Chemical oxidation of N,N-diethyl-m-toluamide by sulfate radical-based oxidation: kinetics and mechanism of degradation

A study was undertaken in order to understand the kinetics and mechanism of the chemical oxidation of N,N-diethyl-m-toluamide, an insect repellent, by sulfate radical. In this experiment, sulfate radical was generated using peroxymonosulfate with iron(II) and cobalt(II) as activator. The second-order rate constant for the reaction of the sulfate radical with N,N-diethyl-m-toluamide was found to be (1.9 +/- A 0.1) x 10(9) M-1 s(-1) at pH 7 and a temperature of 25 A degrees C. Experiments for the chemical oxidation of N,N-diethyl-m-toluamide in river water and secondary wastewater revealed that the percentage of the removal of N,N-diethyl-m-toluamide was slightly influenced by the water matrices. However, the selected oxidation systems are not effective for the removal of N,N-diethyl-m-toluamide in seawater. Transformation by-products of N,N-diethyl-m-toluamide generated using peroxymonosulfate/iron(II) sulfate, peroxymonosulfate/iron(II) chloride, peroxymonosulfate/cobalt(II) sulfate and peroxymonosulfate/cobalt(II) chloride systems were identified. The results indicated that there are slight differences in the distributions of the transformation by-products detected depending on the activator. The common transformation by-products detected in all selected oxidation systems are N,N-diethylbenzamide, N-ethyl-m-toluamide, N,N-dimethyl-m-toluamide, N-ethyl-N-acetyl-m-toluamide, 2-(diethylamino)-1-m-tolylethanone, monohydroxylated N-ethyl-m-toluamide, and dihydroxylated N,N-diethyl-m-toluamide. Monohydroxylated N,N-diethyl-m-toluamide were detected only when the peroxymonosulfate/iron(II) system was applied. For the peroxymonosulfate/cobalt(II) systems, additional isomers of monohydroxylated N-ethyl-m-toluamide were detected. Peroxymonosulfate/cobalt(II) also transformed 2-(diethylamino)-1-m-tolylethanone into N-ethyl-N-(2-oxo-2-m-tolylethyl)acetamide and monohydroxylated 2-(ethyl(vinyl)amino)-1-m-tolylethanone as transformation by-products.