Application of runaway reaction mechanism generation to predict and control reactive hazards

Many industrial incidents are caused by thermal runaway reactions. Therefore, a good understanding of runaway reactions is necessary to predict and control reactive hazards. A detailed kinetic modeling approach is proposed to simulate runaway reactions under industrial conditions. This paper addresses the first step of this approach—mechanism generation. Computational chemistry was employed to estimate thermodynamic properties of reactants, intermediates, and products, and the Evans–Polanyi linear free energy relationship was used to estimate activation barriers of elementary reactions. To illustrate this mechanism generation approach, hydroxylamine is used as an example. The distribution of the predicted final products agrees with experimental results.