Abstract
AbstractThe kinetics of the gas phase pyrolysis of dimethyl sulfide (DMS) was studied in a static system at 681–723 K by monitoring total pressure‐time behavior. Analysis showed the pressure increase to follow DMS loss. The reaction follows two concurrent paths: equation image with a slow, minor, secondary reaction: equation image In a seasoned reactor the reaction follows a 3/2 order rate law with rate coefficient given by with θ = 2.303 RT in kcal/mol. A free radical mechanism is proposed to account for the data and a theoretical rate coefficient is derived from independent data: which agrees well with the experimental one over the range studied. The reaction is initiated by Me2S → Me + MeS⋅ and propagated by metathetical radical attack on Me2S. C2H4 is formed by an isomerization reaction which may in part be due to a hot radical: equation image Thermochemical data are listed, many from estimations, for both molecular and radical species of interest in the present system.
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