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Kinetic and thermodynamic study of 2-bromo-2-methylbutane, 2-chloro-2-methylbutane and 3-chloro-3-methylpentane in diols

✍ Scribed by Lídia C. Albuquerque; Luisa C. Moita; Ana N. Simões; Raquel C. Gonçalves; Eugénia A. Macedo

Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
91 KB
Volume
11
Category
Article
ISSN
0894-3230

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✦ Synopsis

Rate constants, k, were determined for the solvolytic reactions of 2-bromo-2-methylbutane, 2-chloro-2methylbutane and 3-chloro-3-methylpentane in 10 pure diols at 298.15 K. The Gibbs energies of activation were calculated in order to study the influence of the solvent and to provide mechanistic information about the activation process. By combining these values with a set of infinite dilution activity coefficients, g ? , the transfer Gibbs energies of the reactants (initial state) and of the activated complex (transition state) were obtained, which allowed the solvent effects on both states to be quantitatively analysed. The g ? values were calculated using the UNIFAC group contribution method. The modified Flory-Huggins equation was used in the combinatorial term. The interaction parameters were taken from the specific UNIFAC g ? interaction parameter table, except for the g ? values of 2chloro-2-methylbutane and 3-chloro-3-methylpentane in diethylene glycol and triethylene glycol, which were obtained using the g ? UNIFAC-VLE interaction parameter tables. For comparative purposes all the other infinite dilution activity coefficients of the three solutes in the diols were also calculated using the UNIFAC-VLE parameter tables.

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