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http://dx.doi.org/10.5012/bkcs.2005.26.8.1241

Stoichiometric Solvation Effects. Solvolysis of Trifluoromethanesulfonyl Chloride  

Koo, In-Sun (Department of Chemistry Education and Research Institute of Natural Science, Gyeongsang National University)
Yang, Ki-Yull (Department of Chemistry Education and Research Institute of Natural Science, Gyeongsang National University)
Park, Jong-Kuen (Department of Chemistry Education and Research Institute of Natural Science, Gyeongsang National University)
Woo, Mi-Young (Department of Chemistry Education and Research Institute of Natural Science, Gyeongsang National University)
Cho, Jun-Mi (Department of Chemistry Education and Research Institute of Natural Science, Gyeongsang National University)
Lee, Jong-Pal (Department of Chemistry, Dong-A University)
Lee, Ik-Choon (Department of Chemistry, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.26, no.8, 2005 , pp. 1241-1245 More about this Journal
Abstract
Solvolyses of trifluoromethanesulfonyl chloride (TFMSC) in water and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25, 35 and 45 ${^{\circ}C}$. The Grunwald-Winstein plot of first-order rate constants for the solvolytic reaction of TFMSC with YCl (based on 2-adamantyl chloride) shows marked dispersions into three separate curves for three aqueous mixtures. The extended Grunwald-Winstein plots for the solvolysis of TFMSC show better correlation. The large negative ${\Delta}S^{\neq}$ and relatively small positive ${\Delta}H^{\neq}$ reveals that the solvolytic reaction proceeds via a typical bimolecular reaction mechanism. The l and m values determined in various solvents are consistent with the proposed mechanism of the general base catalysis $S_AN/S_N2$reaction mechanism for TFMSC solvolyses based on mass law and stoichiometric solvation effect studies.
Keywords
Dispersion; Stoichiometric solvation effects; Kinetic solvent isotopic effects;
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