1987•OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information)Requires access
EPR study of the catalytic radical decomposition of tertiary butyl hydroperoxide on metalloporphyrin catalysts
S.S. Bagdasaryan, I.A. Vardanyan, A.B. Nalbandyan, S.E. Isabekyan, S.A. Sargisyan
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Abstract
The kinetics of decomposition of vapors of tertiary butyl hydroperoxide on metalloporphyrin catalysts, CuTMEHP-IX, CuCP, and CuTMOPP, was studied over the 293-480 K temperature range. It was shown by the techniques of freezing out the radicals in conjunction with EPR that the decomposition of TBHP takes place with the formation of radicals that pass from the surface into the gas phase. In the 293-399 K temperature range, it is primarily radicals of the type (CH/sub 3/)/sub 3/CO/sub 2/ that are observed in the gas phase; in the 399-480 K range, it is CH/sub 3/O/sub 2/ type radicals. It is shown that TBHP decomposes most rapidly on CuTMOPP. From the point of view of radical yield, the activity of the catalysts at 10% conversion of the TBHP decreases at all temperatures in the order CuTMEHP > CuCP > CuTMOPP.