Kinetics of three commercial textile dyes decomposition by UV/H2O2 and UV/acetone processes: An experimental comparative study and DFT calculations

Abstract

Acetone photolysis was investigated and compared with the UV/H2O2 process for the removal of three commercial textile dyes, Reactive Red 184 (RR184), Reactive Orange 4 (RO4), and Direct Red 80 (DR80), in aqueous solution at 254 nm, pH = 6.5–6.8, and T = 20 ± 2 °C. The removal efficiency of RR184, RO4, and DR80 by UV/H2O2 was 35 %, 59 %, and 69 %, respectively, whereas UV/acetone exhibited a removal efficiency of 81 %, 99 %, and 88 %, within 30 min ([Dye]0 = 0.1 mM and [acetone]0 = [H2O2]0 = 50 mM). However, as the initial doses of H2O2 and acetone were increased, the decolorization increased, and the experimental kinetic data always agreed with the pseudo-first-order reaction model (R2 = 0.94–0.99). Additionally, UV/acetone was consistently shown to be significantly more efficient than UV/H2O2 under all conditions tested. For instance, the rate constant ratios kUV/acetone/kUV/H2O2 are 3.19, 1.95, and 1.67 for RR184, RO4, and DR80, respectively ([Dye]0 = 0.1 mM and [acetone]0 = [H2O2]0 = 50 mM). Scavenging tests using specific probes revealed that •OH and •CH3 radicals were the main responsible for dyes degradation (greater than80 %) in the UV/H2O2 and UV/acetone processes, respectively. In both systems, the dyes' reactivity order was found to be RO4 > DR80 > RR184, indicating that chemical structure is an important factor in evaluating the efficiency of the degradation process. This reactivity order was supported by the density functional theory (DFT)-based thermodynamic calculations used to explain the HO•-initiated degradation of the studied azo dyes in the UV/H2O2 process.