By Noyes W
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Extra info for Advances in Photochemistry, Volume 2
Mm. 5 8 6 * The dashes denote products that were not analyzed. It may be seen from Table I11 that in reactions of oxygen atoms with ethylene, formaldehyde and CO are obtained practically in equal amounts, as in the reaction involving ethane. It will be taken into account that the amount of formaldehyde obtained is practically equal to that of oxygen atoms (Table 11). This is indication that CHzO is formed by a nonchain mechanism. On the basis of these facts it should be considered that the main reaction between oxygen atoms and ethylene is 0 + CHz-CHz + CHzO + CH2 (11) A reaction of CHz with O2yields CO CHz + Oz+CO + H + OH The similar behavior of CO and CH20 in reactions 0 + CzHBand 0 + C2H4 provided confirmation to the conclusion that the same CH2 radical is formed by the primary steps of these reactions.
Consequently, some conclusions on the CHa-CH= radical may be drawn from analysis of the reaction products, for example of CO. If the CHaCH= radical were to isomerize into ethylene only, the CO amount would be equal to that of CHaCHO. This is indication that the CH3CH= radical partly isomerizes, and partly reacts with O2 to form CO. If the CH3CH= radical were to react with O2 only, the amount of CO would be equal to the overall amount of aldehyde. Small amounts of acetone were also found in reaction products, which shows that 0 atoms are incorporated into C3Hamolecules.
In experiments using a discharge in 0 2 the amount of alcohol obtained was 4 times less than that of CH20. Analysis for CO was carried out in these experiments. CO was converted into CO2 in the reactor filled with Iz06and then condensed. The amount of CH2O was determined simultaneously. It appeared that formaldehyde and CO were formed in practically equal amounts. Therefore, analysis of the reaction products for 0 C2Hs has shown that the main reaction products were CH,O and CO. 5 mm. /sec. are summarized in Table 11.
Advances in Photochemistry, Volume 2 by Noyes W