Accurate thermodynamic analysis of the rate constants of solvolysis of t-butyl chloride in t-butanol. An unexpectedly high negative value of the heat capacity of activation

Abstract

A thermodynamic analysis of the rate constants of solvolysis of t-butyl chloride in t-butanol is made in the temperature range 27–60 °C and at 1 atm pressure. A mixed graphical and analytical method is used to obtain ΔH^{[graphic omitted]}_P, ΔS^{[graphic omitted]}_P and ΔC^{[graphic omitted]}_P over the whole temperature interval. An unexpected, high negative value of ΔC^{[graphic omitted]}_P and a ΔS^{[graphic omitted]}_P value which decreases with increasing temperature, are obtained. Some conclusions about the solvent involvement in the activated complex are drawn from these results.