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Mechanism and kinetics of the shock-tube decomposition of vinylsilane

✍ Scribed by S. F. Rickborn; M. A. Ring; H. E. O'Neal; D. Coffey Jr.

Publisher: John Wiley and Sons
Year: 1984
Tongue: English
Weight: 798 KB
Volume: 16
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550160402

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✦ Synopsis

The shock-induced thermal decompositions of vinylsilane and vinylsilane-d, (0.2% on argon) have been studied in the temperature range of 1085-1275 K, and at total pressures of about 3100 tom. In systems without silylene traps, some induced decomposition occurs which is attributed to the silylene chain sequence VSiH + C,H, + SiH,, SiH2 + VSiH, VSiH,SiH, + VSiH,SiH + Hz, VSiH,SiH + VSiH + SiH2. In the presence of silylene traps (butadiene and acetylene), the overall decomposition kinetics are log HVSiH,, s-'1 = 14.95 -63,268 ca1/2.303RT and log MVSiD,, s-l) = 15.14 -64,815 ca1/2.303RT. Three primary processes contribute to the decomposition: l,l-H, elimination, 1,2-H2 elimination, and ethylene elimination. Two mechanisms are proposed, one for exclusive primary process formation of C2H4, and the other for both primary and secondary formation routes. Modeling studies are reported which show that both mechanisms can be made compatible with the rate and product yield data within experimental errors.

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