Mechanism of the gas-phase oxidation of carbon disulfide at elevated temperatures (the C-S-O system)

Chernysheva, A. V.; Basevich, V. Ya.; Vedeneev, V. I.; Arutyunov, V. S.

doi:10.1007/bf01150882

Cited by 7 publications

(8 citation statements)

References 25 publications

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“…Other processes were investigated using the lower-cost CBS-QB3 approximation, which begins with B3LYP/6-311G(2d,d,p) geometries and frequencies followed by several steps that are combined to approximate the CCSD(T) energy at the infinite basis set limit. Chernysheva et al included the reaction of CS with SO, assuming two product channels, CS + SO ⇌ OCS + normalS CS + SO ⇌ CO + normalS 2 Reaction is a four-center reaction, and the occurrence of this step is not supported by our ab initio calculations.…”

Section: Detailed Kinetic Modelmentioning

confidence: 79%

“…21 It is larger than the value derived by Murakami 35,47 accepted the measurements at room temperature but, because Other processes were investigated using the lower-cost CBS-QB3 approximation, 48 which begins with B3LYP/6-311G-(2d,d,p) geometries and frequencies followed by several steps that are combined to approximate the CCSD(T) energy at the infinite basis set limit. Chernysheva et al 24 included the reaction of CS with SO, assuming two product channels,…”

Section: ■ Detailed Kinetic Modelmentioning

confidence: 99%

“…In addition to CS + SO discussed above, Chernysheva et al 24 included reactions of CS with OCS and SO 2 ,…”

Section: ■ Detailed Kinetic Modelmentioning

confidence: 99%

“…In addition to CS + SO discussed above, Chernysheva et al included reactions of CS with OCS and SO 2 , CS + OCS ⇌ CS 2 + CO CS + SO 2 ⇌ OCS + SO We consider these steps plausible and include them with estimated rate constants. However, with the current rate constants, which are considerably smaller than the values proposed by Chernysheva et al, they are too slow to influence modeling predictions.…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

“…Previous studies of the reaction mechanism of carbon disulfide oxidation have mostly been restricted to fuel-lean, dry conditions. ,,,, 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 CS 2 and evaluate it over a broad range of conditions.…”

Section: Introductionmentioning

confidence: 99%

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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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