Molecular decomposition of polyolefins: Kinetic parameters and geometry of the transition state

Abstract

The experimental data on the molecular decomposition of olefins ( 1 -pentens) of various structures to two olefins in a gas phase were analyzed by means of the parabola intersection method. The enthalpies and kinetic parameters characterizing such decomposition were calculated for eighteen reactions. Decomposition of olefins representing two-centered concerted re action was found to be characterized by a very high classic potential barrier of thermoneutral reaction (197.4 kJ/mol). The kinetic parameters (activation energy and velocity constant) of fifteen reverse reactions of formation of olefins from two alkenes were calculated using the parabola-intersection method. The factors affect ing the activation energy of the reactions of olefin decomposition and formation are discussed. Quantum chemical calculations of the transition state energy and geometry for six reactions of olefin decomposition were performed.