ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 30, Number 2
JKCSEZ 30(2)
April 20, 1986 

The rate constants for the solvolysis reactions of p-chlorobenzyl chloride in ethanol-water mixtures were determinded at 30° and 40℃ up to 1,600bar. Rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. The plots of ln k against pressure are fitted to a second-order function in P, and values of ΔV≠ and Δβ≠ are obtained. The values of ΔV≠ and Δβ≠ extremum behavior at about 0.20 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation. From the relation between the plots of ln k versus the solvent parameter, q ≡ (D-1)/(2D+1), or the logarithmic molar water concentration, In Cw, it could be estimated that the reaction proceeds through SN1(2) mechanism.