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The gas‐phase elimination kinetics of 3‐buten‐1‐methanesulphonate and 3‐methyl‐3‐buten‐1‐methanesulphonate
Author(s) -
Chuchani Gabriel,
Martin Ignacio,
Dominguez Rosa M.
Publication year - 1995
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550270705
Subject(s) - chemistry , arrhenius equation , kinetics , bromide , torr , atmospheric temperature range , gas phase , allyl bromide , reaction rate constant , medicinal chemistry , pyrolysis , thermodynamics , organic chemistry , activation energy , physics , quantum mechanics
Abstract The elimination kinetics of the title compounds were carried out in a static system over the temperature range of 290–330°C and pressure range of 29.5–124 torr. The reactions, carried out in seasoned vessels with allyl bromide, obey first‐order rate law, are homogeneous and unimolecular. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: for 3‐buten‐1‐methanesulphonate, log k 1 (s −1 ) = (12.95 ± 0.53) − (175.3 ± 5.9)kJ mol −1 (2.303 RT ) −1 ; and for 3‐methyl‐3‐buten‐1‐methanesulphonate, log k 1 (s −1 ) = (12.98 ± 0.40) − (174.7 ± 4.5)kJ mol −1 (2.303 RT ) −1 . The olefinic double bond appears to assist in the rate of pyrolysis. The mechanism is described in terms of an intimate ion‐pair intermediate. © 1995 John Wiley & Sons, Inc.