Oxidation of Chlorophenols in Aqueous Solution by Excess Potassium Permanganate

Abstract

A simple spectrophotometric method was developed to quantify chlorophenol (CP) concentrations after reaction with potassium permanganate and quenching with sodium sulfite. Other quenching agents (peroxide, sodium thiosulfate and hydroxylamine hydrochloride) were found to create absorbance in the spectral range required for CP quantification. Analysis at pH 12 gave greater absorption and sensitivity for the method compared with pH 5.6. The calibration curves of the proposed methods were linear in the concentration ranges 0.0061–0.61 and 0.0078–0.78 mM with detection limit of 0.0006 and 0.0008 mM for dichlorophenols and monochlorophenols, respectively. The oxidation kinetics of five chlorophenols in aqueous solution with excess potassium permanganate were evaluated using the analytical method. The pseudo-first-order reaction rates were found to be relatively rapid 1.42 × 10−3 to 0.024 s−1 and followed the sequence 2-chlorophenol (2-CP) > 2,6-dichlorophenol (2,6-DCP) > 4-chlorophenol (4-CP) > 2,4-dichlorophenol (2, 4-DCP) > 3-chlorophenol (3-CP). The apparent second-order rate constant was calculated from the measured pseudo-first-order rate constant with respect to CP with initial KMnO4 concentration (1.5 mM) and follows the same sequence of pseudo-first-order rate constant. This shows that chlorine atoms in the structure of chlorophenol had a significant influence on the oxidation of chlorophenols by potassium permanganate. Permanganate can be used for the treatment of chlorophenol-contaminated soil and groundwater.