Solvolysis of t-butyl chloride in water-rich methanol + water mixtures

Abstract

The rates of reaction between t-butyl chloride and water + methanol mixtures (mole fraction of methanol 0.0 to 0.4) have been measured in the temperature range 0 to 20°C. The activation parameters E^*_A, ΔS^*, ΔH^* and ΔG^* are temperature dependent, and the variation of E^*_A with mole fraction of methanol (x_m) is complicated. At 5°C E^*_A has a maximum at x_m= 0.065 and a minimum at x_m= 0.3. The maxima and minima, which are less pronounced at higher temperatures, can be explained in terms of the structure of the mixed solvent. ΔG^* varies almost linearly with x_m.