Quantitative Measurements of HO2 and Other Products of n-Butane Oxidation (H2O2, H2O, CH2O, and C2H4) at Elevated Temperatures by Direct Coupling of a Jet-Stirred Reactor with Sampling Nozzle and Cavity Ring-Down Spectroscopy (cw-CRDS)

Djehiche, M.; Tan, Ngoc Linh Le; Jain, Chaithanya D.; Dayma, Guillaume; Dagaut, Philippe; Chauveau, Christian; Pillier, Laure; Tomás, A.

doi:10.1021/ja510719k

Cited by 28 publications

(27 citation statements)

References 27 publications

(56 reference statements)

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“…[168], [169] have also made indirect relative rate measurements with the most recent recommendations (2002) for rate of abstraction from alkanes, aromatics and related compounds [170]. Indeed, it has only been in recent years that methods have been developed to quantitatively measure HȮ2 radicals using the FAGE (Fluorescence assay by Gas Expansion) technique [171], dual-modulation Faraday spectroscopy [172], [173] and cavity ring-down spectroscopy [174]. It would be a considerable development for the community if it became possible to measure rates of H-atom abstraction reactions by HȮ2 radicals from stable molecules.…”

Section: Intermediate Temperature Chemistrymentioning

confidence: 99%

Developing detailed chemical kinetic mechanisms for fuel combustion

Curran

2019

Proceedings of the Combustion Institute

264

159

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This paper discusses a brief history of chemical kinetic modeling, with some emphasis on the development of chemical kinetic mechanisms describing fuel oxidation. At high temperatures, the important reactions tend to be those associated with the H2/O2 and C1-C2 sub-mechanisms, particularly for non-aromatic fuels. At low temperatures, and for aromatic fuels, the reactions that dominate and control the reaction kinetics are those associated with the parent fuel and its daughter radicals. Strategies used to develop and optimize chemical kinetic mechanisms are discussed and some reference is made to lumped and reduced mechanisms. The importance of accurate thermodynamic parameters for the species involved is also highlighted, as is the littlestudied importance of collider efficiencies of different third bodies involved in pressuredependent reactions.

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Section: Intermediate Temperature Chemistrymentioning

confidence: 99%

Developing detailed chemical kinetic mechanisms for fuel combustion

Curran

2019

Proceedings of the Combustion Institute

264

159

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“…The CRDS instrument used in this work allows for more sensitive measurements of HO 2 than in the above-cited references. However, the instrument has insufficient sensitivity to detect ambient levels of HO 2 , where typical maximum concentrations are very dependent upon NO x and range from (0.5-10) × 10 8 molecule cm −3 (Carslaw et al, 2001;Heard et al, 2004;Dusanter et al, 2009;Holland et al, 2003), and ideally a detection limit < 1 × 10 7 molecule cm −3 is required. However, the sensitivity (LOD for [HO 2 ] with 30 s averaging at 1000 mbar ∼ 1.5 × 10 9 molecule cm −3 ) is more than adequate for chamber studies, where in general [HO 2 ] > 3 × 10 10 molecule cm −3 can be generated and 30 s averaging should provide good temporal resolution as experiments typically take between 10 and 120 min (Malkin et al, 2010;Winiberg et al, 2016).…”

Section: Discussionmentioning

confidence: 99%

An intercomparison of HO2 measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)

et al. 2017

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Abstract. The HO2 radical was monitored simultaneously using two independent techniques in the Leeds HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry) atmospheric simulation chamber at room temperature and total pressures of 150 and 1000 mbar of synthetic air. In the first method, HO2 was measured indirectly following sampling through a pinhole expansion to 3 mbar when sampling from 1000 mbar and to 1 mbar when sampling from 150 mbar. Subsequent addition of NO converted it to OH, which was detected via laser-induced fluorescence spectroscopy using the FAGE (fluorescence assay by gas expansion) technique. The FAGE method is used widely to measure HO2 concentrations in the field and was calibrated using the 185 nm photolysis of water vapour in synthetic air with a limit of detection at 1000 mbar of 1.6 × 106 molecule cm−3 for an averaging time of 30 s. In the second method, HO2 was measured directly and absolutely without the need for calibration using cavity ring-down spectroscopy (CRDS), with the optical path across the entire ∼ 1.4 m width of the chamber, with excitation of the first O-H overtone at 1506.43 nm using a diode laser and with a sensitivity determined from Allan deviation plots of 3.0 × 108 and 1.5 × 109 molecule cm−3 at 150 and 1000 mbar respectively, for an averaging period of 30 s. HO2 was generated in HIRAC by the photolysis of Cl2 using black lamps in the presence of methanol in synthetic air and was monitored by FAGE and CRDS for ∼ 5–10 min periods with the lamps on and also during the HO2 decay after the lamps were switched off. At 1000 mbar total pressure the correlation plot of [HO2]FAGE versus [HO2]CRDS gave an average gradient of 0.84 ± 0.08 for HO2 concentrations in the range ∼ 4–100 × 109 molecule cm−3, while at 150 mbar total pressure the corresponding gradient was 0.90 ± 0.12 on average for HO2 concentrations in the range ∼ 6–750  ×  108 molecule cm−3.For the period after the lamps were switched off, the second-order decay of the HO2 FAGE signal via its self-reaction was used to calculate the FAGE calibration constant for both 150 and 1000 mbar total pressure. This enabled a calibration of the FAGE method at 150 mbar, an independent measurement of the FAGE calibration at 1000 mbar and an independent determination of the HO2 cross section at 1506.43 nm, σHO2, at both pressures. For CRDS, the HO2 concentration obtained using σHO2, determined using previous reported spectral data for HO2, and the kinetic decay of HO2 method agreed to within 20 and 12 % at 150 and 1000 mbar respectively. For the FAGE method a very good agreement (difference within 8 %) has been obtained at 1000 mbar between the water vapour calibration method and the kinetic decay of the HO2 fluorescence signal method. This is the first intercomparison of HO2 between the FAGE and CRDS methods, and the good agreement between HO2 concentrations measured using the indirect FAGE method and the direct CRDS method provides validation for the FAGE method, which is used widely for field measurements of HO2 in the atmosphere.

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“…[205] Thelaminar flow reactor provides ignition delay times at very low temperatures.T urbulent flow reactors and JSRs are typically used to provide detailed species data obtained from probe measurements combined with gas chromatographs and mass spectrometers or laser techniques. [206,207] TheJ SR also has the unique feature of being asteady-state experiment, where the Damkçhler number-the ratio of residence time to chemical time-can be controlled as an independent parameter. Species concentrations are not only important for am ore thorough validation than of just ignition delay times,but also to assess mechanism reliability for intermediate species that are important for pollutant formation.…”

Section: Experimental Strategies and Configurationsmentioning

confidence: 99%

“…The laminar flow reactor provides ignition delay times at very low temperatures. Turbulent flow reactors and JSRs are typically used to provide detailed species data obtained from probe measurements combined with gas chromatographs and mass spectrometers or laser techniques . The JSR also has the unique feature of being a steady‐state experiment, where the Damköhler number—the ratio of residence time to chemical time—can be controlled as an independent parameter.…”

Section: Biofuels—propulsion and Emissionsmentioning

confidence: 99%

Advanced Biofuels and Beyond: Chemistry Solutions for Propulsion and Production

et al. 2017

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Sustainably produced biofuels, especially when they are derived from lignocellulosic biomass, are being discussed intensively for future ground transportation. Traditionally, research activities focus on the synthesis process, while leaving their combustion properties to be evaluated by a different community. This Review adopts an integrative view of engine combustion and fuel synthesis, focusing on chemical aspects as the common denominator. It will be demonstrated that a fundamental understanding of the combustion process can be instrumental to derive design criteria for the molecular structure of fuel candidates, which can then be targets for the analysis of synthetic pathways and the development of catalytic production routes. With such an integrative approach to fuel design, it will be possible to improve systematically the entire system, spanning biomass feedstock, conversion process, fuel, engine, and pollutants with a view to improve the carbon footprint, increase efficiency, and reduce emissions.

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Quantitative Measurements of HO₂ and Other Products of n-Butane Oxidation (H₂O₂, H₂O, CH₂O, and C₂H₄) at Elevated Temperatures by Direct Coupling of a Jet-Stirred Reactor with Sampling Nozzle and Cavity Ring-Down Spectroscopy (cw-CRDS)

Cited by 28 publications

References 27 publications

Developing detailed chemical kinetic mechanisms for fuel combustion

Developing detailed chemical kinetic mechanisms for fuel combustion

An intercomparison of HO<sub>2</sub> measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)

Advanced Biofuels and Beyond: Chemistry Solutions for Propulsion and Production

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Quantitative Measurements of HO2 and Other Products of n-Butane Oxidation (H2O2, H2O, CH2O, and C2H4) at Elevated Temperatures by Direct Coupling of a Jet-Stirred Reactor with Sampling Nozzle and Cavity Ring-Down Spectroscopy (cw-CRDS)

Cited by 28 publications

References 27 publications

Developing detailed chemical kinetic mechanisms for fuel combustion

Developing detailed chemical kinetic mechanisms for fuel combustion

An intercomparison of HO&lt;sub&gt;2&lt;/sub&gt; measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)

Advanced Biofuels and Beyond: Chemistry Solutions for Propulsion and Production

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Product

Resources

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Quantitative Measurements of HO₂ and Other Products of n-Butane Oxidation (H₂O₂, H₂O, CH₂O, and C₂H₄) at Elevated Temperatures by Direct Coupling of a Jet-Stirred Reactor with Sampling Nozzle and Cavity Ring-Down Spectroscopy (cw-CRDS)

An intercomparison of HO<sub>2</sub> measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)