Thermal decomposition of alcohols. II. 2-Methylpropan-2-ol

Abstract

The thermal decomposition of 2-methylpropan-2-ol has been investigated from 503 to 612°C, over initial pressures ranging from 40 to 275 mm and in the presence of toluene from 520 to 602°C. The decomposition is homogeneous and first order with respect to the initial concentrations of alcohol giving the Arrhenius equation (R = 8.31 J mol^-1 K^-1)                            K=10^12.7exp(-249,800/RT) s^-1 for the initial rate. The decomposition of this alcohol is inhibited by the reaction products, mainly 2-methylpropene, and by the addition of toluene. There are contributions from the unimolecular elimination of water (k = 10^13.6exp(-268,000/RT)s^-1) and from a flee radical process (k = 10^11.0 x exp(-227,000/RT) s^-1). A free radical mechanism, which explains the minor products of the reaction and the varying results of other workers, is proposed.