ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
3,3-Dimethylbutanol-2 (3,3-DMB-ol-2) and 2,3-dimethylbutanol-2 (2,3-DMB-ol-2) have been decomposed in comparative-rate single-pulse shock-tube experiments. The mechanisms of the decompositions are The rate expressions are \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm B} (2,3{\rm - DBM - ol - 2}) = 10^{16.24} {\rm exp}(- 37,400/T)\sec ^{- 1}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm EP} (2,3{\rm - DBM - ol - 2}) = 10^{14.17} {\rm exp}(- 32,300/T)\sec ^{- 1}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm ET} (2,3{\rm - DBM - ol - 2}) = 10^{13.66} {\rm exp}(- 32,700/T)\sec ^{- 1}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm B} (3,3{\rm - DBM - ol - 2}) = 10^{16.33} {\rm exp}(- 37,500/T)\sec ^{- 1}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm EP} (3,3{\rm - DBM - ol - 2}) = 10^{14.0} {\rm exp}(- 34,200/T)\sec ^{- 1}$$\end{document} They lead to D(iC3H7—H) - D((CH3)2(OH) C—H) = 8.3 kJ and D(C2H5—H) - D(CH3(OH) CH—H) = 24.2 kJ.These data, in conjunction with reasonable assumptions, give \documentclass{article}\pagestyle{empty}\begin{document}$$k(t{\rm C}_{\rm 4} {\rm H}_{\rm 9} {\rm OH} \to {\rm CH}_{\rm 3} \cdot + \cdot {\rm C(CH}_{\rm 3} {\rm)}_{\rm 2} {\rm OH}) = 10^{16.8} {\rm exp}(- 40,900/T)\sec ^{- 1} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k(i{\rm C}_{\rm 3} {\rm H}_{\rm 7} {\rm OH} \to {\rm CH}_{\rm 3} \cdot + \cdot {\rm CH(CH}_{\rm 3} {\rm)OH}) = 10^{16.5} {\rm exp}(- 41,100/T)\sec ^{- 1}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k(n{\rm C}_{\rm 3} {\rm H}_{\rm 7} {\rm OH} \to {\rm CH}_{\rm 3} \cdot + \cdot {\rm CH}_{\rm 2} {\rm CH}_{\rm 2} {\rm OH}) = 10^{16.2} {\rm exp}(- 41,100/T)\sec ^{- 1}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$k({\rm C}_{\rm 2} {\rm H}_{\rm 5} {\rm OH} \to {\rm CH}_{\rm 3} \cdot + \cdot {\rm CH}_{\rm 2} {\rm OH}) = 10^{16.4} {\rm exp}(- 42,500/T)\sec ^{- 1}$$\end{document}andThe rate expressions for the decomposition of 2,3-DMB-1 and 3,3-DMB-1 are \documentclass{article}\pagestyle{empty}\begin{document}$$ k(2,3{\rm - DMB - 1} \to {\rm CH}_3 \cdot + {\rm H}_2 {\rm C} = {\rm C}({\rm CH}_3 ) - \mathop {\mathop {\rm C}\limits^{\rm .} {\rm H}({\rm CH}_3 )) = 10^{16.0} \exp ( - 35,700/T)\sec ^{ - 1} } $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k(3,3{\rm - DMB - 1} \to {\rm CH}_{\rm 3} \cdot + {\rm H}_2 {\rm C = CH} - \mathop {\rm C}\limits^{\rm .} ({\rm CH}_3 )_2 ) = 10^{16.2} \exp ( - 35,500/T)\sec ^{ - 1} $$\end{document}
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550080203
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