The photooxidation of allyl chloride

The photooxidation of allyl chloride was studied by irradiation either in 100‐L Teflon bags or in a 22.7‐m³ Teflon smog chamber in the presence of added NO_x. In the absence of added hydrocarbons, the reaction involves a Cl atom chain, which leads to a highly reactive system. A reaction mechanism is presented to account for the following photooxidation products: chloroacetaldehyde, formaldehyde, 1,3‐dichloroacetone, 3‐chloroacrolein, acrolein, glyoxal, chloroperoxyacetyl nitrate, and peroxypropenyl nitrate. The rate constant for OH reaction with allyl chloride at 298 K was measured by a relative rate method under conditions where the Cl atom chain length was small and was found to be k_OH = 1.7 × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹. The rate constant for O₃ reaction with allylchloride at 298 K was found to be k_O3 = 1.5 × 10⁻¹⁸ cm³ molecule⁻¹ s⁻¹.