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Hydrolysis in supercritical water: Solvent effects as a probe of the reaction mechanism

✍ Scribed by Michael T. Klein; Lori A. Torry; Benjamin C. Wu; Susan H. Townsend; Stephen C. Paspek

Publisher
Elsevier Science
Year
1990
Tongue
English
Weight
531 KB
Volume
3
Category
Article
ISSN
0896-8446

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✦ Synopsis

The extreme pressure dependence of the solvent properties -density, dielectric constant, and solubility parameter -has been exploited in the scrutiny of the mechanism of hydrolysis in supercritical water. Molecules containing the structural moiety of a saturated carbon attached to a heteroatom-containing leaving group undergo parallel pyrolysis and hydrolysis reactions in supercritical water. Herein, kinetics, labelling studies, and salt effects are used to assess likely mechanisms. Under isothermal conditions, the selectivity to the hydrolysis pathway increased with water density. Moreover, the rate constant for hydrolysis also increased with water density and with the addition of salts. An sN2 mechanism with Hz0 as the nucleophile appears to be the most likely candidate.

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