Advances in Photochemistry, Volume 2 by Noyes W

By Noyes W

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Contrary to the C2Hsreaction, the amounts of CH,O and CO appeared to be different, especially at low temperatures. At 60OC. the amount of CO was three times, and at 250OC. one and a half times that of CH20. A conclusion m y be drawn that the reaction of oxygen atoms with CH4 proceeds by two parallel steps resulting in CHzO and CO formation. 64 c. Reactions Involving Other Saturated Hydrocarbons. , propane, n - b ~ t a n e have , ~ ~ shown that formaldehyde and acetaIdehyde are the main reaction products.

1). The free hydroxyl, together with other active species and nondisssociated water molecules, was pumped out of the highvoltage discharge zone into the reaction vessel, through a nozzle. The substance studied was introduced into the reaction vessel from a flask of prefixed volume, through a stopcock valve. The reaction vessel was heated by means of an electric furnace. The temperature constancy was checked by means of thermocouples at various sites in the reaction vessel. ELEMENTARY GAS PHASE REACTIONS 29 Traps cooled with liquid nitrogen were so placed as to collect the water and the condensed reaction products.

43The stable products formed by the first step were called primary (B) , those formed by a subsequent reaction involving a second oxygen atom and the primary product were defined as quadratic (D), and consecutive reactions involving three atoms were defined as cubic (F). The products yielded by reaction between primary radicals and 0 2 mdecules are called secondary (C). The following scheme was suggested : 40 Ti. I. AVRAMENKO AND R. V. KOLESNIKOVA k’ ... +B+ O f A1 +R+ ... k’ R + ks 0 2 + C k’, k = k’ + k” + RI R - t Ci ki O+B(C)-Df - ..

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