Kinetics and mechanism of catalytic decomposition and oxidation of chlorine dioxide by the hypochlorite ion

V. Csordás, B. Bubnis, I. Fábián, G. Gordon

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The oxidation of ClO2 by OCl-is first order with respect to both reactants in the neutral to alkaline pH range: -d[ClO2]/dt = 2kOCl[ClO2][OCl-]. The rate constant (T = 298 K, μ = 1.0 M NaClO4) and activation parameters are kOCl = 0.91 ± 0.02 M-1 s-1, ΔH = 66.5 ± 0.9 kJ/mol, and ΔS = -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 ClO2/OCl- and HOCl/ClO2- reactions, respectively.

Original languageEnglish
Pages (from-to)1833-1836
Number of pages4
JournalInorganic Chemistry
Volume40
Issue number8
DOIs
Publication statusPublished - Apr 9 2001

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Hypochlorous Acid
dioxides
chlorine
Ions
Decomposition
decomposition
Oxidation
oxidation
Kinetics
kinetics
ions
Chlorates
chlorates
Theophylline
products
Stoichiometry
stoichiometry
Rate constants
Chemical activation
chlorine dioxide

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Kinetics and mechanism of catalytic decomposition and oxidation of chlorine dioxide by the hypochlorite ion. / Csordás, V.; Bubnis, B.; Fábián, I.; Gordon, G.

In: Inorganic Chemistry, Vol. 40, No. 8, 09.04.2001, p. 1833-1836.

Research output: Contribution to journalArticle

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abstract = "The oxidation of ClO2 by OCl-is first order with respect to both reactants in the neutral to alkaline pH range: -d[ClO2]/dt = 2kOCl[ClO2][OCl-]. The rate constant (T = 298 K, μ = 1.0 M NaClO4) and activation parameters are kOCl = 0.91 ± 0.02 M-1 s-1, ΔH‡ = 66.5 ± 0.9 kJ/mol, and ΔS‡ = -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 ClO2/OCl- and HOCl/ClO2- reactions, respectively.",
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AU - Bubnis, B.

AU - Fábián, I.

AU - Gordon, G.

PY - 2001/4/9

Y1 - 2001/4/9

N2 - The oxidation of ClO2 by OCl-is first order with respect to both reactants in the neutral to alkaline pH range: -d[ClO2]/dt = 2kOCl[ClO2][OCl-]. The rate constant (T = 298 K, μ = 1.0 M NaClO4) and activation parameters are kOCl = 0.91 ± 0.02 M-1 s-1, ΔH‡ = 66.5 ± 0.9 kJ/mol, and ΔS‡ = -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 ClO2/OCl- and HOCl/ClO2- reactions, respectively.

AB - The oxidation of ClO2 by OCl-is first order with respect to both reactants in the neutral to alkaline pH range: -d[ClO2]/dt = 2kOCl[ClO2][OCl-]. The rate constant (T = 298 K, μ = 1.0 M NaClO4) and activation parameters are kOCl = 0.91 ± 0.02 M-1 s-1, ΔH‡ = 66.5 ± 0.9 kJ/mol, and ΔS‡ = -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 ClO2/OCl- and HOCl/ClO2- reactions, respectively.

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