Abstract

The photolysis of benzoic acid in the vapor phase has been investigated in a flow system at temperatures ranging from 110–305 °C, pressures from 0.06–1.73 Torr, and at various incident light intensities. Carbon dioxide and benzene are the main products and carbon monoxide is a minor product. The rate of formation of carbon dioxide is proportional to the first power of the light intensity and is independent of benzoic acid concentration at pressures from 0.29–1.73 Torr. The activation energy for carbon dioxide formation is approximately 3 kcal per mol. A radical chain mechanism has been suggested, in which initiation results from decomposition of vibrationally excited ground state benzoic acid molecules, and termination occurs at the wall. A molecular mechanism is a possibility if the rate of formation of vibrationally excited ground state is a function of temperature.

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