Hydroxyl radical reaction with alkanes

Greiner, N.R. (1970) Hydroxyl radical kinetics by kinetic spectroscopy. VI. Reactions with alkanes in the range 300-500 K. J. Chem. Phys. 53, 1070-1076. 

DeMore, W.B., Bayes, K.D.(1999) Rate constants for the reactions of hydroxyl radical with several alkanes, cycloalkanes, and dimethyl ether. J. Phys. Chem. A, 103, 2649-2654. 

Harris, S.J., Kerr, J.A. (1988) Relative rate measurements of some reactions of hydroxyl radicals with alkanes studied under atmospheric conditions. Int. J. Chem. Kinet. 20, 939-955. 

Lloyd, A.C., Darnall, K.R., Winer, A.M., Pitts, Jr., J.N. (1976) Relative rate constants for reaction of the hydroxyl radical with a series of alkanes, alkenes, and aromatic hydrocarbons. J. Phys. Chem. 80, 189-794. 

Hydroxy radicals are intermediates in the reaction of Ti3+ and H2O2 (175). This system is also capable of hydroxylation of aromatics and alkanes but, in contrast to reactions with Fenton s reagent (Fe2+ + H202, reductive, homolytic cleavage, Eq. (11)), only non-chain processes are possible, because Ti4+ is not usually an oxidant. Hence, relatively high selectivities are feasible. 

Figure 9.25 shows the correlation coefficient of 0.9636 between the hydroxyl radical rate constants and UV/Ti02 rate constants for chlorinated alkanes. Therefore, the reaction mechanism for the degradation of chlorinated alkanes by UV/Ti02 is similar to the reaction with hydroxyl radical. This correlation suggests that the reaction proceeds via hydroxyl radical attack on the chlorinated alkane. 

---