Kinetic Study of Di‐Tert‐Butyl Peroxide: Thermal Decomposition and Product Reaction Pathways

Abstract

ABSTRACTThe major reaction path for oxidation of di‐tert‐butyl peroxide (DTBP) is generally considered to occur via fission of the weak peroxide ROOR bond at temperatures above 393 K. The initial stable intermediates in the thermal decomposition or combustion of DTBP are acetone and ethane, and the overall reaction is accompanied by an important heat release which when mixed with air (oxygen) may exceed the self‐ignition temperatures. A kinetic study on plausible DTBP reaction paths was initiated in this work, and a detailed study of the thermochemistry of new intermediates, transition state structures, and products is reported. The density functional theory (DFT; B3LYP/6‐311g(d,p)), which is practical for large compounds along with the composite ab initio G3MP2B3 and G3 calculations, (when possible), are used. Computational chemistry results from DFT and ab initio calculations are coupled with isodesmic reaction analysis which, as demonstrated in previous studies, results in good accuracy. Over 10 unimolecular decomposition pathways are identified and reported.