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 CH 3 Cl and CH 3 Br are followed for additions of up to three molecules of solvent for F − solvated with D 2 O, CH 3 OH, and C 2 H 5 OH and for Cl − solvated with CH 3 OH, C 2 H 5 OH, CH 3 COCH 3 , HCOOH, and CH 3 COOH. The observed precipitous response of the specific rate to solvation is attributed to intermediate features of plausible reaction energy profiles.
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Böhme et al. (1985) studied this question.