Abstract
Intrinsic ionic heats of transport q * o (ion) and ionic heats of transport Q * o (ion) have been evaluated for 53 aqueous ions at infinite dilution at 25°C using the reduction rule proposed by the authors and the limiting laws of Agar, and of Helfand and Kirkwood without electrophoretic terms. q * o (ion) have been found to correlate linearly with the standard ionic entropies of hydration for the 38 ions investigated. The correlation yields three distinctive proportionality constants indicating that the ions may be divided into three distinctive groups. Although the sign of Q * o (ion) is not definite, all values of q * o (ion) are positive. For 17 ions Q * o (ion) are in good agreement with TS * o (ion). Here, S * o (ion) is the ‘absolute’ standard ionic entropy of transport which can be obtained from potentiometric measurements on cells. The values of S * o (ion) were determined by Agar, and recently by Lin and coworkers.
Similar content being viewed by others
References
J. N. Agar,Advances in Electrochemistry and Electrochemical Engineering, Vol. 3, P. Delahay and C. W. Tobias, eds., (Interscience, New York, 1963), Chap. 2.
E. D. Eastman,J. Am. Chem. Soc. 48, 1482 (1926);49, 794 (1927);50, 283; 292 (1928).
J. N. Agar and J. C. R. Turner,Proc. Roy. Soc. (London) A255, 307 (1960);J. Phys. Chem. 64, 1000 (1960).
J. Chanu,Electrochim. Acta 22, 1025 (1977) and the references cited therein.
P. N. Snowdon and J. C. R. Turner,Trans. Faraday Soc. 56, 1409 (1960).
P. N. Snowdon and J. C. R. Turner,Trans. Faraday Soc. 56, 1812 (1960).
A. D. Payton and J. C. R. Turner,Trans. Faraday Soc. 58, 55 (1962).
H. K. Yow, B. P. Chakraborty, and J. Lin,Electrochim. Acta 22, 1013 (1977).
C. J. Petit, J. Lin, and K. E. Renner,J. Solution Chem. 13, 419 (1984).
R. W. Gurney,Ionic Processes in Solution, (McGraw-Hill, New York, 1953).
N. Takeyama and K. Nakashima,J. Phys. Soc. Jpn. 52, 2692 (1983).
N. Takeyama and K. Nakashima,J. Phys. Soc. Jpn. 52, 2699 (1983).
Z. Yogi, H. Kitano, I. Toma, K. Kijima, and T. Ikeda,Bull. Chem. Soc. Jpn. 53, 885 (1980).
R. Mills,J. Phys. Chem. 77, 685 (1973).
K. F. Alexander,Z. Physik. Chem. (Leipzig) 203, 181; 203; 228; 357 (1954).
E. Helfand and J. G. Kirkwood,J. Chem. Phys. 32, 857 (1960).
J. N. Agar,Ann. Rev. Phys. Chem. 15, 469 (1964).
P. Y. Kahana and J. Lin,J. Chem. Phys. 74, 2993 (1981);75, 5043 (1981); T. S. Thacher, C. Y. Mou, U. Mohanty, and J. Lin,J. Chem. Phys. 84 6401 (1986).
S. R. de Groot,Thermodynamics of Irreversible Processes (North-Holland, Amsterdam, 1951).
A. Katchalsky and P. F. Curran,Nonequilibrium Thermodynamics in Biophysics (Harvard Univ. Press, Cambridge, 1965), Chap. 13.
J. Lin, J. A. Bierlein, and J. G. Becsey,J. Solution Chem. 3, 827 (1974).
T. Ikeda, H. Ohe, and S. Kawamura,Bull. Chem. Soc. Jpn. 41, 2858 (1968);
T. Ikeda, Y. Takatsuka, and T. Watanabe,Bull. Chem. Soc. Jpn. 48, 2531 (1975);
T. Ikeda and K. Mita,Rep. Fac. Sci. Shizuoka Univ. 15, 15 (1981).
H. L. Friedman and C. V. Krishnan,Water: A Comprehensive Treatise, Vol. 3, F. Franks, ed., (Plenum, New York, 1973) Chap. 1, p. 55.
Y. Marcus,Introduction to Liquid State Chemistry (John Wiley, London, 1977) Chap. 6, Appendix 6.1.
A. P. Altshuller,J. Chem. Phys. 24, 642 (1956).
S. L. Bertha and G. R. Choppin,Inorg. Chem. 8, 613 (1969).
A. Loewenshuss and Y. Marcus,Chem. Rev. 84, 89 (1984).
K. Nakashima and N. Takeyama,J. Phys. Soc. Jpn. 55, 1021 (1986).
CRC Handbook of Chemistry and Physics, 61st edn., R. C. Weast and M. J. Astle, eds., (CRC Press, Boca Raton, 1980), D-71.
W. G. Breck and J. Lin,Trans. Faraday Soc. 61, 2223 (1965).
H. K. Yow and J. Lin,J. Solution Chem. 12, 487 (1983).
G. Jones and M. Dole,J. Am. Chem. Soc. 51, 2050 (1929).
E. R. Nightingale, Jr.,Chemical Physics of Ionic Solutions, B. E. Conway and R. G. Barradas, eds., (John Wiley, New York, 1966) p. 87.
E. Asmus,Z. Naturforsch., A 4, 589 (1949).
E. R. Nightingale, Jr.,J. Phys. Chem. 63, 1381 (1959).
J. E. Desnoyers and C. Jolicoeur,Comprehensive Treatise of Electrochemistry, Vol. 5, B. E. Conway, J. O'M. Bockris, and E. Yeager, eds., (Plenum, New York, 1983) Chap. 1
W.-Y. Wen,Water and Aqueous Solution, R. A. Horne, ed., (John Wiley, New York, 1972) Chap. 15.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Takeyama, N., Nakashima, K. Proportionality of intrinsic heat of transport to standard entropy of hydration for aqueous ions. J Solution Chem 17, 305–325 (1988). https://doi.org/10.1007/BF00650412
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00650412