The gas-phase elimination kinetics of 3-buten-1-methanesulphonate and 3-methyl-3-buten-1-methanesulphonate

✍ Scribed by Gabriel Chuchani; Ignacio Martin; Rosa M. Dominguez

• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 259 KB
• Volume: 27
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550270705

✦ Synopsis

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 ally1 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-l-methanesulphonate, log Kl(s-I) = (12.95 -+ 0.53) -(175.3 -+ 5.9)kJ mol-l (2.303IW-l; and for 3-methyl-3-buten-l-methanesulphonate, log kl(s-') = (12.98 2 0.40) -(174.7 2 4.5)kJ m01-~(2.303RT)-~. The olefinic double bond appears to assist in the rate of pyrolysis. The mechanism is described in terms of an intimate ion-pair intermediate.