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The pyrolysis of dimethyl sulfide, kinetics and mechanism

โœ Scribed by Lilian G. S. Shum; Sidney W. Benson

Publisher
John Wiley and Sons
Year
1985
Tongue
English
Weight
581 KB
Volume
17
Category
Article
ISSN
0538-8066

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โœฆ Synopsis

The kinetics of the gas phase pyrolysis of dimethyl sulfide (DMS) was studied in a static system a t 681-723 K by monitoring total pressure-time behavior. Analysis showed the pressure increase to follow DMS loss. The reaction follows two concurrent paths:

Me2S

C2H4 + H2S --% CH, + CHzS with a slow, minor, secondary reaction:

In a seasoned reactor the reaction follows a 3/2 order rate law with rate coefficient given by log[k(L"2/mo11'2 s)] = 13.84 _f 0.21 -(51.4 2 0.7)/0 with 0 = 2.303 R T in kcal/mol. A free radical mechanism is proposed to account for the data and a theoretical rate coefficient is derived from independent data: log[k(L'2/mo11'2 s)] = 12.8 t 0.3 -(47 5 1.5)/0 which agrees well with the experimental one over the range studied. The reaction is initiated by Me$ + Me + MeS and propagated by metathetical radical attack on Me$. C2H, is formed by a n isornerization reaction which may in part be due to a hot radical:

Thermochemical data are listed, many from estimations, for both molecular and radical species of interest in the present system.

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