ISSN:
0894-3230
Keywords:
haloalkanes
;
diols
;
kinetics
;
thermodynamics
;
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
Rate constants, k, were determined for the solvolytic reactions of 2-bromo-2-methylbutane, 2-chloro-2-methylbutane 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, γ∞, 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 γ∞ 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 γ∞ interaction parameter table, except for the γ∞ values of 2-chloro-2-methylbutane and 3-chloro-3-methylpentane in diethylene glycol and triethylene glycol, which were obtained using the γ∞ 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. © 1998 John Wiley & Sons, Ltd.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
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