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At relatively high levels the peroxyl radicals interact with each other to form non-radical products by the termination reaction (11). (11) At atmospheric pressure, termination (kt) occurs first by the combination of peroxyl radicals to an unstable tetroxide intermediate followed rapidly by its decomposition by the Russell mechanism, to yield non-radical products (12). (12) Many complexities can be considered when hydroperoxides undergo thermal or metal-catalysed homolysis generating peroxyl and alkoxyl radicals 18 LIPID OXIDATION leading either to additional radicals that continue the chain or to non-radical end-products.

I. The thermal oxidation of ethyl linoleate. Proc. Royal Soc. (London) A186, 218–236 (1946). L. Kinetic studies in the chemistry of rubber and related materials. VI. The benzoyl peroxide-catalyzed oxidation of ethyl linoleate. Trans. Faraday Soc. 44, 669–677 (1948). L. Kinetics of olefin oxidation. Quart. Rev. Chem. Soc. 3, 1–21 (1949). , The mechanism of autoxidation, in Autoxidation of Unsaturated Lipids, pp. 1–16, (1987) (edited by H. -S. Chan), Academic Press, London. F. A. The kinetics of the autoxidation of polyunsaturated fatty acids.

The loss of oxygen leads to a pool of pentadienyl radicals that undergo rearrangement. 6). Accordingly, the interconversion of cis,trans- and trans,trans-hydroperoxides results from the loss of oxygen from the peroxyl radicals by reversible β-scission to produce carbon pentadienyl radicals of different conformations. 6. , 1980). product ratio is determined by the relative rate of the reversible β-scission or βfragmentation (kβ) of the carbon–oxygen bond of the peroxyl radicals and their rate of hydrogen abstraction (KP) to form the corresponding hydroperoxides.

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Physics Reports vol.72


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