Abstract
In a continuing effort to predict the physicochemical properties of seawater from the properties of single aqueous electrolyte solutions, the pairwise heats of mixing at constant molal ionic strength,I=1.0 ional, have been determined for the six possible pairs of salts from the set (NaCl, Na2SO4, MgCl2, MgSO4) at 30°C. In addition, heats of dilution for two aqueous solutions formed from these salts and havingI=1.0 ional have been determined at 30°C. In order to present the most thermodynamically consistent results, it was found necessary to apply a correction term to the relative apparent equivalent enthalpies given in the literature at 30°C. These correction terms derived from a consideration of published results on heats of dilution at very low concentrations. Further, in order to make predictions for seawater at 25°C, it was deemed desirable to refit existing heat-capacity data. The heats relative apparent equivalent enthalpies for the two mixtures mentioned as well as for seawater. The estimates are based on the theoretical equation of Reilly and Wood for charge-asymmetric mixtures which derives from the work of Friedman. In the most applicable cases, the estimates agree with experimental relative apparent equivalent enthalpies to within 5%. In general, the results substantiate the theoretical equation.
Similar content being viewed by others
References
F. J. Millero,J. Solution Chem. 2, 1 (1973).
T. F. Young,Rec. Chem. Prog. 12, 81 (1951).
T. F. Young and M. B. Smith,J. Phys. Chem. 70, 716 (1954).
Y. C. Wu,J. Phys. Chem. 74, 3781 (1970).
F. J. Millero, inThe Sea, Vol. 5,Marine Chemistry, A. E. Maxwell et al., eds. (John Wiley and Sons, New York, 1974).
H. S. Harned and R. A. Robinson,Multicomponent Electrolyte Solutions (Pergamon Press, New York, 1968).
H. S. Anderson and R. H. Wood, inWater, a Comprehensive Treatise, Vol. 3, F. Franks, ed. (Plenum Press, 1973), Chap. 2.
R. H. Wood and P. J. Reilly,Ann. Rev. Phys. Chem. 21, 287 (1970).
H. L. Friedman,Ionic Solution Theory (John Wiley-Interscience, New York, 1962).
H. L. Friedman,J. Solution Chem. 1, 387, 413, 419 (1972).
H. L. Friedman and C. V. Krishnan,J. Phys. Chem. 78, 1927 (1974).
R. H. Wood and M. V. Falcone,J. Phys. Chem. 79, 1540 (1975).
P. J. Reilly and R. H. Wood,J. Phys. Chem. 73, 4292 (1969).
W. H. Leung and F. J. Millero,J. Chem. Thermodyn. 7, 1067 (1975).
F. J. Millero, L. D. Hansen, and E. V. Hoff,J. Mar. Res. 31, 21 (1973).
R. H. Wood, M. Ghamkhar, and J. D. Patton,J. Phys. Chem. 73, 4298 (1969).
R. B. Cassel and R. H. Wood,J. Phys. Chem. 78, 1924 (1974).
R. F. Srna and R. H. Wood,J. Phys. Chem. 79, 1535 (1975).
W. H. Leung and F. J. Millero,J. Solution Chem. 4, 145 (1975).
H. P. Hopkins, Jr., W. C. Duer, and F. J. Millero,J. Solution Chem. (1976), in press.
S. Lee, The Apparent and Partial Molal Volumes of Electrolytes in Water and in Aqueous Sodium Chloride Solutions, Dissertation, Yale University (1965).
F. J. Millero and W. Masterton,J. Phys. Chem. 78, 1287 (1974).
G. N. Lewis and M. Randall, inThermodynamics, 2nd rev. ed., K. S. Pitzer and L. Brewer, eds. (McGraw-Hill, New York, 1961).
H. S. Jongenburger and R. H. Wood,J. Phys. Chem. 69, 4231 (1965).
V. B. Parker,Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. 2 (NSRDS-NBS 2), U.S. Department of Commerce, April 1, 1965.
H. P. Snipes, C. Manly, and D. D. Ensor,J. Chem. Eng. Data 20, 287 (1975).
P. T. Thompson, D. E. Smith, and R. H. Wood,J. Chem. Eng. Data 19, 386 (1974).
E. Lange and H. Streeck,Z. Phys. Chem. 152A, 1 (1931).
E. Lange and H. Streeck,Z. Phys. Chem. 157A, 1 (1931).
J.-L. Fortier, P.-A. Leduc, and J. E. Desnoyers,J. Solution Chem. 3, 323 (1974).
G. Perron, J. E. Desnoyers, and F. J. Millero,Can. J. Chem. 53, 1134 (1975).
G. Perron, J. E. Desnoyers, and F. J. Millero,Can. J. Chem. 52, 3738 (1974).
F. J. Millero, inThe Oceans Handbook, R. A. Horne, ed. (Marcel Dekker, New York, 1976, in press), Chap. 4.
F. J. Millero, G. Perron, and J. E. Desnoyers,J. Geophys. Res. 78, 4499 (1973).
V. B. Parker, D. D. Wagman, and W. H. Evans, Selected Values of Chemical Thermodynamic Properties,Nat. Bur. Stand. Tech. Note 270-6, U. S. Government Printing Office, November 1971.
J. E. Desnoyers, C. de Visser, G. Perron, and P. Picker,J. Solution Chem., submitted.
Author information
Authors and Affiliations
Additional information
Taken in part from the Ph.D. dissertation of W. H. Leung, University of Miami, Miami, Florida 33149.
Rights and permissions
About this article
Cite this article
Duer, W.C., Leung, W.H., Oglesby, G.B. et al. Seawater—A test of multicomponent electrolyte solution theories. II. Enthalpy of mixing and dilution of the major sea salts. J Solution Chem 5, 509–528 (1976). https://doi.org/10.1007/BF00650467
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00650467