Time-resolved LMR measurement of the rate constants of the reactions SiH3+SiH3 and SiH3+Cl
In: Chemical Physics, Jg. 181 (1994-03-01), S. 119-128
Online
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Zugriff:
The kinetics of the reactions SiH 3 +SiH 3 and SiH 3 +Cl were studied using time-resolved laser magnetic resonance (LMR). The silyl radical arising in KrF laser (248 nm) photolysis of SiH 4 /COCl 2 /Ar mixture was detected. The rate constants obtained from the decay kinetics of SiH 3 signals at T =295 are k 1 (SiH 3 +SiH 3 )=(1.6±0.5)×10 −11 cm 3 /s and k 2 (SiH 3 +Cl)=(3.2±1.0)×10 −11 cm 3 /s. The values of k 1 and k 2 were found to be unchanged under variation in argon pressure from 6 to 17.3 Torr. The other rate constants measured and estimated are k 3 (SiH 4 +Cl)=(2.5±0.5)×10 −10 cm 3 /s, k 4 (SiH 3 +CO)⩽7×10 −16 cm 3 /s, k 5 (SiH 3 +HCl)⩽(1.8±0.5)×10 −15 cm 3 /s, k 6 (SiH 3 +COCl 2 )⩽5×10 −15 cm 3 /s and k 7 (SiH 3 +NF 3 )⩽5×10 −15 cm 3 /s. Possible reasons for the lower rate constants of hydrogen atom abstraction by chlorine atom for the reaction involving SiH 3 compared to that for the reaction with the molecule SiH 4 are discussed. It is assumed that in collision SiH 3 and Cl species are oriented so that the probability of their approach in the configuration favourable for the abstraction reaction decreases.
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Time-resolved LMR measurement of the rate constants of the reactions SiH3+SiH3 and SiH3+Cl
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Autor/in / Beteiligte Person: | Baklanov, A.V. ; Chichinin, A.I. |
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Zeitschrift: | Chemical Physics, Jg. 181 (1994-03-01), S. 119-128 |
Veröffentlichung: | Elsevier BV, 1994 |
Medientyp: | unknown |
ISSN: | 0301-0104 (print) |
DOI: | 10.1016/0301-0104(94)85020-8 |
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