The fraction of bonds broken in thermal degradation of polyethylene was estimated. Activation energy of the degradation was then calculated from the fraction of bonds broken. It was found that the activation energy thus obtained is close to the values for beta C-C bond scissions and beta C-H bond scissions of hydrocarbon radicals. beta C-H bond scission of radicals is proposed as part of the mechanism of thermal degradation of polyethylene, which provides an understanding of detail of hydrogen transfer in the polymer melt and provides a route for hydrogen gas formation in pyrolysis of polyethylene. (C) 2003 Elsevier Science Ltd. All rights reserved.