Journal of Physical Chemistry A, Vol.103, No.2, 235-242, 1999
Self-recombination rate constants for 2-propanol and tert-butyl alcohol radicals in water
The techniques of electron pulse radiolysis and direct detection ESR have been used to determine Arrhenius parameters for the self-recombination of 2-propanol (hydroxymethylethyl) and tert-butyl alcohol (2-hydroxy-2,2-dimethyl-propyl) radicals in water. Rate constants of 2k(7) = (1.56 +/- 0.10) x 10(9) and 2k(23) = (1.18 +/- 0.20) x 10(9) dm(3) mol-(1) s-(1) for these radicals were measured at 26.4 and 26.6 degrees C, respectively, with corresponding activation energies of 18.8 +/- 1.2 (5.3-71.7 degrees C) and 15.83 +/- 0.92 (8.5-69.8 degrees C) kJ mol(-1) for these two reactions. These data are compared to available literature rate constants, and also to the results of diffusion-controlled rate constant calculations, which demonstrate that radical reactivity, not diffusion, dominates both recombination processes in water.