Carbon monosulfide-oxygen flame reaction chemistry

Richardson, R. J.

doi:10.1021/j100579a003

Cited by 24 publications

(16 citation statements)

References 10 publications

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“…The recommendation given for k(298 K) is based on the work of Black et al [150] using laser-induced fluorescence to monitor CS. This value agrees with the somewhat less precise determination by Richardson [1117] using OCS formation rates. The latter author presents evidence that this reaction channel dominates over the one producing SO + CO by more than a factor of 10.…”

Section: -104supporting

confidence: 89%

Environmental effects of large igneous province magmatism: a Siberian perspective

Black

Lamarque

Shields

et al. 2015

Volcanism and Global Environmental Change

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Section: -104supporting

confidence: 89%

Environmental effects of large igneous province magmatism: a Siberian perspective

Black

Lamarque

Shields

et al. 2015

Volcanism and Global Environmental Change

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“…The highest energy path is abstraction by the central carbon atom to yield CS 2 O + O, which with a barrier of 332 kJ mol −1 will be too slow to be significant under most combustion conditions. The most favorable spin-allowed pathway involves addition over a barrier 41 Richardson, 21 and Murakami et al 25 The solid line denotes the rate constant calculated in the present work. of 202 kJ mol −1 to make a triplet CS 2 OO adduct, followed by dissociation over a second, slightly higher barrier of 227 kJ mol −1 (relative to the reactants) to form OCS + SO,…”

Section: ■ Detailed Kinetic Modelmentioning

confidence: 53%

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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“…An alternative possibility that would cause local high concentrations of the interacting groups, depends on the formation of ordered regions in the polystyrene.5 It has been suggested that for the density of polystyrene to be as high as it is, there must exist regions where the chains lie parallel to give good packing. 6 The presence of substituents on the chain, particularly the bulky nitrophenol groups would disrupt this packing and these groups would tend to be concentrated in the disordered regions. This increased concentration would cause an apparent increase in the global association constant.…”

Section: Resultsmentioning

confidence: 99%

Interpenetration of polystyrene chains in bulk polymer

Worsfold¹

1977

J. Polym. Sci. Polym. Phys. Ed.

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Polystyrenes lightly substituted with either tertiary amine groups or nitrophenol groups have been allowed to interact in concentrated t‐butylbenzene solution and in bulk polymer. Above the glass transition temperature a temperature dependent equilibrium is achieved in the bulk polymer between the two substituents and the amine salt of the phenol. The degree of association found is considerably greater in the bulk polymer than in solution. The results show that much interpenetration of the polymer occurs, and the results are discussed in terms of models of the bulk amorphous state of the polymer.

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Carbon monosulfide-oxygen flame reaction chemistry

Cited by 24 publications

References 10 publications

Environmental effects of large igneous province magmatism: a Siberian perspective

Environmental effects of large igneous province magmatism: a Siberian perspective

Oxidation of Reduced Sulfur Species: Carbon Disulfide

Interpenetration of polystyrene chains in bulk polymer

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