A database of alkaline and alkaline earth chloride solubilities in water at various temperatures was created using data from more than 670 publications over about the last two centuries. Statistical critical evaluations of the created database were produced since there were enough independent data sources to justify such evaluations. The reliable experimental data were adequately described by polynomial expressions over various temperature ranges. Using the Pitzer approach for ionic activity and osmotic coefficients, the thermodynamic solubility products for the discussed minerals have been calculated at various temperature intervals and also represented by polynomial expressions. The solubility products calculated in the current study yield excellent agreement between the predicted and experimental mineral solubility values in natural waters over a wide range of temperature and ionic solution matrices.

6.
1.
Akhumov
,
E. I.
and
Pylkova
,
E. V.
, “
About overcooling of two-component saturated solutions
,”
Dokl. Akad. Nauk USSR
108
,
857
860
(
1956
).
2.
Akhumov
,
E. I.
and
Pylkova
,
E. V.
, “
The metastable equilibrium in the ternary system NaCl-KCl-H2O
,”
Zh. Neorg. Khim.
5
,
1819
1831
(
1960
).
3.
Akhumov
,
E. I.
and
Spiro
,
N. S.
, “
Activity and activity coefficients of water in saturated solutions of NaCl–H2O, KCl–H2O and NaBr–H2O
,”
Zh. Neorg. Khim.
4
,
692
694
(
1959
).
4.
Akhumov
,
E. I.
and
Vasil’ev
,
B. B.
, “
Problems of study of aqueous solutions at high temperatures. Article 2. An equilibrium in the quaternary system KCl-NaCl-MgCl2-H2O
,”
Zh. Obshch. Khim.
2
,
282
289
(
1932
).
5.
Akhumov
,
E. I.
and
Vasil’ev
,
B. B.
, “
Problems of study of aqueous solutions at high temperatures
,”
Izv. Sect. Fiz.-Khim. Anal. AN SSSR
9
,
295
315
(
1936
).
6.
Akhumov
,
E. I.
and
Vasil’ev
,
B. B.
, “
Study of water solutions at high temperatures
,” in
Solikamskie Karnallity
(
ONTI
,
Moscow, Leningrad
,
1935
), pp.
88
108
.
7.
Akhumov
,
E. I.
and
Vasil’ev
,
B. B.
, “
Technological calculations of equilibrium of potassium, sodium and magnesium chlorides in aqueous systems at high temperatures
,”
Trudy Gos. Ins. Prikl. Khim.
18
,
14
32
(
1933
).
8.
Anathaswamy
,
J.
and
Atkinson
,
G.
, “
Thermodynamics of concentrated electrolyte mixtures. V. A review of the thermodynamic properties of aqueous calcium chloride in the temperature range 273.15-373.15 K
,”
J. Chem. Eng. Data
30
,
120
128
(
1985
).
9.
Assarsson
,
G. O.
, “
Equilibrium in aqueous systems containing Sr2+, K+, Na+ and Cl
,”
J. Phys. Chem.
57
,
207
210
(
1953
).
10.
Balarew
,
C.
,
Christov
,
C.
,
Valyashko
,
V.
, and
Petrenko
,
S.
, “
Thermodynamics of formation of carnallite type double salts
,”
J. Solution Chem.
22
,
173
181
(
1993
).
11.
Balarew
,
C.
,
Tepavitcharova
,
S.
,
Rabadjieva
,
D.
, and
Voigt
,
W.
, “
Solubility and crystallization in the system MgCl2-MgSO4-H2O at 50 and 75°C
,”
J. Solution Chem.
30
,
815
823
(
2001
).
12.
Bassett
,
H.
,
Barton
,
G. W.
,
Foster
,
A. R.
, and
Pateman
,
R. J.
, “
The ternary systems constituted by mercuric chloride, water and an alkaline-earth chloride or cupric chloride
,”
J. Chem. Soc.
,
151
164
(
1933
).
13.
Benrath
,
A.
, “
Uber loslichkeit von salzen und salzgemischen in wasser bei temperaturen oberhalb von 100 °C. III
,”
Z. Anorg. Chem.
247
,
147
160
(
1941
).
14.
Bergman
,
A. G.
and
Kuznetsova
,
A. I.
, “
The diagram of solubility of the ternary system H2O-KCl-CaCl2 in the temperature range from the full freezing point up to 300 oC
,”
Zh. Neorg. Khim.
4
,
194
204
(
1959
).
15.
Bergman
,
A. G.
and
Vlasov
,
N. A.
, “
Geomorphism of halogen salts of potassium and polytherms of quaternary system KCl-KBr-H2O, NaCl-NaBr-H2O, NaCl-KCl-H2O, NaBr-KBr-H2O
,”
Izv. Sect. Fiz.-Khim. Anal. AN SSSR
17
,
312
337
(
1949
).
16.
Cheremnykh
,
L. M.
and
Shestakov
,
N. E.
, “
Phase equilibrium in system NaCl-KCl-MgCl2-H2O at 273-373 oK
,”
Zh. Prikl. Khim.
65
,
507
512
(
1992
).
17.
Christov
,
C.
, “
Thermodynamic study of the CuCl2-MCl2-H2O systems (M=Mg, Co) at 298.15 K
,”
Collect. Czech. Chem. Commun.
61
,
507
511
(
1996a
).
18.
Christov
,
C.
, “
A simplified model for calculation of the Gibbs energy of mixing in crystals: Thermodynamic theory, restrictions and applicability
,”
Collect. Czech. Chem. Commun.
61
,
1585
1599
(
1996b
).
19.
Christov
,
C.
, “
Thermodynamic study of the KCl-K2SO4-K2Cr2O7-H2O system at the temperature 298.15 K
,”
Calphad
22
,
449
457
(
1998
).
20.
Christov
,
C.
, “
Study of (m1KCl + m2MeCl2) (aq) and (m1K2SO4 + m2MeSO4) (aq) where m denotes molality and Me denotes Cu, or Ni at the temperature 298.15 K
,”
J. Chem. Thermodyn.
31
,
71
83
(
1999
).
21.
Christov
,
C.
, “
Thermodynamic study of quaternary systems with participation of ammonium and sodium alums and chromium alums
,”
Calphad
26
,
341
352
(
2002
).
22.
Christov
,
C.
,
Petrenko
,
S.
,
Balarew
,
C.
, and
Valyashko
,
V.
, “
Thermodynamic simulation of four-component carnallite type systems
,”
Monatsh. Chem.
125
,
1371
1382
(
1994a
).
23.
Christov
,
C.
,
Petrenko
,
S.
,
Balarew
,
C.
, and
Valyashko
,
V.
, “
Calculation of the Gibbs energy of mixing in crystals using Pitzer’s model
,”
J. Solution Chem.
23
,
795
812
(
1994b
).
24.
Christov
,
C.
,
Velikova
,
S.
, and
Ivanova
,
K.
, “
Study of (m1LiX + m2CaX2)(aq) where mi denotes molality and X denotes Cl, or Br at the temperature 298.15 K
,”
J. Chem. Thermodyn.
32
,
1505
1512
(
2000
).
25.
Christov
,
C.
,
Ivanova
,
K.
,
Velikova
,
S.
, and
Tanev
,
S.
, “
Thermodynamic study of aqueous sodium and potassium chloride and chromate systems at the temperature 298.15 K
,”
J. Chem. Thermodyn.
34
,
987
994
(
2002
).
26.
Clarke
,
E. C. W.
and
Glew
,
D. N.
, “
Evaluation of the thermodynamic functions for aqueous sodium chloride from equilibrium and calorimetric measurements below 154 °C
,”
J. Phys. Chem. Ref. Data
14
,
489
610
(
1985
).
27.
Clynne
,
M. A.
and
Potter
,
R. W
, “
Solubility of some alkali and alkaline Earth chlorides in water at moderate temperatures
,”
J. Chem. Eng. Data
24
,
338
340
(
1979
).
28.
Alkali Metal and Ammonium Chlorides in Water and Heavy Water (Binary Systems)
, IUPAC Solubility Data Series Vol. 47, edited by
Cohen-Adad
,
R.
and
Lorimer
,
J. W.
(
Pergamon Press
,
Oxford
,
1991
).
29.
Collins
,
E. M.
and
Menzies
,
A. W. C.
, “
A comparative method for measuring aqueous vapor and dissociation pressures with some of its applications
,”
J. Phys. Chem.
40
,
379
397
(
1936
).
30.
de Lima
,
M. C. P.
and
Pitzer
,
K. S.
, “
Thermodynamics of saturated electrolyte mixtures of NaCl with Na2SO4 and MgCl2
,”
J. Solution Chem.
12
,
187
199
(
1983
).
31.
Druzhinin
,
I. G.
and
Shepelev
,
A. I.
, “
Metastable solutions of calcium chloride and temperature ranges of their existence
,”
Dokl. AN SSSR
72
,
703
706
(
1950
).
32.
Filippov
,
V. K.
,
Charykov
,
N. A.
, and
Rumyantzev
,
A. V.
, “
The application of Pitzer’s method to salt-aqueous system with complex formation in solution
,”
Dokl. AN SSSR
296
,
665
668
(
1987
).
33.
Garrels
,
R. M.
and
Thompson
,
M. E.
, “
A chemical model for seawater at 25 °C and one atmosphere total pressure
,”
Am. J. Sci.
260
,
57
66
(
1962
).
34.
Glynn
,
P. D.
,
Reardon
,
E. J.
,
Plummer
,
L. N.
, and
Busenberg
,
E.
, “
Reaction paths and equilibrium end-points in solid-solution aqueous solution systems
,”
Geochim. Cosmochim. Acta
54
,
267
282
(
1990
).
35.
Greenberg
,
J. P.
and
Moller
,
N.
, “
The prediction of mineral solubilities in natural waters, a chemical equilibrium model for Na-K-Ca-Cl-SO4-H2O system to high concentration from 0 to 250 °C
,”
Geochim. Cosmochim. Acta
53
,
2503
2518
(
1989
).
36.
Harvey
,
A. H.
and
Salomon
,
M.
, “
Editorial: IUPAC-NIST Solubility Data Series
,”
J. Phys. Chem. Ref. Data
39
,
020401
(
2010
).
37.
Harvie
,
C. E.
and
Weare
,
J. H.
, “
The prediction of mineral solubilities in natural waters, the Na-K-Mg-Ca-Cl-SO4-H2O system from zero to high concentration at 25 °C
,”
Geochim. Cosmochim. Acta
44
,
981
997
(
1980
).
38.
Harvie
,
C. E.
,
Eugster
,
H. P.
, and
Weare
,
J. H.
, “
Mineral equilibria in the six-component seawater system Na-K-Mg-Ca-Cl-SO4-H2O system at 25 °C. II. Compositions of the saturated solutions
,”
Geochim. Cosmochim. Acta
46
,
1603
1618
(
1982
).
39.
Harvie
,
C. E.
,
Moller
,
N.
, and
Weare
,
J. H.
, “
The prediction of mineral solubilities in natural waters, the Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system to high ionic strengths at 25 °C
,”
Geochim. Cosmochim. Acta
48
,
723
751
(
1984
).
40.
Harvie
,
C. E.
,
Weare
,
J. H.
,
Hardie
,
L. A.
, and
Eugster
,
H. P.
, “
Evaporation of seawater, calculated mineral sequences
,”
Science
208
,
498
500
(
1980
).
41.
Helgeson
,
H. C.
, “
Thermodynamics of hydrothermal systems at elevated temperatures and pressures
,”
Am. J. Sci.
267
,
729
804
(
1969
).
42.
Keevil
,
N. B.
, “
Vapor pressures of aqueous solutions at high temperatures
,”
J. Am. Chem. Soc.
64
,
841
850
(
1942
).
43.
Krumgalz
,
B. S.
, “
Application of the Pitzer ion interaction model to natural hypersaline brines
,”
J. Mol. Liq.
91
,
3
19
(
2001
).
44.
Krumgalz
,
B. S.
, “
Ion interaction approach to geochemical aspects of the Dead Sea
,” in
The Dead Sea: The Lake and its Setting
, edited by
Niemi
,
T. M.
,
Ben-Avraham
,
Z.
, and
Gat
,
J. R.
(
Oxford University Press
,
New York, Oxford
,
1997
), pp.
145
160
.
45.
Krumgalz
,
B. S.
and
Millero
,
F. J.
, “
Halite solubility in Dead Sea waters
,”
Mar. Chem.
27
,
219
233
(
1989
).
46.
Krumgalz
,
B. S.
and
Millero
,
F. J.
, “
Physico-chemical study of the Dead Sea waters. I. Activity coefficients of major ions in Dead Sea water
,”
Mar. Chem.
11
,
209
222
(
1982
).
47.
Krumgalz
,
B. S.
and
Millero
,
F. J.
, “
Physico-chemical study of the Dead Sea waters. III. On gypsum saturation in Dead Sea waters and their mixtures with Mediterranean Sea water
,”
Mar. Chem.
13
,
127
139
(
1983a
).
48.
Krumgalz
,
B. S.
,
Hecht
,
A.
,
Starinsky
,
A.
, and
Katz
,
A.
, “
Thermodynamic constraints on Dead Sea evaporation, can the Dead Sea dry up?
,”
Chem. Geol.
165
,
1
11
(
2000
).
49.
Krumgalz
,
B. S.
,
Magdal
,
E.
, and
Starinsky
,
A.
, “
The evolution of a chloride sedimentary sequence–simulated evaporation of the Dead Sea Lake
,”
Isr. J. Earth Sci.
51
,
253
267
(
2002
).
50.
Kurilenko
,
V. V.
,
Filippov
,
V. K.
,
Charykov
,
N. A.
, and
Shwarts
,
A. A.
, “
The application of Pitzer’s method for hydrogeochemical modeling of the processes of development of modern evaporative basins
,”
Dokl. AN SSSR
311
,
193
196
(
1990
).
51.
Physikalish Chemische Tabellen
, edited by
Landolt
,
H.
and
Bornstein
,
R.
(
Verlag von Julius Springer
,
Berlin
,
1894
).
52.
Solubilities of Inorganic and Metal Organic Compounds: A Compilation of Solubility Data from the Periodical Literature
, 4th ed. (A Revision and Continuation of the Compilation Originated by A. Seidell), edited by
Linke
,
W. F.
(
American Chemical Society
,
Washington, DC
,
1958
), Vol. I.
53.
Solubilities of Inorganic and Metal Organic Compounds: A Compilation of Solubility Data from the Periodical Literature
, 4th ed. (A Revision and Continuation of the Compilation Originated by A. Seidell), edited by
Linke
,
W. F.
(
American Chemical Society
,
Washington, DC
,
1965
), Vol. II.
54.
Makarov
,
S. Z.
and
Blidin
,
V. P.
, “
Polytherms of the quaternary system Na2CO3-Na2SO4-NaCl-H2O and solid solutions of berkeite type
,”
Izv. AN SSSR, Ser. Khim.
,
865
892
(
1938
).
55.
Marcus
,
Y.
and
Soffer
,
N.
, “
Solubilities and vapour pressures in the quinquinary system NaCl-KCl-MgCl2-CaCl2-H2O. Part 2. Predictions and measurements at 30-45 °C
,”
J. Chem. Soc. Faraday Trans.
86
,
495
500
(
1990
).
56.
Marliacy
,
P.
,
Hubert
,
N.
,
Schuffenecker
,
L.
, and
Solimando
,
R.
, “
Use of Pitzer’s model to calculate thermodynamic properties of aqueous electrolyte solutions of Na2SO4 + NaCl between 273.15 and 373.15 K
,”
Fluid Phase Equilib.
148
,
95
106
(
1998
).
57.
Marliacy
,
P.
,
Solimando
,
R.
,
Bouroukba
,
M.
, and
Schuffenecker
,
L.
, “
Thermodynamics of crystallization of sodium sulfate decahydrate in H2O-NaCl-Na2SO4, application to Na2SO4·10H2O-based latent heat storage materials
,”
Thermochim. Acta
344
,
85
94
(
2000
).
58.
Meissner
,
H. P.
and
Manning
,
M. P.
, “
Prediction of solubilities and activity coefficients in sodium-potassium-magnesium chloride brines
,” in
Chemical Engineering Thermodynamics
, edited by
Newman
,
S. A.
(
Ann Arbor Science
,
1983
), Chap. 28, pp.
339
348
.
59.
Menzies
,
A. W. C.
, “
A method of solubility measurement. Solubilities in the system SrCl2-H2O from 20 to 200 °C
,”
J. Am. Chem. Soc.
58
,
934
937
(
1936
).
60.
Moller
,
N.
, “
The prediction of mineral solubilities in natural waters: A chemical equilibrium model for Na-Ca-Cl-SO4-H2O system, to high temperature and concentration
,”
Geochim. Cosmochim. Acta
52
,
821
837
(
1988
).
61.
Pabalan
,
R. T.
and
Pitzer
,
K. S.
, “
Apparent molar heat capacity and other thermodynamic properties of aqueous KCl solutions to high temperatures and pressures
,”
J. Chem. Eng. Data
33
,
354
362
(
1988
).
62.
Pabalan
,
R. T.
and
Pitzer
,
K. S.
, “
Mineral solubilities in electrolyte solutions
,” in
Activity Coefficients in Electrolyte Solutions
, 2nd ed., edited by
Pitzer
,
K. S.
(
CRC Press
,
Boca Raton, FL
,
1991
), pp.
435
490
.
63.
Pabalan
,
R. T.
and
Pitzer
,
K. S.
, “
Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl-SO4-H2O
,”
Geochim. Cosmochim. Acta
51
,
2429
2443
(
1987
).
64.
Reference Book of Experimental Data of the Solubility of Multicomponent Aqueous-Salt Systems
, 2nd ed., edited by
Pel'sh
,
A. D.
(
Khimiya
,
Leningrad
,
1973
).
65.
Phutela
,
R. C.
,
Pitzer
,
K. S.
, and
Saluja
,
P. P. S.
, “
Thermodynamics of aqueous magnesium chloride, calcium chloride and strontium chloride at elevated temperatures
,”
J. Chem. Eng. Data
32
,
76
80
(
1987
).
66.
Pitzer
,
K. S.
, “
Ion interaction approach, theory and data correlation
,” in
Activity Coefficients in Electrolyte Solutions
, 2nd ed., edited by
Pitzer
,
K. S.
(
CRC Press
,
Boca Raton, FL
,
1991
), pp.
75
153
.
67.
Pitzer
,
K. S.
, “
Theory, ion interaction approach
,” in
Activity Coefficients in Electrolyte Solutions
, edited by
Pytkowicz
,
R. M.
(
CRC Press
,
Boca Raton, FL
,
1979
), pp.
157
208
.
68.
Pitzer
,
K. S.
, “
Thermodynamics of electrolytes. I. Theoretical basis and general equations
,”
J. Phys. Chem.
77
,
268
277
(
1973
).
69.
Pitzer
,
K. S.
,
Peiper
,
J. C.
, and
Busey
,
R. H.
, “
Thermodynamic properties of aqueous sodium chloride solutions
,”
J. Phys. Chem. Ref. Data
13
,
1
102
(
1984
).
70.
Plummer
,
L. N.
,
Parkhurst
,
D. L.
,
Fleming
,
G. W.
, and
Dunkle
,
S. A.
, “
A computer program incorporating Pitzer’s equations for calculation of geochemical reactions in brines
,” U.S. Geological Survey, Water Resources Investigation, Report 88-4153, Reston, Virginia, 1988, 310 pp.
71.
Potter
,
R. W.
 II
and
Clynne
,
M. A.
, “
Solubility of highly soluble salts in aqueous media. Part 1. NaCl, KCl, CaCl2, Na2SO4, and K2SO4 solubilities to 100 °C
,”
J. Res. U.S. Geol. Surv.
6
,
701
705
(
1978
).
72.
Richards
,
T. W.
and
Yngve
,
V.
, “
The transition temperatures of strontium chloride and strontium bromide as fixed points in thermometry
,”
J. Am. Chem. Soc.
40
,
89
95
(
1918
).
73.
Roozeboom
,
B.
, “
Etude experimentale et theorique sur les conditions de l'equilibre entre les combinaisons solides et liquides de l'eau avec des sels, particulierement avec le chlorure de calcium
,”
Rec. Trav. Chim.
8
,
1
146
(
1889
).
74.
Shul'gina
,
M. P.
,
Kharchuk
,
O. S.
, and
Yanat’eva
,
O. K.
, “
New solid phases in the system KCl-K2SO4-H2O
,”
Izv. Sect. Fiz.-Khim. Anal. AN SSSR
26
,
198
210
(
1955
).
75.
Spencer
,
R. J.
,
Moller
,
N.
, and
Weare
,
J. H.
, “
The prediction of mineral solubilities in natural waters, a chemical equilibrium model for the Na-K-Ca-Mg-Cl-SO4-H2O system at temperatures below 25 °C
,”
Geochim. Cosmochim. Acta
54
,
575
590
(
1990
).
76.
Sterner
,
S. M.
,
Hall
,
D. L.
, and
Bodnar
,
R. J.
, “
Synthetic fluid inclusions. V. Solubility relations in the system NaCl-KCl-H2O under vapor-saturated conditions
,”
Geochim. Cosmochim. Acta
52
,
989
1005
(
1988
).
77.
Tukhtaev
,
S.
,
Osichkina
,
R. G.
,
Bergman
,
A. G.
, and
Nabiev
,
M. N.
, “
Solubility in the system containing chlorides and sulfates of potassium and magnesium. Polytherms ‏‏‏‏‏of diagonal section of the system K2SO4-MgCl2-H2O
,” in
Mineral and Organic-Mineral Fertilizers, Formers of Soil Structures and Herbicides
(
Inst. Khim. AN UzbSSR
,
Tashkent
,
1967
), pp.
208
234
.
78.
Valyashko
,
V. M.
,
Urusova
,
M. A.
, and
Kravchuk
,
K. G.
, “
New type of full phase diagram of double systems with the components of various volatility
,”
Dokl. AN SSSR
272
,
390
394
(
1983
).
79.
Valyashko
,
V. M.
,
Urusova
,
M. A.
,
Ketzko
,
V. A.
, and
Kravchuk
,
K. G.
, “
Phase equilibrium and thermodynamic properties of solutions in the systems MgCl2-H2O, CaCl2-H2O, SrCl2-H2O, BaCl2-H2O
,”
Zh. Inorg. Khim.
32
,
2811
2819
(
1987
).
80.
van't Hoff
,
J. H.
and
Kenrick
,
F. B.
, “
Untersuchungen uber die bildungsverhaltnisse der oceanischen salzablagerungen, insbesondere des stassfurter salzlagers. IV. Die existenzbedingungen und loslichkeitsverhaltnisse von tachhydrit
,”
Sitzungsber. Preuss. Akad.
,
508
515
(
1897
).
81.
van't Hoff
,
J. H.
and
Meyerhoffer
,
W.
, “
Conditions of existence and composition of solutions of magnesium chlorides and its hydrates above 0 °C
,” in
Untersuchungen uber die Bildungsverhaltnisse der ozeanischen Salzablagerungen insbesondere des Stassfurter Salzlagers
(
Akademische Verlagsgesellschaft m. b. H.
,
Leipzig
,
1912
), pp.
1
4
.
82.
Vlasov
,
N. A.
and
Bergman
,
A. G.
, “
Polytherms of the ternary system sodium chloride–sodium bromide–water at the temperature range from the full freezing point up to +50 °C
,”
Dokl. AN SSSR
38
,
193
195
(
1943
).
83.
Voigt
,
W.
, “
What we know and still not know about oceanic salts
,”
Pure Appl. Chem.
87
,
1099
1126
(
2015
).

Supplementary Material

You do not currently have access to this content.