Apparent Rate Constants and Activation Energies for the Photochemical Decomposition of Various Olefins

Abstract

The photochemical reaction of various olefins and nitrogen dioxide was studied under conditions of controlled temperature, pressure, and humidity in a 200 liter stirred glass reactor. The hydrocarbon concentration in the reactor during four and five hour irradiation periods was monitored with a flame ionization chromatograph. Reaction rate constants, based on three consecutive first order reactions, were calculated for reactor temperatures of 20, 25, 30, and 35 degrees centigrade. Activation energies for the three consecutive reactions were calculated from the Arrhenius equation. Branched and straight chain olefins were studied at initial concentrations of 5.0 to 10.0 parts per million.s