title: Kinetics modeling and reaction mechanism of ferrate(VI) oxidation of benzotriazoles.
abstract: Benzotriazoles (BTs) are high production volume chemicals with broad application in various industrial processes and in households, and have been found to be omnipresent in aquatic environments. We investigated oxidation of five benzotriazoles (BT: 1H-benzotriazole; 5MBT: 5-methyl-1H-benzotriazole; DMBT: 5,6-dimethyl-1H-benzotriazole hydrate; 5CBT: 5-chloro-1H-benzotriazole; HBT: 1-hydroxybenzotriazole) by aqueous ferrate (Fe(VI)) to determine reaction kinetics as a function of pH (6.0-10.0), and interpreted the reaction mechanism of Fe(VI) with BTs by using a linear free-energy relationship. The pK(a) values of BT and DMBT were also determined using UV-Visible spectroscopic method in order to calculate the species-specific rate constants, and they were 8.37 ± 0.0 and 8.98 ± 0.08 respectively. Each of BTs reacted moderately with Fe(VI) with the k(app) ranged from 7.2 to 103.8 M(-1)s(-1) at pH 7.0 and 24 ± 1 °C. When the molar ratio of Fe(VI) and BTs increased up to 30:1, the removal rate of BTs reached about >95% in buffered milli-Q water or secondary wastewater effluent. The electrophilic oxidation mechanism of the above reaction was illustrated by using a linear free-energy relationship between pH-dependence of species-specific rate constants and substituent effects (σ(p)). Fe(VI) reacts initially with BTs by electrophilic attack at the 1,2,3-triazole moiety of BT, 5MBT, DMBT and 5CBT, and at the N-OH bond of HBT. Moreover, for BT, 5MBT, DMBT and 5CBT, the reactions with the species HFeO(4)(-) predominantly controled the reaction rates. For HBT, the species H(2)FeO(4) with dissociated HBT played a major role in the reaction. The results showed that Fe(VI) has the ability to degrade benzotriazoles in water.
authors.affiliation: State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China.
authors.forename: Bin
authors.initials: B
authors.lastname: Yang
authors.forename: Guang-Guo
authors.initials: GG
authors.lastname: Ying
authors.forename: Li-Juan
authors.initials: LJ
authors.lastname: Zhang
authors.forename: Li-Jun
authors.initials: LJ
authors.lastname: Zhou
authors.forename: Shan
authors.initials: S
authors.lastname: Liu
authors.forename: Yi-Xiang
authors.initials: YX
authors.lastname: Fang
mesh_terms: D002021:Buffers; D003198:Computer Simulation; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D016014:Linear Models; D008956:Models, Chemical; D016877:Oxidants / Q000737:chemistry; D010084:Oxidation-Reduction; D013816:Thermodynamics; D014230:Triazoles / Q000737:chemistry*
chemical_list: D002021:Buffers; D016877:Oxidants; D014230:Triazoles; C017311:ferrate ion; C012771:benzotriazole; D007501:Iron