Correlation between Gas-Phase and Solution-Phase Reactivities of Hydroxyl Radicals toward Saturated Organic Compounds

Article abstract of DOI:10.1021/j100328a039

The gas-phase and aqueous-solution-phase reactivities of hydroxyl radicals with a wide variety of organic compounds are compared.When kinetic data are available for the same reaction occuring in both phases, this comparison provides useful information about the reaction mechanism.Through this comparison we can demonstrate a linear correlation between the gas/solution-phase OH reactivities for numerous saturated organic compounds.This empirical relationship can be used together with mechanistic information to estimate the OH reactivity in one phase from the measured rate constant in the other.In order to develop and extend the correlation, we have used the flash photolysis resonance fluorescence technique to measure rate constants for the gas-phase reactions of OH radicals with methanol-d4, ethanol-d6, 2-chloroethanol, 2,2,2-trichloroethanol, 2,2,2-trifluoroethanol, acetone-d6, 1,1,1-trifluoroacetone,and 1,2-butylene oxide at 298 K.These results are reported herein.