Mechanistic proposal for the electrochemical and sonoelectrochemical oxidation of thiram on a boron-doped diamond anode

A comparative study was carried out of sonochemical (SCh), electrochemical (ECh) and sonoelectrochemical (SECh) strategies for the degradation of the fungicide thiram in dilute aqueous solution. The SCh and SECh studies were performed using a sonicator equipped with an 11 mm titanium-alloy probe and operated at 20 kHz with a power intensity of 523 W cm−2. In the ECh and SECh investigations, galvanostatic electrolyses were implemented using a single compartment electrochemical cell with a boron-doped diamond electrode as anode and applied current densities in the range 10–50 mA cm−2. For these processes, the decrease in concentration of thiram was monitored by high performance liquid chromatographic (HPLC) analysis and values of current efficiency and energy consumption were determined. The results showed that the rate of degradation of thiram and the amount of energy consumed were directly proportional to the applied current density, while current efficiency was inversely related to current density. The kinetics of thiram degradation followed a pseudo first order model with apparent rate constants in the region of 10−3 min−1. Thiram in aqueous solution was subjected to “exhaustive” degradation by ECh and SECh processes for 5 h at applied current densities of 35 mA cm−2 and the intermediates/byproducts so-formed were identified by HPLC–mass spectrometry. Mechanisms of the degradation reactions have been proposed on the basis of the results obtained.