Identification of chlorinated oligomers formed during anodic oxidation of phenol in the presence of chloride.

Chlorinated oligomer intermediates formed during the anodic electrochemical oxidation of phenol with a boron-doped diamond electrode were studied at two different concentrations of chloride (5mM and 50mM). Under the same ionic strength, with sodium sulfate being the make-up ion, a 10-fold increase in Cl(-) led to removal rates 10.8, 1.5, and 1.4 times higher for phenol, TOC, and COD, respectively. Mono-, di- and trichlorophenols resulting from electrophilic substitution were the identified by-products. Nevertheless, discrepancies between theoretical and measured TOC values along with gaps in the mass balance of chlorine-containing species indicated the formation of unaccounted-for chlorinated by-products. Accurate mass measurements by liquid chromatography quadrupole time-of-flight mass spectrometry and MS-MS fragmentation spectra showed that additional compounds formed were dimers and trimers of phenol with structures similar to triclosan and polychlorinated dibenzo-p-dioxins.