Multivariate optimization for electrochemical oxidation of methyl orange: Pathway identification and toxicity...

Electrochemical oxidation of methyl orange (Sodium 4-[(4-dimethylamino) phenyldiazenyl] benzenesulfonate) with lead dioxide coated on mild steel was modelled using response surface methodology (RSM) to analyze the influence of pH, NaCl dose and current on color and chemical oxygen demand (COD) removal. Higher current, acidic pH and 0.8-1.2 g L(-1) NaCl dose had an enhancing effect on the removal efficiencies. Interaction effect of the variables highlights the action of (•)OH and HOCl in the oxidation of methyl orange, where HOCl has effect at lower current range. More than 90% COD removal efficiency and ∼100% color removal efficiency was obtained in 5 h at optimum conditions for an initial concentration of 50 mg L(-1). High performance liquid chromatography-mass spectroscopy (HPLC-MS) analysis carried out to identify degradation intermediates revealed the absence of chlorinated intermediates, which was further verified with Fourier transform infrared spectroscopy (FTIR) analysis. The postulated pathway of degradation indicated breakdown through dealkylation, deamination, desulfonation and cleavage of an azo bond and benzene ring. The degradation of methyl orange to smaller compounds was also confirmed by Ion Chromatography (IC). Cytotoxicity analysis on HaCaT cells revealed the intermediates to be more cytotoxic than the dye, possibly due to the aromatic amines and diazines formed during the degradation process.