Kinetic modelling for concentration and toxicity changes during the oxidation of 4-chlorophenol by UV/H2O2.

This work develops a kinetic model that allow to predict the water toxicity and the main degradation products concentration of aqueous solutions containing 4-chlorophenol oxidised by UV/H2O2. The kinetic model was developed grouping degradation products of similar toxicological nature: aromatics (hydroquinone, benzoquinone, 4-chlorocatechol and catechol), aliphatics (succinic, fumaric, maleic and malonic acids) and mineralised compounds (oxalic, acetic and formic acids). The degradation of each group versus time was described as a mathematical function of the rate constant of a second-order reaction involving the hydroxyl radical, the quantum yield of lump, the concentration of the hydroxyl radicals and the intensity of the emitted UV radiation. The photolytic and kinetic parameters characterising each lump were adjusted by experimental assays. The kinetic, mass balance and toxicity equations were solved using the Berkeley Madonna numerical calculation tool. Results showed that 4-chlorophenol would be completely removed during the first hour of the reaction, operating with oxidant molar ratios higher than R = 200 at pH  6.0 and UV = 24 W. Under these conditions, a decrease in the rate of total organic carbon (TOC) removal close to 50% from the initial value was observed. The solution colour, attributed to the presence of oxidation products as p-benzoquinone and hydroquinone, were oxidised to colourless species, that resulted in a decrease in the toxicity of the solutions (9.95 TU) and the aromaticity lost.