Prediction of the thermal decomposition of organic peroxides by validated QSPR models.

Organic peroxides are unstable chemicals which can easily decompose and may lead to explosion. Such a process can be characterized by physico-chemical parameters such as heat and temperature of decomposition, whose determination is crucial to manage related hazards. These thermal stability properties are also required within many regulatory frameworks related to chemicals in order to assess their hazardous properties. In this work, new quantitative structure-property relationships (QSPR) models were developed to predict accurately the thermal stability of organic peroxides from their molecular structure respecting the OECD guidelines for regulatory acceptability of QSPRs. Based on the acquisition of 38 reference experimental data using DSC (differential scanning calorimetry) apparatus in homogenous experimental conditions, multi-linear models were derived for the prediction of the decomposition heat and the onset temperature using different types of molecular descriptors. Models were tested by internal and external validation tests and their applicability domains were defined and analyzed. Being rigorously validated, they presented the best performances in terms of fitting, robustness and predictive power and the descriptors used in these models were linked to the peroxide bond whose breaking represents the main decomposition mechanism of organic peroxides.

Vent sizing: analysis of the blowdown of a hybrid non tempered system.

The runaway and blowdown of a non tempered hybrid chemical system (30% cumene hydroperoxide) exposed to an external heat input was investigated using a 0.1l scale tool. The maximum temperature and the maximum temperature rise rate were showed to be sensitive to the vent size. An Antoine type correlation between the maximum temperatures and pressures was observed. These resulted from the presence of vapour, mainly generated by the reaction products. Increasing the initial filling ratio resulted in an earlier vent opening but did not have a significant influence on the blow-down. Three types of mass venting behaviour were observed, when changing the vent area to volume ratio (A/V): • for large A/V, two-phase venting occurred from the vent opening until the end of the second pressure peak; • for medium A/V, two-phase venting occurred before and after the turnaround. The data seem to indicate that gas only venting occurred at turn-around; • for low A/V, two-phase venting was observed only after the second pressure peak. Two-phase venting after the second pressure peak probably results from the boiling of the hot reaction products at low pressure.