Decomposition of hydrogen peroxide in aqueous solutions at elevated temperatures

Lin, Chien Chung; Smith, Frank; Ichikawa, Nagayoshi; Baba, Toshihide; Itow, Mikiro

doi:10.1002/kin.550231103

Cited by 107 publications

(56 citation statements)

References 17 publications

(16 reference statements)

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“…For the decomposition reaction of H 2 O 2(aq) , the linear temperature dependence of the observed k H 2 O 2 in the homogeneous H 2 O 2 -H 2 O-HCOOH system is in excellent agreement with previously published data (Lin et al, 1991;Croiset et al, 1997;Foustoukos et al, 2011) (Fig. 4a).…”

Section: The Effect Of H 2 O 2(aq) and Magnetite On Hcooh (Aq) Decompsupporting

confidence: 89%

“…4a) (Table 3). This is consistent with the enhanced stability of intermediate and short-lived OH and HO 2 radicals described in metal-catalyzed hydrogen peroxide decomposition experiments (Hart et al, 1963;Hoare et al, 1967;Takagi and Ishigure, 1985;Lin et al, 1991). Accordingly, the surface area of the reactant solids is expected to play a key role on the extent of H 2 O 2(aq) decomposition and hydroxyl radical formation (Hiroki and LaVerne, 2005;Grozeva and Foustoukos, 2009), and thus, derived Arrhenius parameters (Table 3) only apply to the amount (1.5 g) and specific surface area (1920 cm 2 /g) of Fe 3 O 4 used in our experiments.…”

Section: The Effect Of H 2 O 2(aq) and Magnetite On Hcooh (Aq) Decompsupporting

confidence: 86%

“…These experiments were designed to assess the role of temperature and hydroxyl radical formation on the oxidation of both H 2 O 2(aq) and HCOOH (aq) . The direct decomposition of H 2 O 2(aq) has been shown to follow a first-order reaction kinetics (Lin et al, 1991;Croiset et al, 1997;Hiroki et al, 2002;Foustoukos et al, 2011) described as:…”

Section: Resultsmentioning

confidence: 99%

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Oxidation pathways for formic acid under low temperature hydrothermal conditions: Implications for the chemical and isotopic evolution of organics on Mars

Foustoukos

Stern

2012

Geochimica et Cosmochimica Acta

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In order to evaluate the oxidation effect of dissolved hydrogen peroxide and the catalytic role of iron oxides on the kinetics of formic acid decarboxylation, a series of flow-through hydrothermal experiments was conducted at temperatures ranging from 80 to 150°C and pressures of 172-241 bar. d 13 C composition of residual HCOOH (aq) was also monitored to examine kinetic isotope effects associated with oxidation processes. Our results reveal that decomposition of H 2 O 2(aq) in presence of magnetite follows pseudo first order kinetics, highly enhanced relative to the homogeneous H 2 O 2(aq) -HCOOOH (aq) -H 2 O system, which possibly reflect synthesis of hydroxyl radicals ( Å OH) through Fenton processes. The kinetic rate constants of HCOOH (aq) decarboxylation to CO 2(aq) are also elevated relative to those previously measured in H 2 O 2(aq) free experiments. However, reaction kinetics are slightly slower in the case of H 2 O 2(aq) aqueous solutions coexisting with magnetite than in the absence of mineral phases. This behavior is attributed to the possible formation of Fe-bearing hydroxyl formate aqueous species that could serve as stable transition states leading to a decrease in the activation entropy of formic acid decomposition.d 13 C values of residual formic acid in the homogeneous H 2 O 2(aq) -HCOOH (aq) -H 2 O system are consistent with previous studies. However, magnetite-bearing experiments produce a negative shift in d 13 C of residual formic acid, perhaps specific to Å OH-imposed oxidation of organic compounds. This would indicate that isotopic fractionations by this oxidation pathway are opposite to kinetic fractionation effects expected in biologically driven oxidation processes. This could have important implications for putative H 2 O 2(aq) -bearing Martian subsurface environments and the evolution of organics at low-temperature hydrothermal conditions.

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Section: The Effect Of H 2 O 2(aq) and Magnetite On Hcooh (Aq) Decompsupporting

confidence: 89%

Section: The Effect Of H 2 O 2(aq) and Magnetite On Hcooh (Aq) Decompsupporting

confidence: 86%

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Oxidation pathways for formic acid under low temperature hydrothermal conditions: Implications for the chemical and isotopic evolution of organics on Mars

Foustoukos

Stern

2012

Geochimica et Cosmochimica Acta

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“…PTFE pipe has been previously well used in cases where unstable chemicals such as hydrogen peroxide were handled. 23,24) Type 304SS pipe and CS pipe were used as the reaction pipe to study the effects of the pipe surfaces. For reaction of hydrogen peroxide with hydrazine, which is known to be present in reactor water of BWRs, only 304SS pipe was used.…”

Section: Apparatus and Experimental Conditionsmentioning

confidence: 99%

Hydrazine and Hydrogen Co-injection to Mitigate Stress Corrosion Cracking of Structural Materials in Boiling Water Reactors, (I) Temperature Dependence of Hydrazine Reactions

Ishida

Wada

Tachibana

et al. 2006

Journal of Nuclear Science and Technology

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Hydrazine and hydrogen co-injection into reactor water is considered a new mitigation method of stress corrosion cracking in BWRs. Fundamental data such as the thermal decomposition of hydrazine, the reaction of hydrazine with oxygen and with hydrogen peroxide at temperatures ranging from 150 to 280 C are needed to evaluate suitability of this method. Reactions in bulk water were studied in a polytetrafluoroethylene pipe to separate surface reaction effects. The results were as follows. (1) The orders of the apparent reaction rate of hydrazine with oxygen were 1 and 0.5 for hydrazine and oxygen concentrations, respectively (À . Based on these data, the applicability of hydrazine and hydrogen co-injection into BWRs was considered. Hydrazine introduction to reactor water was confirmed to be accompanied by only 1% decomposition. The concentration of oxygen, which is injected to suppress the flow-assisted corrosion of carbon steel in current BWR operation, would decrease due to the reaction of hydrazine with oxygen. However oxygen concentration in feed water could be maintained at the required level if the concentration of oxygen injected in condensate water was at most doubled compared to the current operating concentration.

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“…Hydrogen peroxide is easily decomposed into water and oxygen in heated alkaline solutions [16,17]. Additionally, peroxide, O 2 2− , is not stable and the uranyl peroxo carbonato complex solution can self-decompose into uranyl tris-carbonato complex ions, UO 2 (CO 3 ) 3 4− , which are stable in a carbonate solution.…”

Section: Introductionmentioning

confidence: 99%

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

Lee

Chung

Lee

et al. 2012

Journal of Hazardous Materials

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Decomposition of hydrogen peroxide in aqueous solutions at elevated temperatures

Cited by 107 publications

References 17 publications

Oxidation pathways for formic acid under low temperature hydrothermal conditions: Implications for the chemical and isotopic evolution of organics on Mars

Oxidation pathways for formic acid under low temperature hydrothermal conditions: Implications for the chemical and isotopic evolution of organics on Mars

Hydrazine and Hydrogen Co-injection to Mitigate Stress Corrosion Cracking of Structural Materials in Boiling Water Reactors, (I) Temperature Dependence of Hydrazine Reactions

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

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