Abstract
The kinetics of the solvolysis of trans-[Coen2Cl2]+ have been followed in mixtures of water with either ethylene carbonate or propylene carbonate over a range of temperatures. Both the enthalpy and entropy of activation for the first order loss of a chloride ion to give [Coen2Cl]2+ in water + ethylene carbonate show a maximum at low mole fractions of ethylene carbonate. As similar extrema in ΔH‡ and ΔS‡ for the same process for this complex and others in water +2-propanol and in water + t-butanol correlate well with extrema in the physical properties of the mixtures which are influenced by changes in solvent structure, it is suggested that these new extrema can be attributed to solvent structure effects. The application of a free energy cycle to the loss of the chloride ion in water and in the mixtures suggests that, although changes in solvent structure influence the cation in the transition state more than the cation in the initial state in water + ethylene carbonate, in water + propylene carbonate the influence of changes in solvent structure approximately balances. This is compared with the application of the free energy cycle to the same process in mixtures of water with a range of cosolvents using kinetic data available in the literature.
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G. S. Groves and C. F. WellsJ. Chem. Soc. Faraday Trans. I 78, 619 (1982).
G. S. Groves and C. F. Wells,J. Chem. Soc. Faraday Trans. I 81, 2475 (1985).
G. S. Groves and C. F. WellsTransition Metal Chem. 11, 20 (1986).
F. Franks and D. J. G. Ives,Quart. Rev. Chem. Soc. 20, 1 (1966).
M. Prabanic, M. Birus, D. Pavlovic, and S. Asperger,J. Chem. Soc. Dalton Trans., 2518 (1973).
G. Akerlof,J. Amer. Chem. Soc. 54, 4125 (1932); F. E. Critchfield, J. A. Gibson, and J. L. Hall,J. Amer. Chem. Soc. 75, 1991 (1953); C. Moreau and G. Douheret,J. Chem. Thermodynamics 8, 403 (1976).
G. S. Groves and C. F. Wells,Intl. J. Chem. Kinetics 18, 529 (1986).
R. H. Stokes,Australian J. Chem. 20, 2087 (1967); H. S. Frank and F. Franks,J. Chem. Phys. 48, 4746 (1968).
J. Wyman,J. Amer. Chem. Soc. 55, 4116 (1933).
K. J. Laidler,Chemical Kinetics, 2nd edn. (McGraw-Hill, New York. 1965), Chap. 5.
E. A. Moelwyn-Hughes,Physical Chemistry, 2nd edn., (Pergamon, Oxford, 1961), Chaps. 7–9, 24.
E. S. Amis,Solvent Effects on Chemical Phenomena, Vol. 1, (Academic Press, New York, 1973), Chap. 5.
C. F. Wells,J. Chem. Soc. Faraday Trans. I 73, 1851 (1977).
K. Nakanishi,Bull. Chem. Soc. Japan 33, 793 (1960).
M. J. Blandamer,Introduction to Chemical Ultrasonics (Academic Press, London, 1973) Chap. 11.
W. E. Jones, L. R. Carey, and J. W. Swaddle,Canad. J. Chem. 56, 2739 (1972); G. A. Lawrance and S. Suvachittanont,Australian J. Chem. 33, 277 (1980); D. A. Palmer, H. Kelm, and G. Daffner,Inorg. Chimica Acta 61, 57 (1982).
W. G. Jackson and A. Sargeson,Inorg. Chem. 17, 1348 (1978); W. G. Jackson and C. M. Begbie,Inorg. Chimica Acta 60, 115 (1982).
C. F. Wells and G. S. Groves,J. Chem. Soc. Faraday Trans. I 81, 3091 (1985), and references therein.
M. J. Blandamer, J. Burgess, S. J. Hamshere, and F. M. Mekhail,Trans. Metal Chem. 4, 77 (1979).
J. Courtot-Coupez and M. L'Her,Compt. rendus Acad. Sci. Paris C 275, 163 (1972).
A. D'Aprano,Gazz. Chim. Ital. 104, 91 (1974); A. D'Aprano, M. Goffredi, and R. Triolo,Electrochim. Acta 21, 139 (1976).
G. S. Groves, K. H. Halawani, and C. F. Wells,J. Chem. Soc. Faraday Trans I, in press.
G. P. Cunningham, G. A. Vidulich, and R. L. Kay,J. Chem. Eng. Data 12, 336 (1967).
C. N. Elgy and C. F. Wells,J. Chem. Soc. Faraday Trans. I 79, 2367 (1983);81, 2145 (1985).
I. M. Sidahmed and C. F. Wells,J. Chem. Soc. Dalton Trans., 1035 (1983); 1969 (1984).
A. E. Eid and C. F. Wells,J. Chem. Soc. Faraday Trans. I, in press;Trans. Metal Chem. 10, 223 (1985);Intl. J. Chem. Kin. 18, 215 (1986).
V. D. Panasyuk and A. V. Arkharov,Ukrain. Khim. Zhur. 31, 338 (1965).
J. Burgess,J. Chem. Soc., 2351 (1970).
V. D. Panasyuk and E. R. Falendysh,Dop. Akad. Nauk. Ukrain. RSR 26, 741 (1964).
V. D. Panasyuk, V. P. Solomko, and L. G. Reiter,Russ. J. Inorg. Chem. 6, 1033 (1961).
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Groves, G.S., Halawani, K.H. & Wells, C.F. Kinetics of the solvolysis of thetrans-dichlorobis (Diaminoethane)-cobalt(III) ion in aqueous ethylene carbonate and aqueous propylene carbonate. J Solution Chem 16, 399–409 (1987). https://doi.org/10.1007/BF00647186
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DOI: https://doi.org/10.1007/BF00647186