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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 6, Number 5
BKCSDE 6(5)
May 20, 1985 

 
Title
The Effect of Pressure on the Solvolysis of Benzylchlorides(Ⅰ). p-Methylbenzyl Chloride in Ethanol-Water Mixtures
Author
Oh Cheun Kwun, Jin Burm Kyong
Keywords
Abstract
Rate Constants for the solvolysis of p-methylbenzyl chloride in various ethanol-water mixtures were studied at 30 and 40℃ 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 (ΔV≠, Δβ≠, ΔH≠ and ΔS≠) were evaluated. The values of ΔV≠ and Δβ≠ 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 SN1 mechanism.
Page
259 - 263
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