Reactions Related to Oxidations

OF THESIS Vame of Candidate Warren Edgar Falconer. 3.Go. (Hons. ). H.5c. Address 3', Place G-eneral Helser, Brussels 3 , Belgium. z)gg/-ge Doctor of Philosophy Date May* 1961 Title of Thesis Reactions Related to Oxidations Mixtures of methane, ethane, propane, cyclopropane, isobutane, and neopentane have been reacted with molecular oxygen in a static system between 325° and C. The residual alkanes were estimated by gas chromatography, and the relative rates of hydro¬ carbon consumption by the chain-propagating radical X in reactions (1) and (2) RaH + X = Ra + XH (1) RbII + X = Rb + XH (2) were calculated from the equation: lca » ^ax^lnitial " ^RaH^final» kb los initial " log ^RbH^final The relative rate constants found wore independent of total pressure and relative hydrocarbon concentrations, and varied only slightly with temperature. A marked variation of rate constant ratios with the oxygen to hydrocarbon ratio was observed. Alkylperoxy radicals have been generated in mixtures of methane, ethane, propane, cyclopropane, isobutane, n-butane, neo¬ pentane, and propylene between lLj-5° and 230° G by the photolysis of symmetric ketones in an excess of oxygen. The relative rates of consumption of these hydrocarbons by reactions (3) and (Lj.) RaII + R00 » Ra + R00II (3) RbE + R00 = Rb + ROOH (Ip) have been calculated from the equation above. The relative rate constants were found to be independent of reactant concentrations, illumination time, and total pressure, and to be almost inde¬ pendent of temperature and of the alkylperoxy radical attacking the hydrocarbons. Use other side if necessary.