Temperature dependence of the absolute rate constant for the reaction of hydroxyl radical with hydrogen sulfide

Michael, J. V.; Nava, D. F.; Brobst, W. D.; Borkowski, R. P.; Stief, L. J.

doi:10.1021/j100390a016

Cited by 30 publications

(15 citation statements)

References 3 publications

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“…Consistent with an abstraction mechanism at and above room temperature are the results of Friedl et al [196] and Leu and Smith [191] discussed above, the results of an adjusted bond energy-bond order calculation [190], and the similarity of the Arrhenius preexponential factor with II II II II II II II II II V I1 II II that for NH3 and CH4 [187]. An addition mechanism at lower temperatures could explain the non-Arrhenius behavior shown in Figure 6 [190].…”

Section: A Oh-kh~s --+ H~o+shsupporting

confidence: 75%

“…With the exception of the results of Westenberg and deHaas [195], studies either indicate no temperature dependence [187,189], or suggest a minimum in the rate constant between 250 and 300K [190][191][192][193]265]. However, the reported errors associated with most determinations are too large to differentiate the suggested minimum.…”

Section: A Oh-kh~s --+ H~o+shmentioning

confidence: 96%

“…The possible minimum in the Arrhenius plot in Figure 6 led to speculation by Michael et al [190] that the reaction proceeds by two channels, direct abstraction and addition at higher and lower temperatures, respectively. Consistent with an abstraction mechanism at and above room temperature are the results of Friedl et al [196] and Leu and Smith [191] discussed above, the results of an adjusted bond energy-bond order calculation [190], and the similarity of the Arrhenius preexponential factor with II II II II II II II II II V I1 II II that for NH3 and CH4 [187].…”

Section: A Oh-kh~s --+ H~o+shmentioning

confidence: 98%

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Reactions of OH radicals with inorganic compounds in the gas phase

Paraskevopoulos

Singleton

1988

Reviews of Chemical Intermediates

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Section: A Oh-kh~s --+ H~o+shsupporting

confidence: 75%

Section: A Oh-kh~s --+ H~o+shmentioning

confidence: 96%

Section: A Oh-kh~s --+ H~o+shmentioning

confidence: 98%

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Reactions of OH radicals with inorganic compounds in the gas phase

Paraskevopoulos

Singleton

1988

Reviews of Chemical Intermediates

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“…For H 2 S + H (R2), H 2 S + O (R3, R4), and H 2 S + S (R12), we rely on rate constants determined by Marshall and coworkers . The rate constant for H 2 S + OH (R5) was taken from the theoretical study by Ellingson and Truhlar ; it provides an explanation for the unusual temperature dependence of the reaction, and the calculated value is in good agreement with experiment . The H 2 S + O reaction has two product channels, SH + OH (R3) and HSO + H (R4).…”

Section: Detailed Kinetic Modelmentioning

confidence: 93%

An Exploratory Flow Reactor Study of H₂S Oxidation at 30–100 Bar

Song

Hashemi

Christensen

et al. 2016

Int J of Chemical Kinetics

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Hydrogen sulfide oxidation experiments were conducted in O2/N2 at high pressure (30 and 100 bar) under oxidizing and stoichiometric conditions. Temperatures ranged from 450 to 925 K, with residence times of 3–20 s. Under stoichiometric conditions, the oxidation of H2S was initiated at 600 K and almost completed at 900 K. Under oxidizing conditions, the onset temperature for reaction was 500–550 K, depending on pressure and residence time, with full oxidization to SO2 at 550–600 K. Similar results were obtained in quartz and alumina tubes, indicating little influence of surface chemistry. The data were interpreted in terms of a detailed chemical kinetic model. The rate constants for selected reactions, including SH + O2 ⇄ SO2 + H, were determined from ab initio calculations. Modeling predictions generally overpredicted the temperature for onset of reaction. Calculations were sensitive to reactions of the comparatively unreactive SH radical. Under stoichiometric conditions, the oxidation rate was mostly controlled by the SH + SH branching ratio to form H2S + S (promoting reaction) and HSSH (terminating). Further work is desirable on the SH + SH recombination and on subsequent reactions in the S2 subset of the mechanism. Under oxidizing conditions, a high O2 concentration (augmented by the high pressure) causes the termolecular reaction SH + O2 + O2 → HSO + O3 to become the major consumption step for SH, according to the model. Consequently, calculations become very sensitive to the rate constant and product channels for the H2S + O3 reaction, which are currently not well established.

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“…Room temperature rate constants measured by different investigators using a variety of techniques range from 3.1 to 5.5 x 10 -12 cm 3 s -1 , the literature references can be found in Baulch et al (1984). The more recent data (Wine et al, 1981;Lin, 1982;Leu and Smith, 1982;Michael et al, 1982) on the reaction are in good agreement and have been reviewed by Baulch et al (1984) who recommend a value of 4.8 x 10 -12 cm 3 s -1 for atmospheric modelling purposes. The value of (5.0 + -0.3)x 10 -12 cm a s -1 obtained by Cox and Sheppard (1980) also under atmospheric conditions is in particularly good agreement with the present result.…”

Section: H2s + Ohmentioning

confidence: 93%

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide, hydrogen sulphide, aliphatic thiols and thiophenol

et al. 1986

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The reactions of OH radicals with SO2, H 2 S, thiophenol, and a series of aliphatic thiols (1-5 C-atoms) have been investigated in 201 and 381 reaction chambers at 1 atm total pressure and 300 K using a competitive kinetic technique. Initially, OH radicals were produced by photolysis of CH3ONO/NO mixtures in air. Applying this OH source rate constants for OH with SO2, H2S , and thiophenol in synthetic air were determined to be (1.1-+0.2) x l0 -12, (5.5-+0.8) ×10 -12 and (1.1 +-0.2) × 10 -it cm 3 s -1 , respectively. However, when this method was applied to the aliphatic thiols the rate constants obtained were found to be dependent on the partial pressures of Oz and NO. These effects have been attributed to the built-up of a radical species, not yet identified, which leads to uncontrolled chain reactions in the system. Using the photolysis of H202 at wavelengths greater than 260 nm as the OH source in 1 atm N:, rate constants for the 1-5 aliphatic thiols in the range 2.9 to 5.6 × 10 -it cm 3 s -~ were obtained. The rate constants obtained in the present study are compared with recent literature values.

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Temperature dependence of the absolute rate constant for the reaction of hydroxyl radical with hydrogen sulfide

Cited by 30 publications

References 3 publications

Reactions of OH radicals with inorganic compounds in the gas phase

Reactions of OH radicals with inorganic compounds in the gas phase

An Exploratory Flow Reactor Study of H₂S Oxidation at 30–100 Bar

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide, hydrogen sulphide, aliphatic thiols and thiophenol

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Temperature dependence of the absolute rate constant for the reaction of hydroxyl radical with hydrogen sulfide

Cited by 30 publications

References 3 publications

Reactions of OH radicals with inorganic compounds in the gas phase

Reactions of OH radicals with inorganic compounds in the gas phase

An Exploratory Flow Reactor Study of H2S Oxidation at 30–100 Bar

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide, hydrogen sulphide, aliphatic thiols and thiophenol

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An Exploratory Flow Reactor Study of H₂S Oxidation at 30–100 Bar