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

I. Fábián, Gilbert Gordon

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Abstract

The oxidation of iodide ion by chlorine dioxide has been studied by stopped-flow techniques at I = 1.0 M (NaClO4). The following two-term rate law was confirmed for the reaction: -d[ClO2]/dt = kI[ClO2][I-] + kII[ClO2][I-]2. The rate constants at 298 K and the activation parameters are kI = (1.87 ± 0.02) × 103 M-1 s-1, ΔHI = 35.4 ± 0.7 kJ/mol, ΔSI = -63.5 ± 2.3 J/(mol K), kII = (1.25 ± 0.04) × 104 M-2 s-1, ΔHII = 36.7 ± 1.3 kJ/mol, ΔSII = -43.2 ± 4.6 J/(mol K). Both the second- and third-order paths are interpreted in terms of an outersphere electron-transfer mechanism. The calculations based on the Marcus theory yield kI = 1358 M-1 s-1 for the second-order path.

Original languageEnglish
Pages (from-to)2494-2497
Number of pages4
JournalInorganic Chemistry
Volume36
Issue number12
Publication statusPublished - 1997

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Iodides
dioxides
iodides
chlorine
Rate constants
Chemical activation
Ions
Oxidation
Kinetics
Electrons
International System of Units
kinetics
electron transfer
ions
activation
oxidation
chlorine dioxide

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

The Kinetics and Mechanism of the Chlorine Dioxide - Iodide Ion Reaction. / Fábián, I.; Gordon, Gilbert.

In: Inorganic Chemistry, Vol. 36, No. 12, 1997, p. 2494-2497.

Research output: Contribution to journalArticle

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abstract = "The oxidation of iodide ion by chlorine dioxide has been studied by stopped-flow techniques at I = 1.0 M (NaClO4). The following two-term rate law was confirmed for the reaction: -d[ClO2]/dt = kI[ClO2][I-] + kII[ClO2][I-]2. The rate constants at 298 K and the activation parameters are kI = (1.87 ± 0.02) × 103 M-1 s-1, ΔHI ‡ = 35.4 ± 0.7 kJ/mol, ΔSI ‡ = -63.5 ± 2.3 J/(mol K), kII = (1.25 ± 0.04) × 104 M-2 s-1, ΔHII ‡ = 36.7 ± 1.3 kJ/mol, ΔSII ‡ = -43.2 ± 4.6 J/(mol K). Both the second- and third-order paths are interpreted in terms of an outersphere electron-transfer mechanism. The calculations based on the Marcus theory yield kI = 1358 M-1 s-1 for the second-order path.",
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N2 - The oxidation of iodide ion by chlorine dioxide has been studied by stopped-flow techniques at I = 1.0 M (NaClO4). The following two-term rate law was confirmed for the reaction: -d[ClO2]/dt = kI[ClO2][I-] + kII[ClO2][I-]2. The rate constants at 298 K and the activation parameters are kI = (1.87 ± 0.02) × 103 M-1 s-1, ΔHI ‡ = 35.4 ± 0.7 kJ/mol, ΔSI ‡ = -63.5 ± 2.3 J/(mol K), kII = (1.25 ± 0.04) × 104 M-2 s-1, ΔHII ‡ = 36.7 ± 1.3 kJ/mol, ΔSII ‡ = -43.2 ± 4.6 J/(mol K). Both the second- and third-order paths are interpreted in terms of an outersphere electron-transfer mechanism. The calculations based on the Marcus theory yield kI = 1358 M-1 s-1 for the second-order path.

AB - The oxidation of iodide ion by chlorine dioxide has been studied by stopped-flow techniques at I = 1.0 M (NaClO4). The following two-term rate law was confirmed for the reaction: -d[ClO2]/dt = kI[ClO2][I-] + kII[ClO2][I-]2. The rate constants at 298 K and the activation parameters are kI = (1.87 ± 0.02) × 103 M-1 s-1, ΔHI ‡ = 35.4 ± 0.7 kJ/mol, ΔSI ‡ = -63.5 ± 2.3 J/(mol K), kII = (1.25 ± 0.04) × 104 M-2 s-1, ΔHII ‡ = 36.7 ± 1.3 kJ/mol, ΔSII ‡ = -43.2 ± 4.6 J/(mol K). Both the second- and third-order paths are interpreted in terms of an outersphere electron-transfer mechanism. The calculations based on the Marcus theory yield kI = 1358 M-1 s-1 for the second-order path.

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