Quantum chemical and theoretical kinetics studies on the reaction of carbonyl sulfide with H, OH and O(3P)

Saheb, Vahid; Alizadeh, Maliheh; Rezaei, Farideh; Shahidi, Shima

doi:10.1016/j.comptc.2012.06.008

Cited by 22 publications

(32 citation statements)

References 54 publications

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“…The rate constant for the reaction with atomic hydrogen

OCS + H ⇌ CO + SH

has been measured at low temperatures by Rommel and Schiff , Tsunashima et al , and Lee et al , and at high temperatures (1170–1830 K) by Woiki and Roth . In addition, the reaction has been studied theoretically by Rice et al and very recently by Saheb et al . The experimental results, which are captured well by the theoretical expression of Saheb et al, show that the reaction exhibits non‐Arrhenius behavior, and a direct extrapolation of the low‐temperature results yields too small a rate constant at combustion conditions.…”

Section: Detailed Kinetic Modelmentioning

confidence: 86%

“…Singleton and Cvetanovich based their evaluation of k 4 on the shock tube results of Topaluglu , covering the temperature range 1200–1900 K. Later, Isshiki et al determined α between 1120 and 1540 K, reporting values significantly higher than those recommended by Singleton and Cvetanovich. The theoretical studies of the reaction are inconclusive regarding the branching fraction. Isshiki et al performed quantum chemical calculations on this system with G2M(CC1) and CCSD‐based G3 methods.…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

“…2.4 kcal mol −1 below the G2M values they used for their kinetics calculations, and the G3 barriers might give better accord with experiment. Saheb et al explored the reaction by using various quantum chemical methods, with their most sophisticated being W1BD, which also yielded lower barriers than derived by Chiang et al TST was employed to calculate the thermal rate coefficients. Their calculations support the recommendation of Singleton and Cvetanovich, both for the overall rate and the branching ratio, without invoking intersystem crossing.…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

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Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

Glarborg

Marshall

2013

Int J of Chemical Kinetics

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A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts satisfactorily oxidation of OCS over a wide range of stoichiometric air-fuel ratios (0.5 ≤ λ ≤ 7.3), temperatures (450-1700 K), and pressures (0.02-3.0 atm) under dry conditions. The governing reaction mechanisms are outlined based on calculations with the kinetic model. The oxidation rate of OCS is controlled by the competition between chain-branching and -propagating steps; modeling predictions are particularly sensitive to the branching fraction for the OCS + O reaction to form CO + SO or CO 2

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“…The rate constant for the reaction with atomic hydrogen

OCS + H ⇌ CO + SH

Section: Detailed Kinetic Modelmentioning

confidence: 86%

Section: Detailed Kinetic Modelmentioning

confidence: 99%

Section: Detailed Kinetic Modelmentioning

confidence: 99%

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Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

Glarborg

Marshall

2013

Int J of Chemical Kinetics

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“…For instance, as little as 4 mg of sulfur per gram of catalyst on the surface of the Fe-Cu-K catalyst decreases the activity by ca. 50% in the Fischer-Tropsch process [5]. Furthermore, not only does COS cause economic loss, but also affects the environment.…”

Section: Introductionmentioning

confidence: 99%

The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

Zhao

Tang

et al. 2013

The Scientific World Journal

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Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS is a first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the force of the base site has an important effect on the hydrolysis of carbonyl sulfide.

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“…A recent quantum chemical and theoretical kinetics study on the reaction of COS with H, OH, and O ( 3 P) 43 (and references therein) have shown that the fastest chemical sink reaction which may have atmospheric implications is with the hydrogen atom. Whether this mechanism is prevalent in detriment to photolysis is still not known precisely and so UV photolysis may play a significant role in removing carbonyl sulphide from the terrestrial atmosphere.…”

Section: Absolute Photoabsorption Cross Sections and Atmospheric Pmentioning

confidence: 99%

Electronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV

Limão-Vieira

Silva

Almeida

et al. 2015

The Journal of Chemical Physics

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The electronic state spectroscopy of carbonyl sulphide, COS, has been investigated using high resolution vacuum ultraviolet photoabsorption spectroscopy and electron energy loss spectroscopy in the energy range of 4.0–10.8 eV. The spectrum reveals several new features not previously reported in the literature. Vibronic structure has been observed, notably in the low energy absorption dipole forbidden band assigned to the (4π←3π) (1Δ←1Σ+) transition, with a new weak transition assigned to (1Σ−←1Σ+) reported here for the first time. The absolute optical oscillator strengths are determined for ground state to 1Σ+ and 1Π transitions. Based on our recent measurements of differential cross sections for the optically allowed (1Σ+ and 1Π) transitions of COS by electron impact, the optical oscillator strength f0 value and integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis. Subsequently, ICSs predicted by the scaling are confirmed down to 60 eV in the intermediate energy region. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of carbonyl sulphide in the upper stratosphere (20–50 km).

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Quantum chemical and theoretical kinetics studies on the reaction of carbonyl sulfide with H, OH and O(3P)

Cited by 22 publications

References 54 publications

Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

Electronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV

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