Chemical kinetics on thermal decompositions of di-tert-butyl peroxide studied by calorimetry

An overview in the field of chemical kinetics on the thermal decomposition of di-tert-butyl peroxide (DTBP) has been performed in this study. Nowadays, DTBP has been a model compound for studying thermokinetics of organic peroxide and standardization of the DSC or adiabatic calorimeter. Thermal decompositions of DTBP in neat state or solution are conducted by heat flow or adiabatic calorimeters. Chemical kinetics on the thermal decomposition of DTBP obeyed n-th-order reaction and the type of Arrhenius equation. Order of reaction is first without any exception. DTBP in alkyl or aromatic hydrocarbon solvent behaves with excellent precision in activation energy with an averaged value of 157.0 (+/- 4.1) and 159.7(+/- 3.9) kJ mol(-1) determined by DSC and adiabatic calorimeters, respectively. Frequency factors A (in s(-1)) in the form of logA are determined to be 15.8 (+/- 1.1) and 16.3(+/- 0.5) by DSC and adiabatic calorimeters, respectively. In the neat state of DTBP, activation energy and frequency factor in logA both possess the lower value of 128.4 (+/- 6.2) kJ mol(-1) and 12.2 (+/- 0.8) determined by DSC. In ARC, these respective parameters are determined to be 142.0 (+/- 17.7) kJ mol(-1) and 15.5 (+/- 1.3). Arrhenius parameters acquired from published literature with regard to the kinetics and mechanism on thermal decomposition of DTBP are summarized and discussed.