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

Abstract

Plenary lecture given at the XIIkme Journke d'ktude de la section belge du Combustion Institute "Recent achievements of mass spectrometry in ji'arne kinetics", le 28-29 mai I990 ci Louvain-la-Neuve SUMMARYAn experimental investigation in a conventional static ap aratus of as phase reactions between 1,4 dioxane and chlorine has permitted to, observe auto-ignitions agove 1 W 8 a t 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 erformed an experimental investigation of the slow reaction in a flow system; GC-MS analyses were usefto 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,cdioxane. The results of this investigation are used to build a tentative reaction scheme accounting for the experimental features of the reaction.