Abstract
The mechanism of fat autoxidation is elucidated from the rate data. All the data treated here and in an earlier publication follow the same basic rate equation, including the time function f(t) empirically derived for heterogeneous oxidation. Metals and glass (the wall of the reaction vessel) are catalysts. Depending on the state of the catalyst, f(t)=t2 or f(t)=t. When f(t)=t, the kinetics are first-order as found for monolayer autoxidation, but in bulk phase they are complicated by a transient stage caused by the solubilization of O2 into the hydroperoxide micelles produced in the exponential (“autocatalytic”) part of the oxidation. Certain additives, such as inhibitors, affect the catalyst and thereby f(t). The kinetics, as determined by O2 consumption or by analysis of the remaining unreacted substrate, show the first oxidation step. It is unaffected by further chemical changes of the primary oxidation products,e.g., decomposition of hydroperoxides and trimerization in the autoxidation of 9,11-octadecadienoic acid methyl ester.
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References
Browne, C.A.,Ind. Eng. Chem. 17:44 (1925).
Ritsert, E., Untersuchungen über das Ranzigwerden der Fette, p. 3, Inaugural Dissertation, Bern, July, 1890.
Richardson, T., and M. Korycka-Dahl, inDevelopments in Dairy Chemistry, 2, Lipids, edited by P.F. Fox, Applied Science Publishers, London and New York, 1983.
Allen, J.C., and R.J. Hamilton (eds.),Rancidity in Foods, 2nd edn., Elsevier Applied Science Publishers Ltd., 1989.
Frankel, E.N.,Recent Advances in the Chemistry of Rancidity of Fats, Special Publication, Royal Society of Chemists 47:87 (1984).
Labuza, T.P., inCRC Critical Reviews in Food Technology, edited by T.E. Furia, CRC Press, Boca Raton, 1971, pp. 355–405.
Brimberg, U.I.,Fat Sci. Technol. 93:298 (1991).
Berg, T.G.O.,Tenside Deterg. 23:128 (1986).
Uri, N., inAutoxidation and Antioxidants, Vol. I, edited by W.O. Lundberg, Interscience Publishers, New York, 1961, p. 65.
Kern, W., and L. Dulog,Makromolekulare Chemie 29:199 (1959).
Wu, G.-S., R.A. Stein and J.F. Mead,Lipids 12:971 (1977).
Robertson, A., and W.A. Waters,Trans. Faraday Soc. 42:201 (1946).
Wieland, H.,Ber. 45:484 (1912).
Wieland, H., Ibid.:3326 (1913).
Holm, G.E., G.R. Greenbank and E.F. Deysher,Ind. Eng. Chem. 19:156 (1927).
Ingold, K.U.,Can. J. Chem. 34:600 (1956).
Kern, W., and H. Willersinn,Makromolekulare Chemie 15:36 (1955).
Bateman, L., H. Hughes and A.L. Morris,Disc. Faraday Soc. 14:190 (1953).
Kern, W., and H. Willersinn,Makromolekulare Chemie 15:1 (1955).
Elworthy, P.H., A.T. Florence and C.B. Macfarlane,Solubilization by Surface-Active Agents, Chapman and Hall Ltd., London, 1968.
Matheson, I.B.C., and A.D. King Jr.,J. Colloid Interface Sci. 66:464 (1978).
Bolden, P.L., J.C. Hoskins and A., D. King Jr., Ibid.:454 (1983).
Kortenska, V.D., N.V.I. Yanishlieva and V.A. Roginski,J. Am. Oil Chem. Soc. 68:888 (1991).
Marcuse, R., and P.-O. Fredriksson, Ibid.:262 (1969).
Yamauchi, R., K. Kato and Y. Ueno,Lipids 23:779 (1988).
Terao, J., Ibid.:659 (1989).
Kern, W., A.R. Heinz and J. Stallmann,Makromolekulare Chemie 16:21 (1955).
Kern, W., A.R. Heinz and D. Höhr, Ibid.:406 (1956).
Brimberg, U.I.,Fette Seifen Anstrichm. 83:184 (1981).
Brimberg, U.I.,J. Am. Oil Chem. Soc. 59:74 (1982).
Berg, T.G.O., and U.I. Brimberg,Fette Seifen Anstrich. 85:142 (1983).
Brimberg, U.I., Ibid.:295 (1985).
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Brimberg, U.I. On the kinetics of the autoxidation of fats. J Am Oil Chem Soc 70, 249–254 (1993). https://doi.org/10.1007/BF02545304
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DOI: https://doi.org/10.1007/BF02545304