The Kinetics and Mechanism of the Chlorine Dioxide−Iodide Ion Reaction

Fábián, and István; Gordon, Gilbert

doi:10.1021/ic961279g

Cited by 47 publications

(12 citation statements)

References 21 publications

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“…However, our conclusions are corroborated by earlier kinetic studies, which postulated the formation of very similar reactive intermediates in the reactions of oxyhalogen species. 1,3,9, [39][40][41][42][43] The consumption of the chlorite ion is interpreted in terms of the HOCl/ClO 2 -reaction (steps R11-R13). There seems to be a consensus in the literature that this reaction proceeds via the Cl 2 O 2 intermediate and produces only ClO 3 -in excess HOCl.…”

Section: Resultsmentioning

confidence: 99%

Kinetics and Mechanism of Catalytic Decomposition and Oxidation of Chlorine Dioxide by the Hypochlorite Ion

et al. 2001

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The oxidation of ClO(2) by OCl(-)is first order with respect to both reactants in the neutral to alkaline pH range: -d[ClO(2)]/dt = 2k(OCl)[ClO(2)][OCl(-)]. The rate constant (T = 298 K, mu = 1.0 M NaClO(4)) and activation parameters are k(OCl) = 0.91 +/- 0.02 M(-1) s(-1), DeltaH = 66.5 +/- 0.9 kJ/mol, and DeltaS(++) = -22.3 +/- 2.9 J/(mol K). In alkaline solution, pH > 9, the primary products of the reaction are the chlorite and chlorate ions and consumption of the hypochlorite ion is not observed. The hypochlorite ion is consumed in increasing amounts, and the production of the chlorite ion ceases when the pH is decreased. The stoichiometry is kinetically controlled, and the reactants/products ratios are determined by the relative rates of the production and consumption of the chlorite ion in the ClO(2)/OCl(-) and HOCl/ClO(2)(-) reactions, respectively.

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Section: Resultsmentioning

confidence: 99%

Kinetics and Mechanism of Catalytic Decomposition and Oxidation of Chlorine Dioxide by the Hypochlorite Ion

et al. 2001

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“…A comparison of Fe(VI) to oxidize Iwith other conventional oxidants is given in Table 2 ( Kumar, et al, 1986;Nagy, et al, 1988;Fábián and Gordon, 1997;Bichsel and von Gunten, 1999). At a neutral pH, the reactivity of oxidants increased in order of ClO 2 < NH 2 Cl < HFe VI O 4 -~ HOCl < O 3 .…”

Section: Implications In Water Treatmentmentioning

confidence: 99%

Ferrates(FeVI, FeV, and FeIV) oxidation of iodide: Formation of triiodide

et al. 2016

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The presence of iodide (I(-)) in water during disinfection and oxidative treatment of water is a potential health concern because of the formation of iodinated disinfection by-products (DBPs), which may be more toxic than chlorinated DBPs. The kinetics of the oxidation of I(-) by a greener oxidant, ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) was determined as a function of pH. The second-order rate constants (k, M(-1) s(-1)) decreased from 3.9 × 10(4) M(-1) s(-1) at pH 5.0 to 1.2 × 10(1) M(-1) s(-1) at pH 10.3. The kinetics results could be described by the reactivity of monoprotonated species of Fe(VI) (HFe(VI)O4(-)) with I(-). In excess I(-) concentration, triiodide (I3(-)) was formed and the stoichiometry of ∼1:1 ([Fe(VI)]:[I3(-)]) was found in both acidic and basic pH. Ferrate(V) (Fe(V)O4(3-), Fe(V)) and ferrate(IV) (Fe(VI)O4(4-), Fe(IV)) also showed the formation of I3(-) in presence of excess I(-). A mechanism of the formation of I3(-) is proposed, which is consistent with the observed stoichiometry of 1:1. The oxidative treatment of I(-) in water will be rapid (t1/2 = 0.6 s at pH 7.0 using 10 mg L(-1) K2FeO4). The implications of the results and their comparison with the oxidation of I(-) by conventional disinfectants/oxidants in water treatment are briefly discussed.

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“…For reaction (17), we proposed a scheme as shown in reactions (R4)-(R6) based upon the concentration changing trends of the two intermediates in Figures 13 and 14 and in consideration literature [25]. In aqueous solutions putting into the base shown in reaction (R5) may be water or halide ions which are sufficiently basic to act as shown in [26].…”

Section: Online Ftir Analysis During the Oscillation Reactionmentioning

confidence: 99%

“…They suggested a simple mechanism, in which iodine atoms produced by photodissociation of molecular iodine initiate reduction of chlorine dioxide to chlorite and oxidation of iodide ions to iodine. The oxidation of iodide ion by chlorine dioxide has been studied by stopped-flow techniques at I = 1.0 mol/L (NaClO 4 ) [17]. A two-term rate law was confirmed for the reaction.…”

Section: Introductionmentioning

confidence: 96%

Chlorine Dioxide–Iodide–Methyl Acetoacetate Oscillation Reaction Investigated by UV–Vis and an Online FTIR Spectrophotometric Method

Shi

Liu

et al. 2013

J Solution Chem

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In order to study the chemical oscillatory behavior and mechanism of a new chlorine dioxide-iodide ion-methyl acetoacetate reaction system, a series of experiments were done by using UV-Vis and online FTIR spectrophotometric method. The initial concentrations of methyl acetoacetate, chlorine dioxide, potassium iodide, and sulfuric acid and the pH value have great influence on the oscillation observed at wavelength of 289 nm. There is a preoscillatory or induction period, and the amplitude and the number of oscillations are associated with the initial concentration of reactants. The equations for the triiodide ion reaction rate changing with reaction time and the initial concentrations in the oscillation stage were obtained. Oscillation reaction can be accelerated by increasing temperature. The apparent activation energies in terms of the induction period and the oscillation period were 26.02 KJ/mol and 17.65 KJ/mol, respectively. The intermediates were detected by the online FTIR analysis. Based upon the experimental data in this work and in the literature, a plausible reaction mechanism was proposed for the oscillation reaction.

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The Kinetics and Mechanism of the Chlorine Dioxide−Iodide Ion Reaction

Cited by 47 publications

References 21 publications

Kinetics and Mechanism of Catalytic Decomposition and Oxidation of Chlorine Dioxide by the Hypochlorite Ion

Kinetics and Mechanism of Catalytic Decomposition and Oxidation of Chlorine Dioxide by the Hypochlorite Ion

Ferrates(FeVI, FeV, and FeIV) oxidation of iodide: Formation of triiodide

Chlorine Dioxide–Iodide–Methyl Acetoacetate Oscillation Reaction Investigated by UV–Vis and an Online FTIR Spectrophotometric Method

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