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Competitive Photochlorination Reactions of Silane, di-Chloro and tri-Chlorosilanes at 337.1 nm
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  • Competitive Photochlorination Reactions of Silane, di-Chloro and tri-Chlorosilanes at 337.1 nm
  • Competitive Photochlorination Reactions of Silane, di-Chloro and tri-Chlorosilanes at 337.1 nm
저자명
Jung. Kyung-Hoon,Jung. Kwang-Woo
간행물명
Bulletin of the Korean Chemical Society
권/호정보
1987년|8권 4호|pp.242-246 (5 pages)
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대한화학회
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정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

The hydrogen abstraction reactions of $SiH_4, SiH_2Cl_2 ;and; SiHCl_3$ by ground state chlorine atoms generated photochemically from chlorine molecules have been studied at temperatures between 15 and $100^{circ}C.$ The absolute rates for the reactions have been obtained by a competition technique using ethane as a competitor. The rate expressions ($in cm^3/mol/s$) are found to conform to an Arrhenius rate law: $k_{SiH_4} = (7.98 {pm} 0.42) { imes} 10^{13}$ exp $[-(1250 {pm}20)/T].$ $k_{SiH_2Cl_2} = (2.25 {pm} 0.12) { imes} 10^{15}$ exp[-(1010 ${pm}$ 10)/T]. $k_{SiHCl_3} = (9.04 {pm} 0.28) { imes} 10^{14}; exp[-(1200 {pm} 10)/T].$ 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.