Measurement of select radical processes in hydrocarbon pyrolysis

Abstract

Methods for the measurement of absolute and relative rates of reactions of organic free radicals related to hydrocarbon pyrolysis in the condensed phase are illustrated. Examples are provided of methods for the determination of absolute rate expressions. The absolute rate expressions are employed in competition kinetic experiments that measure the ratio of an unknown rate constant to the known basis rate constant, yielding the desired competing reaction rate. Examples of use of the absolute and competition kinetic methods to measure rates of select free radical reactions of interest to hydrocarbon pyrolysis are illustrated. Methods for the measurement of absolute rate expressions for reactions of organic free radicals that will be covered include kinetic laserflash optical spectroscopy (KLS), kinetic electron spin resonance spectroscopy (KESR), and kinetic laserflash time resolved infrared spectroscopy (TRIR).