(27c) 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.