An experimental study of the influence of hydration on the reactivity of the hydroxide anion in the gas phase at room temperature

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Abstract
Flowing afterglow measurements of rate constants and ionic products are reported which explore the influence of step-wise hydration on the reactivity of the hydroxide anion in the gas phase at 296 ± 2 K. Rate constants have been measured for the reactions of OH−•(H2O)n and/or OD−•(D2O)n with CO2, SO2, CH3OH, C2H5OH, C2H2, CH3COCH3, CH3NO2, and HCN, in most instances for values of n from 0 to 3. The reactions with CO2 and SO2 involve ligand addition or exchange and the results of their study corroborate earlier measurements. The remaining reactions proceed by proton transfer. For these reactions the results establish trends in reactivity as a function of step-wise hydration when relative acidity is preserved and when a reversal occurs in the relative acidity upon hydration. The fast hydrated acid–base reactions were observed to establish interesting hydrated product ions many of which underwent secondary reactions involving the exchange of H2O or D2O for the reagent molecule.

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