Insights into the Kinetics of Intermediate Formation during Electrochemical Oxidation of the Organic Model Pollutant Salicylic Acid in Chloride Electrolyte

Abstract

The present study investigated the kinetics and formation of hydroxylated and chlorinated intermediates during electrochemical oxidation of salicylic acid (SA). A chloride (NaCl) and sulfate (Na2SO4) electrolyte were used, along with two different anode materials, boron doped diamond (BDD) and platinum (Pt). Bulk electrolysis of SA confirmed the formation of both hydroxylated and chlorinated intermediates. In line with the density functional theory (DFT) calculations performed in this study, 2,5- and 2,3-dihydroxybenzoic acid, 3- and 5- chlorosalicylic acid and 3,5-dichlorosalicylic acid were the dominating products. In the presence of a chloride electrolyte, the formation of chlorinated intermediates was the predominant oxidation mechanism on both BDD and Pt anodes. In the absence of a chloride electrolyte, hydroxylated intermediates prevailed on the Pt anode and suggested the formation of sulfonated SA intermediates on the BDD anode. Furthermore, direct oxidation at the anode surface only played a subordinate role. First order kinetic models successfully described the degradation of SA and the formation of the observed intermediates. Rate constants provided by the model showed that chlorination of SA can take place at up to more than 60 times faster rates than hydroxylation. In conclusion, the formation of chlorinated intermediates during electrochemical oxidation of the organic model pollutant SA is confirmed and found to be dominant in chloride containing waters.