Primary reaction channels and kinetics of the thermal decomposition of phenylsilane
Date
1995
Authors
O'Neal, H.
Ring, M.
Kim, D.
King, K.
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Advisors
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Volume Title
Type:
Journal article
Citation
The Journal of physical chemistry, 1995; 99(23):9397-9402
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Abstract
The thermally induced decomposition of phenylsilane has been investigated by three different experimental methods: a static method, a comparative rate-single pulse shock tube (CR-SPST) method, and a very low-pressure pyrolysis (VLPP) method. Decomposition is mainly heterogeneous under static conditions but appears homogeneous in the other two systems. Homogeneous dissociations occur by two channels with yields, PhSiH<inf>3</inf> →<sup>1</sup> H<inf>2</inf> + PhSiH, φ<inf>1</inf> ∼ 0.84 ± 0.04; PhSiH<inf>3</inf> →<sup>2</sup> PhH + SiH<inf>2</inf>, φ<inf>2</inf> ∼ 0.16 ± 0.04. Coupling of CR-SPST and homogeneous static reactor data spanning temperatures from 693 to 1236 K for the benzene formation channel and adjusting for falloff by RRKM methods gives high-pressure Arrhenius parameters of A<inf>1</inf> = 10<sup>14.0±0.4</sup>, E<inf>1</inf>= 59.3 ± 2.1 and A<inf>2</inf> = 10<sup>13.9±0.2</sup>, E<inf>2</inf> = 62.0 ± 0.9 (A in s<sup>-1</sup> and E in kcal/mol) for the two primary dissociation channels. These parameters yield RRKM calculated rate constants under VLPP conditions which agree within the errors with experimental rate constants. © 1995 American Chemical Society.