Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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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)
  • Published : 2005.08.20
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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.

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References

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