Photochemistry in the mixed aqueous solution of nitrobenzene and nitrous acid as initiated by the 355nm UV light

The 355nm photon-initiated microscopic reaction mechanisms of the mixed aqueous solution of nitrobenzene and nitrous acid in the presence or absence of O2 were studied by the laser flash photolysis technique. The main transient absorption peaks in the recorded spectra were assigned and the growth/decay trends of several transient species were investigated. It was found that the OH radical formed from the photolysis of nitrous acid triggered most of the subsequent radical reactions. The rate constant of the reaction between OH radical and nitrobenzene was measured to be (3. 4±0. 1)×109 lmol−1 s−1. The product from this reaction, namely C6H5NO2–OH adduct, was found to react with O2 to yield C6H5NO2–OHO2 adduct with a rate constant of (1. 6±0. 2)×109 lmol−1 s−1. Final steady-state products were identified by GC/MS analysis and were in accordance with the transient spectroscopic results. The possible reaction pathways were proposed. [Copyright &y& Elsevier]