Methods for the measurement of absolute and relative rates of reactions of
organic free radicals related to hydrocarbon pyrolysis in the condensed pha
se 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 r
eaction rate. Examples of use of the absolute and competition kinetic metho
ds to measure rates of select free radical reactions of interest to hydroca
rbon pyrolysis are illustrated. Methods for the measurement of absolute rat
e expressions for reactions of organic free radicals that will be covered i
nclude kinetic laserflash optical spectroscopy (KLS), kinetic electron spin
resonance spectroscopy (KESR), and kinetic laserflash time resolved infrar
ed spectroscopy (TRIR). (C) 2000 Elsevier Science B.V. All rights reserved.