Geochimico et Cosmochimica Acto Vol. 46, pp.

I I to22
0 Pcrgamon Press Ltd. 1982.Printed in U.S.A.

The effect of pressure on the solubility of minerals in water and seawater

FRANK J. MILLERO

Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, Florida 33 149

(Received March 9, 1981; accepted in revised form August 28, 1981)

Abstract-The effect of presure on the solubility of minerals in water and seawater can be estimated
from
In (K&/K&) + (-AVP + 0.5AKP2)/RT

where the volume (Av) and compressibility (AK) changes at atmospheric pressure (P = 0) are given
by
AV = r(M+, X-) - v[MX(s)]
AK = E(M+, X--) - K[MX(s)]
Values of the partial molal volume (n and compressibilty (K3 in water and seawater have been tabulated
for some ions from 0 to 50°C. The compressibility change is quite large (- 10 X IO-’ cm’ barr’ mol-‘)
for the solubility of most minerals. This large compressibility change accounts for the large differences
observed between values of AV obtained from linear plots of In KS,, versus P and molal volume data
(Macdonald and North, 1974; North, 1974). Calculated values of K&/K$ for the solubility of CaCOI,
SrS04 and CaF, in water were found to be in good agreement with direct measurements (Macdonald
and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good
agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not
appreciably altered.

lNTRODUCTION not possible to make a reliable estimate of AK for

ionic equilibria. From an examination of the early
IN recent years we have attempted to use molal vol- tabulations of Owen and Brinkley ( 1941). one can
ume and compressibility data to estimate the effect see that K for most ions is about -5 to - 10 X 1O-’
of pressure on ionic equilibria such as the ionization cm3 mol-’ bar-‘. This is equivalent to a change in
of acids (Millero, Hoff and Kahn, 1972; Ward and vof 5 to 10 cm3 mol-’ for a pressure change of 1000
Millero, 1974, 1975; Lo Surdo et al., 1979) the for- bars. For completely ionic reactions, the AK is small
mation of ion pairs (Millero, 1971a; Miller0 and since the Ki of the reactants and products are the
Masterton, 1974; Masterton et al., 1974; Miller0 et same order of magnitude. For the solubility of min-
al., 1974, 1977; Chen and Millero, 1977; Lo Surdo erals, however, the AK can be quite large. For ex-
et al., 1979), and the solubility of minerals (Miller0 ample, the AK for the solubility of calcite in pure
and Berner, 1972; Millero, 1976) in water and sea- water has been estimated by Owen and Brinkley
water. The methods of using 0 nd f( data to estimate (1941) to be -15 X 10e3 cm3 mol-’ bar-’ at 25°C.
the effect of pressure on ionic equilibria was first By neglecting this compressibility effect, one can
demonstrated by Owen and Brinkley (1941). More misinterpret the behavior of direct measurements.
recently, Lown, Thirsk and Wynne-Jones (1968) Macdonald and North (1974) and North (1974)
have shown that the effect of pressure on ionic equi- have measured the effect of pressure on the solubility
libria to pressures below 1000 b can be estimated by of CaCOr, CaF, and SrS04 in water. The values of
AV obtained from a linear fit of In Ksp versus P were
In (K’/p) = -AVP/RT + O.SAKP’/RT (1)
found to be higher than the values estimated from
where P is the applied pressure, R is the gas constant 1 atm molal volume data. They interpreted these
(83.15 crnem3bar K-’ mol-’ or 82.06 crnm3 atm K-l), differences by postulating the formation of a bulk or
T is the absolute temperature (“K). The molal vol- surface hydrate. As will be shown in this paper, this
ume (Av) and compressibility (AK) changes at 1 atm interpretation is not necessary if one considers the
(P = 0) are given by compressibility effect on the AV for ionic equilibria.

AV = c ri (products) - 2 vi (reactants) (2) PARTIAL MOLAL VOLUME AND

COMPRESSIBILITY DATA FOR IONS IN WATER
AK = 2 Ki (products) - 2 Ki (reactants) (3)
A number of tabulations have been made of the
(vi and Ki are the partial molal volume and com- partial molal volumes of salts or ions in water at
pressibility of species i). infinite dilution, p (Owen and Brinkley, 1941; Mil-
Until recently (Millero, Ward and Chetirkin, lero, 1969, 197 lb, 1972). Most of the earlier data
1977) reliable partial molal compressibility data have (Millero, 197 1b) are confined to simple ions and are
not been available for a large number of ions that reliable only at 25°C. Recent work (Dunn, 1968;
are common in the marine environment. It was, thus, Millero, 1970; Miller0 et al., 1972; Miller0 and

11
12 F. J.MILLERO

Table 1. Conventionalvalues of P (cm3 mol-') for ions in pure water at various temperatures+

Ion 0°C S°C 10°C ls"c 2o"c 25°C 3o"c 3s"c 4o"c 45V 5o"c
+
:i+ -0.37
0 -0.51
0 -0.62
0 -0.72
0 -0.81
0 -0.87
0 -0.93
0 -0.95
0 -0.96
0 -0.95
0 -0.93
0

Na' _3.46 -2.93 -2.44 -1.99 -1.58 -1.21 -0.88 -0.58 -0.32 -0.10 0.08
K 9.78 9.88
Rb+ 12.39
7.26 12.79
7.69 13.16
8.08 13.49
8.43 13.80
8.75 14.08
9.03 14.33
9.27 14.55
9.48 14.73
9.65 14.89 15.02
cs+ 19.76 20.11 20.45 20.76 21.06 21.35 21.62 21.87 22.11 22.33 22.53
NHc+ 17.55 17.51 17.52 17.58 17.70 17.87 18.09 18.37 18.70 19.08 19.51
Me*+ -22.32
- -21.93 -21.61 -21.38 -21.22 -21.15 -21.16 -21.24 -21.41 -21.65 -21.98
Ca2+
Sr2+ -19.69 -18.38
-18.44 -19.19 -18.30
-18.76 -18.18
-18.39 -18.04
-18.08 -17.86
-17.83 -17.65 -17.42
-17.53 -17.15
-17.47 -16.86
-17.47 -17.54
-16.53
Ba2+ -15.63 -14.86 -14.16 -13.53 -12.98 -12.49 -12.07 -11.73 -11.45 -11.25 -11.11
F- -3.05 -2.47 -1.98 -1.61 -1.33 -1.16 -1.09 -1.13 -1.26 -1.51 -1.85
cl- 16.37 16.79 17.14 17.43 17.66 17.82 17.92 17.96 17.93 17.84 17.69
Br- 22.98 23.42 23.82 24.16 24.46 24.71 24.91 25.06 25.17 25.22 25.23
I- 33.49 34.10 34.67 35.17 35.63 36.03 36.38 36.67 36.92 37.70 37.20
OH- -7.58 -6.51 -5.61 -4.89 -4.35 -3.98 -3.79 -3.78 -3.94 -4.28 -4.80
NO3- 25.51 26.40 27.20 27.90 28.49 28.99 29.39 29.69 29.89 29.99 29.99
HCOs- -
21.07 21.94 22.70 23.34 23.87 24.29 24.60 24.79 24.87 24.84 24.70
B(OH)b- 15.85 17.40 18.77 19.97 20.99 21.84 22.51 23.00 23.32 23.46 23.43
co32- _
-8.74 -7.34 -6.15 -5.15 -4.37 -3.78 -3.40 -3.22 -3.24 -3.47 -3.90
so42- - 9.26 10.58 11.72 12.66 13.42 13.98 14.35 14.54 14.53 14.33 13.94

tDeterminedfrom the coefficientsin Table 2. The underlinedvalues are based on measurements

at the given temperature. Errors at temperaturesother than 0, 25 and 50°C are estimated to
be within + 0.3 cm3 mol-I.

Knox, 1973; Ward and Millero, 1974; Perron, et al.,
1975) has yielded reliable values of Pat 0 and 50°C.
In Table I the conventional values of P( v(H’)
= 0) of some typical marine ions are tabulated. The
values at 0. 25 and 50°C are based on what I feel
are the best available data and are thought to be
reliable to kO.1 cm3 mol for most of the ions. The
values at other temperatures have been estimated
from quadratic fits of the 0. 25 and 50°C values
P(r) = c70 (OOC) + Ar + Bf2 (4)
The coefficients P (O”C), A and B are given in Table
2. As shown by the work of Dunn (1968) and Miller0
(1970) the ps of Nat, K+, Ca2+, Ba2+, Br.’ and 1..
are cubic functions of temperature between 0 and
50°C. Comparison of cubic and quadratic fits of these
ions indicates that the interpolated values differ by
as much as 20.3 cm3 mol-‘. Thus, the interpolated
values are not as reliable as the values at 0”. 25” and
50°C. New measurements are needed on the p of
electrolytes at more closely spaced temperature in-
tervals to be able to interpolate values to an accuracy
greater than 20.3 cm3 mol-‘.
The most reliable partial molal compressibilities
can be derived from sound speed measurements. The
sound speed measurements yield adiabatic (constant
entropy) partial molal compressibilities, ES. The iso-
thermal compressibility at infintite dilution in water
(denoted by the superscript zero) is related to the
adiabatic values by (Desnoyers and Philip, 1972)
(Millero, 1979) at 25°C (,!? = dP/dT is the partial
molal expansibility, and C,D’ is the partial molal heat
capacity). The substitution of the values of So, a0 and
a0 into equation (5) yields
IO’!? = IO3 pS + 3.676 c -1.13 X lO-4 @” (6)
Since the values of /? - 0.02 to 0.2 cm’ mol-’ K-’
and cp” - 0 to -200 j mol-’ K-’ for most ions
between 0 to 50°C (Millero, 1979), the major con-
tribution to R - pS is the expansibility term. The
value of k - pS at 25°C can be determined from
the temperature dependence of P (,!?’ = aP/dT
= A + 2Bt, Table 2) and the tabulated values of @”
(Millero, 1979). A sample calculation of /? - ps at
25°C for some ions is shown in Table 3. For most
simple ions the values of k - es are 0.2 X IO-’ cm’
mol-’ bar-’ which is nearly within the experimental
error of the pS data ( f 0. I X 1O-.’ cm3 mol-’ bar ‘I).
For all practical purposes, the heat capacity term can
be neglected. These values of R - pS can be used
to obtain values of i? from the 25°C pS data of
Millero, Ward and Chetirkin ( 1977). Values of R
calculated in this manner are tabulated in Table 4.
Only a limited amount of data are available for
the effect of temperature on R or pS (Millero, 1973;
Miller0 ef al., 1974). We have used this data to es-
timate the effect of temperature on the values of f?“’
given in Table 4. Experimental measurements are
needed to confirm these estimates. The values of J?’
at various temperatures have been tit to the equation

R(r) = f?‘(O”C) + AI + Br2 (7)

The coefficients for equation 7 are given in Table 5.

= p - fls= 4.725 X IO-’ bar-‘, a~ = 257.05
where 6,, At present, reliable P and pS data for transition
X 10e6 K-‘, co = 4.1664 j K-’ cme3 for pure water metal and phosphate ions are available at only 25°C
 MINERAL SOLUBILITY IN SEAWATER 13

Table 2. Cocfficimtl for fit* of 7 LO equation P(t) - iio(O'C)+ *t +- 0.01 cm3 mol-’ when transferred from 0.725 m
+ Et2
NaCl to 35%~ salinity seawater (Millero, 1977). The
10" P(O'C) A -BlO) Ref.
values of v for Li+, Rb*+, Cs+, NH:, Sr2+ and Ba*+
H+ 0 0 0 Assigned Value
IA+ -0.37 -0.0288 -0.352 a have been estimated using these empirical differ-
NiI+ -3.46(-3.30)+ 0.1092(0.0974) 0.76UO.586) a
ie 7.260.36) 0.0892(0.0771) 0.73HO.516) a ences. The v of monovalent anions Br- and I- have
Rb+ 12.39 0.0826 0.600 a
C8+ 19.76 0.0718 0.328
been equated to their values in 0.725 m NaCl (as
17.55 -0.0136 -1.056
$2
S?*+
-22.32 0.0868 1.600
-19.69(-19.61) 0.1058(0.0970) 1.256(1.091)
-18.44 0.Oi-N -0,600
found for NO;). Since the F- and OH- ions can
form ion pairs with Mg2+ and Ca2+ ions in seawater
llLLz+
P-
-15.63(-15.50) 0.1608(0.1414) 1.408(1.041)
-3.05 0.1272 2.064
(Millero, 1974), an attempt has been made to correct
cl-
cc-
16.37
22.98(22.98)
0.0896 1.264 for this effect. This was done by noting that the vol-
0.0934(0.1065) 0.968(1.246)
l- 33.49(33.49) 0.1282(0.1467) 1.064(1.450) ume of transfer of HCO;, SO:- and B( OH); divided
OH- -7.58 0.2324 3.536
m3- 25.51 0.1888 1.964 by the fraction of Mg2+ and Ca2+ ion pairs is equal
HCOI- 21.07 0.1850 2.240
B(OH)ll- 15.85U5.68) 0.3276(0.3368) 3.520(3.643) to 2.06 +- 0.16 cm3 mol-‘. Using ( 1 - a) = 0.49 and
ml- -8.74 0.3000 4.064
s0*2- 9.26 0.2840 3.808 0.85 (Millero, 1974) respectively, for the fraction of
a) "illera (1971); b) Mllero ti at. (unpublished);c) nillero and F- and OH- paired with Mg*+ and Ca*+, we obtain
Knox (1973); d) Millem. Hoff and Kahn (1972); e) Perron et & (1975);
f) "ard and Willem (1974). AVTa,+vS(NaCl - SW) = 1.01 and 1.75 cm3 mol-‘,
+The values in parenthesis for Na+. K+, C&+, 8a2+, Br- and I- were respectively.
determined wing data at 5. 15, 35, 45 and 55'C (as "ell as 0, 25
and 50'0. The limited data for the effect of temperature of
ions in seawater show a wide divergence for individ-
ual ions. For the systems studied by Duedall and
(Lo Surdo et al., 1979; Lo Surdo and Millero, 1980). Weyl and Poisson and Chanu, there is reasonable
These values are tabulated in Table 6. The effect of agreement for Na+, K+, Mg2+ and SO:-; the expan-
temperature on the v and & for the transition metal sibility results for Ca2+ show considerable differences
ions can be estimated from divalent ions (Tables 2 except from 0 to 25“. This is caused by unreliable
and 5) of similar size. Similar estimates can be made values of expansibility for NO; ion. The effect of
for H2PO; and HPO:- using HCO; and CO:- as temperature on E = aV/laT is positive for NO;, un-
models; however, estimates for PO:- must await fu- like the other anions as well as NO; in pure water
ture measurements. at the same ionic strength. If one uses the ,??‘s of
NO; from 0 to 25’C determined from pure water
PARTIAL MOLAL VOLUME AND
data at I = 0.73, the effect of temperature on the r
COMPRESSIBILITY DATA FOR IONS IN of Ca*+ by Duedall and Weyl (1967) and Poisson
SEAWATER and Chanu (1975) are in good agreement.
The measured values of vfor ions in seawater have
A number of workers (Duedall and Weyl, 1967;
been fit to the equation
Duedall, 1972; Ward and Millero, 1975; Poisson and
Chanu, 1975) have measured the i7 of electrolytes V(t°C) = B(O”C) + At + Bt2 (8)
in seawater. Results (Millero, Laferriere and Che-
tirkin, 1977) are also available for the 0 of electro- The coefficients for Eq. 8 are given in Table 9. The
lytes in 0.725 m NaCl at 25°C (which is at an ionic values of A and B for ions not measured in seawater
strength similar to average seawater, S = 35%).
Since the 0 of many simple ions are nearly the same Table 3. Calculation of P - i? for ions in water from
in seawater and NaCl at the same ionic strength, conventional values of partias mold expanslbilities
ana heat capacities *t 25OC
these NaCl results can be used to estimate v in sea-
water when no experimental results are available. Ion ~(cm3mol-1~1)a ?+(j mol-lR-l)b (iT- @lo3
cm3m1-'bar 11
Ionic values of ions in seawater from various workers
are given in Table 7. The values of r( HCl) = v( Cl-) R+ 0 0 0
Li+ -0.011 60.5 -0.05
used were taken from the values of HCl in 0.725 m N,+ 0.071 41.2 0.26
NaCl at 25” (Miller0 et al., 1977) and the temper- R+ 0.052 11.5 0.19
Rb+ 0.053 -10.3 0.20
ature dependence of HCl at I = 0.725 m (Miller0 et + 0.055 -23.3 0.20
al., 1972). For the ions Na+, K+, Mg2+, Ca2+ and :$+ 0.039 69.6 0.14
0.007 -17.3 0.03
SO:- the average values from Duedall and Weyl 22: -0.043 -30.5 0.16
(1967) and Poisson and Chanu (1975) are used. For sG+ 0.074 -37.9 0.28
Ba2+ 0.090 -48.7 0.34
Na+, K+, Mg2+ and SO:- ions the differences in the F- 0.024 -115.8 0.10
values (see Table 8) are within the experimental er- Cl- 0.026 -125.7 0.11
BY 0.045 -129.8 0.18
rors (respectively, + 0.14, r+_0.37, + 0.90 and +-0.29 I- 0.074 -119.0 0.29
cm3 mol-‘). The results for Ca2+ differ by as much OH- 0.056 -136.6 0.22
N03- 0.090 -70.7 0.34
as 3.0 cm3 mol-’ which is more than two times the x03- 0.073 -48.4 0.27
expected differences ( f 1.3 cm3 mol-‘). B(OH)I, 0.152 -53.0 0.56
0.097 -261.7 0.39
$$I
At 25°C the Ps of monovalent atoms (Na+ and 0.094 -275.2 0.38
K+) decrease by 0.12 +- 0.03 cm3 mol-‘; while di- Estimated from the coefficients given in Table 2.
a)
valent cations (Mg” and Ca*+) increase by 0.45 b) Taken from the tabulations of Millero, 1979.
14 F.J. MILLER0

Table 4 Conventional values of -103i? (cm3 mol-l bar-') for ions in water at vari-
ous temperatures*

Ion o"c 5°C 10°C 15OC 2o"c 25°C 30°C 35°C 40°C 45OC 5o"c

H+ 0 0 0 0 0 0 0 0 0 0 0
*Li+ 4.06 3.81 3.56 3.32 3.09 2.86 2.65 2.44 2.24 2.05 1.87
Na 5.13 4.88 4.63 4.39 4.16 3.94
-- 3.72 3.51 3.31 3.12 2.94
I@ 4.36 4.17
----- 3.97 3.77 3.57 3.37 3.16 2.95 2.74 2.53 2.31
*Rb+ 4.08 3.89 3.69 3.49 3.29 3.09 2.88 2.67 2.46 2.25 2.03
*cs+ 3.59 3.40 3.20 3.00 2.80 2.60 2.39 2.18 1.97 1.76 1.54
*NHl++ 2.19 2.00 1.80 1.60 1.40 1.20 0.99 0.78 0.57 0.36 0.14
Mg2+ 7.83 7.95 8.03 8.07 8.06 --
8.01 7.92 7.79 7.62 7.40 7.14
*Ca2+ 7.43 7.55 7.63 7.67 7.66 7.61 7.52 7.39 7.22 7.00 6.74
*Sr2+ 9.04 9.16 9.24 9.28 9.27 9.22 9.13 9.00 8.83 8.61 8.35
*Ba2+ 8.87 8.99 9.07 9.11 9.10 9.05 8.96 8.83 8.66 8.44 8.18
*F- 5.57 4.94 4.38 3.87 3.41 3.02 2.68 2.41 2.19 2.02 1.92
cl- 2.51 1.99 1.55 1.20 0.93 0.74
-- 0.63 0.60 0.66 0.80 1.02
Br- 1.49 1.00 0.58 0.24 -0.03 -0.22 -0.34 -0.38 -0.35 -0.25 -0.07
*1- 0.33 -0.16 -0.58 -0.92 -1.19 -1.38 -1.50 -1.54 -1.51 -1.41 -1.23
OH- 6.41 5.78 5.22 4.71 4.25 3.86 3.52 3.25 3.03 2.86 2.76
NOj- 1.31 0.87 0.46 0.08 -0.26 -0.58 -0.87 -1.12 -1.35 -1.54 -1.71
*HC03- 5.30 4.67 4.11 3.60 3.14 2.75 2.41 2.14 1.92 1.75 1.65
B(OH)b- 10.32 8.97 7.83 6.92 6.22 5.75 5.49 5.46 5.64 6.05 6.67
*co 2- 11.04 10.00 9.11 8.37 7.78 7.35 7.07 6.94 6.97 7.15 7.48
%- 10.43 9.39 8.50 7.76 6.74
7.17 -- 6.46 6.33 6.36 6.54 6.87
SO4

*Estimated from temperature dependence of ions of similar ? at 25OC.

tDetermined from the coefficients in Table 5. The underlined values are based on
measurements at the given temperature.

havebeenestimated from theeffect of temperature Table7.The measured values are reliable to kO.5
at I = 0.73.Since the
on the vof Na+ and Cl- salts cm3 mol-’ while the estimated values have an un-
partialmolalexpansibility,/?= aF/;;laT.of ions in known error.
seawater are approximately equal to the values in The partial molal compressibilities of electrolytes
water at I = 0.73,thisrepresents thebestestimate
one can make at present. The values of p for ions
from 0 to 25°C calculated from Ey. 8 are given in Table 6. Conventionalvalues of the par-
tial molal volumes and adiabatic com-
pressibilitiesof ions in water and
Table 5. Coefficients for fits of i? of ions to the
equation p(t"C) = i?(O"C) + At + Bt2
0.725 m NaCl at 25°C

IOll -lo~xo(o"c) A1O3 -B106 Ref. Ion Yea -ps103 a vb -ES103 b

H+ 0 0 0 Assigned Value
Lif 4.06 0.0517 0.156 MT?+ -17.60 7.81 -13.08 7.16
Na+ 5.13 0.0517 0.156 b" co2+ -25.75 8.68 -21.01 8.00
K+ 4.36 0.0382 -0.056 b Ni2+ -29.46 9.12 -24.67 8.39
Rb+ 4.08 0.0382 -0.056 a 6.43
cl_?+ -25.50 8.96 -20.21
Csf 3.59 0.0382 -0.056 a
NH + 2.19 0.0382 -0.056 Zn2+ -26.55 9.06 -18.84 5.77
Mgt+ 7.83 -0.0284 -0.844 b" cd2+ -14.18 6.45 -9.44 5.35
ca2+ 7.43 -0.0284 -0.844 a
sr2+ 9.04 -0.0294 -0.844 a
Ba7+ 8.87 -0.0284 -0.844 a
H2PO - 31.42 4.69 36.39 2.44
F- 5.57 0.1310 1.160
cl- 2.51 0.1120 1.644 b" WB$ -30.46
5.53 16.71
8.78 -7.41
16.01 5.38
7.69
Br- 1.49 0.1056 1.488 b
I- 0.33 0.1056 1.488
OH- 6.41 0.1310 1.160 b" a) Taken from the work of Lo Surdo et &.
NOj- 1.31 0.0908 0.608 b (1980, in press). The units of p and ?
Hcox- 5.30 0.1310 1.160 are, respectively cm3 mol-l and cm3 mol-1
B(OH)+- 10.32 0.2930 4.400 b" bar-l.
;$I 10.43
11.04 0.2240 3.056 b" b) Calculated using the specific inter-
action model (Millero, 1977; Millero,
a) Temperature coefficients were estimated from ions Laferriere and Chetirkin 1977; Milleyo,
of similar size (Li+ = Na+, Rb+ = Cs+ = NH,++= tit,
Ca2+ = Sr*+ = Mg2t, I- = Br-, F- = HC03- = OH-, C03*-
Kembro, $o Surdo, 1980). Values of V and
= SO,Z_) E for Na and Cl- ions were taken from
b) From Millero (1973) and Millero et G?. (1974). Tables 7 and 11 (for 0.725 m NaCl).
 MINERAL SOLUBILITY IN SEAWATER 15

T*ble 7. Co”“enti.J”al values of f(c&ol-‘) for ion, in se*b%tex Table 9. Coefficients for fits of v of ions in
(S - 35 Oloa) at various teuperat*res +
seawater (S - 3z”/oo) to the equation
10” O’C 5*c 1O’C 15.C 20-c 25.C N&l V(t”C) = V(O’C) + At + Bt2

If+ 0 0 0 0 0 0 0
Ion v(O’C) A -B103 Ref.
Li+ 0.14 -0.04 -0.21 -0.35 -0.48 -0.59’ -0.47
N$ -1.90 -1.55 -1.25 -1.02 -0.84 -0.72 -0.58
K+ a.73 8.9) 9.18 9.35 9.M pg 9.70 H+ 0 0 0 Assigned Value
14.26 14.38 l-c% 14.62 14.75 14.88’ 15.00
Li+ 0.14 -0.0384 -0.368
3:
“: 18.39
21.30 -18.96
18.29
21.44 -19.22
21.57
18.21 18.16
21.72 -19.58
21.Bb
18.13 -19.67
18.13
22.01a -20.23
lb.25
22.13 Na+ -1.90 0.0761 1.152 b”
-18.65 -19.63 0.642 b
ti 8.73 0.0512
c.2+ -15.93 -n -izx -m -m -z -16.33
S+ -16.67 -16.52 -16.34 -16.14 -15.92 -15.67’ -16.12 Rb+ 14.26 0.0236 -0.048 a
Ed+ -11.77 -11.34 -10.93 -10.56 -10.21 -9.9Oa -10.35 cs+ 21.30 0.0268 -0.064 a
-0.504
I=- -0.02 0.54 1.01 1.40 1.70 1.910 0.90
cl- 17.85 18.34 18.76 19.12 19.41 19.b,aa 19.64 Et: -18.65
18.39 -0.0230
-0.0685 -1.104 b”
P.r- 24.16 24.75 25.27 25.71 26.09 26.39O 26.39 Ca*+ -15.93 -0.0196 -0.668 b
I- 34.71 35.45 36.11 3b.69 37.20 37.b3a 37.63
OH- -2.01 -1.49 -1.03 -O).b4 -0.31 -O.osa -1.80
sr2+ -16.67 0.0283 0.467 a
NO,- “.xEiEi~~ 31.21 31.18 Ba2+ -11.77 0.0896 0.592 *
Bowc- zs.ss )z 32.15 F- -0.02 0.1210 1.752
&Co - g.7& g&3 26.39 y.$ 2).45 +7.&b 2;:;;
CO) 3 - 10.6 12.6
cl- 17.85 0.1044 1.316 b”
sol,2 - 17.98 19.1320.14 21.03 21.7722.38 21.92 Br- 24.16 0.1250 1.432 a
I- 34.71 0.1552 1.536 a
a) Estlmared from the values in 0.725 I NeCl
- Taken from the work of Duedall and i&y1 (1967). Duedall OH- -2 .Ol 0.1110 1.304
(19721, Ward and Mllero (1975) and Poisson and Chanu (1975). NOg- 27.71 0.2150 3.000 b”
HCOB- 24.72 0.1967 3.006 b
B(OH)r- 28,55 0.1746 0.216
co92- 7.4 0.3725 5,653 d’
in seawater are not readily available. Bradshaw and
sol+2- 17.98 0.2433 2.690 b
Schleicher (personal communication) have measured
the !? of NaCI, KCI, Na2SOd, KHC03, NaNO,, a) Estimated from values In water at I = 0.725m
b) Duedell and Weyl (1967); Poisson and Chanu
Ca(NO3)2 and MgSO, in 34.9% salinity seawater
(1975)
at IO and 25°C. We recently have measured the c) Ward and Miller0 (1975)
adiabatic partial molal compressibility & of a num- d) Miller0 (1976)
ber of electrolytes in 0.725 m NaCl (Miller0 ef al..
1980). Our results indicate that the values of & in
0.725 m NaCl are nearly equivalent to the values in bar-‘). The values of R in 0.725 m NaCl calculated
binary solution at the same ionic strength. It is, thus, from the experimentally measured values (Miller0
possible to make a reasonable estimate of R for ions et ul., 1980) of I?.~ are given in Table I I. A com-
in seawater at 25°C (Millero, 1979). parison of the values of I? for salts in 0.725 m NaCl
The isothermal partial molal compressibilities, K. and S = 35’% seawater (Bradshaw and Schleicher-
of ions in 0.725 m NaCl have been determined from personal communication) are shown in Table 12.
the adiabatic values using These comparisons indicate that the Rs in the two
media agree to within 20.6 X IO-’ cm3 mol-’ bar-’
i? = KS + 4.624E - 1.8 x 10-4cp (9)
(which is nearly within the combined experimental
which is derived from Eq. 5 using values of d = 0.731
X IO-‘. a = 316.2 X 10.’ and u = 4.0784 for 0.725
Table 10. Calculation of k - x, for ions In 0.725 m
m NaCl (Millero, 1979). The estimation of R - &
NaCl from conventional values of partial molal expansi-
for ions in 0.725 m NaCl using values of .!? and cp billties and heat capacities at I = 0.725 and 25’C

of Na+ and Cl- salts at I = 0.725 is shown in Table

Ion ~(cm3rno1-‘K-‘)a ?p(j IU~~-~K-‘)~ (i? - i?S)lO’
10. The values of K - & at I = 0.725 are generally
lower than the values at infinite dilution, but of the H+ 0 0 0
Lit -0.020 58.7 -0.10
same order of magnitude (0.1 - 0.5 X 10.’ cm3 mol.’ Na+ 0.036 55.9 0.16
K+ 0.023 56.3 0.10
Rb+ 0.026 -0.4 0.12
CS+ 0.030 -10.3 0.14
Table 8. Comparisons of the ?’ of ions in seawater (S =
0.002 76.5 0.00,
35) at various temperatures obtained by Duedall and
-0.035 -0.7 -0. lb
Weyl and Poisson and Chanu
0.010 -7.1 0.05
-1 sr2+ 0.048 -12.0 0.22
lwa, cm3 mol
Ba*+ 0.060 -14.0 0.28
F- 0.033 -62.9 O.lh
Ion O’C 5oc 10°C 15OC 2oec 25OC 6
cl- 0.039 -80.9 0.19
Na+ -0.01 0.06 0.10 0.09 0.03 0.07 to.14 Br- 0.053 -84.5 0.26
K+ 0.10 0 -0.08 -0.12 -0.12 -0.11 LO.37 I- 0.078 -74.5 0.37
?4**+ -0.95 -0.74 -0.55 -0.37 -0.19 -0.03 to.90 OH- 0.046 -83.3 0.23
ca2+ -3.03 -2.09 -1.57 -1.47 -1.82 -2.60 11.34 0.045 -9.0 0.21
Ng_ 0.027 10.4 0.12
0 B(O’& 0.072 7.0 0.33
-0.20 -0.22 -0.19 -0.08 0.08 0.32 to.29 C032- 0.090 -116.1 0.44
sor2- 0.103 -119.2 0.50
a) AV - Duedall and Weyl (1967) - Poisson and Chanu
(1975). a) Estimated from the 7 of ions at I = 0.725.
b) 6 is the srrm of the reported errors in the two b) Determined from the values of 3 - ?p - cp” tabu-
studies. lated by Hillero (1979).
16 F.J. MILLER0

Table 11. Conventionalvalues of K for ions In seawater In our recent work (Millero, 1979; Miller0 et al.
(S - 35) at various temperaturee
1980), we have found that the changes in R and r
-10% (cm3 ml-l bar-') when ions are transferred from water to 0.725 m
0.725 m
Ion ov 5°C 1o*c 15-c 2O'C 25'C NaCl
NaCl are linearily related. A plot of AKT~, versus
It+ 0 0 0 0 0 0 0
Arrm, for ions from water to seawater (S = 35%)
Li+ 3.14 3.15 3.15 3.15 3.16 3.16a 3.06 is shown in Figure 1. All of the experimental results
Na+ 3.64 3.65 3.65 3.65 3.66 3.66b 3.66
K+ 2.92 2.91 g 2.89 2.88 i.a7a 3.14 (except CO:-) fit the equation
Kb+ 2.67 2.66 2.64 2.63 2.62a 2.80
2.22 2.21 2:20 2.19 2.18 2.178 2.56 I03AKTKANs= 0.20 + 0.338AprRnNs (10)
0.96 0.95 0.94 0.93 0.92 0.91a 0.97
gz 5.73 6.03 6.33 6.63 6.93 7.23b 7.76
c&2* 5.82 6.46 6.68 m 7.24 with a u = 0.21 X lo-’ cm3 mol-’ bar -‘. This re-
sr2+ 7.20 7.84 8.06 8.27e 8.33
Ba2+ 6.90 7.12 7.33 7.54 7.76 7.978 8.19
lationship has been used to estimate the R of some
F- 3.91 3.64 3.37 3.10 2.83 2.56a 2.14 of the ions given in Table 11. The calculated values
Cl- 1.31 1.04 -0.77 0.50 0.23 -o.o@ -0.04
BT- 0.36 0.09 -0.18 -0.45 -0.72 -m -0.75 of I? for these ions in seawater agree on the average
I- -0.78 -1.05 -1.32 -1.59 -1.86 -2.13' -1.96 with the measured values in 0.725 m NaCl to f 0.23
ox- 4.24 3.85 3.47 3.09 2.70 2.3Za 2.63
NOg- 0.79 0.40 0.02 -0.36 -0.75 -1.13b -1.14 X 10e3 cm3 mol-’ bar-‘. The value of E(CO<-)
HCOQ- 3.01 2.63 2 1.85 1.47 l.OSb 1.33 = -1.5 X 10e3 cm3 mol-’ bar-’ calculated from Eq.
B(OH)r 4.06 3.63 3.21 2.79 2.36 i-w l.67d
cop 7.88 7.05 6.21 5.37 4.54 3.7oc 4.29 (10) is 2.2 X 10e3 cm3 mol-’ bar higher than expected,
sol+2- 7.54 6.71 _5.87 5.03 4.20 3.36b 3.32
apparently due to ion pair formation.
a> Estimated from equation (IO). The effect of temperature on the R of ions in sea-
b) From the measuremente of Bradshaw and Schleicher
(personal
communication,
1977). water have been estimated from the results of Brad-
c) Calculated from AK foe the ionization of BfOHfg and shaw and Schleicher at 10°C. The linear equation
x0$- (xillero,1979).
d) Estimated from the z in water at 1 = 0.725.
R (PC) = R (O°C) f At (11)
error - kO.4 X IO-’ cm3 mol-’ bar-‘). The values has been used to estimate the values of R between
of R measured in seawater are generally higher than 0 and 25°C (given in Table 11). The coefficients for
the values in NaCI; which is what one would expect equation (11) are given in Table 13. The experi-
when ionpairformation becomes important (Millero mentally measured effect of temperature on R of
ez al., 1974). Values of I for B(OH); and CO:- in Bradshaw and Schleicher for the major sea salts are
seawater have been calculated from the AR for the
ionization of B(OH)3 and HCO; (Millero, 1979).
These values of Z? are given in Table 11 along with
the ionic values determined from the work of Brad-
shaw and Schleicher.

Table 12. Comparisons of the E of ions

in seawater (S = 35'/00) and 0.725 JIJ
NaCl at 25'C

-103E (cm3 mol-l bar-l)

Oi.,.,,,..,i
Ion Seawatera 0.725 m NaClb A 0 IO 20

AV trolls
H?- 0 0 0
Na+ 3.66 3.66 0 I ” ’ “. ’ ”

Kc 2.87 3.14 0.27

6
7.23 7.76 0.53
"6",:: 6.89 7.24 0.35
Cl-- -0.04 -0.04 0
N03- -1.13 -1.14 -0.01
HCO - 1.08 1.33 0.25
1- 3.36 3.32 -0.04
SO4
B(OH)4- 1.94 1.67 -0.27
cop- 3.70 4.29 0.59

a) From the work of Bradshaw and Schlei-

cher (personal communication, 1977).
The values for B(OH)h- and C032- have
been estimated from the AK for the ioni- _
zation of B(OH)3 and HC03- in seawater A”trann
(Millero, 1979). FIG.1.Linear
correlation
ofthe metal compre~sibilities
b) From the work of Millero, Kembro and and volumes for the transfer of cations and anions from
Lo Surdo (1980). water to seawater at 25°C.
 MINERAL SOLUBILITY IN SEAWATER 17

Table 13. Coefficients for fits of X of

ions to equation X(t"C) = x(O'C) + At 4.0rl
Ion -lo3x(o"c) Al03 Ref.
H+ 0 0 Assigned Value
Li+ 3.14 -0.0008
%
-
Na+ 3.64 -0.0008 b"
K' 2.92 0.0020 b Y

Rb+ 2.67 0.0020 a

+ 2.22 0.0020 a
0.96 0.0020
$ 5.73 -0.0600 b"
Ca2+ 5.82 -0,0428 b
Sr2+ 7.20 -0.0428 a
0 20 40 60
Ba2+ 6.90 -0.0428 a
F- 3.91 0.0540 a V
cl- 1.31 0.0540 Assigned Value FIG. 2. Plot of the molarcompressibility
versus the molar
Br- 0.36 0.0540 a volumeof various minerals
at 25°C.
I- -0.78 0.0540 a
OH- 4.24 0.0767
N03- 0.79 0.0767 b" ERRORS IN THE ESTIMATION OF Kp/p FROM
HC03- 3.01 0.0773 b MOLAL VOLUME AND COMPRESSIBILITY DATA
B(OH)4- 4.06 0.0847 C
cop 7.88 0.1673 Before proceding to calculate Kp/p for various
so&z- 7.54 0.1673 b" minerals in water and sea water, it is useful to con-
a) Estimated from ion of similar size. sider the errors involved in using molal volume and
b) From Bradshaw and Schleicher (personal compressibility data to estimate the effect of pressure
communication). on ionic equilibria. For these calculations, we will
c) From unpublished measurements at I = 0.7.
consider a mineral (i.e. SrS04) with AV’ = -50.0
f 0.5cm3 mol-’ and lo3 AK0 = -16.0 f 0.5 cm3
slightly smallerthan the values found in water at the mol-’ bar-’ at 25°C. The values of Kp/p calculated
same ionic strength (Miller0 et al. 1974). from equation (1) are given in Table 14. The cal-
culations made by assuming AK = 0 point out the
THE V, AND KS OF CRYSTALLINE MINERALS
importance of the compressibility term. At P = 1000
The partial molar volume of many crystalline min- bars, neglecting the AK term overestimates Kpfp
erals have been tabulated (CRC, 1975; Adams, 1928; by 39%. The errors in K'JK?due to uncertainties in
Clarke, 1928). The effect of temperature on the V, AV and AK become important at high pressures. At
from 0 to 50°C can be determined from expansibility a pressure of 1000 bars, the errors due to uncertain-
data (Adams, 1928; Clarke, 1928). The expansibility ties in AV and AK are about 3%. This represents the
is reasonably consistent over a small temperature maximum error one would expect for pure water
range, thus, V, is given by from 0 to 50°C and P = 1000 b. The errors in sea-
water may be -6% due to the larger uncertainties
V, = Vs (OOC) + at (12) in the molal volume and compressibility data.
When using equation (1) to estimate the effect of
The value of (Y is -20 to 100 X 10e5 K-’ for most
minerals (Adams, 1928; Clarke, 1928). For a small
change in temperature (i.e., SO”C), the volume does Table 14. Errors in estimatingKP/K~ using
not change appreciably (-0.04 cm3 mol-‘) and can molal volume and compressibilitydata
be neglected.
KP/K” 6 (KP/KO)
The effect of pressure on the V,,KS = -ilV,/dP
Errors Errors
is given by
P Full Eq.+ AK = 0 AK(P)* in AV in AK
KS = V&s (13)
Ob 1.00 1.00 1.00 f0 +_O
where ps is the isothermal compressibility of the 100 1.22 1.22 1.22 0.002 0.001
mineral. The KS of most simple alkaline earth halide 200 1.48 1.50 1.48 0.006 0.001
300 1.78 1.83 1.78 0.01; 0.00,
crystals is quite small (Mathieson and Conway,
400 2.13 2.24 2.14 0.017 0.001,
1978) 1 to 5 X 10e4 cm3 mol-’ bar-’ and can be ne- 500 2.53 2.74 2.55 0.02; 0.00,
glected to P = 1000 b. A plot of KS versus V, for 600 2.99 3.35 3.02 0.036 0.011
some minerals is shown in Figure 2. The KS generally 700 3.50 4.10 3.57 0.050 0.017
800 4.08 5.02 4.20 0.066 0.027
increases with an increase in Vs.The halides show
900 4.73 6.14 4.92 0.086 0.039
the greatest values of KS,while sulfate, sulfides and 1000 5.44 7.52 5.74 0.111 0.054
oxide are nearly linear functions of Vs.Correlations
+ AV = -50.0 f 0.5 cm3 mol-’ and 103AK = -16 +
between KS and V, can be used to estimate the KS 0.5 cm3 mol-' bar-'
for minerals where no data are available. * AA = 4 x lo-6 cm3 mol-1 barw3
18 F. J. MILLER0

pressure on ionic equilibria, it is assumed that AK 2.00

is not a function of pressure. At present, few studies
have been made on the effect of pressure on the K I 60
of electrolytes (Chen et al., 1980; Bradshaw and
Schleicher - personal communication). To a pressure I 20
of 1000 b the R of electrolytes can be represented In c
KO
080
by
103KP = 103K(P = 0) + AP (14)
040
Values of A for some electrolytes in water, at I
= 0.723 and seawater for a number of sea salts at 0
0 200 400 600 800 1000
10 and 25°C are given in Table 15. For l-l, 2-l and
P, bars
2-2 electrolytes, the values of lo3 A range from 1
to 3 cm3 mol-’ bar-’ at 25” in seawater. The values FIG. 3. The effect of pressure on the solubility of CaF,
in water (Macdonald and North, 1974). The smooth curve
in pure water are slightly higher (2 to 5 cm3 mol-’
is the estimated pressure effect obtained from molal volume
bars2 at 25°C). At lower temperatures, the effect of and compressibility data (Eq. 1).
pressure on Kin water and seawater are higher. From
25” to lO”C, 10’ A increases by 0.8 f 0.3 in water
and 0.5 * 0.4 in seawater. Further measurements tained in these studies are 2 to 8 cm3 mol-’ higher
are needed to determine reliable values of A for other than the 1 atm values. If the comparisons, however,
electrolytes in vater and seawater. are made by correcting for the effect of pressure on
The effect of neglecting the pressure dependence AV, the measured and calculated values are in rea-
of AK, which is largely due to changes in the I? of sonable agreement. This is demonstrated in Figures
ions, can be examined using 3,4 and 5 by comparing the measured and calculated
values of Kp/p (using Eq. 1) for the solubilities of
In (K’IP) = -AVP/RT •t O.SAKP’fRT
these salts. The values of Vs(CaF*) = 24.56 cm3
+ (1/6)AAP3/RT (15) mol-‘, Vs(SrSO,) = 46.25 cm3 mol-’ and VdCaC03)
= 36.93 cm3 mol-’ and Ks(CaF2) = Ks(CaC03)
The values of Kp/p obtained using AA = 4 X 10m6
= Ks( SrS04) = 0 (CRC, 1974; Adams, 1928; Clarke,
cm3 mol-’ bare2 are given in Table 14. The AA be-
1928) were used in these calculations. The calculated
comes important at pressures above 700 bars. At P
and measured values of Kp/p for CaF at 23” and
= 1000 b, the neglect of the pressure dependence of
25°C shown in Figure 3 are in excellent agreement
AK results in a 4% error. Since this error is of the
(the 2” change in temperature does not cause a sig-
same order as that due to uncertainties in AV and
nificant change in AV and AK).
AK, the hA term is important to consider at pressures
The calculated and measured values of K’/K? for
above 700 b. The limited data (Table 14) available
the solubility of SrSO, at 2”, 22”, and 35°C are
for the pressure dependence of K for electrolytes can
shown in Figure 4. The calculated values (solid,
be used as a guide to make reasonable estimates of
smooth curve) at 22°C are in good agreement with
AA for ionic equilbria in water and seawater.
the measured values. The estimates at 2°C (broken
curve) are too high, while the estimates at 35°C
EFFECT OF PRESSURE ON THE SOLUBILITY OF (dotted curve) are too low. The experimental results
MINERALS IN WATER
from 2 to 35°C show little or no temperature de-
pendence. The Ap and Ap data, however, predicts
Macdonald and North (1974) and North (1974)
have measured the effect of pressure on the solubility
of CaCo,, CaF, and SrSO, in water at various tem-
2.50 7'
peratures. They found that the In Ktp was a linear
function of pressure within the experimental
of the measurements. The mean values of AV ob-
error 200 1 srso, in Pure Water
_.

1.50 -
KP
Table 15. The increase in -10% of the major sea salts in ‘“3
water and seawater for a 1000 bar increase in pressure 1.00 -
A 2oc ----
Water (I = O)a Water (I * 0.723)a Seawater (S - 3s)b
. 220 -
Salt 10°C 25-C 10°C 25-C 1OOC 25°C o 35" ......
N&l 2.6 2.0 2.0 1.6 1.8 1.4
KC1 2.3 2.0 1.7 1.6 1.7 1.3
Km03 - - - _ 2.5 2.7
0 200 400 600 800 1000
NaN03 _ - - - 1.3 0.9
NqSOb 6.3 5.2 4.8 4.0 4.8 3.4 P. bars
WC12 4.8 3.7 4.2 3.2 2.7 1.7
C&l2 - - _ - 3.1 2.9 FIG. 4. The effect of pressure on the solubility of SrSO.,
MgSO4 4.7 3.9 5.0 4.3 3.9 3.3
in water (Macdonald and North, 1974; North, 1974). The
a) Estimated from the density work of Chen et &. (1980).
b) Estimated from the V pressure work of Eradshaw and
smooth curves are the estimated pressure effects obtained
Schleicher (personal comunicatim). from molal volume and compressibility data (Eq. 1).
 MINERAL SOLUBILiTY IN SEAWATER 19

2 50 t I t i

Cciclte in Pure Water Calcite an Pure water

200 - zoo -

I 50 - I50 -
KP
In -
KO
I00 - 100 -

200 400 600 800 1000 0 200 400 600 BOO 1000

P, bars P, bars

2 50 * , 1 I I 2 50 r i 1 I
.
Colclte in Pure Water CalcIte I” Pure Water
200 - 200 -
(23°C) (25°C)

K* I 50 -
In -
KO
100 -

400 600 400 600 800 IO00

P, bars P, bars

FIG. 5. The effect of pressure on the solubility of CaCO, in water (Macdonald and North, 1974). The
smooth curves are the estimated pressure effects obtained from molal volume and compressibility data
(Eq. 1).

a larger pressure effect at lower temperatures. At
present, it is not possible to account for these dis-
crepancies. Errors in the p and k for &SO, at 2”
and 35°C could be the cause of the differences.
Measurements on the p and k Sr*+ salts are needed
to prove this postulation.
The calculated and measured values of KP/K” for
the soiubility of CaCOl (calcite) at lo, S”, 23” and
25’C are shown in Figure 4. The estimated values
of K’/@ are in good agreement with the measured
values over the entire temperature range. The larger
differences at 25°C are probably due to experimental
errors in the measurements. The values of Ap and
Ak” do not change significantly from 23” to 25°C;
thus, one would expect the same pressure depen-
dence, which is not the case.
These comparisons of Kp/K"indicate that reliable
estimates can be made for the effect of pressure on
the solubility of minerals in water if the compressi-
bility effect is considered. Thus, it is not necessary
to invoke the formation of hydrates on the surface
of these minerals (Macdonald and North, 1974;
North, 1974).
EFFECT OF PRESSURE ON THE SOLUBILITY OF
MINERALS IN SEAWATER
A number of studies have been made on the sol-
ubility of minerals in seawater (Pytkowicz and Fow-
ler, 1967; Hawley and Pytkowicz, 1969; fngle, 1975:
North, 1974; Jones and Pytkowicz, 1973; Wilfey,
1974). Pytkowicz and co-workers have measured the
effect of pressure on the solubility of calcite, ara-
gonite and amorphous silica. Willey (1974) has stud-
ied the effect of pressure on the solubility of silica
in seawater; while North ( 1974) has studied the ef-
fect of pressure on the solubility of celestite (SrSO&
The most extensive measurements on the solubility
of CaC03 (calcite) have been made by Ingle (1975).
Comparisons of the measured and calculated values
of Kpfp for calcite are shown in Figure 6. The molar
volume of Vs = 36.93 cm3 mol-’ calcite was taken
from the CRC Handbook (1975). The calculated KP/
ti values for calcite are in good agreement with the
measured values of Ingle (1975). Larger differences
exist for the foraminifera results of Pytkowicz and
Fowler (1967). Similar calculations for aragonite
( Vs = 34.2 cm3 mol-‘, CRC, 1975) are shown in
Figure 7. The differences between the measured val-
ues of Kp/fpfor aragonite by Hawley and Pytkowicz
( 1969) and Pytkowicz and Fowler ( 1967) and the
calculated values are larger than for calcite. This
could be related to surface effects (Morse et al.,
1980)or an insufficient time for equilibrium to be
reached. Further solubility measurements on ara-
gonite in seawater are needed to clear up these dis-
crepancies. More reliable values for the r’ of CaZt
20 F. J. MILLER0

2.0

1.5

KP
I”;;, 1.0

0.5
Howhy and Pyikowicz 1969 -

0
400 600 800 1000
0 200 400 600 BOO 1000 r! bars
P. bars
1.5
Calrih in S*amhr
25-C

1.0

1.0
In%

0.5
0.5
diawley and Pytkowicx 1969
oPylkaicx and Fowler IV67
0
0
400 600 800 1000
0 400 600 800 1000 t bars
P, borr
FIG. 7. The effect of pressure on the solubility of ara-
2.0
gonite in seawater (Hawley and Pytkowicz, 1969; Pytkow-
icz and Fowler, 1967). The smooth curves are the estimated
pressure effects obtained from molal volume and compres-
1.5
sibility data (Eq. 1).

I$ I.0 in seawater can be equated to the value for H3P04

(-0.9 X lo-’ cm3 mol-’ bar-‘). This gives AR
= -2.6 X lo-’ cm3 mol-’ bar-’ at 25°C. A compar-
ison of the measured (Willey, 1974; Jones and Pyt-
Pvtkowirz and Fowlw 1967

2.5
0 200 400 600 800 1000
MO4 in 0.7 NaCl
I? hors
2.0 - 2’C

FIG. 6. The effect of pressure on the solubility of calcite

in seawater (Ingle, 1975; Pytkowicz and Fowler, 1967). The 1.5 -
smooth curves are the estimated pressure effects obtained
from molal volume and compressibility data (Eq. 1). 1.0 -

in seawater would lower the uncertainties in esti-

mations of K’/K” using equation 1. The average
value selected in this paper has an uncertainty of 0 200 400 600 800 1000

+ 1.3 cm3 mol-‘. r: bars

Comparisons of the measured (North, 1974) and ,

2.5 I
calculated values of Kp/p for SrS04 (celestite) at SrSO4in
I
Seowcller
2°C in 0.7 m NaCl and seawater are shown in Figure 2.0 2-c
i
8. The estimated values are higher than the calcu-
1.5
lated values in both media. This effect is similar to In- Kp
the pure water results at 2°C. This could be related K0
1.0
to errors in the v and R data for SrS04 at low tem-
peratures or insufficient time for equilibria in the 0.5
direct measurements.
Since the solubility of silica does not involve ionic 0
200 400 600 800 1000
quantities, (Si(OH), makes up -90% of the total p. bars
Si02 in seawater at the pH of deep waters-Duedall
FIG. 8. The effect of pressure on the solubility of S&O4
et al., 1976); it is not strongly affected by pressure. (celesitite) (North, 1974) in 0.65 M NaCl and seawater.
From the r measurements of Duedall et al., 1976, The smooth curves are the estimated pressure effects ob-
we obtain Av = -8.7 cm3 mol-‘. The R of Si(OH)4 tained from molal volume and compressibility data (Eq. 1).
 MINERAL SOLUBILITY IN SEAWATER 21

0.4 0 Duedall I. W., Dayal R. and Willey J. D. (1976) The partial

SiO2 in Seawater molal volume of silicic acid in 0.725 m NaC1. Geochim.
Cosmochim. Acfa 40, 1185-1189.
Duedall I. W. and Weyl P. K. (1967) The partial equivalent
volumes of salts in seawater. Limnol. Oceanogr. 12, 52-
59.
Dunn L. A. (1968) Apparent molar volumes of electrolytes.
Part 3. Some 1-l and 2-l electrolytes in aqueous solution
. at 0, 5, 15, 35, 45, 55 and 65°C. Trans. Faraday Sot.
. l Willey,
64, 2951-2961.
./ D Jones & Pytkowicz. Hawley J. and Pytkowicz R. M. (1969) Solubility of cal-
ov 0 400 800 1200
cium carbonate in seawater at high pressures and 2°C.
Geochim. Cosmochim. Acta 33, 1557-1561.
p bars Ingle S. E. (1975) Solubility of calcite in the ocean. Mar.
Chem. 3, 301-319.
FIG. 9. The effect of pressure on the solubility of SiOl Jones M. M. and Pytokowicz R. M. (1973) Solubility of
(amorphous silica) in seawater (Willey, 1974, Jones and silica in seawater at high pressures. Bull. Sot. Roy. Sci.
Pytkowicz, 1974). The smooth curve is the estimated pres- Liege 42, 1 I8- 120.
sure effect obtained from molal volume and compressibility Lo Surdo A., Bernstrom K., Jonsson C. A. and Miller0
data (Eq. 1). F. J. ( 1979) Molal volume and adiabatic compressibility
of aqueous phosphate solutions at 25°C. J. Phys. Chem.
83, 1255-1262.
kowicz, 1973) and calculated values of K’/K” for Lo Surdo A. and Miller0 F. J. (1980) The volume and
SiOr in seawater is shown in Figure 9. The calculated compressibility change for the formation of transition
values are in reasonable agreement with the mea- metal sulfate ion pairs at 25°C. J. So/n. Chem. 9, 163-
sured values. 180.
Lo Surdo A. and Miller0 F. J. (1980) The apparent molal
To summarize, we have tabulated what we feel are volumes and adiabatic compressibilities of aqueous tran-
the most reliable values of v and R for a number of sition metal chlorides at 25°C. J. Phys. Chem. 84, 710-
ions in water and seawater from 0 to 50°C. These 715.
data can be used to make reasonable estimates for Lown D. A., Thirsk H. R., and Wynne-Jones L. (1968)
Effect of pressure on ionization equilibria in water at
the effect of pressure on the solubility of minerals
25°C. Trans. Faraday Sot. 64, 2073-2080.
and other ionic equilibria. Molal volume measure- Macdonald R. W. and North N. A. (1974) The effect of
ments over a wider temperature and concentration pressure on the solubility of CaCO,. CaF,, and SrS04
range are needed to make estimations of pressure in water. Can. J. Chem. 52, 3 18 1-3 186.
effects on geothermal brines. Direct measurements Masterton W. L., Welles H., Knox J. H. and Miller0
F. J. (1974) Volume change of ion pair formation: ru-
on the effect of pressure on the solubility of minerals
bidium nitrate and thallium (I) nitrate in water. J. Soln.
over a wider range of temperatures and concentra- Chem. 3,91-102.
tions would be useful to examine surface effects that Mathieson J. G. and Conway B. E. (1974) Partial molal
may be important in natural mixed electrolyte so- compressibilities of salts in aqueous solution and assign-
ment of ionic contributions. J. Soln. Chem. 3, 455-477.
lutions.
Miller0 F. J. (1969) The partial molal volume of ions in
seawater. Limnol. Oceanogr. 14, 376-385.
Acknowledgments-The author acknowledges the support Miller0 F. J. (1970) The apparent and partial molal volume
of the Oceanographic Section of the National Science Foun- of aqueous sodium chloride solutions at various temper-
dation (OCE 7919245 and OCE 7924543) and the Office atures. J. Phys. Chem. 74, 356-362.
of Naval Research (N00014-80-C-0042) for this study. Miller0 F. J. (1971a) Effect of pressure on sulfate ion as-
sociation in seawater. Geochim. Cosmochim. Acfa 35,
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