Kinetic isotope effects. Part 3.—Bromination of acetone in concentrated salt media

Abstract

Measurements are reported on the rates of bromination of acetone and deuterated acetone in alkaline media containing large concentrations of lithium, sodium and potassium bromides. The retarding influence of the cations is in the order Li>Na>K and the results are interpreted in terms of the incomplete dissociation of LiOH, NaOH and KOH, with the catalytic activity of the ion pair apparently being zero at the lower salt concentrations. At the higher salt concentrations the theoretical and experimental results tend to diverge. The apparent kinetic isotope effect decreases in the same order as the rates, but on correcting for ion association the value is constant at the lower salt concentrations.