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Thermal decomposition of hexamethylethane in a flow system
Author(s) -
Walker James A.,
Tsang Wing
Publication year - 1979
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/kin.550110806
Subject(s) - chemistry , thermal decomposition , atmospheric temperature range , bond cleavage , shock tube , decomposition , cleavage (geology) , radical , photochemistry , carbon fibers , thermodynamics , organic chemistry , shock wave , catalysis , composite number , physics , materials science , geotechnical engineering , composite material , fracture (geology) , engineering
Hexamethylethane has been decomposed in a flow system in the temperature range of 700–900 K. The mechanism involves carbon–carbon bond cleavage at the most highly substituted position and rapid formation of isobutene from the t ‐butyl radical. The rate expression is\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c}{k({\rm (tC}_{\rm 4} {\rm H}_{\rm 9})_2 \to 2t{\rm C}_{\rm 4} {\rm H}_{\rm 9}.) = 10^{17.4} {\rm exp(} - 36,000/{\rm T)}} & {{\rm sec}^{ - 1}}\\\end{array} $$\end{document}and is completely consistent with deductions from radical buffer, shock‐tube, and direct recombination studies. Of special importance is experimental evidence for large decreases of the A factor with increasing temperature and a high heat of formation for the t ‐butyl radical, Δ H f ( t C 4 H 9 ·) 300 = 52.7 ± 6 kJ.