Prediction of the Reactivity Hazards for Organic Peroxides Using QSPR Approach

Organic peroxides can thermally decompose and may lead to runaway reactions. These reactivity hazards have been reported as one of the main causes for fire and explosion in process industries. The risk associated with runaway reactions of organic peroxides can be minimized by employing the Inherently Safer Design (ISD) principles: substitution and moderation of hazardous peroxides in chemical processes. However, the application of ISD concepts require a lengthy evaluation and classification of reactivity hazards of organic peroxides, which are impractical to be done through experimental approach due to large number of peroxide members and great variations in reactivity hazards. In this work, the quantitative structure-property relationship (QSPR) was used to predict the onset temperature (T₀) and decomposition heat (Q_d) of organic peroxides for the estimation of thermal stability and severity of runaway reactions. In addition to the conventional descriptors used in QSPR, we used other properties of the peroxides such as concentration as descriptors in order to construct accurate and economic models to predict reactivity hazards. Partial least square method was used to model T₀ and Q_d. Results showed that the QSPR models can be used to predict the hazards associated with the runaway reactions of organic peroxides. The QSPR approach is beneficial to understand the reactivity hazards of organic peroxides and will lead to their process optimization.