Abstract
A WELL-KNOWN problem in the physical chemistry of aliphatic hydrocarbons is to account for the marked dependence of reactivity on molecular structure, especially for reactions in the gas phase. For example, in oxidation of isomeric paraffins below about 300°, reactivity is greatest for the least-branched chain. Among the normal paraffins, the reactivity of homologues increases as the chain-length increases1. Various explanations of this influence of molecular structure on chemical reactivity have been suggested. Marked polar influences or valency drifts of electrons are not likely to be significant in this class of molecules. Molecular structure is, however, likely to have a marked effect on the degree of coupling between vibrations in different parts of the molecule2 and also on the degree of flexibility of the hydrocarbon3.
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McGRATH, W., UBBELOHDE, A. Transfer of Internal Energy in Molecular Collisions of Flexible Hydrocarbons. Nature 173, 990 (1954). https://doi.org/10.1038/173990a0
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DOI: https://doi.org/10.1038/173990a0
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