✦ LIBER ✦

The temperature dependence of the rate constant for the gas phase disproportionation reaction of CH3O2 radicals

✍ Scribed by Michael J. Kurylo; Timothy J. Wallington

Publisher: Elsevier Science
Year: 1987
Tongue: English
Weight: 467 KB
Volume: 138
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(87)80121-5

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✦ Synopsis

Flash photolysis kinetic absorption spectroscopy was used to investigate the gas phase disproportionation reaction of CH302 radicals over the temperature range 228-380 K at pressures between 50 and 400 Torr of nitrogen diluent. The measured secondorder rate constants, defined by the expression -d[ CH302] Idt = 2k, [ CH,OZ] 2, were independent of pressure and were used to derive the Arrhenius expression k, = ( 1.7 ? 0.4) x 1 O-I3 exp [ ( 220 f 70)/T] cm3 molecule-' s-I. The results are compared with previous literature data and the mechanistic implications are discussed.

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The flash photolysis resonance fluorescence technique was used to measure the rate constants of the reaction 0 + 0 2 + M -0 3 + M (M = N2,02. Ar, and He) as a function of temperature. The results for the rate constants are given by knf(218 The activation energies with N2,02, and Ar as third bodies

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Substituent effects on the disproportionation-combination rate constant ratios for gas-phase halocarbon radicals. II. Reactions of •CF3 +CF3CH2CH2• and CF3CH2CH2• + CF3CH2CH2•

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Disproportionation/combination rate constant ratios, k , / k , , have been measured for the collision between CF3CH2CH2 and CF3 radicals to be 0.022 ? 0 002 and for CF3CH2CH2 and CF3CH2CH2 radicals to be 0.100 IT 0.002. Comparison to previous work from this laboratory for the reaction of CF3CH2CHCI

The rate constant of the gas-phase react

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## By observing mass spectrometrically the decay of H# in flames the ratio of the rate constants for the neutmfization of H30t by Cl-and the electron has been measured as 0.11 f 0.03 over the temperature range 1800-2600°K.