{"title":"Features of the Fatty Acid Methyl Esters' Hydroperoxides Formation and Decomposition Processes","authors":"E. A. Savel'ev, A. D. Cherepanova, V. N. Sapunov","doi":"10.1002/aocs.12972","DOIUrl":null,"url":null,"abstract":"<div>\n \n <p>The present work is devoted to studying the regularities of synthesis and decomposition of hydroperoxides of methyl esters of fatty acids. Fatty acid methyl esters of sunflower oil were used as raw material. In the case of non-catalytic oxidation at 70°C, the maximum concentration of hydroperoxides is observed (~45 wt.%), but 14 h of synthesis are required to achieve it. The use of N-hydroxyphthalimide as a catalyst makes it possible to reduce the reaction time to 8 h without affecting the yield of hydroperoxides. In turn, the results of studying the decomposition of hydroperoxides in the temperature range of 90°C–170°C demonstrate the presence of an unusual temperature dependence of the process activation energy. Upon passing to elevated temperatures, from approximately 120°C, a decrease in the activation energy of the process is observed from 83.6 to 35.8 kJ/mol, which means the transition of the process to the region of entropy control, in which the decomposition of hydroperoxides is preceded by the formation of hydrogen bonds of hydroperoxide molecules with each other and/or with other components of the reaction mixture.</p>\n </div>","PeriodicalId":17182,"journal":{"name":"Journal of the American Oil Chemists Society","volume":"102 9","pages":"1363-1372"},"PeriodicalIF":2.4000,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Oil Chemists Society","FirstCategoryId":"97","ListUrlMain":"https://aocs.onlinelibrary.wiley.com/doi/10.1002/aocs.12972","RegionNum":4,"RegionCategory":"农林科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
Abstract
The present work is devoted to studying the regularities of synthesis and decomposition of hydroperoxides of methyl esters of fatty acids. Fatty acid methyl esters of sunflower oil were used as raw material. In the case of non-catalytic oxidation at 70°C, the maximum concentration of hydroperoxides is observed (~45 wt.%), but 14 h of synthesis are required to achieve it. The use of N-hydroxyphthalimide as a catalyst makes it possible to reduce the reaction time to 8 h without affecting the yield of hydroperoxides. In turn, the results of studying the decomposition of hydroperoxides in the temperature range of 90°C–170°C demonstrate the presence of an unusual temperature dependence of the process activation energy. Upon passing to elevated temperatures, from approximately 120°C, a decrease in the activation energy of the process is observed from 83.6 to 35.8 kJ/mol, which means the transition of the process to the region of entropy control, in which the decomposition of hydroperoxides is preceded by the formation of hydrogen bonds of hydroperoxide molecules with each other and/or with other components of the reaction mixture.
期刊介绍:
The Journal of the American Oil Chemists’ Society (JAOCS) is an international peer-reviewed journal that publishes significant original scientific research and technological advances on fats, oils, oilseed proteins, and related materials through original research articles, invited reviews, short communications, and letters to the editor. We seek to publish reports that will significantly advance scientific understanding through hypothesis driven research, innovations, and important new information pertaining to analysis, properties, processing, products, and applications of these food and industrial resources. Breakthroughs in food science and technology, biotechnology (including genomics, biomechanisms, biocatalysis and bioprocessing), and industrial products and applications are particularly appropriate.
JAOCS also considers reports on the lipid composition of new, unique, and traditional sources of lipids that definitively address a research hypothesis and advances scientific understanding. However, the genus and species of the source must be verified by appropriate means of classification. In addition, the GPS location of the harvested materials and seed or vegetative samples should be deposited in an accredited germplasm repository. Compositional data suitable for Original Research Articles must embody replicated estimate of tissue constituents, such as oil, protein, carbohydrate, fatty acid, phospholipid, tocopherol, sterol, and carotenoid compositions. Other components unique to the specific plant or animal source may be reported. Furthermore, lipid composition papers should incorporate elements of yeartoyear, environmental, and/ or cultivar variations through use of appropriate statistical analyses.