1,721,418 research outputs found
High-temperature chemistry of HCl and Cl<sub>2</sub>
Full text linkThe high temperature chlorine chemistry was updated and the inhibition mechanisms involving HCl and Cl2 were re-examined. The thermochemistry was obtained using the Active Thermochemical Tables (ATcT) approach, resulting in improved data for chlorine-containing species of interest. The HCl/Cl2 chemistry discussed in the paper was based on reference and experimental measurements of rate constants available in the literature. By coupling the new HCl/Cl2 subset with the Politecnico di Milano (POLIMI) syngas mechanism a kinetic mechanism consisting of 25 species and 102 reactions was obtained. The validation was carried out on selected experimental data from laminar flames, shock tubes and plug flow reactors. Systems containing Cl2 showed high sensitivity to Cl2 +M⇌Cl+Cl+M; the rate constant for this reaction has a significant uncertainty and there is a need for an accurate high-temperature determination. The importance of the chain propagating steps such as Cl+H2 ⇌HCl+H and Cl2 +H⇌HCl+Cl competing with the branching reaction H+O2 ⇌OH+O and the termination reaction H+Cl+M⇌HCl+M is also pointed out by the kinetic analysis. Other relevant reactions in HCl containing systems are the chain propagation reactions HCl+O⇌Cl+OH, HCl+OH⇌Cl+H2O and Cl+HO2 ⇌ClO+OH, together with the termination reaction Cl+HO2 ⇌HCl+O2. With the present thermochemistry and rate constants, reaction cycles involving HOCl and ClCO were found not to be important under the investigated conditions
Temperature and Pressure Dependence of the Reaction S plus CS (+M) -> CS2 (+M)
Full text linkExperimental data for the unimolecular decomposition of CS2 from the literature are analyzed by unimolecular rate theory with the goal of obtaining rate constants for the reverse reaction S + CS (+M) -> CS2 (+M) over wide temperature and pressure ranges. The results constitute an important input for the kinetic modeling of CS2 oxidation. CS2 dissociation proceeds as a spin-forbidden process whose detailed properties are still not well understood. The role of the singlet triplet transition involved is discussed
SciExpeM - 10.5281/zenodo.5085673
No full textMendiara, Teresa; Glarborg, Peter - Combustion And Flame, 2009, (156), 1937-194
Re-evaluation of rate constants for the reaction N2H4 (+ M) ⇄ NH2 + NH2 (+ M)
No full textArticle describes how rate constants for the dissociation/recombination reaction N2H4 (+ M) ⇄ NH2 + NH2 (+ M) are determined by a combination of quantum-chemical calculations and statistical unimolecular rate theory. Implications of the present re-evaluated rate constants for the modeling of high temperature ammonia oxidation kinetics are discussed, showing an only small influence of their precise values on the overall properties of the process
Oxidation of Reduced Sulfur Species: Carbon Disulfide
Full text linkArticle on the oxidation of reduced sulfur species and carbon disulfide
SciExpeM - 10.5281/zenodo.5085659
No full textMendiara, Teresa; Glarborg, Peter - Combustion And Flame, 2009, (156), 1937-194
Flow Reactor Oxidation of Ammonia–Hydrogen Fuel Mixtures
Full text linkHydrogen-assisted oxidation of ammonia under flow reactor conditions was investigated through experiments and chemical kinetic modeling. Novel experiments, conducted in a tubular laminar flow reactor as a function of the NH3/H-2 ratio, stoichiometry, and temperature (725-1475 K), were analyzed along with literature results from tubular and jet-stirred flow reactors. Ignition and oxidation of NH3 is strongly promoted by the presence of H-2 under all conditions investigated. In general, the behavior is captured well by the kinetic model. With an increasing fraction of H-2 in the fuel mixture, the generation of chain carriers gradually shifts from being controlled by the amine reaction subset to being dominated by the oxidation chemistry of H-2, which is known more accurately. However, under reducing conditions, the H-2 consumption rate is strongly underpredicted. This shortcoming suggests that the thermochemistry of amine radicals and/or the formation of higher amines need further assessment. The present analysis shows that for lean oxidation of NH3/H-2 mixtures in tubular flow reactors, data obtained at higher temperatures, particularly for NO formation, may be strongly affected by the reaction during preheating or by mixing (dependent on reactor design) in the inlet section prior to the isothermal zone. Modeling predictions for the high pressure, medium-temperature ignition conditions in a large diesel engine indicate that NH3/H-2 fuel mixtures may still require a cofuel to secure stable ignition
SciExpeM - 10.5281/zenodo.5084469
No full textAlzueta, Maria U; Bilbao, Rafael; Glarborg, Peter - Combustion And Flame, 2001, (127), 2234-225
SciExpeM - 10.5281/zenodo.5084449
No full textAlzueta, Maria U; Bilbao, Rafael; Glarborg, Peter - Combustion And Flame, 2001, (127), 2234-225
SciExpeM - 10.5281/zenodo.5084467
No full textAlzueta, Maria U; Bilbao, Rafael; Glarborg, Peter - Combustion And Flame, 2001, (127), 2234-225
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