Formation of superoxide ion during the decomposition of hydrogen peroxide on supported metals

Yoshio Ono; Tsuyoshi Matsumura; Nobumasa Kitajima; Shun Ichi Fukuzumi

doi:10.1021/j100528a018

Formation of superoxide ion during the decomposition of hydrogen peroxide on supported metals

Yoshio Ono, Tsuyoshi Matsumura, Nobumasa Kitajima, Shun Ichi Fukuzumi

Department of Chemistry & Nanoscience

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Abstract

Presence of the superoxide ion (O₂^-) in the aqueous phase during the decomposition of hydrogen peroxide over supported metals has been revealed by quenching the reacting solution and measuring the ESR of the quenched ice. Observation of the superoxide ion in an aqueous phase gives direct evidence for the involvement of free-radical intermediates during peroxide decomposition by solid catalysts. The kinetics of hydrogen peroxide decomposition and of superoxide formation were studied. The rate of superoxide formation is expressed by d[O₂^-]/d[W/F] = k₂[H₂O₂]_t - k₃[O₂^-], where [H₂O₂]_t is the total analytical concentration of hydrogen peroxide, W is the amount of catalyst, and F is the flow rate of the solution. A reaction mechanism for the formation of the superoxide ion has been proposed based on the Haber-Weiss mechanism. It was also found that the superoxide ion trapped in ice decayed with second-order kinetics above -70°C with an activation energy of 50 kJ/mol.

Original language	English
Pages (from-to)	1307-1311
Number of pages	5
Journal	Journal of Physical Chemistry
Volume	81
Issue number	13
DOIs	https://doi.org/10.1021/j100528a018
State	Published - 1977

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title = "Formation of superoxide ion during the decomposition of hydrogen peroxide on supported metals",

abstract = "Presence of the superoxide ion (O2-) in the aqueous phase during the decomposition of hydrogen peroxide over supported metals has been revealed by quenching the reacting solution and measuring the ESR of the quenched ice. Observation of the superoxide ion in an aqueous phase gives direct evidence for the involvement of free-radical intermediates during peroxide decomposition by solid catalysts. The kinetics of hydrogen peroxide decomposition and of superoxide formation were studied. The rate of superoxide formation is expressed by d[O2-]/d[W/F] = k2[H2O2]t - k3[O2-], where [H2O2]t is the total analytical concentration of hydrogen peroxide, W is the amount of catalyst, and F is the flow rate of the solution. A reaction mechanism for the formation of the superoxide ion has been proposed based on the Haber-Weiss mechanism. It was also found that the superoxide ion trapped in ice decayed with second-order kinetics above -70°C with an activation energy of 50 kJ/mol.",

author = "Yoshio Ono and Tsuyoshi Matsumura and Nobumasa Kitajima and Fukuzumi, {Shun Ichi}",

year = "1977",

doi = "10.1021/j100528a018",

language = "English",

volume = "81",

pages = "1307--1311",

journal = "Journal of Physical Chemistry",

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TY - JOUR

T1 - Formation of superoxide ion during the decomposition of hydrogen peroxide on supported metals

AU - Ono, Yoshio

AU - Matsumura, Tsuyoshi

AU - Kitajima, Nobumasa

AU - Fukuzumi, Shun Ichi

PY - 1977

Y1 - 1977

N2 - Presence of the superoxide ion (O2-) in the aqueous phase during the decomposition of hydrogen peroxide over supported metals has been revealed by quenching the reacting solution and measuring the ESR of the quenched ice. Observation of the superoxide ion in an aqueous phase gives direct evidence for the involvement of free-radical intermediates during peroxide decomposition by solid catalysts. The kinetics of hydrogen peroxide decomposition and of superoxide formation were studied. The rate of superoxide formation is expressed by d[O2-]/d[W/F] = k2[H2O2]t - k3[O2-], where [H2O2]t is the total analytical concentration of hydrogen peroxide, W is the amount of catalyst, and F is the flow rate of the solution. A reaction mechanism for the formation of the superoxide ion has been proposed based on the Haber-Weiss mechanism. It was also found that the superoxide ion trapped in ice decayed with second-order kinetics above -70°C with an activation energy of 50 kJ/mol.

AB - Presence of the superoxide ion (O2-) in the aqueous phase during the decomposition of hydrogen peroxide over supported metals has been revealed by quenching the reacting solution and measuring the ESR of the quenched ice. Observation of the superoxide ion in an aqueous phase gives direct evidence for the involvement of free-radical intermediates during peroxide decomposition by solid catalysts. The kinetics of hydrogen peroxide decomposition and of superoxide formation were studied. The rate of superoxide formation is expressed by d[O2-]/d[W/F] = k2[H2O2]t - k3[O2-], where [H2O2]t is the total analytical concentration of hydrogen peroxide, W is the amount of catalyst, and F is the flow rate of the solution. A reaction mechanism for the formation of the superoxide ion has been proposed based on the Haber-Weiss mechanism. It was also found that the superoxide ion trapped in ice decayed with second-order kinetics above -70°C with an activation energy of 50 kJ/mol.

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DO - 10.1021/j100528a018

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SN - 0022-3654

VL - 81

SP - 1307

EP - 1311

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 13

ER -

Formation of superoxide ion during the decomposition of hydrogen peroxide on supported metals

Abstract

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