A Shock Tube Study of the Reactions of H Atoms with COS, CS<sub>2</sub>, and H<sub>2</sub>S

Woiki, D.; Roth, P.

doi:10.1002/ijch.199600039

Cited by 9 publications

(13 citation statements)

References 13 publications

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“…Kurylo et al (1971) is an extrapolation of an expression based on data taken between 190 and 460 K. transition state. The agreement they found between experiment and theory and the good agreement with the study of Pratt and Rodgers and the result of Woiki and Roth (1996) for the temperature range 1200 to 1700 K lead us to recommend the expression of Yoshimura et a1. Further confirmation of this result, especially in the 500 to 1500 K temperature range, would be valuable.…”

Section: (18)supporting

confidence: 62%

Kinetics and Mechanisms of the Oxidation of Gaseous Sulfur Compounds

Hynes

Wine

2000

Gas-Phase Combustion Chemistry

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Section: (18)supporting

confidence: 62%

Kinetics and Mechanisms of the Oxidation of Gaseous Sulfur Compounds

Hynes

Wine

2000

Gas-Phase Combustion Chemistry

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“…Indeed, only 15 to 20% of the manometrically injected C2H5I is recovered as H atom behind the reflected shock wave. This discrepancy is attributed to the adsorption of the highly diluted C2H5I at the walls of the storage/mixing vessel, and had been already observed by Woiki and Roth43 when using the exact same experimental device. As a consequence, C2H5I was not used for H-atom calibration and other reacting systems were considered.…”

supporting

confidence: 57%

Theoretical Reassessment and Model Validation of Some Kinetic Parameters Relevant to Si/Cl/H Systems

Diévart

Catoire

2021

J. Phys. Chem. A

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The increasing demand in silicon based materials requires the optimization of silicon deposit manufacturing processes and therefore a better understanding of the gas-phase reactivity of silicon precursors such as silicon tetrachloride (SiCl4). In the present work, hydrogen atoms resonance absorption spectroscopy (H-ARAS) have been used to investigate the high temperature reactivity of SiCl4 behind reflected shock waves at ~1.5 atm in the presence of either ethyl iodide or molecular hydrogen, used as H atoms precursors. Several key reactions of SiCl4 and its main gas-phase decomposition products (SiCl3, Cl, SiHCl3, SiHCl2) have been determined theoretically. The structures and vibrational frequencies of reactants, products, and tight transition states were determined at the B2PLYP-D3/aug-cc-pVTZ level, and final single point energies refined from extrapolated RCCSD(T)/aug-cc-pVnZ (n = D, T, and Q) calculations. The minimum-energy paths of barrierless reactions were calculated at the NEVPT2 level. Final rate constants were then derived from Transition State Theory (TST) and Variational TST/Master Equation analysis within the rigid rotor harmonic oscillations framework. A kinetic mechanism was assembled, based on the present ab initio calculations, to successfully model and interpret the experimental absorption profiles. Sensitivity analysis unambiguously highlighted the need to account for the pressure dependence in the SiCl4 decomposition (SiCl4 ⇄ SiCl3 + Cl), while discarding previous theoretical and experimental determinations of this rate constant.

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“…The reaction of CS 2 with atomic hydrogen, CS 2 + normalH ⇌ CS + SH has been studied by Woiki and Roth, who used time-resolved atomic resonance absorption spectroscopy (ARAS) measurements of H atoms in a shock tube to determine the rate constant. The reverse reaction of CS + SH (R2) is exothermic and we expect it to proceed without a barrier.…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

Oxidation of Reduced Sulfur Species: Carbon Disulfide

et al. 2014

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A detailed chemical kinetic model for oxidation of CS 2 has been developed, on the basis of ab initio calculations for key reactions, including CS 2 + O 2 and CS + O 2 , and data from literature. The mechanism has been evaluated against experimental results from static reactors, flow reactors, and shock tubes. The CS 2 + O 2 reaction forms OCS + SO, with the lowest energy path involving crossing from the triplet to the singlet surface. For CS + O 2 , which yields OCS + O, we found a high barrier to reaction, causing this step to be important only at elevated temperatures. The model predicts low temperature ignition delays and explosion limits accurately, whereas at higher temperatures it appears to overpredict both the induction time for CS 2 oxidation and the formation rate of [O] upon ignition. The predictive capability of the model depends on the accuracy of the rate constant for the initiation step CS 2 + O 2 , which is difficult to calculate due to the intersystem crossing, and the branching fraction for CS 2 + O, which is measured only at low temperatures. The governing reaction mechanisms are outlined on the basis of calculations with the kinetic model. ■ INTRODUCTIONOff-gases containing carbon disulfide (CS 2 ) are produced together with other sulfur containing compounds such as H 2 S from a range of industrial processes, including the Claus process 1−3 and production of viscous fibers, 4 and in gasification of coal 5 and biomass. 6 Similar to H 2 S and the oxidation product SO 2 , carbon disulfide is toxic and harmful to the environment. Efficient treatment of the sulfur containing off gases becomes a bottleneck in these processes as strict emission requirements must be met. Hence, knowledge of the CS 2 oxidation mechanism is important. Investigations have shown that CS 2 / O 2 mixtures are able to autoignite at low temperature and low pressure 7−13 under conditions of negligible self-heating. Two explosion limits have been reported in the literature, 7−9 and studies have been carried out to determine the effect upon the limits with a change in surface conditions and addition of inert gases. The induction times range from a few seconds to several minutes. 9,11,14 At higher temperatures, CS 2 oxidation has been investigated in flow reactors, 2,15 shock tubes, 16−18 and laminar premixed flames. 19−23 Much of the high-temperature work has been motivated by interest in the CO laser. CS 2 /O 2 flames form CO with its vibrational population inverted, facilitating production of a CO flame laser.Previous studies of the reaction mechanism of carbon disulfide oxidation have mostly been restricted to fuel-lean, dry conditions. 17,18,20,24,25 No reported chemical kinetic models are found to satisfactory describe experimental data across a wider range of mixture composition, temperature, and pressure as the mechanism is complex and accurate kinetic data have been unavailable for several important reactions. The objective of the present study is to develop a detailed chemical kinetic model for oxidation of...

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A Shock Tube Study of the Reactions of H Atoms with COS, CS₂, and H₂S

Cited by 9 publications

References 13 publications

Kinetics and Mechanisms of the Oxidation of Gaseous Sulfur Compounds

Kinetics and Mechanisms of the Oxidation of Gaseous Sulfur Compounds

Theoretical Reassessment and Model Validation of Some Kinetic Parameters Relevant to Si/Cl/H Systems

Oxidation of Reduced Sulfur Species: Carbon Disulfide

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A Shock Tube Study of the Reactions of H Atoms with COS, CS2, and H2S

Cited by 9 publications

References 13 publications

Kinetics and Mechanisms of the Oxidation of Gaseous Sulfur Compounds

Kinetics and Mechanisms of the Oxidation of Gaseous Sulfur Compounds

Theoretical Reassessment and Model Validation of Some Kinetic Parameters Relevant to Si/Cl/H Systems

Oxidation of Reduced Sulfur Species: Carbon Disulfide

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Product

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A Shock Tube Study of the Reactions of H Atoms with COS, CS₂, and H₂S