Solvolysis of t-butyl chloride in water-rich methanol + water mixtures
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 (xm) is complicated. At 5°C E*A has a maximum at xm= 0.065 and a minimum at xm= 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 xm.