VAPOR-PHASE REACTIONS OF ORGANIC COMPOUNDS WITH OXYGEN
Abstract
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.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jul 15, 1964
- Accession Number
- AD0603096
Entities
People
- Frank R. Mayo
- Theodore Mill
Organizations
- SRI International