Contribution of GC-MS Analyses to the Determination of the Self-Ignition Mechanism of 1,4-Dioxane in Chlorine

An experimental investigation in a conventional static apparatus of gas phase reactions between 1,4 dioxane and chlorine has permitted to observe auto-ignitions above 100°C at subatmospheric pressure and to map out the limits of reaction zones in a pressure-temperature diagram. To achieve a better understanding of the reaction mechanism leading to these auto-ignitions, we have performed an experimental investigation of the slow reaction in a flow system; GC-MS analyses were used to identify the reaction products. Our results show that at high conversion, 1,4-dioxene is the dominant reaction product; we also obtain smaller amounts of chlorinated by-products of 1,4-dioxane. The results of this investigation are used to build a tentative reaction scheme accounting for the experimental features of the reaction.