Browsing by Author "Massiff, G."

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    Oxidation of Carbon Monoxide by Methoxy-radicals
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1973, 69 (2), 1973) Lissi, E. A.; Massiff, G.; Villa, A. E.
    The thermal decomposition of dimethyl peroxide (DMP) in a static system was investigated over the temperature range 123–153°C at varying pressures of carbon monoxide. The reaction of methoxy-radicals with carbon monoxide produces carbon dioxide and methyl radicals. The rate constant of reaction (2) CH3O·+ CO [graphic omitted] CO2+ CH3(2) was determined to be: k2/l. mol–1 s–1= 1010.2 ± 0.6 exp–(11.800 ± 1500/RT)(R in cal mol–1 K–1). At low carbon monoxide pressures production of carbon dioxide is first order in carbon monoxide and half order in DMP while at high carbon monoxide pressures (> 120 Torr) it is zero order in carbon monoxide and first order in DMP. At high pressures of carbon monoxide and at 127°C reaction (2) is the main reaction of methoxy-radicals. These data are rationalized by a simple free-radical mechanism.