Hydrogen peroxide photolysis in acidic aqueous solutions containing chloride ions. I. Chemical mechanism

Xiao Ying Yu; John R. Barker

doi:10.1021/jp0266648

Hydrogen peroxide photolysis in acidic aqueous solutions containing chloride ions. I. Chemical mechanism

Xiao Ying Yu, John R. Barker

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Abstract

Equilibrium constants and rate constants involving Cl^̇(aq), Cl₂^̇-(aq), H₂O, and H₂O₂(aq) are measured at 297 ± 2 K by analyzing the kinetics of formation and decay of Cl₂^̇-. The new results are in good agreement with previous studies, when available. The reaction between solvated chlorine atoms and hydrogen peroxide is reported for the first time: Cl^̇(aq) + H₂O₂(aq) → H⁺(aq) + Cl^-(aq) + HO₂^̇(aq), k₁₀ = (2.0 ± 0.3) × 10⁹ M^-1 s^-1 (±σ). The new results are used along with evaluations of literature data to arrive at recommendations for several key rate constants and equilibrium constants. Of particular interest, the recommended equilibrium constant for the reaction Cl^̇(aq) + Cl^-1(aq) ↔ Cl₂^̇-(aq) is K₅ = (1.4 ± 0.2) × 10⁵ M^-1(±σ).

Original language	English
Pages (from-to)	1313-1324
Number of pages	12
Journal	Journal of Physical Chemistry A
Volume	107
Issue number	9
DOIs	https://doi.org/10.1021/jp0266648
State	Published - Mar 6 2003
Externally published	Yes

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title = "Hydrogen peroxide photolysis in acidic aqueous solutions containing chloride ions. I. Chemical mechanism",

abstract = "Equilibrium constants and rate constants involving C{\.l}(aq), Cl{\.2}-(aq), H2O, and H2O2(aq) are measured at 297 ± 2 K by analyzing the kinetics of formation and decay of Cl{\.2}-. The new results are in good agreement with previous studies, when available. The reaction between solvated chlorine atoms and hydrogen peroxide is reported for the first time: C{\.l}(aq) + H2O2(aq) → H+(aq) + Cl-(aq) + HO{\.2}(aq), k10 = (2.0 ± 0.3) × 109 M-1 s-1 (±σ). The new results are used along with evaluations of literature data to arrive at recommendations for several key rate constants and equilibrium constants. Of particular interest, the recommended equilibrium constant for the reaction C{\.l}(aq) + Cl-1(aq) ↔ Cl{\.2}-(aq) is K5 = (1.4 ± 0.2) × 105 M-1(±σ).",

author = "Yu, {Xiao Ying} and Barker, {John R.}",

year = "2003",

month = mar,

day = "6",

doi = "10.1021/jp0266648",

language = "English",

volume = "107",

pages = "1313--1324",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Hydrogen peroxide photolysis in acidic aqueous solutions containing chloride ions. I. Chemical mechanism

AU - Yu, Xiao Ying

AU - Barker, John R.

PY - 2003/3/6

Y1 - 2003/3/6

N2 - Equilibrium constants and rate constants involving Cl̇(aq), Cl2̇-(aq), H2O, and H2O2(aq) are measured at 297 ± 2 K by analyzing the kinetics of formation and decay of Cl2̇-. The new results are in good agreement with previous studies, when available. The reaction between solvated chlorine atoms and hydrogen peroxide is reported for the first time: Cl̇(aq) + H2O2(aq) → H+(aq) + Cl-(aq) + HO2̇(aq), k10 = (2.0 ± 0.3) × 109 M-1 s-1 (±σ). The new results are used along with evaluations of literature data to arrive at recommendations for several key rate constants and equilibrium constants. Of particular interest, the recommended equilibrium constant for the reaction Cl̇(aq) + Cl-1(aq) ↔ Cl2̇-(aq) is K5 = (1.4 ± 0.2) × 105 M-1(±σ).

AB - Equilibrium constants and rate constants involving Cl̇(aq), Cl2̇-(aq), H2O, and H2O2(aq) are measured at 297 ± 2 K by analyzing the kinetics of formation and decay of Cl2̇-. The new results are in good agreement with previous studies, when available. The reaction between solvated chlorine atoms and hydrogen peroxide is reported for the first time: Cl̇(aq) + H2O2(aq) → H+(aq) + Cl-(aq) + HO2̇(aq), k10 = (2.0 ± 0.3) × 109 M-1 s-1 (±σ). The new results are used along with evaluations of literature data to arrive at recommendations for several key rate constants and equilibrium constants. Of particular interest, the recommended equilibrium constant for the reaction Cl̇(aq) + Cl-1(aq) ↔ Cl2̇-(aq) is K5 = (1.4 ± 0.2) × 105 M-1(±σ).

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DO - 10.1021/jp0266648

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SN - 1089-5639

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SP - 1313

EP - 1324

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 9

ER -

Hydrogen peroxide photolysis in acidic aqueous solutions containing chloride ions. I. Chemical mechanism

Abstract

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