Geochimica et Cosmochtmtca Acta Vol 52, pp 821-837 OOI6-7037j88j$3.00 +.

00
Copyright © 1988 Pergamon Press pic Pnnted III USA

The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the
Na-Ca-CI-S04-H20 system, to high temperature and concentration
NANCY M0'LLER
Department of Cheimistry, University of California, SanDiego, La Jolla, CA 92093, U.S.A.

(Received January 19, 1987; accepted in revised farm January 13, 1988)

Abstract-This paper describes a chemical equilibrium model for the Na-Ca-CI-S04-H20 system which calculates
solubilities from 25°Cto 250°C and from zero to high concentration (I - 18. m) within experimental uncertainty.
Theconcentration and temperature dependence of the model were established by fitting available activity (solubility,
osmotic andemf)data. Asingle ioncomplex, CaSO~, which increases instrength with temperature, isincluded explicitly
in the model.
Thevalidation of model accuracy bycomparison to laboratory and field solubility data isincluded. Applications of
the model are also given. Phase diagrams constructed forthe Na-Ca-CI-S04-H20 system and predicted solubilities of
anhydrite and hemihydrate in concentrated seawater at high temperature are in very good agreement with the data.
Calculations of the temperature of gypsum-anhydrite coexistence as a function of water activity are compared to
reported values, and are used to estimate tbe composition-temperature relation for gypsum-anhydrite transition in a
natural brine evaporation. A preliminary model for barite solubility in sodium chloride solutions at high tempera-
ture (100°C to 250°C), based on this parameterization of the CaS04-NaCI-H20 system, gives good agreement with
the data.

I. INTRODUCTION eludes a description of the solution model parameters which

VARIABLE TEMPERATURE computer models of natural brine
geochemistry have important advantages for application to
studies of salt deposition. They can easily accommodate the
many chemical interactions and great variability inherent in
natural settings,such as marine vents and geothermal waters.
They can also easily simulate these conditions, which are
difficult to reproduce in the laboratory. However, to be ap-
plicableto many natural brine-saltinteractions, a geochemical
model must be reliable to high concentration. Recently,
HARVIE et al. (1984) have shown that geochemical models
can be developed which reliably predict solubilities in com-
plex brines, Na-K-H-Ca-Mg-CI-OH-HS04-S04-C03-HC03-
H 20-C02 (g), from zero to high concentration at 25°C.
The 25°C models of Weare and co-workers (recently re-
viewed in WEARE, 1987) have been successfully applied to
interpreting the geochemistry of diverse natural settings:
studies of ancient (Zechstein II: HARVIE et aI., 1980) and
modern (Bocana de Virrila: BRANTLEY et al., 1984) marine
evaporite systems, studies of the solar evaporation of seawater
(M0'LLER et al., in preparation), studies of mineral precipi-
tation in lakes (Great Salt Lake: SPENCER et al., 1985;Searles
Lake (with borate species added): FELMY and WEARE, 1986)
and in fluid inclusions (B. LAZAR and H. D. HOLLAND, pers.
commun.). Generalizing these 25°C models to include a
variabletemperature capabilitywillsignificantly broaden their
applicability.
This article describes a variable temperature model which
accurately calculates solubilities in the Na-Ca-CI-S04-H20
system from 25°C to 250°C and from dilute (0. m) to high
concentration (I '" 18. m) (for 1. atm. pressure to 100°C
and for pressuresalong the water vapor saturation curve above
100°C). For solubility modeling, the activity and osmotic
coefficient expressions are the principal thermodynamic
quantities of interest. The model expressions, given in section
II, are based on those of PITZER (1973). Section II also in-
821
are adjusted to fit the concentration-dependent solution be-
havior at constant temperature and pressure. Pitzer and co-
workers have shown that the temperature-dependence of ac-
tivity and osmotic coefficients for various aqueous salt so-
lutions can be well represented by temperature functions of
these solution model parameters. Their work on the NaCl-
H20 (PITZER et al.. 1984), Na2S04-H20 (ROOERS and PITZER,
1981)and CaCh-H 20 (PHUTELA and PITZER, 1983)systems
has been incorporated within the framework of the present
model when possible. PABALAN and PITZER (1987) have re-
cently modeled the quinary Na-K-Mg-CI-S04-H20 system
to high temperature. In this model, they evaluated the pa-
rameters for all the binary (e.g., NaCI-H20) solutions and for
several of the common ion ternary (e.g., NaCl-Na2S04-H20)
solutions. They compared calculated solubilities with exper-
imental data but they did not do quarternary and quinary
solubilitycalculations. The fitting equation used to determine
the temperature-dependence of the solution model param-
eters and of the standard chemical potentials for the various
species in the Na-Ca-CI-S04-H20 model is given in sec-
tion II.
Parameterization of the model is described in section III.
Data from relatively simple binary and ternary systems can
be used to completely parameterize highly complex brine
models based on the PITZER (1973) equations. The work of
the Oak Ridge group (HOLMES and MESMER, 1986;HOLMES
et al., 1978, 1981; MARSHALL and SLUSHER, 1966; MAR-
SHALL et al., 1964) provided many of the reliable high tem-
perature data necessary to parameterize the model. The 25°C
solubility models of Weare and co-workers showed that it is
necessary explicitly to include only strongly associated ion
complex species (e.g., HS04"; see HARVIE et al., 1984) to
model concentrated brine behavior sucessfully, even for
complex chemical systems such as borate-seawater (FELMY
and WEARE, 1986). In modeling the quarternary Na-Ca-CI-
S04-H20 system to high temperature.a CaSO~ complex was
822
included in order to fit the data from 25°C to 250°C using
a simple parameterization scheme for the calcium sulfate
interactions. Only solubility data were used to evaluate these
calcium sulfate interaction parameters because binary os-
motic and emf measurements are not feasibledue to the very
low solubility of the calcium sulfate salts.
Comparisons of model calculations with the data used in
the model parameterization are given in section III. Section
III also compares predictions ofEQ3/6 (WOLERY, 1983)with
the experimental data at high temperature. The EQ3/6 results
at high temperature, similar to those at 25°C, are generally
in fair agreement with experiments in dilute solutions. Newer
versionsof the EQ3NR code provide options to use the Pitzer
equations and various model parameterizations by Pitzer and
co-workers as well as the HARVIE et al. (1984) model for the
seawater system at 25°C (T. J. WOLERY, pers. commun.,
1986).
Comparisons with data more complex than binary and
ternary systems and with field data establish the reliability of
the predictive capabilities of the model for natural waters.
Section IV describes such comparisons. Phase diagrams for
the CaS04-bearing minerals calculated by the model are in
good agreement with experimental data not used in the mod-
el's parameterization. The model is also used to predict the
mineral sequence which would occur during the equilibrium
evaporation at 100°C of a seawater-type brine. The agreement
between the model and experimental results (LANGELIER et
al., 1950) is excellent. To illustrate another possible appli-
cation of the model, the gypsum-anhydrite transition in a
natural brine evaporation undergoing solar heating (HERR.
MANN et al., 1973) has been calculated.
Sufficientexperimental data are available for the calcium
sulfate system to parameterize a temperature-dependent
model by detailed evaluation of the system's concentration
dependence at many temperatures from 25°C to 250°C.
However,to model systemswith insufficient data, parameters
must be estimated using information from well-characterized
chemicallysimilar systems. The success of this approach using
the Pitzer formalism is illustrated in section V, where reliable
calculations of the high temperature behavior of BaS04 in
NaC! aqueous solutions are made with a model based on the
CaS04 (T) model described here. For a complete high tem-
perature Na-Ba-CI-S04-H20 model, solubilities in NaC!-
BaCh-H20 and Na2S04-BaS04-H20 solutions must also be
accurately modeled.
II. MODEL EQUATIONS
The solubilitymodeling approach of Weare and co-workers
is based on the PITZER (1973) equation which expresses, in
virial expansion form, the molality-dependence of the excess
Gibbs free energy, GO<, of an aqueous electrolyte solution.
Expressions for activity and osmotic coefficients, described
in detail in HARVIE et al., (1984) and FELMY and WEARE
(1986), are derived from appropriate derivatives of the excess
Gibbs free energy equation.
Theexpressions fortheosmotic coefficient (et»and fortheactivity
coefficient (In'YM) of a cation (M) and of a neutral species (N) are
given below:
N. Meller
+ L L m.m; (4)tc' + L mal/;cc'a)
c-cc' a
+ L L mama' (4)~a' + L mcl/;aa'c) + L L mnmcAnc
a-ca' c nc
+ L L mnmaAna + L L L mnmcmalnca} , (II-I)
nan c a
a-ca' c a
n a
and
c a
where
c a c-cc' a-ce'
In Eqns, (II-I and 11-4), I is the ionic strength. Thesubscripts c and
a refer to cations andanions in general; whereas, M refers to a specific
cation and X to a specific anion. Nand n designate neutral species
similarly. Themolality and charge of an ionare indicated by m and
z, respectively.
Z = L Iz,lm, and (11-5)
(11-6)
Since Eqn. (11-2) issymmetric forcations and anions, the activity
coefficient expression foran anion, X, isomitted (see HARVIE et al.,
1984). When the single ion expressions such as Eqn. (11-2), which
are defined by convention only, are used to calculate mean activity
coefficients or solubilities they are equivalent to the equations de-
veloped by Pitzer and coworkers (PITZER, 1973; PITZER and MAY.
ORGA, 1973, 1974; PITZER and KIM, 1974).
Thebracketed term in F (Eqn. (11-4» represents the contribution
to theactivity coefficient expression from theelectrostatic, long-range
interaction between solution species. Theform selected byPitzer for
theelectrostatic term in thevirial expansion (see first termin brackets
of Eqn. (11·1» gave the best agreement of the model and osmotic
data. Atvery low ionic strength, it reduces to the limiting law. In the
electrostatic term A· (one third the Debye-Hiickellimiting slope) is
dependent on temperature and pressure.
A. = ! [21rNOP~]1/2[~]3/2
3 1000 DkT' (11-7)
where the variables are p~, the density of pure water, and D, the
dielectric constant of purewater. No is Avogadro's number, k is the
Boltzman constant, and e is the absolute electronic charge.
The second virial coefficients, Band 4>, are dependent on ionic
strength; C·(see Eqn, (11·6», 1/;, Aand I areassumed tobeindependent
ofionic strength. Theconcentration-dependence, developed byPitzer
andco-workers, foreach oftheabove virial coefficients hasbeen dis-
cussed in detail in an earlier paper (HARVIE et al., 1984). J!P and 4>.
in Eqn. (II-I) refer to specific forms forBand 4> found by Pitzer to
give thebest agreement with osmotic data. Gibbs-Duhem integrations
yield the appropriate forms for the activity coefficient expressions.
In Eqn. (11-2),
 Prediction of mineral solubilities
(I1-8)
where
(I1-9)
The parameter, a, is set equal to 2.0 when an electrolyte has a uni-
valent ion. For 2-2 or higher valence electrolytes, a = 104. <P in the
activity coefficient expression (Eqn. (I1-2)) has the following form:
(11-10)
EO,}(I), which is a function only of ionic strength and electrolyte pair
type, is nonzero only for nonsymmetric electrolytes (e.g., 1-2 types).
(See PITZER, 1975, and HARVIE and WEARE, 1980, for integrals de-
fining these terms.) In Eqn, (I1-4)the forms of the derivatives, B' and
<p', are obtained by taking the derivative of the appropriate function
with respect to ionic strength. Therefore, at constant temperature
and pressure, the solution model parameters are: {f0l, (fl), {f2l, and
C' for each cation-anion pair; 0 for each unlike cation-cation or
anion-anion pair; 1/; for each triple ion interaction where the ions are
all not of the same sign; ,\ for ion-neutral pairs; and \' for ion-ion-
neutral interactions (see FELMY and WEARE, 1986). The third virial
coefficients, C, 1/;, and \'. are important only at higher concentrations
(;:::2. m).
For solubility modeling, the standard chemical potentials, IlJ, of
the various solution and solid phase model components may also be
used as parameters. In a solution. these are used along with the activity
and osmotic coefficients to calculate the chemical potentials, Il}, for
the solute species by
aG
-
° + RTln "(}m),
= Il} = Il} (II-II)
an}
and for the solvent by
eo = IlH,O = Il~,o + R.~\ -
dnH,O
W )
1000 ~ m}<p. (I1-12)
In Eqn, (I1-l2), <P is the osmotic coefficient, R is the universal gas
constant and W is the molecular weight of water (gms.). For a charge-
balanced set of mole numbers, n}, which minimizes the free energy
(see HARVIE et al.. 1984, and references therein) equilibrium con-
ditions are defined at constant temperature and pressure.
Parameterization of the Na-Ca-Cl-S04-HzO variable temperature
model consisted of three principal steps. ( I) Using the above equations,
the model parameters were evaluated by minimizing (Via nonlinear
least square analyses) a standard deviation of the variable concen-
tration data in the binary and ternary subsystems at given temper-
atures from 25°C to 250°C. (2) These preliminary isothermal results
were studied to test consistency of the various data sets and to suggest
appropriate data weighting schemes. When possible, all data sets for
a given temperature were used. However. when a data set was clearly
inconsistent with the other data sets, it was not used. Priority was
given to sets which yielded smooth temperature variations in the
parameter values throughout the 25°C to 250°C temperature range.
(3) Temperature-dependent equations for the various model param-
eters were established by fitting the isothermal parameter values as
a function of temperature with selected terms in the fitting equation
given below (Eqn. (I1-l3)) using linear least square analyses. This
fitting equation,
Parameter (T) = at + azT + aliT + a4 In T + as/(T - 263.)
+ a6Tz + a7/(680. - T) + as/(T- 227.), (I1-l3)
is based on those used by ROGERS and PITZER (1981) and PITZER
et al. (1984) to describe the temperature dependence of the solution
model parameters for the Na zS04-HzO and NaCI-HzO systems, re-
spectively. It has been shown by these workers to be consistent with
both activity and thermal data.
The relative error of the model's fit to the data is described in terms
of a sigma value, which is defined as:
(I1-14)
823
where n is the total number of data points, x(l)data is the value of the
ith experimental point and x(l)catculated is the calculated (model) value
of the ith point.
Ill. EVALUATION OF PARAMETERS FOR THE
TEMPERATURE-DEPENDENT GYPSUM/ANHYDRITE
SOLUBILITY MODEL OF THE
Na-Ca-CI-S04-H20 SYSTEM
Sections III-2 through III-7 describe the evaluation to high
concentration and temperature of the solution model pa-
rameters (see section II) and of the standard chemical poten-
tials (f.L°/RT) for the Na·Ca-Cl·S04-H 20 model (for I atm.
pressure to lOO°C and for the pressure of the saturated water
vapor above 100°C). Note that for this model the parameters
r,
for the various neutral species interactions, A and are zero,
and that a values (see description in section II) do not vary
with temperature. Parameterization of the temperature-de-
pendence of A¢ (see Eqn. (11-7» is described in section III-I.
In the present model, the standard chemical potentials (f.L °/
RT) of the ionic species, Na+, Ca'", cr and S04-, are set
equal to zero throughout the 25°C to 250°C temperature
range. In the 25°C solubility models of Weare and co-workers,
the standard chemical potentials of the species in solution
represent the free energy of formation of each ion from the
elements, Using the zero standard state convention, the stan-
dard chemical potentials (f.L°/RT) of the solid phases are the
natural logarithms of the solubility products. Regardless of
the convention selected, the solubility model results are iden-
ticaL
To fit all the data for the binary and ternary subsystems
in the Na-Ca-CI-S0 4-H20 model from 25°C to 250°C, a sin-
gle ion complex, CaSO~(aq), was introduced. The evaluation
of its standard chemical potential as a function of temperature
is discussed in section III-7, The study of BUSEY and MESMER
(1978) was used to establish the temperature dependence of
the standard chemical potential for H 20. The remaining
standard chemical potentials evaluated as a function of
temperature were those for halite (NaCl), mirabilite
(Na ZS04' lOH20), thenardite (Na2S04), gypsum (CaS04'
2H 20), hemihydrate (CaS04' O.5H20), anhydrite (CaS04),
glauberite (Na2S04' CaS04) and labile salt (2Na2S04'
CaS04' 2H 20) (sections IIIA and III-7). The aqueous solu-
bility of the dihydrate calcium chloride salt is too high (I
> 20.m) to reliably calculate the temperature variation of its
standard chemical potential with this model.
Note that a large number of significant figures is reported
for the values of the constants in the variable temperature
equations for the various model parameters (see Tables 1-
3), In the temperature-dependent fitting equation (11-13) there
is a large amount of cancellation between terms; therefore
high accuracy in the calculation of each term is required in
order to retain experimental accuracy in the model predic-
tions, The determination of the values of the constants in
the temperature-dependent equations for each ofthe Na-Ca-
Cl-S04-H20 model parameters is described below.
//I-I) Evaluation of A"
PITZER et al. (1984) give a table of A" VS, temperature values from
O°C to 300°C (in degrees Kelvin and pressures along the saturation
curve). These tabulated values were put into equation form using
824 N. M011er

Eqn. (11-13) and least square analysis. The resulting fitting constant
values, listed in Table I, agreedwell (0" = 6.5 X 10-6) with those of
PITZER et al.
III-2) Evaluation of Na, CI interaction parameters
PITZER et al. (1984) developed a complete equation of state for
NaCI(aq) validfrom O°C to 300°C,saturation pressure to 1000. bars
and 0.-6.m. They give two sets of fitting constants for their T, P-
dependentequations. One set is to be usedbelow65°C and the other
setabove65°C. At 200°C (and pressures of200. bars),they estimate
that the uncertainty is .004 for osmotic coefficients calculated from
0.-6. m NaCI. PITZER et al. (1984)did not considersolubility data.
Therefore, to testtheirsolubility predictions, theycalculated the mean
activitycoefficient for NaCI at saturation molality ('Y~ (T, P») from
the properties of the solidand the infinitely dilute solution as wellas
from solubility data at I atm. below 100°C and at the saturation
pressure of water above 100°C. Their results agree with the data
within the uncertainties of the solubility measurements for 0° < T
~ 300°C.
Giventhe accuracy of the data available in the Na-Ca-CI-S04-H20
system, it wasdecided to generateone set of fittingconstantsfor the
aqueous NaCI(T) model instead of using the two sets of PITZER et
al. Their tabulated valuesof the Na,CIbinary parametersfrom O°C
to 300°C at saturation pressure werethereforefit usingEqn. (11-13).
The resulting NaCI(T) model described by the constants in Table I
and Eqn. (11-13), agrees wellwith PITZER et al.'s tabulated values of
I3lSta, i3lJta and C~a, a (C~a,a = 2C; see HARVIE et al., 1984) from
0° to 300°C (0" = 3.09 X 10-6 , 0" = 5.36 X 10-7 and 0" = 6.16 X 10-7,
respectively). Note that ~l.a is set equal to zero.
III-3) Evaluation ofNa,S04 interaction parameters
ROGERS and PITZER (1981; see also ROGERS, 1981) developed
temperature-dependent equationsforthe activity coefficient and other
thermodynamicpropertiesof Na2S04 aqueous solutionsfrom 30°C
to 200°C usingthermal and activitydata. ROGERS (1981)calculated
that below 120°C this Na2S0iT) model reproduces osmotic coef-
ficient data within±2%up to 2.5 m and that above 120°Creasonable
agreement with the data is limited to concentrationsbelow 1.5 m.
In building the model described here, it was found that activity
curvesgenerated by the Na2S04(T) model of ROGERS and PITZER
(1981) lead to nonconvex free energy at concentrations below the
solubility ofNa 2S04 at hightemperatures(T,,= 200°C).HOLMES and
MESMER (1986)developed temperature-dependent equationsfor the
aqueous Na2S04 system to 225°C from their isopiestic data. Com-
paring values of In 'Y for Na2S04(aq) against molality at different
temperatures, the model of HOLMES and MESMER (1986)is in good
agreement with ROGERS and PITZER'S (1981) results at 110°C but
differs from these resultsby 15% at 225°C. In their model of the Na-
K-Mg-CI-S04-H20 system, PABALAN and PITZER (1987) incorporated
the variable temperatureequations of HOLMES and MESMER (1986)
for Na2S04(aq). SinceHOLMES and MESMER (1986)used a equal to
1.4in their calculations, whereas our modelingapproach(seesection
II) uses a equal to 2.0 for Na2S04, their parameterization was not
adopted for the present model. For this model, the ion-interaction
parametersfor Na2S04(aq) were evaluatedas a function of temper-
ature with a equal to 2.0 usingsolubility data in the Na-CI-S04-H20
system (see following section). The resulting parameterization de-
scribes activities in aqueoussodiumsulfate solutions to concentrations
above 1.5 m from 25°C to 250°C whilemaintaining necessary con-
vexity relationships.
III-4) Evaluation of parameters in the Na-S04"CI-H20 system
Values of I3lSl.so. and i3lJl.so. weregeneratedfrom 25°C to 2OD°C
by the Na2S04(T) model of ROGERS and PITZER (1981). Values of
~l.so. were set equal to zero from 25°C to 250°C. Using solubility
data in NaCI-Na2S04-H20 solutions, I3lStso. and i3lJtso. above200°C
and C~a.SO., 9a.so., "'C).so•.Na as well as the salt standard chemical
potentials(/Lo jRT's) wereevaluatedfrom 25°C to 250°C.The above
temperature-dependent equations for A" (Table I) and for the Na,
CI interaction parameters(Table I) were used in these fits. The sol-
ubilitydata were taken from LINKE (1965), STEPHEN and STEPHEN
(1963)and BUKSHTEIN et al. (1953) for temperatures up to 100°C
and from SCHROEDER et al. (1935)from 150°Cand above.
BUSEY and MESMER (1978) give a table of log Qw (Qw
'" [H+][OH-]) vs. temperature (0-300°C) valuesat infinite dilution
(I = 0.). Using Eqn. (11-13), these tabulated valueswerefit in a least
squares calculation with the constants listed in Table 3 (0" = 2.63

Table 1. Values of the fitting constants (Eq. (II-13» for the Debye-Hiickel model parameter, A., and for the binary interaction parameters L as a
function of temperature (OK) b..

Parameter Constants
a, .., a. 84 a. a~ a? 8R
lA' 3.3690l532d-ol -6.3210043Od-04 9.l4252359dOO -1.35l43986d-02 2.26089488d-03 1.92118597d-06 4.52586464d+01 O.

~~a1)
1.43783204d+Ol 5.60767406d-03 -4.22l85236d+02-2.5l226677dOO O.
-4.83060685d-ol 1.40677479d-03 1.19311989d+02 O. O.
-2.6l7l8l35d-06 4.4385450SdOO -1.70502337dOO
O. O. -4.23433299dOO
l-o., ..a
~oi,a -1.005887l4d-ol -1.805294l3d-05 8.61l85543dOO 1.24880954d-02 O. 3.41172l0Sd-086.83040995d-o2 2.939226l1d-01
8.l6920027d+Ol 3.01 104957Od-02-2.32l93726d+03-1.43780207d+0l-6.66496l 1ld-Ol-1.03923656d-05 O. O.
~ ..so.
1)
..SO. 1.004630l8d+03 5.77453682d-ol -2.l8434467d+04-l.89ll0656d+02-2.035505488-ol-3.23949532d-04 1.46772243d+03 O.
~~a.So. -8.078l6886d+01-3.5452l126d-02 2.0243883Od+03 1.46l9773Od+Ol-9.l697474Od-02 1.43946005d-05-2.42272049dOO O.

P~a -9.4l895832d+01-4.04750026d-02 2.34550368d+03 1.709l2300d+Ol-9.2288584ld-ol 1.5l488l22d-05-1.39082000dOO O.

~~
3.47870000dOO -1.54l70000d-02 O. O. O. 3.l7910000d-05 O. O.
-3.0357873ld+Ol-1.3626472Sd-02 7.64582238d+025.S045806ldOO -3.27377782d-ol 5.69405869d-D6-5.36231106d-Ol O.
13&>,50. 0.15dOO O. O. O. O. O. O. O.
p~so. 3.OdOO O. O. O. O. O. O. O.
Pbto. -1.29399287d+02 4.0043 1027d-o1 O. O. O. O. O. O.
~~.so. O. O. O. O. O. O. O. O.

a. The p(2) values for all binaries except p~so. are equal to zero from 25°C to 250"C. The temperature variation of p~so. given in the table
above was used from 25-50"C to improve the fit to the pure Waler gypsum data (see text).
b. The Na-Cl, Na-S04, Ca-Cl, and Ca-s04 parameters were evaluated from 0°C-300°C, 25°C-250"C, 25°C-250°C, and 25°C-2500C, respec-
tively, with the exception of Pbto.(see above).
c. In Tables (1-3) a high number of significant figures is necessary in the constant values to retain experimental accuracy in the model predictions
(see text, section Ill).
 Prediction of mineral solubilities 825

Table 2. Values of the fitting constants L (Eq. (Il-B) for the mixing parameters b. of the ternary solutions as a functionof temperature
(OK) c'.

Parameters Constants
al a2 a3 84 as a6
90050. (25°-150"C) O.07dO O. O. O. O. O.
90 050• (1500-2500C) 5.67983244<1+01 -1.6302l206d-Ql -1.8747982Od+04 5.70511185dOO 8.90099309d+02 9.2l443436<1-Q5
'l'O,sO..Na (25°-150°C) -.009d0 O. O. O. O. O.
'l'o,SO.,Na (15Q0-2S00C) -3.298ll409d+02 -4.424l0302d-02 1.6295735ld+04 5.l6258079d+Ol -3.5334175ld+02 O.
'l'o,so..ea(2S0-2500C) -Q.01SdO O. O. O. O. O.
~..ea(25°-2S00C) O.05dO O. O. O. O. O.
'l'Na,Ca,O (25°-250"C) -Q.OO3dO O. O. O. O. O.
'l'Na,Ca,SO. (25°-250°C) -Q.012d0 O. O. O. O. O.

a. The constants., and as in Eq.(ll-13) are equalto zerofor all the aboveparameters.
b. Note that all ",'s and ~'s for neutralspeciesinteractions (see Fehny and Weare(1986» are zero from 25-2500C.
c. The temperature range listed with each parameterindicatesthe temperatures wherethe associated constants (aca~ are to be used. Note
that data for parameterizing the NaCl-QICl 2- H20 systemextendedonly to 2000C(seetext).

x 10-1) . The resulting temperature-dependent equation was used to
calculate equilibrium constants for the hydrated minerals such as
mirabilite (Na2S0•• IOH 20 ).
Isothermal fitsfrom 25°C to 250°C of the solubilitydata indicated
that the mixing parameters (Table 2) could be held constant (8CI•SO,
= .07 and 1J'cl.SO"Na = - .009) and the data fit within I 0% from 25°C
to 150°C (see Figs. la, b). Using the resulting model described by
Tables 1-3, the experimental data for halite solubility,mirabilite sol-
ubility and thenardite solubility in the NaCl-Na2S0.-H20 solutions
at 30°C (Fig. la) are fit with sigmas of .020, .028, and .056, respec-
tively. At 50°C, the halite and thenardite solubilitydata are fit with
sigmas of .038and .078,respectively. Note that above32°C, rnirabilite
becomes metastable. At 50°C, the model calculates thenardite sol-
ubility in pure water 7.6%higher than the lowestexperimental value
(3.150 m). The agreement of the model with solubilitydata at 100°C
and 150°C (Fig. lb) is also excellent (Ubal = .033 and Ulben = .046 at
100°C and Ubal = .020 and Ulben = .035 at 150°C).
Above 150°C, it was necessary to vary the values of 80 •so, and
1J'C1,SO"Na with temperature (Table 2) in order to fit the temperature
variation of the solubility data (see SCHROEDER et al., 1935) within
10%. Note that about 230°C, the solubilityofNa2S0. in water drops
sharply (see SCHROEDER et aI., 1935). This break in the solubility

a. b.

TEMPERATURE' 30°C TEMPERATURE' 150°C

20 2.0
o
U'J 1.6
o
";., 1.6
o'" o
z
E 12 E 1.2
o
08 08
04 0.4
O~----:--~+-~~+--<------;~--g, O!:---'--~-"--+-~---;~-'-O
o 2 3 4 5 o 2 4 6
mNaCI mNaCI
c. d.

TEMPERATURE' 200°C TEMPERATURE' 250°C

o
U'J
2 0
(J)
2
N

z'"
o 0
z
E E

'"
l> '"
l>
C
S; --<
'" '"
0
2 4 6 8 0 2 4 6 8
mNaCI mNaCI
FIG. I. A comparison of model calculations (solid lines) of mineral solubilitiesin Na2S0.-NaCl-H20 solutions with
experimental data (see text). (la): mirabilite, thenardite and halite solubilities at 30°C; (I b): halite and thenardite
solubilities at 150°C; (Ie): halite and thenardite solubilitiesat 200°C; (ld): halite and thenardite solubilitiesat 250°C.
826
vs. temperature curve occurs at a temperature corresponding to a
change in the stable form of Na2S04(S) (BRODALE and GIAUQUE,
1972). A comparison of solubilities calculated by the model with
experimental data for 200°C (Uhal = .054 and U'hen = .037) and for
250°C (Uhal = .063 and Uthen = .034) are given in Figs. Ic and Id,
respectively. The agreement of the model and experimentaldata for
the solubility of NaCI and Na2S04 in pure water from 25° to 250°C
is excellent (see previous figures). PABALAN and PITZER (1987) report
good agreement of their model calculations with the experimental
data to about 185°e. They suggest that additional data are needed
to more clearly define the temperature dependency of the model
parametersat high temperature.
1II-5) Evaluation of Ca.Cl interaction parameters
The activity coefficient for CaCh rapidly increases with concen-
tration. The consequent difficulty of modelingat highconcentration
solubilities which are dependent on Ca,CI interactions is discussed
in HARVIE and WEARE (1980). (Seealso the discussion in PHUTELA
and PITZER, 1983.) PHUTELA and PITZER (1983)established a tem-
perature-dependentCaCh-H20 model from 25°C to 200°C by com-
bining their 25°C Ca,C1 parameter valueswith those determined by
HOLMES et al. (1978) at 108.85°, 140.65°, 172.25° and 200.85°C
from isopiestic data. The maximum concentration of the Phutela
and Pitzer model is 4.3 m. The accuracy of the osmotic coefficients
calculatedby HOLMES et al. is ±.005.
In the presentmodel, 13&0 is set equalto zeroand the temperature-
dependent equation ofPhutela and Pitzerfor {jgl,o is usedfrom 25°C
to 250°e. Using Eqn. (11-13), temperature-dependentequations for
~.Cl and Ct..Cl wereestablished(Table I) by fittingisothermalvalues
determined above200°C from the vapor pressuredata OfZAREMBO
et al. (1980) and WOOD et at. (1984) along with values generated
from 25°C to 200°C by the PHUTELA and PITZER (1983)equations.
In thesecalculations, the data wereweighted such that the parameter
values ofPhutela and Pitzerwerenot signifcantly degraded. At 200°C,
the data OfZAREMBO etal. (1980)and WOOD etal. (1984), converted
to osmotic coefficient data, are fit with the model (Tables 1-3) with
sigmas of .085and .132,respectively. When the lowestconcentration
point in each data set are given low weighting, the ZAREMBO et al.
and the WOOD et al. data are fit with sigmas of .055 and .046, re-
spectively. These fits are comparable to those reported by WOOD et
al. in their isothermal parameterization of the Pitzer equations at
200°e. At 250°C, the model fits the ZAREMBO et al. data with a
sigmaof .052 and the WOOD et al. data with a sigmaof .041.
III-6} Evaluation 01parameters in the Na-Ca-CI-H]O system
The availability of solubilitydata for evaluatingthe mixingparam-
eters, I1Na,ea and "'Na,ea.a in the NaCI-CaCh-H20 system is seriously
limitedfor temperaturesabove 100°e. For temperaturesup to about
130°C,data are found in LINKE (1965)and BUKSHTEIN et al. (1953).
From 100° to 200°C, the isopiestic study in the NaCI-CaCh-H20
system of HOLMES et al. (1981) was used. Above this temperature,
the 200°C-values wereretaineddue to lackofdata fortheirevaluation.
Constant values of 11 (.05) and e (-.003) were selected which are
suitablefor both the solubilityand isopiestic data (see Table 2).
Using the model described by Tables 1-3, the NaCI-CaCh-H 20
solubilitydata are fit to approximately 5. m CaCh (I = 15.m)from
25°C to 200°C within 10%. The chemical potentials for CaCl2' 6H20
(antarcticite) and CaCh· 2H20 were not determined becauseof the
very high solubility of these salts. The solubility data for halite-sat-
urated calciumchloridesolutionsat 25°C are fitwitha sigmaof .074.
The model calculation is about 6.% lower than the data at 5.27 m
CaCho At 50°C (seeFig.2a), the sigmafor the halite data set is .067,
the difference between the model and experiment being about 3.%
for the 5.18 m datum. Sigmafor the halite data set at 100°C is .076
(see Fig. 2b). Compared to the 5.12 m CaCh data point, the model
is about 5.3% low. At 125°C, the difference betweenthe model and
data is 5.2% for the 5.19 m CaCh data point, with the data set being
fit with a sigmaof .052. Above about 5.m CaCh, the difference be-
tween model calculations and experimental data rapidly increases.
Note that this maximum concentration range is similar to that used
to establish the PHUTELA and PITZER (1983) binaryCa,C1 parameters
N. Meller
a.
5
TEMPERATURE' 50·C
4
3
zs'"
c
u
E 2
0
0
0 2 3 4
mNoCI
b.
5
TEMPERATURE' lOO·C
4
uc'" 3
u
E
2
1
0
0 23456
mNoCI
FIG. 2. A comparison of model calculations (solid line) of halite
solubility in CaCh-NaCI-H 20 solutions with experimental data (see
text). (2a): 50°C; (2b): 100°e.
from 25°C to 200°e. With 11 = .05 and'" = -.003, the isopiestic
data of HOLMES et al. (1981) are fit with U = .0029 at lOO.36°C, U
= .0031 at 139.9°C, U = .0030 at 172°Candu = .0041 at201.02°e.
III-7) Ca,S04 interactions and the Na-Ca-CI-S04-H]O system
The variations between data setsforthe solubility ofvariouscalcium
sulfate salts have been discussed by several authors (e.g., HARDIE,
1967). Figs. 3 and 4 illustrate the variability between several examples
of pure water solubility data for gypsum,anhydrite and hemihydrate
from 25°C to 250°e. Note that some of these data were not used to
parameterize the model(seebelow). Solubilities of the calciumsulfate
salts in water and in aqueous NaCI solutions are low and decrease
with temperature. At 250°C, anhydrite solubilityis only about .0002
m. Since the model parameters for the Ca,S04 binary interactions
tend to be insensitive to solubility data in non-common ion systems,
solubility data in common ion ternary systems(e.g., CaS04-Na2S04-
H20) were used when possible to evaluate these parameters. There
are several reportsof such data at temperatures from 25°C to 100°e.
Abovethis temperature rangethe amount of appropriate data is lim-
ited.
The many diverse calcium sulfate solubility data sets from 25°C
to 250°C could be fitwithin experimentaluncertainty usingconstant
values for the calcuim sulfate interaction parameters: ~.so"
~.so" l3l?~so" aa,so" and"'N a,o.so, by introducing a CaSO~(aq) ion
pair which increases in strength with temperature. To avoid redun-
dancy problems between ~.so, and p.°/RT for CaSO~, the value of
~l.so, wasset equal to 3.0 (~l.so, = 3.1973in HARVIE et al. (1984).
The third virial coefficients, C~ a,so, and "'a.so,.ea, which were both
insensitive to the solubilitydata, were set equal to the 25°C-values
of HARVIE et al. (1984)(seeTables 1-2). J3l5l.so, was set equal to zero
(seediscussion below). Varyingthe standard chemicalpotentials (p.o/
RT) of the salts and the CaSO~ ion pair as well as ~.so, and
 Predictionof mineral solubilities 827

024 icalpotentials(J.l0 /RT) of the variouscalciumsulfatemineralsin the

model. Note that parameterizations of the gypsum, glauberite and
labilesalt standard chemical potentialsdo not extendto 250°C. Ex-
trapolation much beyond the temperature range listed in the table
.022 is not suggested. Extrapolating the glauberite chemical potential pa-
021 rameterization established from25°Cto 100°Cto higher temperatures
0205 results in inappropriately large amounts of glauberite precipitation
.020 above about 120°C. Therefore, the temperature variation of the
glauberite standard chemical potential above 100°C givenin Table
3 is used in the model to raise the chemical potential artificially in
order to increase glauberite solubility. This avoids the interference
018 ofglauberite precipitation in anhydritesolubility studiesat hightem-
perature. Additional measurements of stable and metastable gypsum,
glauberite and labile salt solubilities are necessary to model the be-
016
havior of these minerals in concentrated brines to 250°C. For the
metastable hemihydrate only solubility data in pure water (e.g.,
>- 015 D'ANS, 1933 and PARTRIDGE and WHITE, 1929), smoothed data
I-
:::; Table II were found to 250°C.
<t
-'
0 .014 In the following sections, the evaluationof the model parameters
::;;
relating to the calcium sulfate system isdiscussed from25°Cto 250°C.
013 Model calculations are also compared with the solubility data used
in the model parameterization from 25°C to 250°C.
012

011

.010 004,...---..----..---,---...,.-----,

009

008 o PW
o D'Ans
....>-
007 ::i

006
i 002

005 ~
70 100 125 o
0 25 50 001

TEMPERATURE (Oe) 0018,...---,---,---,---,----,

FiG. 3. A comparison of model calculations (solid lines)of pure

water solubilities of gypsum and anhydrite with experimental data x DBT
as a function of temperature from 25°C to 125°C. The model cal- .. BD
culationsof the pure water solubility of hemihydrateare compared I> BB
DOl
to the experimental data from 70°C to 125°C. The gypsum data I> 0 PW
(opencircles) are those of:BARBA et al. (1984), BLOCK and WATERS o TR
(1968), Bocx (1961), HILL and WILLS (1938), INNORTA et al.(1980), 0012 • Marshall
MADGIN and SWALES (1956), MARSHALL and SLUSHER (1966), ... Slroub (Linke r p6621
MARSHALL et at. (1964), and OSTROFF and METLER (1966). The
anhydrite data (closed circles) are those of: BLOUNT and DICKSON >-
.... 001
(1969), Bocx (1961), INNORTA et at. (1980), MADGIN and SWALES ...::i
(1956), MARSHALL et al. (1964), PARTRIDGE and WHITE (1929)and ...J
o
POSNJAK (1938). The hemihydrate data (crosses) are those of: Bocx "'0008
(1961), D'ANS (1933), MARSHALL et al. (1964) and PARTRIDGE and
WHITE (1929).
0006

0004
'ltNa.ea.SO. to fitthe calcium sulfate solubility data from 25°Cto 250°C,
indicated that ~so. and 'It~.so. could be held constant (.15 and
-.012, respectively) over the entire temperature range. A simplein- 0002 II!
verse linear relationship (solidline, Fig. 5) between temperatureand o
the ion pair standard chemical potential resultedin good (typically
within 10%) fits to the data sets from 25°C to 150°C. However, 250 275
above 150°C, the strength of the ion pair complex increased more
rapidlywithincreasing temperature(seeFig.5).For comparison, the
In K", values for CaSO~(aq) calculated by YEATTS and MARSHALL FiG. 4. Acomparison ofmodelcalculations (solid lines) ofanhydrite
(1969) as a function of temperature using solubility data in caSo4- and hemihydrate solubilities in pure water with experimental data
Na2S04-NaN03-H20 solutionsare alsoshownin Fig. 5 (dashedline). as a function of temperature from 150°Cto 250°C. The data refer-
Note that in the Na-Ca-CI-S04-H20 model described here, J.l°/RT ences are: BB = BOOTH and BIDWELL (1950); BD = BLOUNT and
(CaSO~) equals In K", since the standard chemical potentials of the DICKSON (1969); D'Ans = D'ANS (1933); DBT = DICKSON et al.
ions have been set equal to zero (seeabove). (1963); Marshall = MARSHALL et al. (1964); PW = PARTRIDGE and
Table3 indicates the temperature range of the solubility data (stable WHITE (1929); Straub = STRAUB (1932); TR = TEMPLETON and
and metastable) usedin establishing the values of the standardchem- ROOERS (1967).
828 N. M011er

TEMP ('CI the model generally falls belowthe majority of data values(seesolid
25 50 75 100 125 150 175 200 225 250 line in Fig. 3). However, the percentage disagreement between the
-30 model and experimentis low. At 25°C, the calculated value (.0148
m) of gypsum-Hjf) solubility is only 2.6% lower than the majority
-40 of measuredvalues(.0152 m).
* The optimal value(asterisk, Fig. 5) for the standard chemicalpo-
0- 50 -----.... - ........ tential (Jlo jRT) of the CaSO~(aq) complexis calculated to be -4.19
~
o~_60
(with j3g~,so. equal to zero)at 25°C. Note that u" jRT(CaSO~) equals
<3 In Kd (seediscussion above). This valuefor In ~ is lessnegative than
.... -70
values reported by other authors at 25°e. For example, this pKd
0;
Q::;

valueof 1.82comparesto 2.032for pKd determined by YEATTS and

~-80
-90
-tOO
0030 0025
I/'K
FIG. 5. The variation of the standard chemical potential (JlOjRT)
for the CaSO~ complex species with the reciprocal of temperature
(degrees Kelvin) calculated by the present model (solidline) and by
YEATTS and MARSHALL (1969)(dashedline).The asterisk indicates
the optimal value (seetext) of this standard chemical potential cal-
culated at 25°e.
1I1-7a) Evaluation at 25°C
Smoothedsolubility data in the Na-Ca-CI-S04-H20 system, gen-
erated usingthe HARVIE et al. (1984)parameters, were used in par-
ameterizing the modelat 25°C. At 25°C, our previousmodels(HAR-
VIE and WEARE, 1980; HARVIE et al., 1984) demonstrated that a
CaSO~ ion pair was not required for accurate modeling. However,
note that a negative I3&so. accounted for the observed negative de-
viation from the limiting law in these models. Use of a negative
l3ru.so. (with or without a caSo~ ion pair) gives the best fit to the
verydilute gypsum solubility data below 50°C. Therefore, the final
model equations include the CaSO~ ion complex species as wellas
negative j3g~.so. values (seeTable I) below50°e.
Using the model described in Tables 1-3, halite, thenardite, an-
hydrite, gypsum, g1auberite and labile salt generated solubilities in
the Na-Ca-C1-S04-H20 system at 25°C are fit within less than 5%.
The sigmas for these fits are: .0109, .0083, .0284, .0569, .0251 and
.0333,respectively. The solubility of gypsum in water calculated by
MARSHALL (1969) (dashed line, Fig. 5) from solubility data in the
CaS04-Na2S04-NaN03-H20 system. (See YEATTS and MARSHALL,
1969, for a description of other reported p~ values.) Note that the
negative (f2) values included in the model below 50°C account for
some additional association. Valuesof pKd are always a function of
the model. It has been our experience that accurate valuesof pKd in
this rangeare difficult to obtain from solubility data (HARVIE, 1981).
llI-7b) Evaluation at 35°C
At 35°C, the sodium-rich, common ion data of HILL and WILLS
(1938) and MADGIN and SWALES (1956)were used to parameterize
the model. The Hill and Wills data with the double salt,
5CaS04. Na2S04 •3H20, were not included because of the scarcity
and scatterof the available data at varioustemperatures. The model
isin excellent agreement withthe Hill and Willsdata for halite,then-
ardite, gypsum and g1auberite solubilities (0' = .0118, 0' = .0632, 0'
= .0402 and 0' = .0551, respectively). The fit to the Hill and Wills
labile salt data is also within 15% (0' = .1324). The Madgin and
Swales gypsum data set was fit with a sigmaof .0795. MADGIN and
SWALES (1956) also report anhydrite and gypsum solubility data at
25°e. The model agreement with these data, which were not used
in the model parameterization, is: O'anh = .2123 and O'gyp = .0173.
llI-7e) Evaluation at 40°C
The NaCl-Na2S04-CaS04-H20 data of BLOCK and WATERS (1968),
the NaCI-CaS04-H20 data of MARSHALL et al. (1964;68 hr. points)
and MARSHALL and SLUSHER (1966) and the Na2S04-CaS04-H20
data of BARBA et al. (1984)were used in parameterizing the model
at 40°e. The model'scalculationof halite,thenardite,g1auberite and
labilesalt solubility in these aqueous solutionscomparesto the data
withsigmas of .0355, .0637, .1506 and .1239, respectively. The sigmas
for the fitsto the gypsumsolubility data of BARBA et al., BLOCK and
WATERS, MARSHALL et al., and MARSHALL and SLUSHER are: .0346,
.0534,.0650 and .0650, respectively.

Table 3. Valuesof the fitting constants L (Eq. (11-13» for the standardchemicalpotentials (if) as a function of temperature(OK) b..

Parameters Constants
a a? a. a. a~ lit; a7
K,. (2S0-2S0OC) 1.0403113Od03 4.860928S1d-Ol -3.262243S2d04 -1.90877133d02 -S.3S2048SOd-Ol -2.32009393d-04 S.20S49183dOI
Halite (2S0 -2S00C) S,47825646d03 2.60407906dOO -1.31078912dOS -1.00232512d03 3.5S4S2179dOI -1.l6346S18d-03 7.21138559d02
Thenarditc(25°-250"C) -S.12ISS332d03 -~617S19SOdOO 1.1422S946dOS 9.50777893Od02 -~88441000dOO 1.19461496d-03 -1.907S9987d03
Mirabilite(25°-32°C) -S.7S709707d02 8,40961924d-Ol O. O. O. O. O.
Anhydrite(250-250"C) 3.9383771Od02 -4.30644041d-Ol -3.02S20897d04 -3.60047281dOl S.283SS203dOl 3.96964291d-04 -2.l2549985d03
Hemihydrate(25°-250"C) -2.20114425d03 -1.647S3737dOO 2.9691189Sd04 4.37226849d02 2.376106S2dOI 9.3043S4S2d-04 -2.50170197d03
Gypsum (25°-IIOOC) 1.3S486062d03 2.268779SSd-Ol -6.07006342d04 -2.27071423d02 O. O. O.
Glauberite(25°-1OOOC) z,72477417d04 -2.9S491928dOl -1.4723427Sd06 -2.70490647d03 S.02823869d02 4.80848099d-02 -9.l2078602d05
Glauberite" (IOOOC-2S0°C) -4.8250S7d03 -1.184927dOO 1.477336dOS 8.200287d02 O. O. O.
Labile Salt (25°-7S°C) S.18724792d03 -2.44078217dOI -8.2625S863dOS 4.68697S4Od02 S.38646IS3d02 2.36032300d-02 O.
CaS04'(aq)(25°-ISO"C) -1.4747774SdOI O. 3.26409496<103 O. O. O. O.
CaS04'(aq) (ISO"-2S0OC) 7.16726968dOI -1.0398963Od-01 -1.46847796d04 O. O. O. O.

a. The constant lisin Eq.(II-13)is equal to zero for all the abovepotentials.
b. The temperaturerange listed with each parameterindicatesthe temperatures wherethe associatedconstants(at-Ii?) are to be used.
c. Above about 120OC, Eq. (11-13) and constants a1 - ~ are used in the model only to artificially destabilize the glauberite potential in order to prevent
glauberiteprecipitation(see sectionill-7a).
 Prediction of mineral solubilities
III-7d) Evaluation at 50 0 e
Figures 6a, b show the model's agreementwith the solubility data
at 50°e. The data used in the model's parameterizationat this tem-
perature were those of OSTROFF and METLER (1966) (see triangles
in Fig. 6a) and HILL and WILLS (1938), with the exception of their
5CaS04' Na2S04' 3H20 data (seeFig.6b). The valuesfor the glaub-
erite-thenardite and glauberite-gypsum coexistence points of BARRE
(1911)werealso used in the fit. The sigmavaluesfor the fitsto these
thenardite, gypsum, anhydrite, glauberite and labile salt data are:
.0929,.0604,.0372,.0938and .1295,respectively. BOCK (1961)also
reported data for the solubility of gypsum(Fig. 6a, open circles) and
anhydrite(Fig. 6a, crosses) in aqueous NaCIsolutionsat 50°e. These
data (lTanh = .2076; lTgyp = .1295) were not used to parameterizethe
model.The data of BOCK (1961)forgypsumand anhydritesolubility
in aqueous NaCl solutions below 50nC were generally inconsistent
with the data used in the model parameterization (see above). At
40°C, the model's fit to these data is lTanh = .1869 and lTgyp = .1305.
At 25°C, the sigma valuesfor the fitsto their anhydrite and gypsum
data are .1591 and .0770, respectively. Figure6b showsthe excellent
agreement of the model with the complexsolubilitydata in the Na-
Ca-CI-S04-H20 system at 50°C of Hill and Wills.
III-7e) Evaluation at 55°e
The data of BLOCK and WATERS (1968) for the NaCI-Na2S04-
CaS04-H20systemat 55°C, whichincludesthenardite, gypsumand
glauberitesolid phases,were used in parameterizing the model. The
sigmasfor the finalmodel's agreementwith thesedata are: IT = .0675
for thenardite solubility, IT = .1090 for glauberite solubility and IT
= .0579 for gypsumsolubility. The Russian data reference (BUKSH-
TEIN et al., 1953) gives smoothed data summarizingvariousdata sets
for gypsum solubility in aqueous NaCl solutions. The model agrees
with these data with IT = .0537.
III-7f) Evaluation at 70° e
The common ion data of BLOCK and WATERS (1968) at 70°C
includes data for the doublesalt,5CaS04· Na2S04'3H20, in addition
to gypsum, glauberite and thenardite solid phase data. Their data,
without the 5CaS04' Na2S04 . 3H20 salt, as well as NaCI-CaS04-
H20 data with gypsum as the solid phase (OSTROFF and METLER,
1966; MARSHALL and SLUSHER, 1966) were used to parameterize
the model at 70°e. The agreement with the data is excellent. The
sigmas for the fit to the thenardite, gypsum and glauberitedata sets
are .0614, .0503 and .0867, respectively.
III-7g) Evaluation at 75°e
The HILL and WILLS (1938)data for the Na2S04-CaS04-H20 sys-
tem (with the exceptionof the data for the 5CaS04' Na2S04' 3H20
solid phase)were used to parameterizethe model at 75°e. The data
sets for thenardite, gypsum,glauberiteand labile salt solubilities are
<5
en
8 BLOCK and WAtERS (1968) and BLOUNT and DICKSON (1969) for
E anhydritesolubility in aqueous NaClsolutionsat lOO·C is significant
002
TEMPERATURE ; 50·C
OOt
00 2 3 4 5 6 (1964) anhydrite solubilities (Fig. 7a, triangles) are about 30.8% higher
mNaCI
FIa. 6a.Acomparison of modelcalculations (solid lines) ofgypsum,
anhydrite and halitesolubilities in CaSO.-NaCl-H 20 solutions at 50°C
with experimentaldata (seetext).
829
TEMPERATURE; 50·C
003
o
~'¢ 002
<3
E
o
FIa. 6b.Acomparison ofmodelcalculations (solid lines) ofgypsum,
anhydrite,glauberite, labilesalt and thenardite solubilities in CaS04'
Na2S04-H20 solutionsat 50°C with experimentaldata (seetext).
fit by the model with sigmas of .0856, .0566, .0443 and .0864, re-
spectively. The anhydrite data could also be fit wellisothermally (IT
= .0851). However, establishing the smooth temperature variation
for the anhydrite standard chemical potential given in Table 3, in-
creases the sigmafor the fit to the anhydrite data to .1568.
III-7h) Evaluation at 80°C
At 80°C,MARSHALL and SLUSHER (1966) reportgypsum solubility
data in the NaCI-CaS04·H20 system. The model agrees well with
thesedata, whichwereusedin parameterizing the model (IT = .0279).
III-7i) Evaluation at 85°e
At 85°C, the solubility data of BLOCK and WATERS (1968) with
thenardite, gypsum and glauberiteas the solid phases were used to
parameterize the model. The sigmas for the fit to the data sets for
thenardite, glauberite and gypsumare low (IT = .0348, IT = .0996and
IT = .0370, respectively). Their data for the anhydrite solid phase
exhibitconsiderable scatter. The fit to these data, which has a sigma
of .2307, lies within the spread of the experimentalmeasurements.
III-7)) Evaluation at 95°e
At 95°C, the data of MARSHALL and SLUSHER (1966)for [NaCl]
,,; 2.043 m are in good agreement with the model's prediction (IT
= .0328). However, the model's agreement with the Marshall and
Slusherdata over the entire concentration range (to [NaCI] = 5.16
m) is considerably poorer (sigma equals .4268). MARSHALL and
SLUSHER (1966)report in a footnotethat the data for concentrations
of NaCIabove 2.043 m are for solutionssaturated with gypsumand
a double salt ofCaS04 and Na2S04. Moreover, they state that at the
highest molalities NaCI(s) is also present. Note that below95°C, the
model is in good agreement with the data of Marshall and Slusher
over the entire concentration range.
III-7k) Evaluation at lOOoe
The variation in the measured valuesof MARSHALL et al. (1964),
(see Fig. 7a). The pure water solubilityvalue of anhydrite (see Fig.
3) reportedby MSJand by BD(.00553 m and .00535 m, respectively)
are in good agreement. The .0131 m pure water value reported by
Block and Waters appears in error (Fig. 3). The MARSHALL et al.
than the valuesof BLOUNT and DICKSON (1969)(Fig. 7a, crosses) in
I.m NaCI solutions and about 21.5% higher in 4. m NaCl. The an-
hydrite solubilities of BLOCK and WATERS (1968)(Fig. 7a, open cir-
cles)are betweenthe BLOUNT and DICKSON (1969)and MARSHALL
et al (1964) valuesabove NaCI = I. m.
830 N. Meller

a. and allowing p.°/RT (anhydrite) to vary, the linear dependence of

P.0 /RT for CaSO~(aq) with I/T (degrees Kelvin) used from 25°C to
Ii
005 HEMIHYDRATE
Ii 100°C (see Table 3 and Fig. 5) can be retained and the solubility
data of BLOUNT and DICKSON at 150°Cfit within 10%. The solubility
data of MARSHALL et al. at 150°C cannot be fit within 15% unless
004
",,~---.:r-~~~~---- the CaS04-H20 point of BLOUNT and DICKSON (1969)is substituted
Ii for their point; or, unless both In Kd (CaSO~(aq» and p.°/RT (an-
c5
(/) 003 "
x ,p 0 hydrite)are allowed to vary. The resultingvalue for In ~ is consid-
0
<..> ANHYDRITE erably less negative than the valuepredicted bythe linear I/T variation
E
002 (see Fig. 5). Since the value of p.°/RT for CaSO~(aq) is not wellde-
TEMPERATURE ' 100·C termined by the data in CaS04-NaCI-H20, it was decided to keep
001 the linearvariation between p.°/RTand I/T(OK) in the presentmodel
and to weight the BLOUNT and DICKSON (1969)data more heavily
0 than the MARSHALL et al. (1964)data.
0 2 3 4 5 6 The agreement with the BLOUNT and DICKSON (1969)data set is
mNoCI very good (u = .0893). The choice of P.0 /RT (anhydrite), resulting
from the weighting scheme selected, caused a larger sigma for the
FIG. 7a. A comparison of model calculations (solid lines) of an-
hydrite and hemihydrate solubilities in CaS04-NaCI-H20 solutions
at 100°C with experimental data (seetext). The dashed line is pre- b.
dicted by EQ3/6. Note that the agreementof the EQ3/6 calculations
0010
with the data in NaCI-CaS04 aqueous solutionsis atypically goodat
100°C(seediscussion in section III).
0008

Varying p.°/RT for anhydrite, each of the above data sets can be ;%'0006
fit well separately. However, since the data sets differ significantly
from one another, the resulting values for the anhydrite standard <3
E
chemical potential also differ. An intermediate value was selected
whichyielded a goodfit to the Na2S04-CaS04-H20 data. This results
in a model(Table3) whichagrees verywell(Fig. 7a; a = .0773)with 0002
the Block and Waters anhydrite data (using the Marshall et al. CaSo4-
H20 point). This model fits the MARSHALL et al. (1964)anhydrite 0
0 04 08 12 16 20 24 28
data with a sigma of .1547 and BLOUNT and DICKSON (1969) an-
hydrite data witha sigma of .1913. At 4. m NaO, the modelcalculates mNo2S04
anhydrite solubilities about 9% higher than the BLOUNT and DICKSON c.
(1969) valueand about II %lowerthan the MARSHALL et al. (1964)
value (Fig. 7a). Therefore, these model calculations are well within
0.024 TEMPERATURE ' 1000C
the spread of the data (see Fig. 7a). Using the p.°/RTvalues for he-
mihydratedescribed in Table 3, the modelfitsthe NaCI-CaS04-H20 NoCI-lm
0.020
data at 100°Cwith hemihydrateas the solidphase of MARSHALL et
al. (1964)with an overallsigmaof .1161 (seeFig. 7a, triangles). c5 0.016
The agreementof the model and the BLOCK and WATERS (1968) (/)
0
common ion Na2S04-CaS04-H20 data with and without NaCI is <..> 0012
E
verygood(seeFigs. 7b-d). Calculated glauberite solubilities compare
with the experimental data with a sigmaof .0787.(The sigmafor the
anhydrite data has been givenabove.)
Predictions of anhydrite solubilities in aqueous NaCI solutions 0004
and in aqueous Na2S04 solutionsat 100°Cby EQ3/6 (seesectionI) 0
are shown by the dashed lines in Fig. 7a and 7b, respectively. The 0 04 08 1.2 1.6 2.0
agreementwith the NaCIsolutiondata at 100°Cshouldnot be taken mNo 2S04
as indicative of EQ3/6's agreement with data in this system at all
temperatures. The agreement is best at 100°C because of the tem- d.
peraturedependence of the EQ3/6parameterization forCaS04-NaO-
H20 solutions. It is important to note that below and above this 003 TEMPERATURE - iOOOC
temperature the difference betweenEQ3/6 calculatedvaluesand the Noel '4m
NaCI-CaS04-H20 experimental data increases significantly (e.g.. see
Fig. 8a). The agreement of EQ3/6 calculations and experiment in
the sulfate-rich solutions is poor over the entire temperature range c5
(/)
(e.g.• Fig. 7b). The addition ofNaO to the Na2S04-CaS04-H20 so- 0
<..>
lutions does not improve the agreement. For example, at 100°C in E
the common ion system withoutNaO, EQ3/6calculates an anhydrite
solubility only about 55% of the experimental valueat 0.5 m Na2S04
(seeFig. 7b). With the addition of 1. m NaCI, the EQ3/6 value (not
shown) is about 53% of the experimental value at 0.5 m Na2S04,
whereas the present model calculates a value about 97% of the ex- 02 0.4 0.6 08
perimental value (see Fig. 7c).
mNo 2S04
III-7l) Evaluation at i50°C
FIG. 7b-d. A comparison of model calculations (solid lines) of
At 150°C, the data of MARSHALL et al. (1964) and of BLOUNT anhydrite, glaubertie and thenardite solubilities in CaS04-NaCI-
and DICKSON (1969)in the NaCI-CaS04-H20 systemwere used to Na2S04-H20 solutions at 100°C with experimental data (see text).
parameterize the model since appropriate common ion data were (7b): NaO = O. m; (7c): NaCI = 1. m; (7d):NaCI = 4. m. The dashed
not found. Usingthe parameterization schemedescribed in Table I line is predictedby EQ3/6 (seediscussion in section III).
 Prediction of mineral solubilities
model'sfitto the MARSHALL et al. data (u = .2121). The MARSHALL
et al. valuesfor anhydrite solubility are higherthan those calculated
by the model (12.5% at I. m NaCl and 24.4% at 6. m NaCl). Figure
4 illustrates the significant variation in the reportedanhydritesolubility
data in water taken at or near the vapor pressure curve from 150°C
to 250°C. Minimum and maximum solubilities at 150°C differ by
23.1 %. The model calculationof anhydrite solubility in water (solid
line) is compared to the data in Fig. 4.
III-7m) Evaluation at 200°C
Common ion data at 200°C also were not found. Since solubility
data in common ion ternary systems are very important for para-
meterizing the Ca,S04binaryinteractions, it wasdecided to interpolate
data at 200°C usingSTRAUB'S (1932)valuesfor anhydrite solubility
in the common ion system, CaS04-Na2S04-H20, at 182°C, 207°C,
244°C and 316°C. These interpolated data were used along with
those of MARSHALL et al. (1964)and BLOUNT and DICKSON (1969)
in the NaCI-CaS04-H20 systemto parameterizethe modelat 200°C.
Using the resultingtemperature-dependent equations (Tables 1-3),
the model fits the anhydrite solubilitydata in aqueous NaCl (MAR.
SHALL et al. (1964)and BLOUNT and DICKSON (1969), Fig. 8a) with
a sigmaof .1328.
The model (Figs. 8a, b) agrees wellwith the CaS04-H20 point of
BLOUNT and DICKSON (1969) (2.6% higher) whereas, the MARSHALL
etal. and interpolated StraubCaS04-H20 pointsare fitless well (11.6%
and 8% higher, respectively). At this temperature, the BLOUNT and
DICKSON (1969)point is similarto several other reported values(see
Fig. 4). Note that maximum and minimum pure water anhydrite
solubilities differ by 28.% at 200°C (Fig. 4). Above I. m NaCl, the
model fits the BLOUNT and DICKSON (1969) data (Fig. 8a, crosses)
with sigmalessthan .06; the total data set has a sigmaof .1062. The
MARSHALL et al. data (Fig. 8a, open circles) are fit with a sigma of
.1984, the model agreeing well (u ,,; .10) with their .0I, .03, 2. and
3. m NaCl points. The model calculationsof anhydrite solubility in
the common ion system, CaS04-Na2S04-H20, at 200°C compares
with the interpolated data of Straub (Fig. 8b) with a sigmaof .0524.
The dashedline shownin Fig.8a represents the anhydrite solubilities
in aqueous NaCl solutions predicted at 200°C by EQ3/6 (see dis-
cussionabove).
III-7n) Evaluation at 250°C
At 250°C, in addition to the measurementsof BLOUNT and DICK-
SON (1969) (Fig. 9, crosses) in the CaS04-NaCl-H20 system, there
are the anhydrite solubility data of TEMPLETON and ROGERS (1967)
for the CaCh and Na2S04 common ion systemsand for the NaCI
system(Fig. 9, triangles) as wellas the interpolatedpoints of STRAUB
(1932,see above)for the Na2S04-CaS04-H20 system. The variation
of anhydritesolubility with NaCIconcentration forboth the BLOUNT
and DICKSON (1969)and TEMPLETON and ROGERS (1967)data sets
0016
~ 0012
en
o
u en
E 0008
2 6 8
FIG. 8a.Acomparison of modelcalculations (solid line)ofanhydrite
solubility in CaS04-NaCl-H20 solutionsat 200°C with experimental
data (seetext). The dashedline is predictedby EQ3/6 (seediscussion
in section III).
831
6 TEMPERATURE' 2000C
5
- 4~
....0
0<1'
en
u
0 3
ANHYDRITE
000
E
2
o0L......'-:0-:!07'04:'"""70.J.:00-8.......".00:t-:-12"..-.'--0""'.0!-;-;16..........0~02.0
mNo 2S04
FIG. 8b. A comparison of model calculations (solid line) of an-
hydrite solubility in CaS04-Na2S04-H20 solutions at 200°C with
interpolated experimentaldata (seetext).
is similar, although the percentage difference between the two data
setsis significant. For example, at 0.5 m NaCIthe anhydritesolubility
of BLOUNT and DICKSON (1969) is about 30% less than the TEM·
PLETON and ROGERS (1967)value.There is a considerable spreadin
the purewateranhydritesolubility data takenat 250°Cor extrapolated
to this temperature (seeFig.4). The maximum and minimum values
differby 85.1%.
The TEMPLETON and ROGERS Na2S04-CaS04-H20 data could not
be fit well, (having sigmas> .3), using a variety of data weighting
schemesas wellas adjusting many model parameters. However, the
interpolatedNa2S04-CaS04-H20 data of STRAUB (1932)could be fit
along with the NaCl·CaS04-H20 data of BLOUNT and DICKSON
(1969) and the NaCl-CaS04-H20 ofTEMPLETON and ROGERS (1967)
(~.3 m NaCl). Using the standard chemical potentials describedby
Table 3, the TEMPLETON and ROGERS (1967) NaCl-CaS04-H20 data,
which were more heavily weighted (~0.3 m NaCl), were fit by the
model(Fig. 9) witha sigmaof .0691. Withthe omission of the CaSo 4-
H20 point, the BLOUNT and DICKSON (1969) data are fit with a
sigmaof .195.At0.5 m NaCl,the modelcalculates anhydritesolubility
about midway between the value of BLOUNT and DICKSON (1969)
(modelis about 17% higher)and the valueof TEMPLETON and ROG-
ERS (1967)(modelis about 19% lower). Asshownin Fig.4, the model
calculation(solidline)of anhydrite solubility in pure water (.000262
m) falls about in the middle of the experimental values. The final
modelagrees withthe interpolated Straubcommon ion data at 250°C
(not shown)with a sigmaequal to .0554.
Solubilities predictedby the modelin the NaCI-CaCh-CaS04-H20
systemagree with those of TEMPLETON and ROGERS (1967) with a
sigma of .1505. Note that these data were not used in the parame-
terization of the model. When the replicate points and the single
0020 x
TEMPERATURE'
250·C
0.016
~
)'
0<1' 0.012
u
0
E 0008
0.004
0 2 4 6 8
mNoCI
FIG. 9. A comparison of modelcalculations (solid line)of anhydrite
solubility in CaS04-NaCl-H20 solutionsat 250°C withexperimental
data (seetext).
832
highlydivergentpoint (CaS04 solubilityin .0333 m CaCh) of TEM-
PLETON and ROGERS (1967)are removed, the model's predictedsol-
ubilities agree well with the TEMPLETON and ROGERS (1967) data
(0- = .1099).
Comparisons with data more complicated than the binary and
ternary data used in the model's parameterization help to evaluate
the reliability of the model's predictions. They also help to assess the
applicability to natural waters. Some predictionsof the model in the
NaCI-Na2S04-CaS04-H20 and NaCl-CaClrCaS04-H20 systems have
been discussed in this section.Further model validation is presented
by the applicationsof the model described in the following section.
IV. TESTING AND APPLICATIONS OF THE MODEL
Phase diagrams for equilibria involving the CaS04-bearing
minerals are difficult to determine experimentally because of
the relatively low solubility and reactivity of these minerals.
At 25°C (1 atm. pressure), the phase relations in the 6-com-
ponent system, Na-K-Mg-Ca-CI-S04-H20, and its various
5-, 4-, and 3-component subsystems have been calculated
(HARVIE et al., 1982; see also EUGSTER et al., 1980). For the
quaternary system, Na-Ca-CI-S04-H20, at equilibrium (T,
P) there coexists a maximum of three solids and solution.
Because of the low gypsum solubility, the gypsum field dom-
inates the 25°C reciprocal diagram with solution composi-
tions projected from the H 20 comer (see HARVIE et al., 1982).
The invariant solutions, saturated with various combinations
of antarcticite (CaClz' 6H 20), halite, gypsum, anhydrite,
glauberite, thenardite and mirabilite (Na2S04' IOH20), are
located close to the ternary sidelines because of the large dif-
ferences between the mineral solubilities.
GROMOVA (1960) has reported solubility data for the so-
lutions: NaCI-Na2S04-CaS04-H20 and NaCi-CaClz-CaS04-
H 20 at 110°C. For comparison with these data, which were
not used in the model parameterization, the algorithm of
GI 2
.996 994 .9 0 Figure lOa expands the "Na" side of the reciprocal diagram
'tfl:
I I !
(
l92
HA 1
9 HAGI
.1-
'; HThGI
2 "Ca" sideline has been expanded in Fig. lOb.
x .4
GI
4 6
.2 x .8
o GIA
.004 .008
504
FIG. lOa. Model calculations (solid lines) are compared with the
data ofGROMOVA (1960)(crosses) for the Na-rich side of the recip-
rocal diagram for the quarternary system, Na-Ca-Cl-S04-H20, at
110°C. (See also Table 4.) In this diagram, solution compositions
are projected from the H20 corner and the arrows point in the di-
rection of decreasing OH,o concentration. The invariant points cal-
culated by the model (#2-#6) and the halite-anhydrite univariant
point of maximum water activity(OH,O) (#1) are shownby the closed
circles.
N. Meller
CI2
1 8 2 0
H ---ll--
x .... 7,8,9
998 r
x 002
996 A
004 Co
N02
994 T=100 oC 006
t(HA)
992 008
0 2 8
FIG. lOb. Model calculations (solid line) are compared with the
data (crosses) ofGROMOVA (1960) for the Ca-richsideofthe reciprocal
diagram of the quarternary system, Na-Ca-Cl-S04-H20, at 110°C.
In this diagram, solution compositions are projected from the H20
comer,and the arrowspoint in the directionof decreasing OH,O values.
The model calculationsare carried out to an ionic strength of about
18. m (see text for the concentration limit of the model parameter-
ization in this system). Point #1 is the halite-anhydrite univariant
point shownin Fig. lOa. Crosses #7, #8 and #9 are the halite-calcium
chloride dihydrate, halite-anhydrite-calcium chloride dihydrate and
and anhydrite-calcium chloride dihydrate invariant points, respec-
tively, at 110°C calculated from the Gromova data.
HARVIE et al. (1987) was used to calculate the equilibrium
configuration at 110°C of the NaCl-Na2S04-CaS04-H20 and
NaCI-CaClz-CaS04H20 quaternary systems as functions of
concentration. At 110°C, the anhydrite field dominates the
reciprocal diagram and mirabilite and antarcticite no longer
appear on the diagram. The relatively low solubility of an-
hydrite causes the invariant points for the NaCI-NazS04-
CaS04-H20 system to be located close to the "Na" sideline.
in order to more clearly distinguish these points. The very
high solubility of calcium chloride dihydrate results in its
field lying very close to the CaClz comer ofthe diagram. The
In Figs. lOa, b the Gromova data (crosses) have been com-
pared to the model calculations (solid lines). In these figures,
Co the closed circles indicate the calculated compositions of the
invariant solutions for the stable equilibria (#2-#9), and for
the univariant point (#1) in the Na-Ca-Cl-S04 reciprocal sys-
tem at 110°C, projected from H 20. Note that the halite-
thenardite-glauberite (HThGI) invariant point (#3) is a "eu-
tectic". The arrows in these figures indicate the direction of
increasing concentration by pointing to lower values of
aH,O' The invariant mineral assemblages and solutions cor-
responding to the points (closed circles) given in Fig. lOa are
listed in Table 4 along with the values for the activity ofwater
(aH,O)' The experimental data are given in parentheses in
Table 4. Figure lOa and Table 4 show that the agreement
between the experimental data and the calculated values is
very good (comparable to that found in reciprocal diagrams
calculated with the HARVIE et al., 1984, model). Note that
this agreement represents predictions of the model since the
Gromova data were not used in the model parameterization.
 Prediction of mineral solubilities 833

Table 4. Invariant PointsL for the Quarternary System, NaC- resulting solution has an ionic strength (.67) as well as Ca'"
NazSOCCaS04-HzO at IIO"C. (Experimental valuesb . are given in and S04- molalities similar to those of seawater.
parentheses)
At 25°C, both the present model and the HARVIE and
Solution Composition WEARE (1980) and HARVIE et al. (1984) models predict the
Point Solid Phases a1\o
mN, me. rna mso same evaporation mineral sequence when the same 4-com-
I" 6.734 .0259 6.734 .0259 H,A .7413 ponent "seawater" (Na-Ca-Cl-S04-H20) composition is used.
2 6.930 .00637 6.664 .1391 H,A,Gl .7401 However, the omission of key seawater components alters
(6.934) (.00590) (6.716) (.1150) this 25°C evaporation sequence from that observed at 25°C
3 7.381 .00121 6.509 .4374 H,Th,G1 .7364 for the 6-component seawater system (HARVIE and WEARE,
4 7.382 .0 6.590 .4366 H,Th .7365
(7.614)
1980) and for the full seawater and carbonate system (HARVIE
(.0) (6.586) (.5143)
5 5.976 .00371 .0 2.992 Th,Gl .9040 et al., 1984). For example, with the 4-component "seawater",
(5.838) (.00312) (.0) (2.922) halite appears in the evaporation path after glauberite (aH20
6 3.292 .00794 .0 1.654 A,Gl .9445 '= .749) instead of before glauberite as in the 6-component
(2.586) (.00835) (.0) (1.301) model.
At lOO°C, gypsum is metastable relative to anhydrite and
a. Point no. 1 is a maximum in a1\Oalong the univariant line of halite-
therefore does not appear in the equilibrium evaporation
anhydritecoexistence.
mineral sequence. The "seawater" (Na-Ca-Cl-S04-H20) only
b. Gromova (1960). has to be concentrated by a factor of 1.22 at lOO°C before
anhydrite precipitates. If anhydrite is withheld in the calcu-
lations at lOO°C (simulating kinetic or other barriers to an-
The calculated univariant point (#1, Figs. lOa, b) is also hydrite precipitation), hemihydrate would appear at: e.F.
given in Table 4. This point is on the univariant line for (concentration factor) '= 2.98, aH20 '= .940 and I '= 1.97.
halite and anhydrite coexistence and is a point where there LANGELIER et al. (1950), in their research on scale control
is a maximum in aH20. At this point, mea '= mso. in the in distillation equipment, studied the solubilities of anhydrite
halite-anhydrite saturated solution. The role of such points and hemihydrate in concentrated seawater brines at lOO°e.
in controlling the eventual solution composition and mineral Their results, which indicated a concentration factor of about
assemblage occurring as a result of brine concentration is 1.5 for anhydrite precipitation and of about 3.05 for hemihy-
discussed for the 6-component (Na-K-Ca-Mg-Cl-S04-HzO) drate precipitation are in very good agreement with those of
seawater system at 25°C in HARVIE et al. (1982). the present model at 100°e. If both anhydrite and hemihy-
The concentration path from the halite-anhydrite point drate are withheld in the model calculations at 100°C, gypsum
(HA, # 1) to the CaCh' 2H 20 region is shown in Fig. lOb. would appear at: CF. = 3.16; aH20 = .936 and I
Using the Gromova data, the ionic strength of the solution = 2.09.
at the halite-anhydrite-calcium chloride dihydrate invariant If the unconcentrated "seawater" medium is "heated"
point (see #8 in Fig. lOb) is about 43. m. The present model, (brought to equilibrium at increasing temperatures), anhydrite
based on a third virial coefficient expansion ofthe free energy would first precipitate at lO8°e. Disallowing the precipitation
expression, does not extend to these high ionic strengths. of anhydrite results in the precipitation of hemihydrate at
Moreover, the NaCI-CaCh-H 20 system was parameterized 144°e. (Gypsum was not parameterized to sufficiently high
by data having maximum CaCh concentrations of about 5. temperatures to calculate at what temperature it would pre-
m (l '= 15. m) (see above). Therefore in Fig. lOb, the solid cipitate.)
line representing model predictions extends to I - 18. m. The present model has been used to calculate the temper-
The agreement with the Gromova data to this concentration ature of gypsum-anhydrite coexistence as a function of the
is excellent. In Fig. lOb, the halite-calcium chloride dihydrate activity of water and ionic strength in CaS04-NaCI-H20 so-
(#7), the halite-anhydrite-calcium chloride dihydrate (#8) and lutions (Fig. 11). For pure solid phases, the gypsum-anhydrite
the anhydrite-calcium chloride dihydrate (#9) invariant points equilibrium at atmospheric pressure is dependent on tem-
at llOoC are from the Gromova data. perature and aH20. In these calculations, NaCI was added to
Gypsum and/or anhydrite are common marine evaporite gypsum-saturated solutions to vary aH20 and the ionic
facies. Therefore, their thermodynamic behavior in NaCl- strength. In Fig. 11, the aH20 vs. transition temperature curve
rich brines has considerable geological importance. The calculated with the present model (solid line) consistently
chemistry of brines containing calcium sulfate can also be predicts higher aH20 values at specific transition temperatures
important to mineral recovery programs and in processes than does HARDIE (1967). On the other hand, the model
involving the manipulation of seawater-type brines at high curve predicts lower QH20 values than predictions based on
temperature. the solubility data of BOCK (1961) (see Fig. 6 in HARDIE,
The equilibrium evaporation mineral sequence at 25°C 1967). In the HARVIE et al. (1984) model, the gypsum stan-
and lOO°C for a 4-component "seawater" solution was cal- dard chemical potential is well-established to high ionic
culated with the present Na-Ca-Cl-S04-H20 solution model. strength using available solubility data (see HARVIE, 1981,
The composition of the "seawater" was derived from the and HARVIE and WEARE, 1980). The standard chemical po-
molal concentrations of seawater (salinity '= 35%0) given in tential of anhydrite was calculated in the HARVIE et al. 25°C
HARVIE (1981, Table 8). The HCO) and CO)- (X2) concen- model using this gypsum standard chemical potential and
trations were added to the Cl" molality and the K+ and Mg''" HARDIE'S (1967) determination of the activity of water at
(X2) concentrations were added to the Na" molality. The gypsum and anhydrite coexistence. Since the present model
834
IO,--------..,-----.------,--,-----;r-,-----,--------,
TEMP lOCI
FiG. II. The variation of the temperature of gypsum-anhydrite
coexistence with the activity of water (aH,O) in CaS04-NaCI-H20
solutions calculated by the present model (seetext; solid line). The
variation ofthe coexistence temperaturewithionicstrength (increas-
ing NaCl concentration) is also shown(dashed line).
uses data generated from the HARVIE et al. model in its pa-
rameterization at 25°C, the model calculations approach
Hardie's curve as the transition temperature decreases.
In pure water, the gypsum-anhydrite transition is calculated
by the present model to occur at 49°C (see the solid line in
Fig. 11; aH,O = 1.0). A gypsum-anhydrite coexistence tem-
perature of 49°C is lower than that calculated by several
workers; e.g., 63.5°e (VAN'T HOFF et al., 1903), 58°C ± 2°C
(HARDIE, 1967) and 55°C (BLOUNT and DICKSON, 1973). It
is higher than values generally calculated from solubility data.
For example, POSNJAK (1938), HILL and WILLS (1938),
MARSHALL and SLUSHER (1966) and BOCK (1961) all predict
values of about 42°C. In assessing the discrepancies of the
published gypsum and anhydrite solubility data below wooe,
HARDIE (1967) argued that since most solubility measure-
ments approached equilibrium only from the undersaturation
side, the transition temperature predicted from these data
would be a minimum value only. However, the model cal-
culation of 49°C for the gypsum-anhydrite coexistence tem-
perature in water is in excellent agreement with the value
(49.5°e ± 2'soC) calculated by INNORTA et al. (1980) from
their solubility measurements which approached equilibrium
both from undersaturated and supersaturated solutions. As
more NaCl is added to the solution, the temperature of gyp-
sum and anhydrite coexistence decreases (see dashed line,
Fig. II). The transition temperature would be 25°C for the
gypsum-saturated solution when sufficient NaCl is added to
reach an ionic strength of 5.45 m. Note that variations in the
specific composition of brines at the same ionic strength will
slightly alter the predicted transition temperature. For con-
centrated, 4-component "seawater," a transition temperature
of 25°C occurs at I = 5.72 m (arrow; Fig. II).
Models with variable temperature and concentration ca-
pability can be used to study the effects of changing temper-
ature on brine evaporation. HERRMANN et al. 's (1973) study
of salt pan brines (Secovlje, Yugoslavia) undergoing solar
evaporation has been used to illustrate such an application.
In this study, HERRMANN et al. sampled the major ion con-
centrations and the temperatures of the different salt pan
N. M0IIer
brines. Assuming that the chloride ion concentration is con-
servative to halite precipitation, the temperatures of these
salt pan brines are plotted as a function of brine evaporation
ratio (E.R.) in Fig. 12 (crosses). Those brines which were
sampled in the early morning and had much lower solution
temperatures were not included. Note that HERRMANN et af.
report a rise in the air temperature of only about one degree
(31.4 "C to 32.4 "C) during the sampling of the points given
in Fig. 12. Except for canal 12 (E.R. = 5.01) where turbulent
flow is reported, the brine temperatures reported by HERR-
MANN et al. increase with concentration, suggesting a solar
heating effect in this natural system. To simulate this effect,
the model was used to determine the equilibrium configu-
ration of the 4-component "seawater" system as water was
removed (evaporation) and the temperature was increased
simultaneously. A path (solid line, Fig. 12) was produced
which roughly approximates the temperature vs. brine con-
centration profile found in the salt works. The algorithm of
GREENBERG (pers. commun.) was used in these calculations.
In their report, HERRMANN et al. do not evaluate the pre-
cipitated solid phases. However, they report that the measured
calcium ion concentration in the salt works system increases
continuously to about pan II (E.R. = 3.84) (see circled point
in Fig. 12), suggesting the start of gypsum precipitation. The
arrow in Fig. 12 indicates the start of gypsum precipitation
in the simulation (E.R. = 3.28; T = 34.85°C). For "seawater"
evaporation simulated at 25°C (arrow at ordinate in Fig. 12),
gypsum precipitates at a similar evaporation ratio (E.R.
= 3.29). On the other hand, the brine composition at which
the gypsum-anhydrite transition takes place is strongly af-
fected by solar heating. In the 25°C isothermal evaporation
path this transition occurs at an evaporation ratio of 9.03
1O,-----------,----~----~
9 ANH
2 7
!«
c::
z 6
o
;:::
~ 5
oo,
...~ 4
GYP
30 35 40
TEMP rC)
FiG. 12. Usingthe data (X) of HERRMANN et af. (1973) from the
saltworks ofSecovlje (Yugoslavia), the solution temperature of brines
increasingly concentrated duringevaporation are plotted as a function
of temperature. A simulation (using the present CaS04(T) model)
of this natural evaporation process is shown by the solid line. The
arrows (GYP) indicate the start of gypsum precipitation predicted
byan isothermal evaporation at 25°Cand by the variable temperature
simulation. The arrows (ANH)indicatethe transition from gypsum
to anhydritepredicted at 25°C and by the variable temperaturesim-
ulation.The circled datum indicateswhere calciumis first shownto
be removed from solution in the salt works.
 Prediction of mineral solubilities
(see arrow at ordinate in Fig. 12); whereas in the solar heated
path the transition occurs at E.R. = 5.02. This implies that
in a natural evaporation system in which there is solar heating,
anhydrite should begin to replace gypsum at a much earlier
stage in the process than predicted by the 25°C models
(HARVIE and WEARE, 1980; HARVIE et al .. 1984).
V. MODEL OF BaS04 SOLUBILITY IN AQUEOUS NaCl
SOLUTIONS AT HIGH TEMPERATURE
The Weare solubility modeling approach requires careful
evaluation and validation of a large number of parameters
(similar to the number required by ion pairing models (HAR-
VIE and WEARE, 1980). At present this approach seems to
be the only one which can be used with confidence to model
solution behavior accurately above moderately dilute con-
centration. Since only a limited database exists for many sys-
tems, it is useful to investigate whether a validated parame-
terization of a well-characterized system can be successfully
transferred to other chemically similar systems.
BLOUNT (1977) measured barite (BaS04) solubility in
aqueous NaCl solutions from 100°C to 300°C and for pres-
sures of I bar and higher. To model the Na-Ba-CI-S04-H20
system at these high temperatures, would require the eval-
uation of binary and mixing parameters similar to those just
described for the Na-Ca-CI-S0 4-H20 system. Values of
11W~.S04' I3ill..S04' 13\l~.S04' eta.SO.' ONa,Ba, ""Na,Ba,Cl, ONa.Ba.SO. and
OCl,SO.,5o from 100°C to 250°C were assumed to be the same
as the corresponding calcium interaction parameter values
generated with the model described by Tables 1-2. A
BaSO~ ion pair which increased in strength with temperature
was introduced as in the calcium sulfate system. Its standard
chemical potential values from 100°C to 250°C were taken
to be the same as those for the CaSO~ ion pair generated by
the model (see Table 3). The Ba, Cl binary interaction pa-
rameter values were taken from the Ca, Cl values. A¢, the
Na,CI and Na,S04 binary parameter values and the mix-
ing parameter values for the NaCI-Na2S04-H20 system
were calculated at high temperature as described above
(Tables 1-2).
Using the above solution parameter values, the standard
chemical potential (/oL°/RT) for barite was evaluated at each
temperature by fitting the pure water BaS04-H20 solubility
points of BLOUNT (1977). The resulting /L°/RT values at
100°C, 150°C, 200°C and 250°C are: -22.0901, -22.4073,
-23.5356, and -25.0543, respectively. In these isothermal
fits, /Lo/RT for BaH was set equal to zero. The results of this
model for the BaS04-NaCI-H20 system (dashed lines) are
compared with the Blount data (crosses) from 100°C to
250°C in Fig. 13. The fit to the data is within approximately
20% from O. m to a little over 1. m NaCl.
To improve the agreement with the data at high concen-
tration ONa,5o was adjusted at each temperature to fit the single
BaS04 solubility point in 3. m NaCl using the previously
established values of /oL0 /RTfor BaSOis). The resulting values
of ONa.Ba at 100°C, 150°C, 200°C and 250°C are: -.0523,
- .0343, -.0269, and -.0217, respectively. This model is
compared with the Blount data at the different temperatures
in Fig. 13 (solid lines; lTlOO' = .049; lTlW = .056; lT200' = .138
and lT250' = .217). Therefore, using the parameter values for
the Na-Ca-CI-S0 4-H20 system and fitting two additional pa-
835
TEMPERATURE' TEMPERATURE' 150OC
100'C
/+
/,..,~-----------­
+
,/~
".
TEMPERATURE' 200'C TEMPERATURE' 250'C
12
/
+/ / / / ' / / /
+ ,.-'
4 //
+ -:,,/"
o
..
/
2 3
ffiNaCI
FIG. 13. The prediction of barite solubility in aqueous NaCI so-
lutionsat 100°C, 150°C, 200°Cand 250°C using parameters forthe
BaS04 system takenfrom the Na-Ca-CI-S04-H20(T) modeland:(I)
the chemical potential (/1°/RT) for baritedetermined from a single
BaS04-H20 point(dashed line) or (2)the chemical potential forbarite
determined in step 1 and ONa.Ra fit from the 3. m NaCI point (solid
line). The data (X) are thoseof BLOUNT (1977).
rameters specific for the BaS04 system (/oL0 /RT for BaS04(s)
and IJNa•Ba) with only two data points at each temperature
yields a model for barite solubility in aqueous NaCI solutions
which is in good agreement with the data to high concentra-
tion from 100°C to 250°C. Since this model was not devel-
oped by evaluating data in the common ion solutions (BaS04-
Na2S04-H20 and BaS04-BaCIz-H20), its reliability in pre-
dicting data in such systems is in question (see WEARE, 1987).
When these data, which are particularly important for eval-
uating the strength of the ion complex association, are avail-
able a reliable model ofthe entire Na-Ba-CI-S0 4-H20 system
can be developed.
VI. SUMMARY
The variable temperature model for the Na-Ca-Cl-S04-
H 20 system presented in this article calculates solubilities
from zero to high concentration (I - 18. m) within experi-
mental uncertainty over the 25°C to 250°C temperature
range for which it was parameterized. Generally, this uncer-
tainty is less than 15%. For well-characterized systems with
few discrepancies in the data, the disagreement of the model
and experiment is usually less than 5%. For the complicated
calcium sulfate system, this good agreement of model and
experiment was achieved by varying only the standard chem-
ical potentials of the solids and of a CaSO~ (aq) ion pair.
The discussion of the model parameterization points out
several areas where there were problems in the availability
and/or accuracy of the data. From 25°C to 150°C, solubility
data in the NaCI-Na2S04-H20 system could be fit well when
the mixing parameters for this system were held constant.
However, to fit the data above 150°C, it was necessary to
vary these parameters. A very sharp decrease in the solubility
836 N. Meller
vs. temperature curve for Na2S04(aq) is reported (see
SCHROEDER et al.. 1935) at about 230°C. Additional data
are needed better to define the high temperature behavior of
Na2S04 solubility in water and sodium chloride solutions.
Data for the common ion NaCl-CaCh-H 20 system above
200°C were not available and therefore above 200°C the
mixing parameters for this system were held constant at the
200°C values. BRANTLEY (1987) has recently reported vapor
pressure measurements for the NaCl-CaCh-H 20 system at
these high temperatures. Solubility data for the NaCl-CaCh-
H 20 system are limited above 25°C. Additional studies are
needed to model the behavior of high concentration calcium
chloride solutions (CaCh > 6. m) to high temperature.
To fit the available data in calcium sulfate solutions, it was
necessary to allow the strength of the CaSO~(aq) ion pair to
increase significantly above 150°C. Since the aqueous solu-
bility of calcium sulfate is so low, osmotic and emf experi-
ments are not feasible. Therefore solubility data in solutions
with ions common to CaS04 were used when possible to
evaluate the standard chemical potential of the CaSO~(aq)
complex. Such data for the common ion system, CaCh-
CaS04-H20, were not found for most temperatures above
25°C. Above lOO°C, such data in the Na2S04-CaS04-H20
system are limited. From 150°C to 250°C, the sulfate-rich
common ion data of STRAUB (1932), interpolated at the
temperatures of the isothermal fits, were used to parameterize
the model. Solubility data of TEMPLETON and ROGERS (1967)
in Na2S04 common ion solutions at 250°C could not be fit
well (having sigmas> .3). However, their 250°C measure-
ments in the quaternary NaCI-CaCh-CaS04-H20 system at
250°C, which were not used in the model parameterization,
agreed well with model predictions. In interpreting their
250°C data, Templeton and Rogers postulated the existence
ofthree Ca-S04 complexes. The present model includes only
a single complex. Additional CaS04 common ion solubility
data are required to more closely evaluate Ca-S04 complexing
as a function of temperature.
Stable and metastable solubility data for most ofthe various
calcium sulfate salts in ternary solutions also were not avail-
able over the entire 25°C to 250°C temperature range.
Hemihydrate data in pure water were used from 25°C to
250°C. The gypsum, glauberite and labile salt parameteriza-
tions ranged from 25°C to only llOoC, lOO°C and 75°C,
respectively. Extrapolation outside of these temperature
ranges is not advisable. The sensitivity of model predictions
to the quality and availability of data underscores the desir-
ability of closely coupling experimental and modeling efforts.
The applications of the variable temperature Na-Ca-Cl-
S04-H20 model discussed here suggest the usefulness of a
full seawater variable temperature model in geochemical and
industrial studies. We are presently constructing such a model
and have recently completed a model of the quinary system,
Na-K-Ca-Cl-S04-H20, from 25°C to 250°C (GREENBERG
and M0LLER, in prep.).
Acknowledgements-A wish to thank Professor John H. Weare and
Dr. Jerry Greenberg for their generous assistance throughout this
work. This work has been supported by funds from the Department
of Energy:DOE DE-AC03-85SF-15522, the National Science Foun-
dation: NSF OCE 85-07902 and the American Chemical Society:
ACS-PRF 14550-AC-2, 5-C.
Editorial handling: G. R. Holdren, Jr.
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