Abstract
It is found for common aprotic solvents that the logarithm of the dielectric constants can be represented by a linear combination of the acceptor numbers (AN) and the donor numbers (DN) (or equivalent parameters),
With this equation, concepts of specific and non-specific solvation are brought under the umbrella of one treatment. The equation does not hold for the highly structured solvents. For these, the dielectric constants predicted on the basis of the acceptor and donor numbers are orders of magnitude larger than the experimental values, revealing how poorly the associates are dissociated by the macroscopically attainable electric fields.
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References
I. A. Koppel and V. A. Palm, inAdvances in Linear Free Energy Relationships, N. B. Chapman and J. Shorter, eds., (Plenum Press, London/New York, 1972).
H. Suhr.Ber. Bunsenges. Phys. Chem. 67, 893 (1963).
W. R. Fawcett and T. M. Krygowski,Aust. J. Chem. 28, 2115 (1975).
A. J. Parker, U. Mayer, R. Schmid, and V. Gutmann,J. Org. Chem. 43, 1843 (1978).
U. Mayer,Pure & Appl. Chem. 51, 1697 (1979).
F. W. Fowler, A. R. Katritzky, and R. J. D. Rutherford,J. Chem. Soc., B 460 (1971).
V. Gutmann,The Donor-Acceptor Approach to Molecular Interactions (Plenum Press, New York, 1978).
A. G. Burden, G. Collier, and J. Shorter,J. Chem. Soc. Perkin Trans. 2, 1627 (1976).
P. M. Spaziante and V. Gutmann,Inorg. Chim. Acta 5, 273 (1971).
C. Reichardt,Solvent Effects in Organic Chemistry (Verlag Chemie, Weinheim/New York, 1979).
E. M. Kosower,J. Am. Chem. Soc. 80, 3253 (1958).
R. Schmid and V. N. Sapunov,Non-formal Kinetics in Search for Chemical Reaction Pathways (Verlag Chemie, Weinheim/New York, 1982).
T. Kagiya, Y. Sumida, and T. Inoue,Bull. Chem. Soc. Japan 41, 767 (1968).
V. Gutmann and R. Schmid,Coord. Chem. Rev. 12, 263 (1974).
U. Mayer and V. Gutmann,Struct. Bonding (Berlin) 12, 113 (1972).
W. B. Jensen,The Lewis Acid-Base Concepts (Wiley, New York, 1980).
M. Herlem and A. I. Popov,J. Am. Chem. Soc. 84, 1431 (1972).
A. I. Popov,Pure Appl. Chem. 41, 275 (1975).
T. Ogata, T. Fujisawa, N. Tanaka, and H. Yokoi,Bull. Chem. Soc. Japan 49, 2759 (1976).
S. G. Smith, A. H. Fainberg, and S. Winstein,J. Am. Chem. Soc. 83, 618 (1961).
R. W. Taft, E. Price, I. R. Fox, I. C. Lewis, K. K. Andersen, and G. T. Davis,J. Am. Chem. Soc. 85, 3146 (1963).
A. Fainberg and S. Winstein,J. Am. Chem. Soc. 78, 2770 (1956).
Y. Tanaka and H. Takenchi,Tetrahedron 24, 6433 (1968).
H. Block and S. M. Walker,Chem. Phys. Lett. 19, 363 (1973).
M. J. Kamlet, J. L. M. Abbound, and R. W. Taft,Prog. Phys. Org. Chem. 13, 485 (1982).
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Schmid, R. Re-interpretation of the solvent dielectric constant in coordination chemical terms. J Solution Chem 12, 135–152 (1983). https://doi.org/10.1007/BF00645354
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DOI: https://doi.org/10.1007/BF00645354