Biphasic reduction model for predicting the impacts of dye-bath constituents on the reduction of tris-azo dye Direct Green-1 by zero valent iron (Fe)

Influence of common dye-bath additives, namely sodium chloride, ammonium sulphate, urea, acetic acid and citric acid, on the reductive decolouration of Direct Green 1 dye in the presence of Fe⁰ was investigated. Organic acids improved dye reduction by augmenting Fe⁰ corrosion, with acetic acid performing better than citric acid. NaCl enhanced the reduction rate by its ‘salting out’ effect on the bulk solution and by Cl⁻ anion-mediated pitting corrosion of iron surface. (NH₄)₂SO₄ induced ‘salting out’ effect accompanied by enhanced iron corrosion by SO₄^2 − anion and buffering effect of NH₄⁺ improved the reduction rates. However, at 2 g/L (NH₄)₂SO₄ concentration, complexating of SO₄^2 − with iron oxides decreased Fe⁰ reactivity. Urea severely compromised the reduction reaction, onus to its chaotropic and ‘salting in’ effect in solution, and due to it masking the Fe⁰ surface. Decolouration obeyed biphasic reduction kinetics (R² > 0.993 in all the cases) exhibiting an initial rapid phase, when more than 95% dye reduction was observed, preceding a tedious phase. Maximum rapid phase reduction rate of 0.955/min was observed at pH 2 in the co-presence of all dye-bath constituents. The developed biphasic model reckoned the influence of each dye-bath additive on decolouration and simulated well with the experimental data obtained at pH 2.