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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 8, Number 4
April 20, 1987 

Competitive Photochlorination Reactions of Silane, di-Chloro and tri-Chlorosilanes at 337.1 nm
Kyung-Hoon Jung*, Kwang Woo Jung
The hydrogen abstraction reactions of SiH4, SiH2Cl2 and SiHCl3 by ground state chlorine atoms generated photochemically from chlorine molecules have been studied at temperatures between 15 and 100℃. The absolute rates for the reactions have been obtained by a competition technique using ethane as a competitor. The rate expressions (in cm3/mol/s) are found to conform to an Arrhenius rate law: kSiH4 = (7.98 ± 0.42) × 1013 exp [-(l250 ± 20)/T]. kSiH2Cl2 = (2.25 ± 0.12) × 1015 exp[-(1010 ± 10)/T]. kSiHCl3 = (9.04 ± 0.28) × 1014 exp[-(1200 ± 10)/T]. The activation energies obtained from this study represent the same trend as with the carbon analogues, while this trend was not found with respect to the bond dissociation energies among silicon compound homologues. These anomalous behaviors were interpreted in terms of electronic effects and of the structural differences between these compounds.
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