A new parametric crossover model for the phase behavior of a binary mixture is presented that corresponds to the Leung–Griffiths model in the critical region and is transformed into the regular classical expansion far away from the critical point. The model is optimized to, and leads to excellent agreement with, isothermal vapor–liquid equilibrium data for dilute aqueous solutions of sodium chloride by Bischoff and co-workers. It then accurately predicts constant-composition phase equilibrium loci as measured by independent workers. This crossover model is therefore capable of representing the thermodynamic surface of ionic solutions in a large range of temperatures and densities around the critical points of vapor–liquid equilibrium.
REFERENCES
1.
L. D. Landau and E. M. Lifshitz, Statistical Physics, 3rd ed. (Pergamon, New York, 1980).
2.
A. Z. Patashinskii and V. L. Pokrovskii, Fluctuation Theory of Phase Transitions (Pergamon, New York, 1979).
3.
M. E. Fisher, in Critical Phenomena, Lecture Notes in Physics, edited by F. J. W. Hahne (Springer-Verlag, Berlin, 1982) Vol. 186, p. 1.
4.
J. V.
Sengers
and J. M. H.
Levelt Sengers
, Annu. Rev. Phys. Chem.
37
, 189
(1986
).5.
M. A. Anisimov, Critical Phenomena in Liquids and Liquid Crystals (Gordon and Breach, Philadelphia, 1991).
6.
7.
8.
9.
M. A.
Anisimov
, S. B.
Kiselev
, J. V.
Sengers
, and S.
Tang
, Physica A
188
, 487
(1992
).10.
The length should not be associated with the Debye length In the Debye-Hückel theory is always larger than and in the limit of the pure solvent, see Ref. 1, while tends to its final value in the pure solvent. Actually is an effective range of the interaction between molecules, which is different for the Coulomb forces and for the Lennard-Jones potential, for example.
11.
12.
13.
14.
15.
P. C.
Albright
, J. V.
Sengers
, J. F.
Nicoll
, and M.
Ley-Koo
, Int. J. Thermophys.
7
, 75
(1986
).16.
P. C.
Albright
, Z. Y.
Chen
, and J. V.
Sengers
, Phys. Rev. B
36
, 877
(1987
).17.
Z. Y.
Chen
, P. C.
Albright
, and J. V.
Sengers
, Phys. Rev. A
41
, 3161
(1990
).18.
Z. Y.
Chen
, A.
Abbaci
, S.
Tang
, and J. V.
Sengers
, Phys. Rev. A
42
, 4470
(1990
).19.
20.
C.
Bagnuls
, C.
Bervillier
, D. I.
Meiron
, and B. G.
Nickel
, Phys. Rev. B
35
, 3585
(1987
).21.
22.
23.
24.
25.
D. W.
Hair
, E. K.
Hobbie
, A. I.
Nakatani
, and C. C.
Han
, J. Chem. Phys.
96
, 9133
(1992
).26.
S.
Janssen
, D.
Schwahn
, and T.
Springer
, Phys. Rev. Lett.
68
, 3180
(1992
).27.
28.
H.
Weingärtner
, S.
Wiegand
, and W.
Schröer
, J. Chem. Phys.
96
, 848
(1992
).29.
30.
K. C.
Zhang
, M. E.
Briggs
, R. W.
Gammon
, and J. M. H.
Levelt Sengers
, J. Chem. Phys.
97
, 8692
(1992
).31.
32.
F. W.
Balfour
, J. V.
Sengers
, M. R.
Moldover
, and J. M. H.
Levelt Sengers
, Phys. Lett. A
65
, 223
(1978
).33.
J. V.
Sengers
and J. M. H.
Levelt Sengers
, Int. J. Thermophys.
5
, 195
(1984
).34.
35.
M. A.
Anisimov
, S. B.
Kiselev
, and I. G.
Kostyukova
, Int. J. Thermophys.
6
, 465
(1985
).36.
37.
38.
39.
40.
A. A.
Povodyrev
, G. X.
Jin
, S. B.
Kiselev
, and J. V.
Sengers
, Int. J. Thermophys.
17
, 909
(1996
).41.
42.
S. B. Kiselev and J. C. Rainwater, Fluid Phase Equilib. (submitted).
43.
J. C. Rainwater, in Supercritical Fluid Technology, edited by J. F. Ely and T. J. Bruno, (CRC Press, Boca Raton FL, 1991), p. 57.
44.
45.
46.
J. V.
Sengers
and J. M. H.
Levelt Sengers
, Annu. Rev. Chem.
37
, 189
(1986
).47.
48.
J. M. H.
Levelt Sengers
, B.
Kamgar-Parsi
, F. W.
Balfour
, and J. V.
Sengers
, J. Phys. Chem. Ref. Data
12
, 1
(1983
).49.
B.
Kamgar-Parsi
, J. M. H.
Levelt Sengers
, and J. V.
Sengers
, J. Phys. Chem. Ref. Data
12
, 513
(1983
).50.
Kh. S.
Abdulkadirova
, S. B.
Kiselev
, I. G.
Kostyukova
, and L. V.
Fedyunina
, J. Eng. Phys.
61
, 902
(1991
).51.
52.
53.
P.
Schofield
, J. D.
Litster
, and J. F.
Ho
, Phys. Rev. Lett.
23
, 1098
(1969
).54.
55.
56.
J. C. Rainwater, Vapor-Liquid Equilibrium of Binary Mixtures in the Extended Critical Region. I. Thermodynamic Model, NIST Technical Note 1328 (U. S. Gov’t Printing Office, Washington, DC, 1989).
57.
58.
59.
60.
61.
62.
63.
F. C. Zhang, Ph.D. thesis, Department of Physics, Virginia Polytechnic Institute, Blacksburg, 1983.
64.
S. B.
Kiselev
and A. A.
Povodyrev
, Fluid Phase Equilibria
79
, 33
(1992
).65.
J. M. H.
Levelt Sengers
, C. M.
Everhart
, G.
Morrison
, and K. S.
Pitzer
, Chem. Eng. Commun.
47
, 315
(1986
).66.
A. A.
Povodyrev
, S. B.
Kiselev
, and M. A.
Anisimov
, Int. J. Thermophys.
14
, 1187
(1993
).67.
J. C. Rainwater and M. R. Moldover, in Chemical Engineering at Supercritical-Fluid Conditions, edited by M. E. Paulaitis, J. M. L. Penninger, R. D. Gray, and P. Davidson, (Ann Arbor Science, Ann Arbor, MI, 1983), p. 199.
68.
69.
70.
K. S.
Pitzer
, J. L.
Bischoff
, and R. J.
Rosenbauer
, Chem. Phys. Lett.
134
, 60
(1987
).71.
A. H.
Harvey
and J. M. H.
Levelt Sengers
, Chem. Phys. Let.
156
, 415
(1989
).72.
S. B.
Kiselev
, I. G.
Kostyukova
, and A. A.
Povodyrev
, Int. J. Thermophys.
12
, 877
(1991
).73.
M. A.
Anisimov
, A. A.
Povodyrev
, V. D.
Kulikov
, and J. V.
Sengers
, Phys. Rev. Lett.
75
, 3146
(1995
).74.
J. L.
Bischoff
and R. J.
Rosenbauer
, Geochim. Cosmochim. Acta
52
, 2121
(1988
).75.
76.
77.
78.
N. S.
Osborne
, H. F.
Stimson
, and D. C.
Ginnings
, J. Res. Nat. Bur. Stand.
23
, 261
(1939
).79.
A. Wyczalkowska and J. V. Sengers, in “Thermodynamic properties of steam in the critical region: A preliminary scaled crossover equation, Technical Report prepared for IAPWS” Institute for Physical Science and Technology, University of Maryland, College Park, MD, 1995.
80.
A. Pruss and W. Wagner, in Physical Chemistry of Aqueous System: Meeting the Needs of Industry, edited by H. J. White, J. V. Sengers, D. B. Neumann, and J. C. Bellows (Begell House, Wallingford, 1995) pp. 66–77.
81.
82.
R. J. J.
Chen
, P. S.
Chappelear
, and R.
Kobayashi
, J. Chem. Eng. Data
19
, 58
(1974
).83.
K. S.
Pitzer
and R. T.
Pabalan
, Geochim. Cosmochim. Acta
50
, 1445
(1986
).84.
J. C.
Tanger
, IV and K. S.
Pitzer
, Geochim. Cosmochim. Acta
53
, 973
(1989
).85.
B. E. Novikov, “Investigation of thermodynamic properties and behavior of salts with common ions in boiler water at high temperatures,” Ph.D. dissertation, G. M. Krzhizhanovskii State Reserch Power Engineering Institute, Moscow, USSR, 1973.
86.
A.
Anderko
and K. S.
Pitzer
, Geochim. Cosmochim. Acta
57
, 1657
(1993
).87.
I. G.
Economou
, C. J.
Peters
, and J.
de Swaan Arons
, J. Phys. Chem.
99
, 6182
(1995
).88.
89.
90.
R. C. Reid, J. M. Prausnitz, and T. K. Sherwood, The Properties of Gases and Liquids (McGraw-Hill, New York, 1977).
91.
S. M. Walas, Phase Equilibria in Chemical Engineering (Butterworth, Boston, MA, 1985).
This content is only available via PDF.
© 1997 American Institute of Physics.
1997
American Institute of Physics
You do not currently have access to this content.
