Abstract: | Benzyl chloride and benzyl acetate were photolyzed in 30% methanol–water mixtures (V/V) at 0°C. The photolysis produces benzyl carbocations that react with nucleophiles. The reaction products were analyzed by gas chromatography or liquid chromatography. From the amounts of products the relative values of rate constants of reactions of benzyl carbocation with nucleophiles N and water k(N)/k(H2O) were calculated. Benzyl carbocation reacts with I?, Br?, Cl?, and Ac? ions with approximately diffusion-controlled rate. A value of 2.4 × 107 dm3 mol?1 s?1 for the rate constant k(H2O) and a lifetime of 0.7 ns were estimated for benzyl carbocation in the aqueous solution. |