Mechanisms and kinetics models for hydrocarbon pyrolysis

Kinetics models based on the governing mechanism for a multi-step chemical reaction provide insight into the underlying chemistry and they can be extrapolated more confidently than can empirical kinetics models. The field of thermal hydrocarbon chemistry is sufficiently mature that the types of free-radical reactions that are important have been reasonably well elucidated. Moreover, rate constants for many elementary reactions have been measured experimentally, and rate constants for other reactions can be estimated from thermochemical kinetics considerations. These circumstances facilitate the development of quantitative mechanism-based mathematical models for hydrocarbon pyrolysis. This paper provides an overview of the current approaches for mechanistic modeling of hydrocarbon pyrolysis. The steps involved in developing both analytical and numerical models are described and illustrated with examples from the literature.