Thermodynamic functions of activation of the alkaline hydrolysis of ethyl benzoate and of ethyl p-nitrobenzoate in ethanol–water mixtures of various compositions at different temperatures

Abstract

This paper presents second-order rate constants for the alkaline hydrolysis of ethyl benzoate and of ethyl p-nitrobenzoate in ethanol–water mixtures in the ethanol mol fraction range 0.16–0.72 and at 278.15–318.15 K measured by a specially developed titrimetric technique. The results show interesting variations in the rate constants with ethanol content at the various temperatures, especially over the mol fraction ranges 0.16–0.25 and 0.4–0.5. The rate constant (k₂ ) data, the Arrhenius activation energy (E_A ) and pre-exponential factor (A) for ethyl benzoate and the parameters of the fitted polynomials from which other derived thermodynamic functions may be calculated are provided as supplementary material.

References

1. P. G. N. Moseley, M. Ohag and M. E. H. El Turabi, Electrochim. Acta, 1980, 25, 943.
2. M. Ohag, A Study of Solute-Solvent Interactions in Aqueous and Partly Aqueous Electrolyte Solutions, Ph.D. Thesis, University of Khartoum, Sudan, 1975.
3. Water, A Comprehensive Treatise, ed. F. Franks, Plenum Press, New York, 1972.
4. F. Franks and J. E. Desnoyers, Water Science Rev., ed. F. Franks, CUP, Cambridge, 1985, 1, 171.
5. F. Franks and D. J. G. Ives, Quart. Rev., 1966, 20 (1), 1.
6. P. G. N. Moseley and M. Ohag, Lab. Practice, 1976, 25, 399.
7. Y. Iskander, R. Tewfik and S. Wasif, J. Chem. Soc., 1966, 424.
8. D. P. Evans, J. J. Gordon and H. B. Watson, J. Chem. Soc., 1937, 1430.
9. E. A. Moelwyn-Hughes, Proc. Roy. Soc. (London) Sect. A, 1953, 220, 386.
10. A. H. Fainberg and S. Winstein, J. Am. Chem. Soc., 1956, 78, 2770.
11. M. J. Blandamer, Advances in Physical Organic Chemistry, ed. V. Gold, Academic Press, New York, 1977, vol. 14, p. 280.
12. J. E. Quinlan and E. S. Amis, J. Am. Chem. Soc., 1955, 77, 4183.
13. E. S. Amis, Solvent Effects on Reaction Rates and Mechanisms, Academic Press, New York and London, 1966, 31.
14. J. Engberts, in Water, A Comprehensive Treatise, ed. F. Franks, Plenum Press, New York, 1979, vol. 6, ch. 4.