Gas-phase measurements of the influence of stepwise solvation on the kinetics of S_N2 reactions of solvated F⁻ with CH₃Cl and CH₃Br and of solvated Cl⁻ with CH₃Br

1 November 1985

journal article
Published by Canadian Science Publishing in Canadian Journal of Chemistry

Vol. 63 (11) , 3007-3011
https://doi.org/10.1139/v85-499

Abstract

Flowing afterglow measurements are reported which reveal the influence of stepwise solvation on the nucleophilicity of F⁻ and Cl⁻ in the gas phase at room temperature. The specific rates of nucleophilic displacement reactions with CH₃Cl and CH₃Br are followed for additions of up to three molecules of solvent for F⁻ solvated with D₂O, CH₃OH, and C₂H₅OH and for Cl⁻ solvated with CH₃OH, C₂H₅OH, CH₃COCH₃, HCOOH, and CH₃COOH. The observed precipitous response of the specific rate to solvation is attributed to intermediate features of plausible reaction energy profiles.

Keywords

KINETICS

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Gas-phase measurements of the influence of stepwise solvation on the kinetics of SN2 reactions of solvated F− with CH3Cl and CH3Br and of solvated Cl− with CH3Br

Abstract

Keywords

Gas-phase measurements of the influence of stepwise solvation on the kinetics of S_N2 reactions of solvated F⁻ with CH₃Cl and CH₃Br and of solvated Cl⁻ with CH₃Br