Kinetics and mechanisms of reactions for hydrated electron with chlorinated benzenes in aqueous solution

doi:10.1007/s11783-014-0691-8

Front. Environ. Sci. Eng.

2015, Vol. 9

Issue (4) : 583-590 https://doi.org/10.1007/s11783-014-0691-8

RESEARCH ARTICLE

Kinetics and mechanisms of reactions for hydrated electron with chlorinated benzenes in aqueous solution

Haixia YUAN^1,²,Huxiang PAN²,Jin SHI¹,Hongjing LI^1,^*(

),Wenbo DONG^1,^*(

)

1. Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science & Engineering, Fudan University, Shanghai 200433, China
2. Institutes of Naval Medicine, Shanghai 200433, China

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Abstract

The reactions between chlorinated benzenes (CBzs) and hydrated electron (eaq-) were investigated by the electron beam (EB) and laser flash photolysis (LFP) experiments. Under the EB irradiation, the effects of irradiation dose, initial concentration and the number of Cl atoms on the removal efficiencies were further examined. At 10 kGy, the removal efficiencies of mono-CB, 1,3-diCB, 1,2-diCB and 1,4-diCB were 41.2%, 87.2%, 84.0%, and 84.1%, respectively. While irradiation dose was 50 kGy, the removal efficiencies increased to 47.4%, 95.8%, 95.0%, and 95.2%, respectively. Irradiation of CBzs solutions has shown that the higher the initial concentration, the lower the percentage of CBzs removal. In addition to this, the dechlorination efficiencies of 1,2-dichlorobenzene (1,2-diCB), 1,3-dichlorobenzene (1,3-diCB) and 1,4-dichlorobenzene (1,4-diCB) were much higher than that of chlorobenzene (mono-CB). The kinetics of the reactions was achieved with nanosecond LFP. The rate constants of second-order reaction between eaq- with mono-CB, 1,2-diCB, 1,3-diCB and 1,4-diCB were (5.3±0.4) × 10⁸, (4.76±0.1) × 10⁹, (1.01±0.1) × 10¹⁰ and (3.29±0.2) × 10⁹ L·mol^-1·s^-1, respectively. Density functional theory (DFT) calculations were performed to determine the optical properties of unstable CBzs anion radicals, and the main absorption peaks lied in the range of 300–550 nm. The primary reaction pathway of CBzs with eaq- was gradual dechlorination, and the major products were Cl^- and benzene (CBzs(-Cl^-)). Furthermore, biphenyl (or chlorobiphenyl) was observed during the LFP, which was probably formed by recombination of benzene radicals.

Keywords chlorinated benzenes hydrated electron electron beam laser flash photolysis

Corresponding Author(s): Hongjing LI,Wenbo DONG

Online First Date: 10 April 2014 Issue Date: 25 June 2015

Cite this article:

Haixia YUAN,Huxiang PAN,Jin SHI, et al. Kinetics and mechanisms of reactions for hydrated electron with chlorinated benzenes in aqueous solution[J]. Front. Environ. Sci. Eng., 2015, 9(4): 583-590.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-014-0691-8
https://academic.hep.com.cn/fese/EN/Y2015/V9/I4/583

Tab.1 Removal efficiency of CBzs under different initial concentrations

Fig.1 HPLC chromatogram at 30 kGy of mono-CB and 1,2-diCB

Fig.2 Concentrations of irradiation products of mono-CB (a), 1, 2-diCB (b), 1, 3-diCB (c) and 1, 4-diCB (d) in N₂ saturated ethanol aqueous solution

Tab.2 G values at 10 kGy of 150 mg·L^-1 CBzs solution in the presence of ethanol (mole·100 ev^-1)

Fig.3 Decay kinetics of e a q - at 690 nm in the presence of mono-CB measured by LFP. Insert: linear dependence of the pseudo-first-order decay rate of e a q - with mono-CB concentration

Tab.3 Rate constants for reactions of e a q - with CBzs

Tab.4 Optical properties of CBzs anions radical

Fig.4 Major reaction pathway of CBzs with e a q -

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