Abstract
A CONFLICT apparently exists between the aldehyde degradation mechanism indicated by the recent findings of Bailey and Norrish1 and of Knox and Norrish2, on one hand, and the preferential attack at the tertiary and secondary carbon atoms deduced, indirectly, by Walsh3, Boord4 and Badin and Pease5. A possible solution is provided by some recent studies, by gas-phase chromatography, of the products of slow oxidation of n-heptane, in a flow system. Although no tests for formaldehyde were made, aldehydes from C2 to C6 were detected at 300° C.; at 280° C., however, the extent of reaction was very small, and the only products condensed at − 80° C., apart from traces of peroxides, consisted of propionaldehyde and n-butyraldehyde. This suggests that the initial attack is at one of the secondary carbon atoms, with subsequent fission of one of the central C—C bonds. The more reactive chain carriers formed during this process can then attack the primary carbon also, and lead to the formation of higher aldehydes.
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References
Bailey and Norrish, Proc. Roy. Soc., A, 212, 311 (1952).
Knox and Norrish, Proc. Roy. Soc., A, 221, 151 (1954).
Walsh, Trans. Farad. Soc., 42, 269 (1946).
Boord, Third Symp. on Combustion, 416 (Williams and Wilkins, Baltimore, 1949).
Badin and Pease, Third Symp. on Combustion, 384 (Williams and Wilkins, Baltimore, 1949).
Burt and Minkoff, Anal. Chim. Acta, 16, 259 (1957).
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BURT, R., EBEID, F. & MINKOFF, G. Point of Attack in Hydrocarbon Oxidation. Nature 180, 188 (1957). https://doi.org/10.1038/180188a0
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DOI: https://doi.org/10.1038/180188a0
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