Kinetics and Mechanisms of Radiolytic Degradation of Nitrobenzene in Aqueous Solutions资料.pdfVIP

Kinetics and Mechanisms of Radiolytic Degradation of Nitrobenzene in Aqueous Solutions S H U - J U A N Z H A N G , † H O N G J I A N G , † M I N - J I E L I , † H A N - Q I N G Y U , * , † H A O Y I N , ‡ A N D Q I A N - R O N G L I ‡ Department of Chemistry and Structure Research Laboratory, University of Science & Technology of China, Hefei, Anhui 230026, China Steady-state radiolysis experiments were performed to gain insight into the kinetics and mechanisms of nitrobenzene (NB) degradation in aqueous solutions. The degradation of NB under γ-ray irradiation followed pseudo-first-order kinetics, and the pseudo first-order rate constant and the initial G value of NB decomposition were functionally related to both the initial NB concentration and the irradiation dose rate. Under oxidative conditions, complete mineral- ization of NB was achieved, whereas no total organic carbon reduction was observed under reductive conditions. The radiolytic products of NB under various conditions were identified using FTIR and GC-MS analyses. The mechanisms behind the radiolytic degradation of NB under both oxidative and reductive conditions were proposed schematically in light of the degradation products observed. In addition, calculations based on ab initio molecular orbital and density functional theory provided support for the proposed mechanisms and the preferred pathways among all the possible reactions. Introduction As an important raw material in the chemical industry, nitrobenzene (NB) is widely present in various wastewaters, constituting a serious threat to the environment. Due to the electron-deficient property of the aromatic ring resulting from the substitution of the nitro group, NB is a biorefractory compound. Conventional biological processes are not ef- ficient for the treatment of NB-laden wastewaters. Therefore, intense efforts have been made to find efficient and cost- effective treatment methods. Both oxidative and reductive approaches have been developed for