Acta Phys. -Chim. Sin. ›› 2007, Vol. 23 ›› Issue (11): 1677-1682.doi: 10.1016/S1872-1508(07)60081-3

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Cross-Reaction Mechanism between HNO2 and C6H5Br in Aqueous Solution under Irradiation at 355 nm

QIN Yan; HUANG Li; DONG Wen-Bo; FANG Hao-Jie; HOU Hui-Qi   

  1. Institute of Environmental Science, Fudan University, Shanghai 200433, P. R. China; College of Environmental Science and Engineering, Donghua University, Shanghai 200051, P. R. China
  • Received:2007-06-14 Revised:2007-07-06 Published:2007-11-01
  • Contact: HOU Hui-Qi

Abstract: The reaction mechanism between HNO2 and C6H5Br in aqueous solution in the presence or absence of O2 was studied using laser flash photolysis transient absorption spectrum technique under irradiation at 355 nm. The experimental results suggested the generation of·OH radical through the photolysis of HNO2. The addition of·OH radical to bromobenzene to form an OH-adduct, C6H5Br…OH, involved a second-order rate constant of (8.1±0.7)×109 L·mol-1·s-1 C6H5Br…OHcould be oxidized by O2 or HNO2. The second-order rate constant (3.0±0.5)×107 L·mol-1·s-1 for the reaction of C6H5Br…OHwith HNO2was much slower than (4.0±0.6)×108 L·mol-1·s-1 for the reaction of C6H5Br…OH with O2. The decay constant of C6H5Br…OHO2 produced by the reaction of C6H5Br…OH with O2 decayed was (2.4±0.1)×104 s-1. Gas chromatography and mass spectrometric (GC-MS) analysis suggested the formation of multiple compounds containing nitryl or quinone formed by the reaction of C6H5Br…OH with HNO2 or O2.

Key words: Bromobenzene, Laser flash photolysis, HNO2, Transient absorbance spectrum, ·OH radical, Cross-reaction


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