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Single pulse shock tube study on the thermal stability of ketones
Author(s) -
Tsang Wing
Publication year - 1984
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.550161208
Subject(s) - chemistry , shock tube , thermal decomposition , thermal stability , tube (container) , shock (circulatory) , pulse (music) , decomposition , carbon fibers , stability (learning theory) , medicinal chemistry , thermodynamics , computational chemistry , organic chemistry , shock wave , composite number , medicine , physics , materials science , electrical engineering , composite material , detector , engineering , mechanical engineering , machine learning , computer science
5‐Methyl‐hexanone‐2, 3‐methyl‐pentanone‐2, and hexanone‐2 have been decomposed in comparative rate single pulse shock tube experiments. The mechanism of decomposition involves the breaking of carbon‐carbon bonds as well as molecular processes involving 6‐center complexes. The following rate expressions at 1100 K have been obtained:\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{rcl} k(3{\rm - methyl - pentanone - 2} \to {\rm CH}_{\rm 3} {\rm \dot CO} + {\rm sC}_4 {\rm H}_9 .) = 10^{16.4} \exp (- 38,300/T)/{\rm s} \\ k(5{\rm - methyl - hexanone - 2} \to {\rm CH}_{\rm 3} {\rm \dot CO} + {\rm iC}_4 {\rm H}_9 .) = 10^{16.6} \exp (- 40,600/T)/{\rm s} \\ k(5{\rm - methyl - hexanone - 2} \to {\rm CH}_{\rm 3} {\rm COCH}_{\rm 3} + {\rm iC}_4 {\rm H}_8) = 10^{12.56} \exp (- 31,600/T)/{\rm s} \\ k({\rm hexanone - 2} \to {\rm CH}_{\rm 3} {\rm COCH}_{\rm 3} + {\rm C}_3 {\rm H}_6) = 10^{13.28} \exp (- 32,400/T)/{\rm s} \\ \end{array} $$\end{document}These results lead to Δ H f (CH 3 ĊO) = − 13.8 kJ and Δ H f (CH 3 COCH 2· ) = − 12.6 kJ at 300 K. They are compared with existing literature values and some generalizations are made with regard to the stability of carbonyl compounds.