Abstract
The volumetric specific heats and densities of alkali fluorides, alkali bromides, and soduum halides were measured in D2O at 25°C in the concentration range 0.05 to 1 aquamolal. The results can be combined with data in H2O to give the corresponding standard and excess transfer functions from H2O to D2O. The volumes and heat capacities of transfer are both negative but, contrary to the hydration functions, show little dependence on ionic size and sign. Also, while heats, entropies, and volumes of transfer are usually small compared with the hydration functions, the heat capacity of transfer is of comparable magnitude. These observations, when interpreted with the Frank and Wen model, suggest that the total number of water molecules in the hydration cosphere is approximately constant for all alkali halides and that heat capacities are more sensitive to structural interactions than volumes and enthalpies. The sign of the excess transfer functions is consistent with the presence of structural ion-ion interactions, but no systematic trend with ionic size can be detected in view of the large experimental uncertainty.
Similar content being viewed by others
References
J. E. Desnoyers, M. Arel, G. Perron, and C. Jolicoeur,J. Phys. Chem. 73, 3346 (1969).
J.-L. Fortier, P.-A. Leduc, and J. E. Desnoyers,J. Solution Chem., in press.
P. R. Philip and J. E. Desnoyers,J. Solution Chem. 1, 353 (1972); see other references cited therein.
E. M. Arnett and D. R. McKelvey, inSolute-Solvent Interactions, J. F. Coetzee and C. D. Ritchie, eds. (M. Dekker, 1969).
B. E. Conway and L. H. Laliberté,Trans Faraday Soc. 66, 3032 (1970).
P. Picker, E. Tremblay, and C. Jolicoeur,J. Solution Chem., in press.
P. Picker, P.-A. Leduc, P. R. Philip, and J. E. Desnoyers,J. Chem. Thermodyn. 3, 631 (1971).
O. Redlich and D. M. Meyer,Chem. Rev. 64, 221 (1964).
P. H. Bevington,Data Reduction and Error Analysis for the Physical Sciences (McGraw-Hill, New York, 1969).
H. S. Frank and J. V. Kennedy, private communication.
D. H. Everett and C. A. Coulson,Trans. Faraday Soc. 36, 633 (1940).
G. N. Lewis and M. RandallThermodynamics (McGraw-Hill, New York, 1923), Chap. 7.
H. S. Frank and M. W. Evans,J. Chem. Phys. 13, 507 (1945).
C. V. Krishnan and H. L. Friedman,J. Phys. Chem. 74, 2356 (1970).
J. Greyson and H. Snell,J. Phys. Chem 73, 3208 (1969).
R. L. Kay,Advan. Chem. Ser. 73, (1968).
J. E. Desnoyers and G. PerronJ. Solution Chem. 1, 199 (1972).
J. E. Desnoyers and C. Jolicoeur, inModern Aspects of Electrochemistry, J. O'M. Bockris and B. E. Conway, eds. (Plenum Press, New York, 1969), Vol. 1, p. 1.
H. Rüterjans, F. Schreirer, U. Sage, and Th. Ackerman,J. Phys. Chem. 73, 986 (1969).
C. de Visser and G. Somsen,J. Chem. Soc. Faraday Trans. I 69, 1440 (1973).
F. D. Rossini,Selected Values of Chemical Thermodynamic Properties, N.B.S. Circular 500 (1952).
T. C. Waddington,Trans Faraday Soc. 62, 1482 (1966).
H. S. Frank and W.-Y. Wen,Disc. Faraday Soc. 24, 133 (1957).
A. Ben-Naim,Trans. Faraday Soc. 66, 2749 (1970).
J. O'M. Bockris and A. K. N. Reddy,Modern Electrochemistry, (Plenum Press, New York), Chap. 2.
C. G. Swain and R. F. W. Bader,Tetrahedron 10, 182 (1960).
N. Desrosiers, G. Perron, J. G. Mathieson, B. E. Conway, and J. E. Desnoyers,J. Solution Chem., accepted for publication.
P. R. Philip and C. Jolicoeur,J. Phys. Chem. 77, 3071 (1973).
R. M. Lawrence and R. F. Kruh,J. Chem. Phys. 47, 4758 (1967).
P.-A. Leduc, J.-L. Fortier, and J. E. Desnoyers,J. Phys. Chem., in press.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Fortier, JL., Philip, P.R. & Desnoyers, J.E. Thermodynamic properties of alkali halides. III. Volumes and heat capacities of transfer from H2O to D2O at 25°C. J Solution Chem 3, 523–538 (1974). https://doi.org/10.1007/BF00648137
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00648137