R. J. Kandel, H. Taylor
Oct 1, 1951
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Influential Citations
3
Citations
Journal
Journal of Chemical Physics
Abstract
The photolysis of acetic anhydride probably by 1849A radiation has been studied in the temperature range 80° to 300°C at pressures of 10–60 mm dibutyl phthalate. From 80° to 224°C the rate is first order during a run but the specific rate decreases with increasing pressure. The gaseous products are CO, CO2 and C2H6 in approximately equivalent amounts. Biacetyl and methyl acetate have been identified among the liquid products. At 300°C the reaction is more complex, yields considerable amounts of H2 and CH4 and is not first order. Comparison with formic acid photolysis leads to an approximate quantum yield of 2. A mechanism is suggested which accounts qualitatively for the observations. Deactivation of activated reactant molecules by acetic anhydride and by the gaseous products accounts for the low quantum yield. Added C2H6 and CO2 are shown to increase the rate of photolysis, the more so the lower the pressure of acetic anhydride. Preliminary experiments have shown that the reaction can also be mercury sen...