Structural interpretation of solvolysis of t-butyl chloride and t-butyl bromide in t-butanol based on temperature and pressure dependence of rate constants

Abstract

Pressure and temperature effects on the rate constants of t-butyl chloride and t-butyl bromide in t-butanol have been studied over the intervals 1–1000 bar and 27–60°C, respectively. An exceptionally low absolute value of ΔV≠ connected with a very high and negative ΔC≠p is observed for t-butyl chloride, contrary to t-butyl bromide which presents much more common values for those functions.Some conclusions are drawn in terms of solvent structure and its involvement in the transition state.