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Kinetics of the initiation step of the thermal decomposition of SiCl 4
Author(s) -
Catoire L.,
Woiki D.,
Roth P.
Publication year - 1997
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1997)29:6<415::aid-kin2>3.0.co;2-x
Subject(s) - chemistry , thermal decomposition , decomposition , kinetics , kinetic energy , bar (unit) , thermal , thermodynamics , analytical chemistry (journal) , computational chemistry , organic chemistry , physics , quantum mechanics , meteorology
The initiation reaction of the thermal decomposition of silicon tetrachloride $$SiCl_4\,+\,M\,{\buildrel{k_1}\over{\longrightarrow}} SiCl_3\,+Cl\,+M \eqno(R1)$$ was studied behind reflected shock waves at temperatures between 1550 K and 2370 K and pressures between 1 and 1.5 bar. Atomic resonance absorption spectrometry (ARAS) was applied for time‐resolved measurements of H atoms at the L α ‐line in SiCl 4 /H 2 /Ar systems. Additional experiments were performed in the SiCl 4 /Ar system following the absorption of SiCl 4 at the L α ‐line. Rate coefficients for the reaction (RI) were determined to be: $$k_1=4.8\times 10^{16}\exp(-40954 K/T) cm^3 mol^{-1} s^{-1}.$$ The choice between two possible alternatives of the first decomposition step, namely elimination of either Cl 2 or Cl, has been made in favor of the second reaction on the basis of kinetic and energetic considerations. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 415–420, 1997.