p y and e n t h a l p y f o r NaC1-H20
P i t z e r e t a l . (1984) f o r t h e r a n g e t o 6 m o l - k g - l ,

a r e t a b u l a t e d by

300 C , and 1 k b a r .

For c a l c u l a t i o n s c o n c e r n i n g seawater and r e l a t e d f l u i d s , i t i s o f t e n

s u f f i c i e n t t o t a k e t h e t h e r m a l p r o p e r t i e s of a n a p p r o p r i a t e m o l a l i t y of
N a C l i n H20.

The p a r a m e t e r s of t h e p r e s e n t model, however, a l l o w t h e

e x p l i c i t i n c l u s i o n of o t h e r s u b s t a n t i a l components i f d e s i r e d .
SUPPLEMENTARY COMMENTS

With i n c r e a s i n g a c c u r a c y and p r e c i s i o n of e x p e r i m e n t a l measurements,

e m p i r i c a l f u n c t i o n s t h a t f i r s t seemed a d e q u a t e w i l l need t o b e improved

or r e p l a c e d .

Some comments c o n c e r n i n g t h e d e s i r a b l e p r o c e d u r e for

improvement may be a p p r o p r i a t e .

S i n c e t h e r e i s now a v e r y e x t e n s i v e

b a s e of p a r a m e t e r s f o r v a r i o u s i n t e r a c t i o n s , t h e i r c o n t i n u e d v a l i d i t y
s h o u l d b e r e t a i n e d as f a r as p o s s i b l e .

S i n c e t h e extended Debye-Huckel

term f ( 1 ) or i t s d e r i v a t i v e e n t e r s t h e e q u a t i o n s f o r a l l p r o p e r t i e s . i t

s h o u l d remain unchanged.

I t i s shown i n Appendix A t h a t m o d i f i c a t i o n s

49
of t h e i o n i c - s t r e n g t h dependence of t h i s t e r m w i l l o n l y make c o r r e s ponding changes i n t h e i o n i c - s t r e n g t h dependence of t h e second v i r i a l
coefficients.

Thus one c a n accomplish an improvement of t h i s t y p e by a

change i n t h e second v i r i a l c o e f f i c i e n t s i n s t e a d of f ( 1 ) .
I m p l i c i t i n f ( 1 ) i s t h e Debye-Hickel p a r a m e t e r A
d i e l e c t r i c constant or relative permittivity.

and i n t u r n t h e

A t 25OC t h e u n c e r t a i n t y

i s s o s m a l l , t h a t no problem seems l i k e l y , b u t t h e t e m p e r a t u r e dependence

of t h e d i e l e c t r i c c o n s t a n t i s n o t as a c c u r a t e l y known as would b e
desired.

Most of t h e h i g h - t e m p e r a t u r e c o r r e l a t i o n s w i t h i n t h e p r e s e n t

model have used t h e e q u a t i o n of Bradley and P i t z e r (1979) f o r t h e

d i e l e c t r i c constant.

T h i s e q u a t i o n i s v a l i d t o 350C and 1 k b a r .

Until

an a l t e r n a t e e q u a t i o n i s c l e a r l y e s t a b l i s h e d as s u p e r i o r , i t seems
d e s i r a b l e t o r e t a i n t h e Bradley and P i t z e r e q u a t i o n .
A t p r e s e n t , t h e o t h e r e q u a t i o n i n s i g n i f i c a n t u s e i s t h a t of

Uematsu and Franck (1980).

I t i s somewhat more complex b u t h a s t h e

a d v a n t a g e of v a l i d i t y t o h i g h e r t e m p e r a t u r e , 550OC.

I n t h e r a n g e below

350C i t i s n o t c l e a r which e q u a t i o n b e t t e r r e p r e s e n t s t h e t r u e p r o p e r t y
of water, s i n c e measurements d i s a g r e e by more t h a n t h e d i f f e r e n c e
between t h e e q u a t i o n s .

The v a l u e s from 0 t o 100C recommended by t h e

I n t e r n a t i o n a l Union of P u r e and Applied Chemistry ( K i e n i t z and Marsh,

1 9 8 l > , f a l l c l o s e r t o t h o s e g i v e n by t h e Bradley and P i t z e r e q u a t i o n .
Thus, for work below 350C t h e r e i s no need t o change a t t h i s t i m e .
When a change t o a d e f i n i t e l y s u p e r i o r e q u a t i o n i s made, i t w i l l b e
n e c e s s a r y t o p r e s e n t a l t e r n a t e s e t s of v a l u e s of t h o s e o t h e r p a r a m e t e r s
t h a t a r e v e r y a c c u r a t e l y known f o r u s e w i t h e a c h d i e l e c t r i c c o n s t a n t
e q u a t i o n u n t i l t h e e n t i r e a r r a y i s a v a i l a b l e on t h e new b a s i s .
F o r t u n a t e l y , a c t i v i t y and o s m o t i c c o e f f i c i e n t s and as a r e s u l t ,

50

s o l u b i l i t i e s and v a p o r p r e s s u r e s , depend o n l y on t h e d i e l e c t r i c c o n s t a n t
i t s e l f , a n d t h e u n c e r t a i n t i e s are q u i t e small.

The problem i s more

s e r i o u s where t h e t e m p e r a t u r e d e r i v a t i v e i s r e q u i r e d f o r e n t h a l p i e s and
e n t r o p i e s , and i t i s much more s e r i o u s f o r h e a t c a p a c i t i e s which
i n v o l v e t h e second temp era t u r e d e r i v a t i v e

I n c o n t r a s t t o changes i n f ( 1 ) which have a g e n e r a l e f f e c t , changes

can b e made i n t h e i o n i c - s t r e n g t h dependence of t h e second v i r i a l coe f f i c i e n t f o r a p a r t i c u l a r i o n i n t e r a c t i o n o r even f o r a s u b c a t e g o r y
of i o n s w i t h o u t any a f f e c t on t h e rest of t h e model.

Thus Holmes and

Mesmer (1986) recommend t h e u s e of a1 = 1.4 i n s t e a d of 2.0 f o r t h e

a l k a l i metal s u l f a t e s .
of a

B(2)

Kodytek and D o l e j s (1986) found t h a t i n c l u s i o n

term ( w i t h a2 = 6) f o r 3-1 e l e c t r o l y t e s gave a n a p p r e c i a b l y

better f i t .

S i n c e t h e i r 1 3 ' ~ ) v a l u e s are p o s i t i v e , t h i s i s n o t a n i n d i -

c a t i o n of i o n p a i r i n g i n t h e l a n t h a n i d e s a l t s ; r a t h e r i t r e p r e s e n t s j u s t
a more f l e x i b l e e m p i r i c a l e x p r e s s i o n f o r t h e i o n i c - s t r e n g t h dependence

i n t h i s case.

Improvements of t h i s t y p e c a n b e made w i t h o u t d i s t u r b i n g

t h e previously determined e x p r e s s i o n s f o r o t h e r parameters.

51

ACK?AOG.ZEDGEFlENTS
I thank a l l of my c o l l a b o r a t o r s i n r e s e a r c h on t h i s e l e c t r o l y t e

model and e s p e c i a l l y D r . Roberto Pabalan whose a d v i c e and a s s i s t a n c e

w a s p a r t i c u l a r l y r e l a t e d t o p a r t s of t h i s c h a p t e r .

It h a s been a

p l e a s u r e t o c o o p e r a t e w i t h D r . John Weare i n t h i s area of r e s e a r c h .

T h i s work was s u p p o r t e d by t h e D i r e c t o r , O f f i c e of Energy R e s e a r c h ,
O f f i c e of B a s i c Energy S c i e n c e s , D i v i s i o n of E n g i n e e r i n g , and Geosciences

of t h e U. S. Department of Energy under C o n t r a c t No. DE-AC03-76SF00098.

52
APPENDIX A:

THEORETICAL BACKGROUSD

There a r e a l t e r n a t e f o r m u l a t i o n s of r i g o r o u s s t a t i s t i c a l mechanics
f o r multicomponent f l u i d systems.

The XcMillan-Mayer

(1945) system is

a p p r o p r i a t e where a s o l v e n t , i n o u r case water, i s always t h e most

abundant component.

I n t h i s system t h e i n t e r a c t i o n s between s o l u t e

s p e c i e s are g i v e n by p o t e n t i a l s o f mean f o r c e i n t h e s o l v e n t and t h e

d e t a i l e d i n t e r a c t i o n of i n d i v i d u a l s o l v e n t m o l e c u l e s can l a r g e l y b e
ignored.

The excess Helmholtz energy c a n b e e x p r e s s e d i n a power

series i n c o n c e n t r a t i o n s c

The q u a n t i t i e s B

i j ijk

of s o l u t e s p e c i e s
icj**

e t c . a r i s e from t h e b i n a r y , t e r t i a r y , e t c .

s o l u t e - s o l u t e i n t e r z c t i o n s i n t h e p r e s e n c e of t h e s o l v e n t and i n t h e

l i m i t of low s o l u t e concentration; t h e y depend on t h e s o l v e n t and t h e

t e m p e r a t u r e b u t not on t h e s o l u t e c o n c e n t r a t i o n s .

They can be c a l c u -

l a t e d from t h e p o t e n t i a l s of mean f o r c e and can be c a l l e d t h e second,

third, etc. v i r i a l coefficients.

-1
When i o n s a r e p r e s e n t , w i t h long-range (R ) i n t e r p a r t i c l e poten0

t i a l s , t h e i n t e g r a l s f o r Bi j i j k
diverge.

etc. f o r interionic interactions

Mayer (1950) showed how t h e c a l c u l a t i o n c o u l d be r e a r r a n g e d

t o a v o i d t h i s d i v e r g e n c e and Friedman (1962) developed f u r t h e r t h i s

method.

Friedmans e q u a t i o n s (6.10) and (13.44), w i t h minor changes i n

symbols, g i v e f o r t h e e x c e s s Helmholtz energy

The f i r s t term on t h e r i g h t i s j u s t t h e Debye-Huckel

the reciprocal length

d e f i n e d by

limiting l a w with

53
K~

= (4ne /EkT)

1 cizi -7
i

Here

i s t h e d i e l e c t r i c c o n s t a n t o r r e l a t i v e p e r m i t t i v i t y of t h e s o l v e n t ,

e t h e e l e c t r o n i c c h a r g e , and z

t h e number of c h a r g e s on p a r t i c l e i.

The

sum i n e q u a t i o n (A3) i s c l e a r l y r e l a t e d t o t h e i o n i c s t r e n g t h .
I n e q u a t i o n (A2) t h e v i r i a l c o e f f i c i e n t s B i j ,
0

from t h e c o r r e s p o n d i n g B i j , C i j k ,

Cijk,

etc. differ

e t c . i n e q u a t i o n (Al) by t h e o m i s s i o n

of t h e terms which, when r e a r r a n g e d , became t h e Debye-Huckel

transformation gives B

i j ijk

e t c . a dependence on

term.

This

i n addition t o

t h e i r dependence on s o l v e n t p r o p e r t i e s , e t c .
I n p r o c e e d i n g t o t h e g e n e r a l e q u a t i o n of t h e model, one s h i f t s t o
t h e Gibbs energy and t o m o l a l i t i e s i n s t e a d of c o n c e n t r a t i o n s .
Debye-HGckel

term can be transformed e x a c t l y .

The

I t i s assumed t h a t o t h e r

e f f e c t s o f t h i s t r a n s f o r m a t i o n can b e absorbed i n t h e v i r i a l c o e f f i c i e n t s
which w i l l b e determined e m p i r i c a l l y .

One t h e n h a s

where nw is number of kp of water and a i s t h e Debye-Huckel p a r a m e t e r .

I f one sums o n l y o v e r i n t e r a c t i o n s of i o n s o f o p p o s i t e s i g n and i g n o r e s

t h e i o n i c s t r e n g t h dependency of 0
proposed by Bronsted ( 1 9 2 2 ) .
dependency of 6

ij

ij

t h i s is equivalent t o t h e equation

One now f i n d s t h a t t h e i o n i c s t r e n g t h

is v e r y g r e a t , b u t t h a t i t can b e reduced by r e p l a c i n g

t h e Debye-Hiickel l i m i t i n g l a w by an extended term.

T h i s was f i r s t sug-

g e s t e d on an e m p i r i c a l b a s i s by Guggenheim ( 1 9 3 5 ) .

A t e s t of s e v e r a l

extended forms f o r t h e Debye-HSckel term ( P i t z e r , 1973) l e d t o t h e

choice (a/b)Ilr(l+bI)
r e a r r an ped

w i t h b an e n p i r i c a l c o n s t a n t .

T h i s can b e

54

where q ( 1 ) i s a f u n c t i o n of i o n i c s t r e n g t h b u t n o t of i n d i v i d u a l
molalities.

Thus, i n a d d i t i o n t o t h e l i m i t i n g l a w term .I3/,

the

remaining c o n t r i b u t i o n of t h e e x t e n d e d D-H term h a s e x a c t l y t h e same

m o l a l i t y dependence a s t h e second v i r i a l c o e f f i c i e n t term of e q u a t i o n
( A 4 ) and t h e s e c a n b e combined.

D-H

The p a r t i c u l a r form f o r t h e extended

term w a s chosen t o minimize t h e i o n i c s t r e n g t h dependence of t h e

r e s u l t i n g second v i r i a l c o e f f i c i e n t term

a t high i o n i c strength.
The h i g h e r - o r d e r e l e c t r o s t a t i c term f o r u n s y m e t r i c a l mixing of
i o n s of t h e same s i g n , which w a s i d e n t i f i e d by Friedman ( 1 9 6 2 ) , a p p e a r s
a s a s p e c i a l term w i t h i n t h e i o n i c s t r e n g t h dependent second v i r i a l coefficient.
point.

Hence i t d o e s n o t need t o b e r e c o g n i z e d s e p a r a t e l y a t t h i s

I t s e v a l u a t i o n on t h e m o l a l i t y b a s i s w a s g i v e n by P i t z e r (1975,

1983) and i s d i s c u s s e d below.

Our f i n a l form of e q u a t i o n can t h e n b e

w r i t t e n as

The Debye-Huckel

term f ( 1 ) i n c l u d e s t h e l i m i t i n g l a w and depends o n l y on

the ionic strength.

The second v i r i a l c o e f f i c i e n t s A

ij

( I ) are functions

of i o n i c s t r e n g t h and i n c l u d e terns f o r mixing of i o n s of t h e same s i g n

55
but d i f f e r e n t charge as appropriate.

With i n c r e a s i n g m o l a l i t i e s of

s o l u t e s , a d d i t i o n a l terms w i l l b e r e q u i r e d i n t h i s power series t o

a t t a i n a given a c c u r a c y .

I n t h e semi-empirical a p p l i c a t i o n , t h e

r e q u i r e d number of terms w i l l become a p p a r e n t .

An a l t e r n a t e p r e s e n t a t i o n of b a s i c t h e o r y ( P i t z e r , 1973, 1979) i s
less a b s t r a c t and g i v e s more of a p h y s i c a l p i c t u r e and an estimate of
t h e p a t t e r n of i o n i c s t r e n g t h dependency of t h e second v i r i a l c o e f f i cient.

These a s p e c t s may b e u s e f u l t o r e a d e r s .

But t h i s a l t e r n a t e

p r e s e n t a t i o n i n c l u d e s a p p r o x i m a t i o n s which t h e Mayer-Friedman

treatment

a v o i d s and which are n o t i n t r i n s i c t o t h e form of e q u a t i o n (A7).

W e r e t u r n now t o t h e h i g h e r - o r d e r e l e c t r o s t a t i c term f o r unsym-

metrical mixing ( P i t z e r , 1975, 1983).

B

ij

(K)

The second v i r i a l c o e f f i c i e n t

of e q u a t i o n (A2) i s sho1.m by Friedman (1962) t o b e g i v e n by

with the electrostatic length

W
e n o t e t h a t t h e i n t e r i o n i c p o t e n t i a l of mean f o r c e can b e w r i t t e n a s

where t h e second term i s t h e e l e c t r o s t a t i c i n t e r a c t i o n and u

i j

f u n c t i o n of t h e i n t e r i o n i c d i s t a n c e r , i s t h e s h o r t - r a n g e p o t e n t i a l .
Then t h e f u n c t i o n J

ij

= -(,:

ij

of (A8) i s

2 /z.z.S)
1 1

rrn

io

[exp(qij

ij

/kT)-l-q

i j - q ij

2/2]r2dr

(All)

with
i j

= -(z

z . t / r ) exp(-lcr)
i J

(A12)

56
The i n t e g r a l i n e q u a t i o n ( A l l ) c a n n o t b e e v a l u a t e d , i n g e n e r a l ,
w i t h o u t knowledge of t h e s h o r t - r a n g e p o t e n t i a l u i j

Since t h a t quantity

i s n o t known a c c u r a t e l y , t h e e n t i r e second v i r i a l c o e f f i c i e n t i s t r e a t e d

as an e m p i r i c a l q u a n t i t y .

But f o r t h e p a r t i c u l a r case of i o n s of t h e

same s i g n , an a p p r o x i m a t i o n y i e l d s u s e f u l r e s u l t s .

Ions of t h e same s i g n r e p e l one a n o t h e r s t r o n g l y enough t h a t t h e y

seldom approach o n e a n o t h e r c l o s e l y ; hence t h e s h o r t - r a n g e p o t e n t i a l
s h o u l d have l i t t l e o r no e f f e c t .

I f q i j i s l a r g e and n e g a t i v e f o r t h e r a n g e of r f o r

equation (All).
which u

ij

This can be s e e n mathematically i n

) i s extremely
ij
is positive (or i f

d i f f e r s from z e r o , t h e n t h e v a l u e of exp(q

s m a l l throughout t h i s range.

Thus, p r o v i d e d u

ij

n e g a t i v e , i s s m a l l ) , t h e e f f e c t of u

w i l l be n e g l i g i b l e .
ij
I n view of t h i s s i t u a t i o n , one c a n e v a l u a t e t h e e f f e c t of e l e c t r o -

s t a t i c f o r c e s on t h e d i f f e r e n c e terms 0
assumption a b o u t . s h o r t - r a n g e f o r c e s .

ij

w i t h o u t making any d e t a i l e d

We w r i t e

where t h e f i r s t term on t h e r i g h t arises from t h e combined e f f e c t s of

s h o r t - r a n g e f o r c e s a c t i n g d i r e c t l y o r t h r o u g h t h e s o l v e n t , of t h e u s e of
m o l a l i t i e s i n s t e a d of c o n c e n t r a t i o n , and of t h e d i f f e r e n c e i n t h e Debye-Hirckel term i n e q u a t i o n ( A 2 ) from t h a t i n (A7) o r ( 2 8 ) .

The second

term E em w i l l b e c a l c u l a t e d from t h e c o r r e s p o n d i n g terms of t h e c l u s t e r i n t e g r a l t h e o r y w i t h t h e o m i s s i o n of s h o r t - r a n g e f o r c e s .

From t h e

w e have

d e f i n i t i o n of Om

(zi z j / 4 1 ) J i j w i t h u i.i = 0

i.i

K2

["

zizjej
,

(1 + q i j

qij

q ij

)r2 dr

57

With t h e s u b s t i t u t i o n s

y =

K r

J ( x ) = x-l

(1 + q +

e q ) y 2 dy

'0

In o u r rorking i n i t s

where f o r i o n s of t h e same s i g n x

ij

i s always p o s i t i v e .

We a l s o need t h e t e m p e r a t u r e d e r i v a t i v e of

I f J ' = a J / 2 x , w e find for E O '

Also

and t h e r e f o r e of J .

t h e expression

For J t h e i n t e g r a l s of t h e second and t h i r d terms i n t h e p a r e n t h e s e s i n

e q u a t i o n (AZO) a r e s t r a i g h t f o r w a r d w i t h the r e s u l t s

J = -1x - 1 + J 2
4
J'

I-

( J 2 / x ) + J3

J 3 = x-l

;0

exp(q-y)ydy

(A27)

58
T h e r e a r e no s i m p l e i n t e g r a l s f o r J 2 and J3 b u t t h e y are r e a d i l y e v a l u a t e d
n u m e r i c a l l y w i t h modern computers.
f o r 2-1,

3-1,

The r e s u l t i n g f u n c t i o n s '8

and

E 8'

and 4-1 mixing a r e shown i n f i g u r e A l .

For more e f f i c i e n t compution of t h e s e f u n c t i o n s t h a n numerical

i n t e g r a t i o n , several methods have been proposed ( P i t z e r , 1 9 7 5 ) , (Roy

e t a l . , 1 9 8 3 ) , ( H a r v i e , 1981).

Harvie's method u s e s two Chebyshev

polynomial a p p r o x i m a t i o n s , one for x 5 1 and t h e o t h e r for x 1 1.

The

a p p r o p r i a t e e q u a t i o n s f o r t h e s e r e g i o n s follow:
x I 1

Region I.
z * 4

-415

-d z= - 4
dx
5

bk =

bk+l

dk

Region 11.

-2

X1l5

bk+l

- bk+2

- dk+2

dk+l

I
ak

(A301
k = 0, 20
(A3 1)

x 2 1

- -229

4 0 x-l/10
9

;e-

-d z
= - -

dx

40
90

bk =

bk+l

dk = bk+l

(A321

-11/10

bk+2
dk+l

I1
+ ak

- dk+2

(A34 )
k = 0, 20
(A351

Using t h e c a l c u l a t e d v a l u e s for t h e bk and t h e dk, J ( x ) and J ' ( x ) c a n

b e c a l c u l a t e d from t h e f o l l o w i n g f o r m u l a s :
J(x) =
J'(x)

1
x
1

1
1 + ?(bo

- b2)

dz
+ -21 (do - d 2 )
dx

(A36)
(A371

59

IO0

IO
\

c
(

} 4-1
} 3-1

0.I

} 2-1
I .OI
0.001

0.01

0.I

IO

I
Figure A l .

The f u n c t i o n s
( s o l i d c u r v e s ) and I
(dashed curves) f o r n i x i n g i o n s of c h a r g e t y p e s
2-1, 3-1, and 4-1.

60
Some d i s c u s s i o n w i t h r e g a r d t o t h e c a l c u l a t i o n of t h e a r r a y s b
and d
Al.

Eq.

is appropriate.

By d e f i n i t i o n b

The c o e f f i c i e n t s a'

21 = b22

and a''
k

= d21 = d22 = 0.

are given i n Table

T h e r e f o r e , by u s i n g

(A30) o r (A34) t h e numbers b c a n b e g e n e r a t e d i n d e c r e a s i n g sequence.

S i m i l a r arguments a p p l y t o t h e a r r a y d.

The v a l u e s J ( 1 ) = 0.116437 and

J ' ( 1 ) = 0.160527 c a n b e used t o check a program f o r t h i s c a l c u l a t i o n .

Another t h e o r e t i c a l t o p i c c o n c e r n s t h e p o s s i b l e i o n i c - s t r e n g t h
dependence of second v i r i a l c o e f f i c i e n t s f o r i n t e r a c t i o n s of i o n s w i t h
n e u t r a l n o l e c u l e s c o n t a i n i n g d i p o l e o r h i g h e r e l e c t r i c a l moments.

The

work of Kirkwood (1934) p e r t a i n s t o t h i s q u e s t i o n , b u t i t c o n s i d e r s o n l y

e l e c t r i c a l e f f e c t s s u b j e c t t o a d i s t a n c e of c l o s e s t a p p r o a c h and i g n o r e s
a l l o t h e r e f f e c t s of s h o r t r a n g e f o r c e s which are normally t h e dominant
terms.

For c h a r g e - d i p o l e e f f e c t s on t h e a c t i v i t y c o e f f i c i e n t of t h e

d i p o l a r m o l e c u l e i , Kirkwood's e q u a t i o n ( 2 1 ) y i e l d s

w i t h p i t h e d i p o l e moment of i and c
c h a r g e on i o n j .

and z

t h e c o n c e n t r a t i o n and

Also a i s t h e d i s t a n c e of c l o s e s t approach of an i o n

t o t h e m o l e c u l e and

to the ionic strength.

i s t h e Debye r e c i p r o c a l l e n g t h which i s r e l a t e d
For e a c h term i n t h e sum, e q u a t i o n (A38) y i e l d s

t h e e l e c t r i c a l c o n t r i b u t i o n t o a second v i r i a l c o e f f i c i e n t X
a p p e a r a n c e of

ij

The

i n t h e denominator i n d i c a t e s a n i o n i c s t r e n g t h dependence.

B u t f o r t y p i c a l v a l u e s of t h e d i F o l e moment and o t h e r q u a n t i t i e s , t h i s

term i s v e r y small compared t o t h a t f o r s h o r t - r a n g e f o r c e s .

For quadru-

p o l e o r h i g h e r noments t h e c o r r e s p o n d i n g term i s even smaller.

Hence

t h e r e i s no p r e s e n t i n d i c a t i o n t h a t an i o n i c - s t r e n g t h dependence need be
c o n s i d e r e d f o r t h e second v i r i a l c o e f f i c i e n t s f o r n e u t r a l - i o n i n t e r a c t i o n s .

61

Table A l .

k
0

1
2
3
4

5
6
7
8
9
10

11
12
13
14
15
16
17
18
19

20

Numerical a r r a y s for c a l c u l a t i n g
J ( x ) and J'(x)

=k
1.925154014814667
-.060076477753119
-.029779077456514
-.007299499690937
.000388260636404
.000636874599598
.000036583601823
-.003045036975204
-.000004537895710
.000002937706971
.000000396566462
-.000000202099617
-.000000025267769
.000000013522610
.000000001229405
-.000000000821969
-.000000000050847
.000000000046333
.000000000001943
-.000000000002563
-.000000000010991

11

.628023320520852
.462762985338493
,150044637187895
-.028796057604906
036552745910311
-.001668087945272
.006519840398744
.001130378079086
-.000887171310131
-.000242107641309
.000087294451594
.000034682122751
-.000004583768938
-.000003548684306
-.000000250453880
.000000216991779
.000000080779570
.000000004558555
-.000000006944757

-.

-.000000002849257

.000000000237816

62
APPENDIX B : NUMERICAL P W - E T E R S FOR TEmERATURE DEPENDENCY EXPRESSIONS
The following are the temperature functions for the parameters of
the present solution model and for the standard state heat capacities
of aqueous electrolytes reported by various investigators.

The pres-

sure dependencies of the ion-interaction coefficients are currently

neglected except for NaCl(aq),

HCl(aq),

and NaOH(aq),

which have the

requisite PVT data available in sufficient quantity to allow their

evaluation.

In the case of standard state heat capacities, only

NaCl(aq) and HCl(aq) have both P- and T-dependent functions.

The

standard state heat capacities of NaOH(aq) are not included since present
information is inadequate.

This lack is not important for the solu-

bility of NaOH, however, since it is beyond the valid concentration

range of the present model.

In all the equations, TR and T refer to the

reference temperature of 298.15 K and the temperature of interest,

respectively.

Pressures are designated by P and are in bars; standard

-1
-1
state heat capacities are in units of J K mol

Ion-interaction parameters

- Pitzer et

al. (1984), 273-573 K and

saturation pressure to 1 kbar. P refers to pressure in bars.

+ 44 P2 + Q5 P3 + 46 Zr.(T) + (47 + 48 P + Q9
2 2
P3)T + (Qll + 412 P + 413 P )T + (Q14 + Q15 P + Q16 P2
p3)/(~-227) + (418 + (219 P + 420 P2 + 021 P3)/(680-T)

f(T) = Ql/T

+ QlO

+ 417

42

+ 43

P2

63
(0)

Q1

42
43

44
Q5
46
47
48
Q9
QlO
Q11
412
413
414
Q15
416
417
Ql8
Q19
420

42 1

c@

-656.81518
24.86912950
5.381275267E-5
-5.588746990E-8
6.589326333E-12
-4.4640952
0.01110991383
-2.657339906E-7
1.746006963E-10
1.046261900E-14
-5.307012889E-6
8.634023325E-10
-4.178596200E-13
-1.579365943
2.202282079E-3
-1.310550324E-7
-6.381368333E-11
9.706578079
-0,02686039622
1.534474401E-5
-3.215398267E-9

Standard state heat capacity

2c

-6.1084589
4.0217793E-1
2.2902837E-5

119.31966
-0.48309327

.o

0
0

0
0

-0.075354649
1.531767295E-4
-9.0550901E-8

1.4068095E-3
0

0
0

0
0
0

-1.538600820E-8
8.6926600E-11

-4.2345814

0.3531041360
-4.3314252E-4

0
0

0
0
0

-0.09187145529
5.1904777E-4

0
0

0
0

the following equation was fit to values

from 273-573 K and at 1 bar or saturation pressure tabulated by Pitzer

et al. (1984), Table A-4).

For values at other pressures, the reader

is referred to the tables and equations given by Pitzer et al. (1984)

which are valid in the range 273-573 K and to 1 kbar pressure.

C" = -1.848175E6 + 4.411878E7/T + 3.390654E5Zn(T)
P
- 8.893249E2T + 4.005770E-1T2 - 7.244279E4/(T-227)

4.098218E5/(647-T)

KC1 (aq)
Ion-interaction parameters
f (T) = Q1

- Holmes and Mesmer

+ Q2(1/T-1/TR) + Q3Zn(T/TR) + Q4(T-TR) +

cc
Q1
42
43
44
Q5
46

0.04808
-758.48
-4.7062
0.010072
-3.7599E-6
0

0.0476
303.9
1.066
0
0
0.0470

(1983a), 273-523 K.
2 2
Q5(T -TR ) + Q6?~(T-260)

2c

-7.88E-4
91.270
0.58643
-0.0012980
4.9567E-7
0

64
Standard state heat capacity
-991.51

Co =

Holmes and Mesmer (1983a), 273-523 K.

5.56452T

0.00852996T2

- 686/(T-270)

MgC12 (aq)
Ion-interaction parameters
equation for C'
f(T)

2
Q1 T

Mx modified
+ 02 T + 43

Q1
42
43

Standard state heat capacity

2.41831E-7
-2.49949E-4
5.95320E-2

2.60169E-5
-1.09438E-2
2.60135

- Phutela et

-7.39872E61T

de Lima and Pitzer (1983b), with

to fit the solubility data, 298-473 K.

5.93915E-7
-9.31654E-4
0.576066

Co =

5.98722E-1T2

al. (1987), 298-453 K

7.96487E4

3.25868E2T
4.21187E-4T 3

-CaCl
2 2(a )
Ion-interaction parameters
mol'kg

-1

- Mdller

(submitted), 298-523 IC, 0-4

f(T)

Q1

+ 42 T +

Q3/T

+ 44

InT

+ Q5/(T-263) + 46 T2 + Q7/(680-T)
CQ = 23/2

-3.03578731El
-1.36264728E-2
7.64582238E2
5.50458061
44
-3.27377782E-1
Q5
5.69405869E-6
46
-5.36231 106E-1
07
-1
is given by Phutela
A simpler equation valid to 473 K and 4.3 mol-kg
Q1
42
43

3.4787
-9.41895832El
-1.5417E-2
-4.0475002E-2
0
2.34550368E3
0
1.70912300El
0
-9.22885841E-1
3.1791E-5
1.51488122E-5
0
-1.39082000

and Pitzer (1983).

Standard state heat capacity
Co =

Phutela et al. (1987), 298-373 K.

-1.26721E6/T

7.41013E3

11.5222 T

65

Ion-interaction parameters
Note:

Holmes and Mesmer (1986), 273-498 K.

these parameters are consistent with using a value of a1 = 1.4,

instead of the usual value of 2.0.

3
2
2
2
2
f (T) = Q1 + Q2(T R -T R /T) + Q3(T + 2TR /T-3TR ) + Q4(T + TR /T-2TR)

+ Q5[Zn(T/TR) + TR/T-11 + Q6{1/(T-263)

+
+

(263T-TR2) /[T(TR-263)2] 1

Q7{1/(680-T)

(TR2-68OT) /[T(680-TR) 211

Q1
42
43

44
Q5
46
47

0.7534
5.61E-3
-5.7513E-4
1.11068
-378.82
0
1861.3

-1.727E-2
1.7828E-3
9.133E-6
0
-6.552
0
-96.90

Standard state heat capacity

C" = -1206.2
P

1.1745E-2
-3.3038E-4
1.85794E-5
-3.92OOE-2
14.2130
0

-24.950

Holmes and Mesmer (1986), 273-498 K.

7.6405T

Ion-interaction parameters
Note:

1.23672E-2T2

6045/(T-263)

- Holmes and Mesmer

(1986), 273-498 K.

these parameters are consistent with u s i n g a v a l u e of u 1 = 1 . 4 ,

instead of the usual value of 2.0.

66

c @ = 23/2
Q1
42
43

0.6179
6.85E-3
5.576E-5
-5.841E-2
0
-0.90
0

0
7.476E-4
0
4.265E-3
-3.088
0
0

44
Q5

46
Q7

9.1547E-3
0
0
-1.81E-4
0
0
0

Standard state heat capacity;

C0(K2SO4) = 2Co(KC1) + C0(Na2SO4)
P
P
P

Ion-interaction parameters

2Co(NaC1)
P

Phutela and Pitzer (1986), 298-473 K.

Note that the final column gives the temperature coefficients for C.
For MgS04, this is related to C 0 by:
f(T)

C'

= 4C (see equation 22).

+ 2982/2T - 298) + Q2(T2/6 + 2983/3T -

Ql(T/2

Q~(T~/,,+ 2984/4~-2983/3)+ Q ~ ( T ~ /+~ o2985/5~- 2984/4)

(298

29S2/T)Q5

2982/2)

+ 46

c = cQ / 4
Q1
42
43

44
Q5
46

-1.0282
8.479OE-3
-2.33667E-5
2.1575E-8
6.8402E-4
0.21499

Standard state heat Capacity

C o = -6.2543E6/T

-2.9596E-1
9.4564E-4
0
0
1.1028E-2
3.3646

-1.3764E-1
1.2 121E-1
-2.7642E-4
0
-2.1515E-1
-32.743

1.0541E-1
-8.9316E-4
2.51E-6
-2.3436E-9
-8.7899E-5
0.006993

Phutela and Pitzer (1386), 2W-473 K.

6.5277E4

2.6044E2T

4.6930E-1T2

3.2656E-4T

HCl(aq)
Ion-interaction parameters

Holmes et al. (1987), 273-523 K. The

-1
equation and parameters listed are valid to 7 mol-kg , but this paper
also includes more complex equations valid to 648 K and to 16 mol-kg-';
also note that the equations use

P ,

the density in k ~ . m -of

~ pure water

at the particular P and T and that they include pressure dependence to

400 bars.

67

c = c Q/ 2
Q1
42
43
44

0.17690
-9.140E-2
0

-4.034E-4
6.20E-6

Q5

Standard State heat capacity

Co
P

0.2973
16.147
-1.7631E-2

0.362E-3
0
0

-3.036E-5

7.20E-5

Holmes et al. (1987), 273-648 K.

- 16.79T/(T-240) + 6.4579E5 T S

17.93

where

xP
with

2
[ ( a 2ZTZE/~T
Ip

2
(~ZYZE/~T)~]/E

the dielectric constant (relative permittivity)

NaOH(aq)
Ion-interaction parameters

Pabalan and Pitzer (1987a), 0-350C

and saturation pressure to 400 bars.

f(T)

Q1

42 P

+ (48 +

P refers to pressure in bars.

+ (43 + 44 P)/T + Q5 Zn(T) + (46 + 47 P)T

Q9 P)T2

+ QlO/(T-227.) +

2.7682478E+2
-2.8131778E-3
-7.3755443E+3
3.7012540E-1
-4.9359970E+l
1.0945106E-1
7.1788733E-6
-4.0218506E-5
-5.88474E-9
1.1931144E-1
2.4824963
-4.8217410E-3

( Q l l + 012 P)/(647.-T)

4.6286977E+2
0
-1.0294181E+4
0

-8.5960581E+l
2.3905969E-1
0

-1.0795894E-4
0
0
0
0

-1.6686897E+l
4.0534778E-4
4.5364961E+2
-5.1714017E-2
2.9680772
-6.5161667E-3
-1.05530373E-6
2.3765786E-6
8.9893405E-10
-6.8923899E-1
-8.1156286E-2
0

Debye-Huckel Parameter
Most calculations for the present model have used the equation of
Bradley and Pitzer (1979) for the dielectric constmt and the density of
water from the equation of Haar et aL(1984).

Tables of values of A 4 and

68
of the corresponding parameters for enthalpy, heat capacity, and volume

were given by Bradley and Pitzer (1979) and are also available in other
papers including Pitzer et a1.(1984)

and Ananthaswamy and Atkinson (1984).

Mdller (submitted) gives a seven-constant equation for A

pressure to 300OC.

at saturation

REFERENCES
69
Akhumov, E. I. and V a s i l ' e v , B. B.
(1932) A s t u d y of aqueous s o l u t i o n s
a t e l e v a t e d t e m p e r a t u r e s . 11. Zh. Obs. Khimii, 2 , 282-289 ( i n
Russian).
Ananthaswamy, J . and Atkinson, G .
(1984) Thermodynamics of c o n c e n t r a t e d
e l e c t r o l y t e m i x t u r e s . 4. Pitzer-Debye-Huckel l i m i t i n g s l o p e s f o r
water from 0 t o 100C and from 1 atm t o 1 kbar. J . Chem. Engr.
Data, 29, 81-87.
Ananthaswamy, J. and Atkinson, G.
(1985) Thermodynamics of c o n c e n t r a t e d
e l e c t r o l y t e m i x t u r e s . 5 . A review of t h e thermodynamic p r o p e r t i e s
of aqueous c a l c i u m c h l o r i d e i n t h e t e m p e r a t u r e r a n g e 273.15-373.15 K .
J. Chem. Engr. Data, 30, 120-128.

Archer, D. G. and Wood, R. H.

(1985) Chemical e q u i l i b r i u m model a p p l i e d
t o aqueous magnesium s u l f a t e s o l u t i o n s . J . S o l u t i o n Chem., 1 4 ,
75 7-780.

B r a d l e y , D. J. and P i t z e r , K. S.
(1979) Thermodynamics of e l e c t r o l y t e s .
12. D i e l e c t r i c p r o p e r t i e s of water and Debye-Huckel p a r a m e t e r s t o
350C and 1 k b a r . J . Phys. Chem. 8 3 , 1599-1603.

Brimblecombe, P. and Clegg, S. L. ( s u b m i t t e d ) The s o l u b i l i t y and

b e h a v i o r of acid g a s e s i n t h e marine a e r o s o l . J. Atmos. Chem.
B r o d a l e , G. E. and Giauque, W. F.
(1958) The h e a t of h y d r a t i o n of
sodium s u l f a t e . Low t e m p e r a t u r e h e a t c a p a c i t y and e n t r o p y of
sodium s u l f a t e d e c a h y d r a t e . J. Am. Chem. SOC. 80, 2042-2044.
B r o d a l e , G. E. and Giauque, W. F.
(1972) The r e l a t i o n s h i p of c r y s t a l l i n e
forms I , 111, I V Y and V of anhydrous sodium s u l f a t e a s determined
by t h e t h i r d law of thermodynamics.
J . Phys. Chem. 76, 737-743.

Bronsted, J. N.
(1922) S t u d i e s on s o l u b i l i t y .
IV.
The p r i n c i p l e of
s p e c i f i c i n t e r a c t i o n o f ions. J . Am. Chem. SOC. --44, 877-898.
B r i t t , H. I . , Boston, J . F . , and Evans, L. B.
(1979) Extension
Chen, C . - C . ,
and a p p l i c a t i o n of t h e P i t z e r e q u a t i o n f o r v a p o r - l i q u i d e q u i l i b r i u m o f
aqueous e l e c t r o l y t e systems w i t h m o l e c u l a r s o l u t e s . AIChE J . 25, 820-831.
(1981) Amorphous s i l i c a s o l u b i l i t i e s
Chen, C.-T.
A. and N a r s h a l l , W. L.
Behavior i n p u r e water and aqueous sodium c h l o r i d e , sodium
IV.
s u l f a t e , magnesium c h l o r i d e , and magnesium s u l f a t e s o l u t i o n s up t o
350OC. Geochim. Cosmochim. Acta, 46, 279-287.
Clegg, S. L. and Brimblecombe, P. ( s u b m i t t e d ) E q u i l i b r i u m p a r t i a l p r e s s u r e s of s t r o n g a c i d s o v e r c o n c e n t r a t e d s a l i n e s o l u t i o n s . P a r t I.
HN03; P a r t 11. HC1.
Atmos. Environment.
Cox, W. P . , Hornung, E. W . , and Giauque, W. F.
(1955) The spontaneous
t r a n s f o r m a t i o n from m a c r o c r y s t a l l i n e t o m i c r o c r y s t a l l i n e p h a s e s a t
low t e m p e r a t u r e s . The h e a t c a p a c i t y of MpS04'6H20. J . Am. Chem.
SOC. 7 7 , 3935-3938.

d e L i m a , M. C . P . and P i t z e r , K. S. (1983) Thermodynamics of s a t u r a t e d

e l e c t r o l y t e m i x t u r e s of N a C l w i t h Na2S04 and FlgC12. J . S o l u t i o n
Chem. 1 2 , 187-199.

70
Domes, C. J. and Pitzer, K. S. (1976) Thermodynamics of electrolytes.
Binary mixtures formed from aqueous NaC1, Na SO CuC12, and CuS04
2 4'
at 25OC. J. Solution Chem. 5, 389-398.
Friedman, H. L. (1962) Ionic Solution Theory. Wiley-Interscience,
New York, 265 pp.
Frost, G. B., Breck, W. G., Clayton, R. N., Reddoch, A. H., and Miller
C. G. (1957) The heat capacities of the crystalline and vacuum
dehydrated form of magnesium sulphate monohydrate. Can. J. Chem.
35, 1446-1453.
Gates, J. A. (1985) Thermodynamics of Aqueous Electrolyte Solutions at
High Temperatures and Pressures, Ph.D. Dissertation, University of
Delaware, 340 pp.
Gates, J. A., Tillett, D. M., White, D. E., and Wood, R. H. (1987)
Apparent molar heat capacities of aqueous NaCl solutions from 0.05
to 3.0 mol-kg'l,
350 to 600 K, and 2-18 MPa. J. Chem. Thermodyn.
19, 131-146.
Gueddari, M., Monnin C., Perret, D., Fritz, B., and Tardy, Y. (1983)
Geochemistry of the brines of Chott El Jerid in Southern Tunisia:
application of Pitzer's equations. Chem. Geol. 39, 165-178.
Guggenheim, E. A. (1935) The specific thermodynamic properties of
aqueous solutions of strong electrolytes. Phil. Mag. 19, 588-643.
Haar, L., Gallagher, J. S., and Kell, G. S . (1984) NBS/NRC Steam Tables:
Thermodynamic and Transport Properties and Computer Programs for
Vapor and Liquid States of Water in SI Units. Hemisphere
Publishing, 318 pp.
Harvie, C. E. (1981) Theoretical investigations in geochemistry and
atom surface scattering. Ph.D. dissertation University of
California at San Diego. Univ. Microfilm Int., Ann Arbor, MI
# AAD82-03026.
Harvie, C. E. and Weare, J. H. (1980) The prediction of mineral solubilities In natural waters: the Na-K-Mg-Ca-C1-SO -H 0 system from
zero t o high concentration at 25OC. Geochim. Cosiocgim. Acta,
44,
- 981-997.
Harvie, C. E., Eugster, H. P., and Weare, J. H. (1982) Mineral equilibria in the six-component seawater system, Na-K-Mg-Ca-SO4-C1H20 at 25OC. 11. Compositions of the saturated solutions.
Geochim. Cosmochim. Acta, 46, 1603-1618.
Harvie, C. E., YQller, N., and Weare, J. H. (1984) The prediction of
mineral solubilities in natural waters: The Na-K-Mg-Ca-H-C1-S04OH-HC03-C03-C02-H20 system to high ionic strengths at 25OC.
Geochim. Cosmochim. Acta, 48, 723-751.
Hershey, J. P. and Millero, F. J. (1986) The dependence of the acidity
constants of silicic acid on NaCl concentration using Pitzer's
equations. Marine Chem. 18, 101-105.

71
!!olloway, J. R. (1977) Fugacity and activity of molecular species in
supercritical fluids. In: Thermodynamics in Geology, D. G.
Fraser, ed., D. Reidel, Dordrecht, Holland, 161-181 pp.
Holmes, H. F., Baes, C. F., and Mesmer, R. E. (1978) Isopiestic studies
of aqueous solutions at elevated temperatures: 1. KC1, CaC12 and
MgC12. J. Chem. Thermodyn. 10, 983-996.
Holmes, H. F., Busey, R. H., Simonson, J. M., Mesmer, R. E., Archer,
D. G., and Wood, R. H. (1987) Thermodynamic properties of HCl(aq)
to 648 K. J. Chem. Thermodyn. 19, xxxx.
Holmes, H. F. and Mesmer, R. E. (1983) Thermodynamic properties of
aqueous solutions of the alkali metal chlorides to 250OC. J. Phys.
Chem. 87, 1242-1255.
Holmes, H. F. and Mesmer, R. E. (1986) Thermodynamics of aqueous solutions of the alkali metal sulfates. J. Solution Chem. 15, 495-518.
Kayser, E. (1923) Die ersatzzahlen inkonstanter Liisungen iiber
Kaliumchlorid und Natriumchlorid. Kali 17, 1-9 (in German).
Kelley, K. K.
(1960) Contributions to the data on theoretical metallurgy.
XIII. High-temperature heat-content, heat-capacity, and entropy
data for the elements and inorganic compounds. U. S. Bur. Mines
Bull. 584, 232 pp.
Kienitz, H. and Marsh, K. N. (1981) Recommended reference materials for
realization of physiochemical properties: Permittivity. Pure and
Appl. Chem. 53, 1847-1862.
Kirkwood, J. G. (1934) Theory of solutions of molecules containing
widely separated charges with special application to zwitterions.
J. Chem. Phys. 2, 351-361.

KO, H. C. and Daut G. E.

(1979( Enthalpies of Fornation of a- and

6-Magnesium S u l f a t e and Magnesium S u l f a t e flonohydrate.

U. S .

Bureau of Mines Report of Investigations 8409, 8 pp.

Kodytek, V. and Dolejs, V. (1986) On the Pitzer equation for the
osmotic coefficient of aqueous solutions of 3:l rare earth
electrolytes. Z. phys. Chem., Leipzig, 267, 743-746.
Krumgalz, B. S. and Millero, F. J. (1982) Physico-chemical study of
Dead Sea Waters. I. Activity coefficients of major ions in Dead
Sea water. Marine Chem. 11, 209-222.
Krumgalz, B. S. and Millero, F. J. (1983) Physico-chemical study of
Dead Sea waters. 111. On gypsum saturation in Dead Sea waters and
13,
their mixtures with Mediterranean Sea water. Marine Chem. 127-139.
Langmuir, D. and Melchior, D. (1985) The geochemistry of Ca, Sr, Ba,
and Ra sulfates in some deep brines from the Palo Duro Basin,
49, 2423-2432.
Texas. Geochim. Cosmochim. Acta, -

72
Levelt Sengers, J. M. H., Everhart, C. M., Morrison, G., and Pitzer,
K. S. (1986) Thermodynamic anomalies in near-critical aqueous
NaCl solutions. Chem. Engr. Commun. 47, 315-328.
Linke, W. F. and Seidell, A. (1965) Solubilities of Inorganic and Metal
Organic Compounds, 4th ed. Am. Chem. SOC.
Liu, C. and Lindsay, W. T. Jr. (1972) Thermodynamics of sodium chloride
solutions at high temperatures. J. Solution Chem. 1, 45-69.
Long, F. A. and McDevit, W. F. (1952) Activity coefficients of nonelectrolyte solutes in aqueous salt solutions. Chem. Rev. 51,
119-169.
Marshall, W. L. and Chen, C.-T. A. (1981) Amorphous silica solubilities.
V. Predictions of solubility behavior in aqueous mixed electrolyte
solutions to 300C. Geochim. Cosmochim. Acta, 46, 289-291.
Mayer, J. E. (1950) The theory of ionic solutions.
1426-1436.

J. Chem. Phys. 18,

McMillan, W. G. and Mayer, J. E. (1945) The statistical thermodynamics

of multicomponent systems. J. Chem. Phys. 13, 276-303.
Millero, F. J. and Byrne, R. H. (1984) Use of Pitzer's equations to
determine the media effect in the formation of lead chloro complexes.
Geochim. Cosmochim. Acta, 48, 1145-1150.
Mdller, N. (submitted) The prediction of mineral solubilities in natural
waters: a chemical equilibrium model for the CaS04-NaC1-CaC1 -H 0
2 .2
system to high temperature and concentration. Geochim. Cosmochim.
Acta.
Monnin, C. and Schott, J. (1984) Determination of the solubility products of sodium carbonate minerals and an application to trona
deposition in Lake Magadi (Kenya). Geochim. Cosmochim. Acta,
48, 571-581.
Pabalan, R. T. and Pitzer, K. S. (1987a) Thermodynamics of NaOH(aq)
in hydrothermal solutions. Geochim. Cosmochim. Acta, 51, xxxx.
Pabalan, R. T. and Pitzer, K. S. (1987b) Thermodynamics of concentrated
electrolyte mixtures and the prediction of mineral solubilities to
high temperatures for mixtures in the system Na-K-Mg-C1-SO fk -OH-H,@.
Geochim. Cosmochim. Acta, 51, xxxx.
Peiper, J. C. and Pitzer, K. S. (1982) Thermodynamics of aqueous
carbonate solutions including mixtures of sodium carbonate, bicarbonate, and chloride. J. Chem. Thermodynamics, 14, 613-638.
Phutela, R. C. and Pitzer, K. S. (1983) Thermodynamics of aqueous
calcium chloride. J. Solution Chem. 12, 201-207.
Phutela, R. C. and Pitzer, K. S. (1986a) Thermodynamics of electrolyte
mixtures. Enthalpy and the effect of temperature on the activity
coefficient. J. Solution Chem. 15, 649-662.

73
(1986b) Heat c a p a c i t y and o t h e r thermoP h u t e l a , R. C. and P i t z e r , K. S.
dynamic p r o p e r t i e s of aqueous magnesium s u l f a t e t o 473 K . J . Phys.
Chem. 90, 895-901.
P h u t e l a , R. C. and P i t z e r , K. S.
( 1 9 8 6 ~ )D e n s i t i e s and a p p a r e n t molar
volumes of aqueous magnesium s u l f a t e and sodium s u l f a t e t o 473 K
and 100 b a r . J . Chem. Engr. D a t a , 31, 320-327.
*

P h u t e l a , R. C . , P i t z e r , K. S . , and S a l u j a , P. P. S.
(1987) Thermodynamics
of aqueous magnesium c h l o r i d e , c a l c i u m c h l o r i d e and s t r o n t i u m
c h l o r i d e a t e l e v a t e d t e m p e r a t u r e s . J . Chem. Enp. Data, 3 2 , 76-80.
P i t z e r , K. S.
(1973) Thermodynamics of e l e c t r o l y t e s . I. T h e o r e t i c a l
77, 268-277.
b a s i s and g e n e r a l e q u a t i o n s . J. Phys. C h e m . (1975) Thermodynamics of e l e c t r o l y t e s . V.
E f f e c t s of
P i t z e r , K. S.
h i g h e r - o r d e r e l e c t r o s t a t i c terms. J . S o l u t i o n Chem. 4 , 249-265.
P i t z e r , K. S.
(1979) Theory: i o n i n t e r a c t i o n approach.
In Activity
C o e f f i c i e n t s i n E l e c t r o l y t e S o l u t i o n s , R. Pytkowicz, e d . , CRC Press,
Boca Raton, FLY 157-208 pp.
P i t z e r , K. S .
(1983) Thermodynamics of unsymmetrical e l e c t r o l y t e
m i x t u r e s : Enthalpy and h e a t c a p a c i t y . J. Phys. Chem. 8 7 , 23602364.
P i t z e r , K. S.
(1986) T h e o r e t i c a l c o n s i d e r a t i o n s of s o l u b i l i t y w i t h
emphasis on mixed e l e c t r o l y t e s . P u r e Appl. Chem. 5 8 , 1599-1610.

P i t z e r , K. S. and K i m , J. J. (1974) Thermodynamics of e l e c t r o l y t e s .

IV.
A c t i v i t y and osmotic c o e f f i c i e n t s f o r mixed e l e c t r o l y t e s . J . Am.
Chen. SOC. 96, 5701-5707.

P i t z e r , K. S. and L i , Y.-g.
(1983) Thermodynamics of aqueous sodium
c h l o r i d e t o 823 K and 1 kbar. Proc. Nat. Acad. S c i . U . S . A . 80,
768 9- 76 9 3.
P i t z e r , K. S . and L i , Y.-g.
(1984) C r i t i c a l phenomena and thermodynamics
o f d i l u t e aqueous sodium c h l o r i d e . Proc. N a t . Acad. S c i . U . S . A .
81, 1268-1271.
P i t z e r , K. S. and Mayorga, G.
(1973) Thermodynamics of e l e c t r o l y t e s : 2 .
A c t i v i t y and osmotic c o e f f i c i e n t s f o r s t r o n g e l e c t r o l y t e s w i t h one
o r b o t h i o n s u n i v a l e n t . J . Phys. Chem. 77, 2300-2308.
P i t z e r , K. S. and Mayorga, G.
(1974) Thermodynamics of e l e c t r o l y t e s .
111. A c t i v i t y and osmotic c o e f f i c i e n t s f o r 2-2 e l e c t r o l y t e s .
J . S o l u t i o n Chem. 3 , 539-546.

P i t z e r , K. S . , P e i p e r , J . C . , and Busey, R. H.
(1984) Thermodynamic
p r o p e r t i e s of aqueous sodium c h l o r i d e s o l u t i o n s . J . Phys. Chem.
Ref. D a t a , 2, 1-102.
P i t z e r , K. S . , P e t e r s o n , J . R . , and S i l v e s t e r , L. F.
(1978) Thermodynamics of e l e c t r o l y t e s . I X . Rare e a r t h c h l o r i d e s , n i t r a t e s ,
7 , 45-56.
and p e r c h l o r a t e s , J . S o l u t i o n Chem. -

74
Pitzer, K. S., Roy, R. N., and Silvester, L. F. (1977) Thermodynamics
of electrolytes. 7. Sulfuric Acid. J. Am. Chem. SOC. 99, 4930-4936.
Pitzer, K. S. and Silvester, L. F. (1976) Thermodynamics of electrolytes.
VI. Weak electrolytes including H3P04. J. Solution Chem. 5,
269-278.
Pitzer, K. S. and Simonsin, J. M. (1986) Thermodynamics of Multicomponent, miscible, ionic systems: theory and equations. J . Phys.
Chem. 90, 3005-3009.
Rard, J. A. and Filler D. G. (1981) Isopiestic determination of the
osmotic and activity coefficients of aqueous MgC12 solutions at
25OC. J. Chem. Eng. Data, 26, 38-43.
Robie, R. A . , Hemingway, B. S., and Fischer, J. R. (1978) Thermodynamic
properties of minerals and related substances at 298.15 K and 1 bar
pressure and at higher temperatures. U. S. Geol. Survey Bull.
1452, 456 pp.

Robinson, R. A. and Stokes, R. H. (1965) Electrolyte Solutions, Znd ed,

revised, Butterworths, London, 571 pp.
Rogers, P. S. Z. and Pitzer, K. S. (1981) High-temperature thermodynamic
properties of aqueous sodium sulfate solutions. J . Phys. Chem. 85,
2886-2895.
Rogers, P. S. Z. and Pitzer, K. S. (1982) Volumetric properties of
aqueous sodium chloride solutions. J. Phys. Chem. Ref. Data,
11, 15-81.
Roy, R. N., Gibbons, J . J., Peiper, J. C., and Pitzer, K. S. (1983)
Thermodynamics o f the unsymmetrical mixed electrolyte HC1-Lac1 3'
J . Phys. Chem. 87, 2365-2369.
Saluja, P. P. S., Pitzer, K. S., and Phutela, R. C. (1986) High-temperature thermodynamic properties of several 1:l electrolytes. Can. J.
Chem. 64, 1328-1335.
Silvester, L. F. and Pitzer, K. S. (1978) Thermodynamics of electrolytes,
X. Enthalpy and the effects of temperature on the activity coefficients. J . Solution Chem. 7, 327-337.
Stull, D. R. and Prophet, H. (1971) JANAF Thermochemical Tables, Znd
ed. Nat'l. Stand. Ref. Data Ser., U.S. Nat'l. Bur. Stand. 37,
1141 p.
Tanger, J. C., IV, and Helgeson, H. C. (1987) Calculation of the
thermodynamic and transport properties of aqueous species at high
pressures and temperatures: Revised equations of state for the
standard partial molal properties of ions and electrolytes. Am. J.
Sci. in press.
Tsonopoulos, C. (1974) An empirical correlation of second virial coefficients. AIChE J. 20, 263-272.

75
Uematsu, M. and Franck, E . U. (1980) S t a t i c d i e l e c t r i c c o n s t a n t of
w a t e r and steam. J . Phys. Chem. Ref. Data, 9 , 1291-1305.
Wagman, D. D . , Evans, W. H . , P a r k e r , V. B . , Schumm, R. H . , Halow, I . ,
B a i l e y , S. M . , Churney, K. L . , and N u t t a l l , R. L.
(1982) The NBS
t a b l e s of chemical thermodynamic p r o p e r t i e s .
Selected values f o r
i n o r g a n i c and C and C 2 o r g a n i c s u b s t a n c e s i n S I u n i t s . J. Phys.
Chem. Ref. Data!. 11, Suppl. 2 , 392 pp.
Zarembo, V. I . and L'vov, S. E. (1982) L i m i t i n g p a r t i a l volumes of
i n d i v i d u a l i o n s i n aqueous s o l u t i o n . Geochim. I n t . 1 9 , no. 2 ,
57-69.