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Kinetics and mechanisms of nonmetal redox reactions of oxyhalogens
The mechanisms of several oxidation/reduction reactions of oxyhalogen species are presented. Bromine chloride (BrCl) catalyzes the decomposition of hypochlorous acid/hypobromous acid (HOCl/HOBr) mixtures. BrCl reacts with hypochlorite ion (OClβ) to form BrOCl, which hydrolyzes to chlorite (ClO2β) and bromide (Br β) ions. Bromite ion (BrO2β) is formed via HOBr disproportionation. Rapid reactions of HOCl/BrO2 β and HOBr/ClO2β produce bromate (BrO3β) and chlorate (ClO3 β) ions, respectively. The study of the HOCl/HOBr decomposition is enabled by the ion chromatography (IC). The preparation of HOCl/HOBr reaction mixtures for IC requires removal of HOCl and HOBr from the samples. Three dehalogenating species, phenol, 4-hydroxybenzoic acid, and sulfite ion, enable ion chromatographic analysis. The reduction of BrO2β by sulfite ion (k = 3.0 Γ 107 Mβ1 sβ1) occurs through the OBr + transfer reaction to sulfite ion, with subsequent general-acid catalyzed hydrolysis of OBrSO3β. Conversely, ClO 2β does not react with sulfite, and the reaction is not general-acid catalyzed. Chlorite and S(IV) react via an oxygen-atom transfer where k(ClO2β/SO 2) = 6.26 Γ 106 Mβ1 s β1 and k(ClO2β/SO 3Hβ) = 5.5 Mβ1 sβ1 . The reaction of HOBr with nitrite ion (NO2β ) proceeds by a bromine-atom transfer reaction. HOBr, NO2 β, and H+ are in equilibrium with nitryl bromide, BrNO2 (K = 2.73 Γ 108 M β2). BrNO2 is detected spectrophotometrically where Ο΅(260 nm) = 956 Mβ1 cmβ1. BrNO2 reacts rapidly with NO2β (k = 6.9 Γ 103 Mβ1 sβ1) to form Brβ and N2O 4 and can dissociate to form NO2+ and Br β (k = 18 sβ1). Rapid reactions of N2O4 and NO2+ with water produce NO3β as a final product. Nitrite levels above 100 mM cause a suppression of the observed rate constant. This suggests that N2O4 hydrolysis occurs by reversible heterolytic dissociation into NO2+ and NO2 β