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Kinetics of reactions between methoxycarbonyl, methyl, and methoxy radicals formed in flash photolysis of dimethyl oxalate in gas phase

✍ Scribed by E. Hassinen; P. Riepponen; K. Blomqvist; K. Kalliorinne; A. M. Evseev; J. Koskikallio

Publisher: John Wiley and Sons
Year: 1985
Tongue: English
Weight: 501 KB
Volume: 17
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550171009

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✦ Synopsis

Flash photolysis of dimethyl oxalate produced the radicals CH3, CH30, and COOCH3. Thermally equilibrated methoxycarbonyl radicals did not decompose during radicalradical reactions in the presence of 40-tom 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, COz, CHI, CH3C6H11, and CH30C6Hll. 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, k l = 2.7 x 10" dm3 mo1-l sK1, measured with the same equipment.

CzH4, CzHfj, CH20, CH,OH, CH3OCH3, HCOOCH,, CH3COOCH3, CH3OCOOCH3,

The rate coefficients for reactions (5)-(8) are: k5 = (3.1 + 0.5) X 10" dm3 mol-' s -' k6 = (2.1 + 0.2) X 10" dm3 mol-'s-' k7 = (2.3 + 0.1) x 10" dm3 m o l -' ~-~

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