The rate constant for the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si16.gif" display="inline" overflow="scroll"><mml:mrow><mml:mtext>CO</mml:mtext><mml:mo>+</mml:mo><mml:msub><mml:mrow><mml:mtext>H</mml:mtext></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mrow><mml:mtext>O</mml:mtext></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math> reaction

Glarborg, Peter; Marshall, Paul

doi:10.1016/j.cplett.2009.05.028

Cited by 3 publications

(2 citation statements)

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“…Many kinetic schemes for syngas combustion do not include reaction of HOCO formation and subsequent reactions of its decomposition and reactions of HOCO with other species arguing that stabilization is only important at very high pressures . HOCO, however, can easily be formed from formic acid, if present in a fuel, and even in the reaction between CO and H 2 O 2 . Mechanisms for syngas and oxygenated hydrocarbons taking HOCO chemistry into account are presented in Table .…”

Section: Reaction Mechanismmentioning

confidence: 99%

“…As a result of this peculiarity, the uncertainty of the rate constant is estimated to be of a factor of 2. The second channel of this reaction was analyzed by Glarborg and Marshall, who reinterpreted earlier experiments of Baldwin et al on carbon-monoxide-sensitized decomposition of hydrogen peroxide at 713 K. Extrapolation to a wider temperature range was guided by ab initio calculations. The rate constant derived by Glarborg and Marshall is much smaller than the earlier estimate of Rasmussen et al and has probably an uncertainty of a factor of 2.…”

Section: Reaction Mechanismmentioning

confidence: 99%

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Role of HOCO Chemistry in Syngas Combustion

Nilsson

Konnov

2016

Energy Fuels

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Chemical kinetic mechanisms for simulation of syngas (H 2 + CO) combustion are important for development of efficient practical applications, such as gas turbines. A useful syngas mechanism has to be able to accurately predict laminar burning velocities, ignition delays, and oxidation of gas mixtures of varying composition over a range of temperatures and pressures. In the present work, the performance of a new H 2 /CO combustion mechanism is analyzed. The mechanism is built on reaction rate constants chosen from the most accurate available kinetic data, and this is thoroughly discussed. The mechanism is validated for a wide range of experimental data from the literature. Particular attention is paid to chemistry of the species HOCO, produced from CO + OH reaction and removed by decomposition or radical reactions. Most available syngas mechanisms do not include HOCO because it is only expected to be of importance at some extreme high-pressure and low-temperature conditions. The species is, however, essential in hierarchically extended mechanisms for small oxygenated hydrocarbons, and its influence on the H 2 /CO subset of reactions needs to be further understood to ensure accurate mechanism development for a range of fuels. In the present study, it is found that inclusion of the HOCO reaction subset does not alter the model predictions of laminar burning velocities, ignition delay times, or oxidation. Sensitivity analysis reveals that HOCO production, its thermal decomposition, and reaction with O 2 are among the 20 most sensitive reactions for conditions of low temperatures and high CO concentrations but with insignificant magnitude of sensitivity compared to that of the major sensitive reactions.

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Section: Reaction Mechanismmentioning

confidence: 99%

Section: Reaction Mechanismmentioning

confidence: 99%

Role of HOCO Chemistry in Syngas Combustion

Nilsson

Konnov

2016

Energy Fuels

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Reaction kinetics and temperature effects in syngas photo-initiated chemical vapor deposition on single-walled carbon nanotubes

et al. 2019

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Photo-initiated chemical vapor deposition (PICVD) is a solvent-free process that can be used to produce thin films on a variety of substrates, with applications in fields ranging from biomedicine to optics and microelectronics. This study presents a kinetic analysis for this process using syngas (CO+H2) as a precursor for the surface treatment of single walled carbon nanotubes (SWCNT) with average dimensions of 1.5×100 nm (diameter × length), and addresses the role of iron pentacarbonyl (Fe(CO)5), a photoactive contaminant found in CO. This work builds upon previously-developed reaction schemes for PICVD, based mainly on surface characterizations, by coupling these analyses with gas-phase monitoring. This allows us to propose two separate reaction schemes for the gas and surface phase reactions and consider temperature effects. Online FTIR, off-line GC-MS and on-line GC characterized the gas phase, while for surface characterizations, XPS and TGA were used. Characterizations showed that a coating with a general formula of CnO3nFen was deposited, corresponding to 0.29±0.04 mg carbon and 0.49±0.03 mg iron on the SWCNT substrate over the course of treatment. The Fe(CO)5 was identified as the key reactant in syngas/PICVD reactions and was nearly completely consumed (94%). Mass balances derived from the gas phase characterization showed that Fe(CO)5 inputted to the plug flow reactor could potentially contribute all the amount of 0.49±0.03 mg of Fe and 0.29±0.04 mg of C to the coating on the SWCNT, indicating that syngas/PICVD can be optimized in future to decrease gas throughput. Temperature did not show a significant effect in the case of PICVD.However, in the absence of ultraviolet light, its role becomes determinant, with rising temperatures causing more Fe deposition.

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