A Novel Reaction of HCrO4− with PH2O2−, Induced by Molecular Oxygen, Forming Peroxodiphosphate Ions in an Aqueous Solution

Kimura, Masao; Takahashi, Aki; Kayanoki, Hiroko; Sakata, Tomomi; Tsukahara, Keiichi

doi:10.1246/bcsj.70.2699

Bulletin of the Chemical Society of Japan

1997

DOI: 10.1246/bcsj.70.2699

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A Novel Reaction of HCrO4− with PH2O2−, Induced by Molecular Oxygen, Forming Peroxodiphosphate Ions in an Aqueous Solution

Masao Kimura¹,

Aki Takahashi²,

Hiroko Kayanoki³

et al.

Abstract: The chromate (VI) ion HCrO4− at pH 2—4 was not appreciablly reduced by the phosphinate ion PH2O2− in the absence of molecular oxygen (O2), but was reduced in the presence of O2, forming peroxodiphosphate ions (denoted by PDP and meaning all forms of P2O84−, HP2O83− etc.) in much higher concentrations than those of the added chromate(VI). Both the rates of the chromate decay and the PDP formation increased with decreasing pH. When the chromate(VI) ion disappeared completely, PDP formation stopped and its concen… Show more

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Cited by 3 publications

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Chapter 27. Mechanisms of reactions in solution

Winterton¹

1999

Annu. Rep. Prog. Chem., Sect. A

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Full understanding of a chemical change requires the identity and nature of intermediates formed between reactants and products to be identified and knowledge of the processes of bond making and breaking and of electron transfer to be established. Inorganic reaction mechanisms are thus of intrinsic interest. Moreover, they underpin our understanding of key environmental, biological, medical and industrial processes. This review of the 1998 literature does not, except for studies of particular importance or interest, cover homogeneous catalysis or redox processes involving organic substrates, organic reactions of the heavier p-block elements, or fluxional, photochemical, electrochemical, solid-state or heterogeneous processes.A new journal, Inorg. React. Mech., and a special issue of Transition Met. Chem. are devoted to inorganic mechanisms. Activation volumes in solution, models for electron transfer, the use of density functional theory and electron-transfer reactions of polyoxymetalates have been reviewed and the application of genetic-algorithm and non-linear optimization methods to the treatment of kinetic data described. Stoppedflow EXAFS has been used to study short-lived intermediates. Studies of processes on the femtosecond timescaleare noted. Redox reactionsA series of papers on electron transfer in proteinsand a review by Marcus on theory and experiment in electron-transfer reactions have appeared in a special issue of J. Electroanal. Chem. Long range electron transferDifferent sites on cytochrome bc are associated with oxidation and reduction, with the Fe-S protein component of cytochrome bc acting as an electron shuttle between †Dedicated to the memory of Professor Bob Hay, an esteemed friend and colleague.

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Chapter 27. Mechanisms of reactions in solution

Winterton¹

1999

Annu. Rep. Prog. Chem., Sect. A

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Kinetics and Mechanisms of the Reaction of PH2O2− with O2, Photocatalyzed by [Ru(bpy)3]2+* (bpy = 2,2′-bipyridine), Forming Peroxodiphosphate Ions in an Aqueous Solution

Kimura¹,

Takahashi²,

Sakata³

et al. 1998

Bulletin of the Chemical Society of Japan

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The formation reaction of peroxodiphosphate (denoted by PDP and meaning P2O84−, HP2O83− etc.) by the reaction of molecular oxygen (O2) with the phosphinate ion (PH2O2−) was extremely accelerated by irradiation with visible light of aqueous solutions containing the tris(2,2′-bipyridine)ruthenium(II) ion ([Ru(bpy)3]2+). The [Ru(bpy)3]2+ acted as a photocatalyst during the reaction. The reaction mechanism consists of a chain reaction being accompanied by the O2-quenching of a photoexcited ruthenium(II) complex ([Ru(bpy)3]2+*) to make the superoxide (O2−•) and [Ru(bpy)3]3+, followed by the reduction of [Ru(bpy)3]3+ by PH2O2− to make [Ru(bpy)3]2+ and PH2O2•. However, such PDP once formed in the presence of O2 began to decrease with a rate law of -d[PDP]/dt = kobsd[PDP] after the solution was saturated with N2 gas, and when the solution was again saturated with air, the PDP began to increase again with light irradiation and remained constant in the dark. Such behaviors are discussed while presenting the reaction mechanisms.

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Mechanisms of Oxidation Reactions of Iodide and Hexacyanoferrate(II) Ions, Induced by the Reaction between Phosphinate Ion and Molecular Oxygen in an Aqueous Solution

Kimura¹,

Ieyama²,

Matsumoto³

et al. 2001

Bulletin of the Chemical Society of Japan

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When an I− solution was mixed with a PH2O2− solution which had been kept standing for given times of 5–40 min in the presence of molecular oxygen (O2), the I2 (or I3−) was rapidly formed and then gradually reduced. The maximum amounts of the formed I2 (or I3−) increased with increasing standing times of the PH2O2− solution, and with increasing concentrations of PH2O2− and H+ in the solution. When the [Fe(CN)6]4− solution was mixed with the PH2O2− solution, [Fe(CN)6]3− was formed quantitatively, but an induction period appeared under the conditions of low concentrations of PH2O2− and high pH’s. The induction period was shortened at higher concentrations of PH2O2−, O2, and/or H+. Both oxidation reactions of I− and [Fe(CN)6]4− were extremely accelerated by the addition of small amounts of the peroxodiphosphate salt (K4P2O8) into the solution, both were inhibited by the presence of radical scavengers, and never occurred in the N2-saturated solution. The mechanisms for such O2-induced/radical reactions, which are regarded as a new type of Fenton-like reagent, are discussed.

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A Novel Reaction of HCrO4− with PH2O2−, Induced by Molecular Oxygen, Forming Peroxodiphosphate Ions in an Aqueous Solution

Cited by 3 publications

References 8 publications

Chapter 27. Mechanisms of reactions in solution

Chapter 27. Mechanisms of reactions in solution

Kinetics and Mechanisms of the Reaction of PH2O2− with O2, Photocatalyzed by [Ru(bpy)3]2+* (bpy = 2,2′-bipyridine), Forming Peroxodiphosphate Ions in an Aqueous Solution

Mechanisms of Oxidation Reactions of Iodide and Hexacyanoferrate(II) Ions, Induced by the Reaction between Phosphinate Ion and Molecular Oxygen in an Aqueous Solution

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