The pyrolysis of alkanethiols. Part 1. Kinetics of the pyrolysis of butane-1-thiol, butane-2-thiol, and 2-methylpropane-2-thiol
- 1 January 1977
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 4,p. 439-443
- https://doi.org/10.1039/p29770000439
Abstract
The kinetics of the pyrolyses of the title alkanethiols into hydrogen sulphide and olefins have been studied in a static system in the temperature range 696.6–762.1 K and found, in the presence of cyclohexene, to be a homogeneous free radical process. For 2-methylpropane-2-thiol, the order of the reaction is 3/2 and the observed rate constant is expressible by the Arrhenius equation(i). For both butane-1- and -2-thiol, the order of the reaction is 3/2k/cm mol–½ s–1= 1012.07 ± 0.04 exp(–169 800 ± 600 J mol–1/RT)(i) 1 and the rate constants are given by (ii) and (iii), respectively. A radical mechanism consistent with the results is proposed. k/s–1= 109.84 ± 0.05 exp(–178 100 ±800 J mol–1/RT)(ii)k/s–1= 108.68 ± 0.02 exp(–174 600 ±300 J mol–1/RT)(iii)Keywords
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