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http://dx.doi.org/10.5012/jkcs.2004.48.3.254

Kinetic Studies for the Reactions of Pyridine with Benzoylchlorides under High Pressure and High Vacuum  

Kim, Se-Kyong (Department of Chemistry, Hanyang University)
Publication Information
Journal of the Korean Chemical Society / v.48, no.3, 2004 , pp. 254-260 More about this Journal
Abstract
The reaction rates of para-substituted benzoyl chlorides ($p-CH_3$, p-H, $p-NO_2$) with pyridine have been measured employing the conductometry method in acetonitrile. The pseudo first-order and second-order rate constants were determined at various pressures and temperatures. The activation parameters (${\Delta}V{\ddagger},\;{\Delta}{\beta}{\ddagger},\;{\Delta}H{\ddagger},\;{\Delta}S{\ddagger},\;{\Delta}G{\ddagger}$) and the Hammett ${\rho}$-values are determined from the values of rate constant. The values of ${\Delta}V{\ddagger},\;{\Delta}{\beta}{\ddagger}\;and\;{\Delta}S{\ddagger}$ are all negative. The Hammett ${\rho}$-values are positive for the substrate (${\rho}_Y$) over the given pressure range. The results of kinetic studies, for the pressure and substituent changes, show that these reactions are proceeded by a typical $SN_2$reaction mechanism and its bond formation is favored with elevating pressure.
Keywords
Conductometry; Kinetic; High Pressure; High Vacuum;
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