Abstract
The process of chain termination in the oxidation of cumene was studied. With the use of the semiempirical PM3 method, the structures of primary and tertiary peroxide radicals (PhCH(CH3)CH2OO· and Ph(CH3)2COO·), the PhCH(CH3)CH2OOOOC(CH3)2Ph tetroxide (TO) (the product of the combination of the above radicals), and TO decomposition products were studied and their heats of formation (ΔH 0 f) were determined; the activation energy of TO decomposition was evaluated. Similar values of ΔH 0 f were obtained by the thermochemical method of group additivity. The PM3 calculation demonstrated that the irreversible decomposition of the asymmetric TO in a six-membered transition complex into the PhCH(CH3)CHO aldehyde, the Ph(CH3)COH alcohol, and O2 is a synchronous process: dramatic changes in the bond lengths and bond orders occurred simultaneously. In this case, ∼100 kcal/mol was released, which is sufficient for the chemiexcitation of triplet R–H=O and singlet O2. A conclusion was drawn that a small impurity of PhCH(CH3)CH2OO· primary radicals plays an important role in chain termination and is the only reason for the excitation of chemiluminescence.
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Vasil'ev, R.F., Fedorova, G.F. Asymmetric PhCH(CH3)CH2OOOOC(CH3)2Ph Tetroxide as an Intermediate in Chain-Termination Processes and Chemiluminescence Excitation in the Oxidation of Cumene. Kinetics and Catalysis 45, 655–661 (2004). https://doi.org/10.1023/B:KICA.0000044976.23380.cd
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DOI: https://doi.org/10.1023/B:KICA.0000044976.23380.cd