Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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The Effect of Pressure on the Solvolysis of Benzylchlorides(Ⅰ). p-Methylbenzyl Chloride in Ethanol-Water Mixtures

  • Published : 1985.10.20
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Abstract

Rate Constants for the solvolysis of p-methylbenzyl chloride in various ethanol-water mixtures were studied at 30 and $40^{\circ}C$ under various pressures up to 1600 bar. The rates of reaction were increased with increasing temperature and pressure, and decreased with increasing solvent composition of ethanol mole fraction. From the rate constants, the values of the activation parameters (${\Delta}V^{\neq},{\Delta}{\beta}^{\neq},{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$) were evaluated. The values of ${\Delta}V^{\neq}\;and\;{\Delta}{\beta}^{\neq}$ exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of solvent structure variation (electrostriction). From the relation between the reaction rate and the dielectric constant of solvent or the number of water molecule participated in the transition state, it could be postulated that the reaction proceeds through $S_N1$ mechanism.

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