VAPOR-PHASE REACTIONS OF ORGANIC COMPOUNDS WITH OXYGEN
Annual rept. for 21 Jun 1963-20 Jun 1964
STANFORD RESEARCH INST MENLO PARK CA
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A series of gas-phase, peroxide-initiated oxidations of isobutane was carried out at 100C with pressures of isobutane ranging from 1 to 13 atmospheres. The yields of hydroperoxide increased with increasing pressure from 16 at one atmosphere to 92 at 13 atmospheres with 1 conversion of isobutane. The rate of the t-Bu2O2-induced decomposition of t-butyl hydroperoxide in the gas phase at 100C in the absence of oxygen depends on the kind and concentration of added hydrocarbon. Liquid-phase data on the oxidations of isobutane at 50C and 80C were used to estimate rates of oxidation, kinetic chain lengths, and times for 99 conversion for oxidations of liquid isobutane and very dilute gaseous isobutane at 30C. The gas-phase oxidation of cyclopentene at 1-3 atmospheres at 100C and 155C gave hydroperoxide and its decomposition products, epoxide and unidentified high-boiling materials in proportions which depend on the concentration of cyclopentene. The liquid-phase oxidation at 100C and below gave more than 90 yield of hydroperoxide. Two postulates were applied to literature data on the gas-phase oxidation of isobutylene and found to provide a useful correlation. Catalysis by hydrogen chloride of free radical chain oxidations of hydrocarbons by alkoxy radical carriers is proposed and discussed.
- Organic Chemistry