Thermal decomposition of tert‐butyl peroxide in a gas chromatographic reactor: A comparison of kinetic approaches

Abstract

AbstractThe thermal decomposition of tert‐butyl peroxide is investigated utilizing both the column and the injection port of a commercial gas chromatograph (GC) as chemical reactors. Using the injector liner as the reactor, the chromatographic peak areas of the reactant, measured at various injector temperatures, are used in the determination of the activation energy of the decomposition (Ea). With the column serving as the reactor, both the reactant peak areas and the product peak shapes are similarly utilized for this purpose. Values of Ea obtained using different mathematical treatments for each of the three approaches are found to range from 115 to 164 kJ/mol. Of these methods, the column reactor approach utilizing peak area measurements (referred to as PACR, for “peak area, column reactor”) is found to be far superior in terms of its speed, robustness, and its accuracy in determining Ea. The PACR method's effectiveness can be largely attributed to the mathematical treatment that is described in the approach. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 386–393, 2004