Formation of peroxides in fatty esters. I. Methyl oleate. Application of the polarographic and direct oxygen methods

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Abstract
Summary: The polarographic method presented here for the quantitative determination of hydroperoxides is simple rapid, and applicable to the analysis of materials containing a mixture of different peroxidic groups. The application of this nonaqueous polarographic technique to the study of the changes occurring during the prolonged autoxidation of methyl oleate at 80°C. has permitted the identification and quantitative estimation of the hydroperoxide formed during this process. The selectivity of the polarographic method makes it possible to identify and measure the hydroperoxide even when present with other peroxidic forms. A comparison of the data obtained by this new technique and by the chemical peroxide method has been made and shows that the polarographic method for hydroperoxides is specific and quantitative.By means of a direct oxygen method it has been possible to follow accurately the change in the oxygen content during the autoxidation. These data have confirmed the work of other investigators using other methods, it that the oxygen absorbed in the initial stages is used primarily in hydroperoxide formation, whereas in the latter stages the oxygen is consumed to form non‐hydroperoxidic materials. The methods used in this study should be of great value in studying the changes which occur in drying oils for these changes are induced by autoxidation.

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