Abstract
The role of the solvent in reactions involving ions is considered in relation to the structure of liquids. The rate constants and activation parameters for ligand substitutions at divalent transition metal cations in various solvents are compared with those for solvent exchanges. The differences are related to structural properties of the solvents, represented by their heats of evaporation and fluidities, and interpreted with the aid of a model developed from that of Frank and Wen. Water is not a typical solvent.
This Paper was presented at the sumposium, “The Physical Chemistry of Aqueous Systems,” held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
Similar content being viewed by others
References
E. A. Moelwyn-Hughes, Kinetics of Reactions in Solution(Clarendon Press, Oxford, 1933).
E. S. Amis, Kinetics of Chemical Change in Solution(Macmillan, New York, 1949).
W. F. K. Wynne-Jones and H. Eyring, J. Chem. Phys. 3, 492 (1935).
R. P. Bell, J. Chem. Soc., 629 (1943).
J. D. Bernal and R. H. Fowler, J. Chem. Phys., 1, 515 (1933).
D. H. Everett and C. A. Coulson, Trans. Faraday Soc. 36, 633 (1940).
J. O’M. Bockris, Quart. Rev. Chem. Soc. 3, 179 (1949).
H. S. Frank and M. W. Evans, J. Chem. Phys. 13, 507 (1945).
H. S. Frank and W. Y. Wen, Disc. Faraday Soc. 24, 133 (1957).
S. F. Lincoln, Coord. Chem. Rev. 6, 309 (1971).
T. R. Stengle and C. H. Langford, Coord. Chem. Rev. 2, 349 (1967).
J. G. Powles, M. Rhodes, and J. H. Strange, Mol. Phys. 11, 515 (1966), and later papers;
H. G. Hertz, Ber. Bunsenges. Physik. Chem. 71, 979, 999, 1008, 1032 (1967), and later papers.
H. G. Hertz, Angew. Chem. Intern. Ed. 9, 134 (1970).
E. M. Arnett, W. G. Bentrude, J. J. Burke, and P. Duggleby, J. Am. Chem. Soc. 87, 1541 (1965);
E. M. Arnett, P. Duggleby, and J. J. Burke, J. Am. Chem. Soc. 85, 1350 (1963);
E. M. Arnett and D. R. Melvey, Rep. Progr. Chem. 26, 185 (1965);
J. B. Hyne, in Hydrogen-Bonded Solvent Systems, A. K. Covington and P. Jones, ed. (Taylor and Francis, London, 1968), p. 99;
I. Lee and J. B. Hyne, Can. J. Chem. 46, 2333 (1968);
R. E. Robertson, Progr. Phys. Org. Chem. 5, 121 (1967).
F. Franks and D. J. G. Ives, Quart. Rev. Chem. Soc. 20, 1 (1966).
H. P. Bennetto and E. F. Caldin, J. Chem. Soc. (A), 2191 (1971);
ibid., 2198 (1971);
ibid., 2207 (1971);
H. P. Bennetto and E. F. Caldin, Chem. Comm., 599 (1969);
H. P. Bennetto, J. Chem. Soc. (A), 2211 (1969);
H. P. Bennetto, R. S. Bulmer, and E. F. Caldin, in Hydrogen-Bonded Solvent Systems, A. K. Covington and P. Jones, eds. (Taylor and Francis, London, 1968), p. 335.
C. H. Langford and T. R. Stengle, Ann. Rev. Phys. Chem. 19, 193 (1968).
C. H. Langford and H. B. Gray, Ligand Substitution Processes(Benjamin, New York, 1966), p. 7.
M. Eigen and R. G. Wilkins, in Mechanisms of Inorganic Reactions, Advan. Chem. Ser., No. 49 (American Chemical Society, 1965), p. 55.
R. G. Wilkins, Accounts Chem. Res. 3, 408 (1970).
R. M. Fuoss, J. Am. Chem. Soc. 80, 5059 (1958);
M. Eigen, Z. Phys. Chem. (Frankfurt) 1, 176 (1954);
J. E. Prue, J. Chem. Soc., 7534 (1965); J. Chem. Ed. 46, 12 (1969).
D. B. Rorabacher, Inorg. Chem. 5, 1891 (1966).
P. K. Chattopadhyay and J. F. Coetzee, Inorg. Chem. 12, 113 (1973).
W. J. Maellar and D. B. Rorabacher, J. Am. Chem. Soc. 93, 4379 (1971).
F. R. Shu and D. B. Rorabacher, Inorg. Chem. 11, 1496 (1972).
E. A. Guggenheim, Mixtures(Clarendon Press, Oxford, 1952), Chaps. 3 and 4;
J. S. Rowlinson, Quart. Rev. Chem. Soc. 8, 186 (1954).
J. Leffler and E. Grunwald, Rates and Equilibria of Organic Reactions(Wiley, New York, 1963);
C. D. Ritchie and W. Sager, Progr. Phys. Org. Chem. 2, 323 (1964);
J. Shorter, Chem. in Britain 14, 269 (1967); Quart. Rev. Chem. Soc. 24, 433 (1970).
D. W. G. Ives and P. D. Marsden, J. Chem. Soc., 649 (1965).
R. Lumry and S. Rajender, Biopolymers, 9, 1125–1227 (1970).
E. M. Arnett and D. R. McKelvey, in Solute-Solvent Interactions, C. D. Ritchie and J. F. Coetzee, ed. (Marcel Dekker, New York, 1969), Chap. 6.
J. H. Norman, P. Winchill, and R. J. Thorn, Inorg. Chem. 10, 2265 (1971).
J. Greyson, and H. Snell, J. Phys. Chem. 73, 3208 (1969).
V. Gutmann, Coordination Chemistry in Non-aqueous Solutions(Springer, Vienna, 1968).
Physico-chemical Processes in Mixed Aqueous Solvents, F. Franks, ed. (Heinemann, London, 1967);
Hydrogen-Bonded Solvent Systems, A. K. Covington and P. Jones, ed. (Taylor and Francis, London, 1968);
Solute-Solvent Interactions, J. F. Coetzee and C. D. Ritchie, eds. (Marcel Dekker, New York, 1969).
S. Winstein and A. H. Fainberg, J. Am. Chem. Soc. 79, 5937 (1957);
S. J. Dickson and J. B. Hyne, Can. J. Chem. 49, 2394 (1971);
J. M. W. Scott and R. E. Robertson, Can. J. Chem. 50, 17 (1972).
Z. Luz and S. Meiboom, J. Chem. Phys. 40, 2686 (1964).
F. Dickert, H. Hoffmann, and W. Jaenicki, Ber. Bunsenges. Physik. Chem. 74, 500 (1970).
R. G. Pearson and P. Ellgen, Inorg. Chem. 6, 1379 (1967).
R. L. Kay, G. P. Cunningham, and D. F. Evans, in Hydrogen-Bonded Solvent Systems, A. K. Covington and P. Jones, eds. (Taylor and Francis, London, 1968).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1973 Plenum Press, New York
About this chapter
Cite this chapter
Caldin, E.F., Bennetto, H.P. (1973). The Role of Solvent Structure in Ligand Substitution and Solvent Exchange at Some Divalent Transition-Metal Cations. In: Kay, R.L. (eds) The Physical Chemistry of Aqueous System. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-4511-4_7
Download citation
DOI: https://doi.org/10.1007/978-1-4613-4511-4_7
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4613-4513-8
Online ISBN: 978-1-4613-4511-4
eBook Packages: Springer Book Archive