Influence of different nominal molecular weight fractions of humic acids on phenol oxidation by permanganate

The effects of humic acid (HA) and its different nominal molecular weight (NMW) fractions on the phenol oxidation by permanganate were studied. Phenol oxidation by permanganate was enhanced by the presence of HA at pH 4-8, while slightly inhibited at pH 9-10. The effects of HA on phenol oxidation by permanganate were dependent on HA concentration and permanganate/phenol molar ratios. The high NMW fractions of HA enhanced phenol oxidation by permanganate at pH 7 more significantly than the low fractions of HA. The apparent second-order rate constants of phenol oxidation by permanganate in the presence of HA correlated well with their specific ultraviolet absorption (SUVA) at 254 nm and specific violet absorption (SVA) at 465 or 665 nm. High positive correlation coefficients (R² > 0.72) implied that π-electrons of HA strongly influenced the reactivity of phenol towards permanganate oxidation which agreed well with the information provided by fluorescence spectroscopy. The FTIR analysis indicated that the HA fractions rich in aliphatic character, polysaccharide-like substances, and the amount of carboxylate groups had less effect on phenol oxidation by permanganate. The negative correlation between the rate constants of phenol oxidation by permanganate and O/C ratios suggested that the oxidation of phenol increased with a decrease in the content of oxygen-containing functional groups.