Solvolysis rates in aqueous–organic mixed solvents. Part 4. Kinetics of the alkaline decarboxylation of trichloroacetate ion in water–methanol solutions
- 1 January 1977
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 10,p. 1237-1240
- https://doi.org/10.1039/p29770001237
Abstract
The kinetics of the alkaline decarboxylation of trichloroacetate ion in water-methanol solutions covering the whole composition range have been studied over the temperature range 30.0–52.0 °C. The results indicate that the rate of reaction is independent of the concentration of the solvoxide ion and point to a mechanism in which the rate-determining step is formation of CCl3 – carbanion. The rate of reaction varies with methanol concentration in the mixed solvent in a non-linear manner. The activation parameters, ΔH‡ and ΔS‡, showed a minimum at a water : methanol mole ratio of ca. 3:2.Keywords
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