ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Flash photolysis of dimethyl oxalate produced the radicals CH3, CH3O, and COOCH3. Thermally equilibrated methoxycarbonyl radicals did not decompose during radicalradical reactions in the presence of 40-torr cyclohexane in the temperature range 298-448 K. Cyclohexyl radicals were also generated during the flash photolysis of the reaction mixture. Rate coefficients of radical-radical reactions were calculated from the amounts of stable products determined by gas chromatography: CO, CO2, CH4, C2H4, C2H6, CH2O, CH3OH, CH3OCH3, HCOOCH3, CH3COOCH3, CH3OCOOCH3, CH3C6H11, and CH3OC6H11. Calculations were performed using an iterative computer integration program. Absolute values of rate coefficients were based on the rate coefficient of the reaction between methyl radicals, k1 = 2.7 × 1010 dm3 mol-1 s-1, measured with the same equipment. The rate coefficients for reactions (5)-(8) are: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} k_5 = (3.1 + 0.5) \times 10^{10} \,{\rm dm}^{\rm 3} \,{\rm mol}^{{\rm - 1}} \,{\rm s}^{{\rm - 1}} \\ k_6 = (2.1 + 0.2) \times 10^{10} \,{\rm dm}^{\rm 3} \,{\rm mol}^{{\rm - 1}} \,{\rm s}^{{\rm - 1}} \\ k_7 = (2.3 + 0.1) \times 10^{10} \,{\rm dm}^{\rm 3} \,{\rm mol}^{{\rm - 1}} \,{\rm s}^{{\rm - 1}} \\ \end{array} $$\end{document}
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550171009
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