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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 21, Number 10
BKCSDE 21(10)
October 20, 2000 

 
Title
Stoichiometric Solvation Effects. Solvolysis of Methanesulfonyl Chloride
Author
In Sun Koo, Kiyull Yang, Sun Kyoung An, Chong-Kwang Lee, Ikchoon Lee
Keywords
Abstract
Solvolyses of methanesulfonyl chloride in water, D²O, CH³OD, and in aqueous binary mixtures of acetone, eth-anol and methanol are investigated at 25, 35 and 45℃. The Grunwald-Winstein plot of first-order rate con-stants for the solvolytic reaction of methanesulfonyl chloride with YCl (based on 2-adamantyl chloride) shows marked dispersions into three separate lines for three aqueous mixtures with a small m value (m < 0.30), and shows a rate maximum for aqueous alcoholic solvents. Stoichiometric third-order rate constants, kww and kaa were calculated from the observed first-order rate constants and (kaw + kwa) was calculated from the kww and kaa values. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed and/or SAN/SN2 reaction mechanism for methanesulfonyl chloride solvolyses based on mass law and stoichiometric solvation effect studies.
Page
1011 - 1014
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