Kinetics of neopentyl chloride pyrolysis. I. The molecular decomposition

Abstract

A detailed investigation of the thermal decomposition of neopentyl chloride over the temperature range of 410–496 °C established that the pyrolysis occurs via two concurrent processes: (i) a unimolecular decomposition accompanied by a Wagner–Meerwein rearrangement giving methylbutenes and hydrogen chloride and (ii) a radical-chain decomposition to methane, isobutene, methyl chloride, 1-chloro-2-methylpropene, 3-chloro-2-methylpropene, 1,1-dimethylcyclopropane, and hydrogen chloride. The molecular reaction accounts for 30–40% of the overall decomposition. The Arrhenius equation for the molecular process is given by k1(s−1) = 1013.26 ± 0.36e−60 000 ± 1640/RT. The nature of the transition state for the decomposition is discussed in terms of the unique molecular structure of neopentyl chloride.