Studies of reactions of atoms in a discharge flow stirred reactor. Part 2.—O+H2+CO system

Campbell, Ian; Handy, Brian J.

doi:10.1039/f19787400316

Cited by 24 publications

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“…Although much of the work in the literature which uses this method has employed relatively expensive instrumentation (4)(5)(6)(7)(8)(9), it has also been used successfully with much less costly apparatus (12)(13)(14). We were surprised, then, when our initial efforts to apply the homogeneous reactor method gave results which were in very poor agreement with data reported in the literature.…”

Section: Introductioncontrasting

confidence: 46%

“…The nature of their experiments made it impossible to directly examine homogeneity. Finally, the reactor design used in the most recent application of such reactors (12)(13)(14) and which also used a chemiluminescent method to measure the atom concentration was quite similar to that of Fig. l(b) although it was of substantially greater volume.…”

Section: Discussionmentioning

confidence: 97%

“…While considerable success has i been attained at the relatively low pressures of the VLPP method of Benson and co-workers (10, l l ) , the validity of the I homogeneity assumption at the higher pressures used in other work (3)(4)(5)(6)(7)(8)(9)(12)(13)(14)(15) is unclear and has not been examined 1 directly. The criteria for efficient mixing have received some attention (4,9,12), but the effect on the use of homogeneous reactors of the homogeneous atom sink represented by the excess reactant has been largely neglected in this higher pressure region.…”

Section: Introductionmentioning

confidence: 99%

“…In the first method (4)(5)(6)(7)(12)(13)(14)(15), the inlet and exit atom concentrations are measured and are related to the rate constant for the reaction by where [Ale and [AIL are the inlet and exit atom concentrations respectively, v is the volumetric flow rate through the reactor and V is the reactor volume. The assumption is made that diffusional mixing is so fast that the exit atom concentration equals the bulk (homogeneous) atom concentration.…”

Section: Theorymentioning

confidence: 99%

“…The principles of kinetic measurements in a "well-stirred or 1 "homogeneous" reactor, first developed by Denbigh (1, 2), 1 have had sporadic application to the study of gas phase reactions 1 of atoms and radicals (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15). While considerable success has i been attained at the relatively low pressures of the VLPP method of Benson and co-workers (10, l l ) , the validity of the I homogeneity assumption at the higher pressures used in other work (3)(4)(5)(6)(7)(8)(9)(12)(13)(14)(15) is unclear and has not been examined 1 directly.…”

Section: Introductionmentioning

confidence: 99%

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The kinetics of gas phase reactions studied in a "homogeneous reactor"

Roscoe¹

1988

Can. J. Chem.

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The use of a "well-stirred" or "homogeneous" reactor in kinetic studies of gas phase reactions has been examined to assess the sensitivity of the method to the criteria upon which its use is based. The effects of heterogeneous and homogeneous secondary reactions are considered and the validity of the assumption of homogeneity has been examined experimentally for conditions similar to those which have been used elsewhere. The atom sink presented by the excess reagent under pseudo first order conditions results in failure of the homogeneity assumption. However, it is found that homogeneity is not required for successful use of the method provided the analytical measurements have good spatial resolution and the reaction volume is well-defined. The method is illustrated by using it to study some reactions of 0 ( 3~) . JOHN M. ROSCOE. Can. J. Chem. 66, 2325 (1988.On a exarnint l'utilisation d'un rtacteur "bien agitC" ou "homogiine" dans les etudes cinttiques des rtactions en phase gazeuse, dans le but d'ttablir la sensibilitt de la mtthodeface i ses critiires d'utilisation. On a considtrt les effets des rtactions secondaires htttrogknes et homogtnes et on a examink exptrimentalement la validitt de l'hypothtse d'homogtntitt dans des conditions semblables i celles deji utilistes. Le puits d'atomes prtsentt par l'exciis de rtactifs dans des conditions de pseudo ordre 1 est di3 i l'insuffisance de l'hypothtse d'homogtntitt. On a trouvt que l'homogtntitt n'est pas ntcessaire pour une utilisation fmctueuse de la mtthode en admettant que les mesures analytiques ont une bonne rtsolution spatiale et que le volume rtactionnel est bien dtfini. On applique la mtthode i l'ttude de quelques rtactions du 0(3p).[Traduit par la revue]

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Section: Introductioncontrasting

confidence: 46%

Section: Discussionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The kinetics of gas phase reactions studied in a "homogeneous reactor"

Roscoe¹

1988

Can. J. Chem.

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A comprehensive kinetic mechanism for CO, CH₂O, and CH₃OH combustion

Li¹,

Zhao²,

Kazakov³

et al. 2007

Int J of Chemical Kinetics

732

579

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New experimental profiles of stable species concentrations are reported for formaldehyde oxidation in a variable pressure flow reactor at initial temperatures of 850-950 K and at constant pressures ranging from 1.5 to 6.0 atm. These data, along with other data published in the literature and a previous comprehensive chemical kinetic model for methanol oxidation, are used to hierarchically develop an updated mechanism for CO/H 2 O/H 2 /O 2 , CH 2 O, and CH 3 OH oxidation. Important modifications include recent revisions for the hydrogen-oxygen submechanism (Li et al., Int J Chem Kinet 2004, 36, 565), an updated submechanism for methanol reactions, and kinetic and thermochemical parameter modifications based upon recently published information. New rate constant correlations are recommended for CO + OH = CO 2 + H (R23) and HCO + M = H + CO + M (R24), motivated by a new identification of the temperatures over which these rate constants most affect laminar flame speed predictions (Zhao et al., Int J Chem Kinet 2005, 37, 282). The new weighted least-squares fit of literature experimental data for (R23) yields k 23 = 2.23 × 10 5 T 1.89 exp(583/T ) cm 3 /mol/s and reflects significantly lower rate constant values at low and intermediate temperatures in comparison to another recently recommended correlation and theoretical predictions. The weighted least-squares fit of literature results for (R24) yields k 24 = 4.75 × 10 11 T 0.66 exp(−7485/T ) cm 3 /mol/s, which predicts values within uncertainties of both prior and new (Friedrichs et al., Phys Chem Chem Phys 2002, 4, 5778; DeSain et al., Chem Phys Lett 2001, 347, 79) measurements. Use of either of the data correlations reported in and DeSain et al. (2001) for this reaction significantly degrades laminar flame speed predictions for oxygenated fuels as well as for other hydrocarbons. The present C 1 /O 2 mechanism compares favorably against a wide range of experimental conditions for laminar premixed flame speed, shock tube ignition delay, and flow reactor species time history data at each level of hierarchical development. Very good agreement of the model predictions with all of the experimental measurements is demonstrated.

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A Hierarchical and Comparative Kinetic Modeling Study of C₁ − C₂ Hydrocarbon and Oxygenated Fuels

Metcalfe

Burke

Ahmed

et al. 2013

Int J of Chemical Kinetics

990

674

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A detailed chemical kinetic mechanism has been developed to describe the oxidation of small hydrocarbon and oxygenated hydrocarbon species. The reactivity of these small fuels and intermediates is of critical importance in understanding and accurately describing the combustion characteristics, such as ignition delay time, flame speed, and emissions of practical fuels. The chosen rate expressions have been assembled through critical evaluation of the literature, with minimum optimization performed. The mechanism has been validated over a wide range of initial conditions and experimental devices, including flow reactor, shock tube, jet‐stirred reactor, and flame studies. The current mechanism contains accurate kinetic descriptions for saturated and unsaturated hydrocarbons, namely methane, ethane, ethylene, and acetylene, and oxygenated species; formaldehyde, methanol, acetaldehyde, and ethanol.

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Studies of reactions of atoms in a discharge flow stirred reactor. Part 2.—O+H2+CO system

Abstract: A discharge-flow stirred reaction system has been used to measure the rate constant for the reaction O(3P) + Hz -+ OH + H over the temperature range 315-490K. Below 350K, carbon monoxide (< 5 %

Cited by 24 publications

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The kinetics of gas phase reactions studied in a "homogeneous reactor"

The kinetics of gas phase reactions studied in a "homogeneous reactor"

A comprehensive kinetic mechanism for CO, CH₂O, and CH₃OH combustion

A Hierarchical and Comparative Kinetic Modeling Study of C₁ − C₂ Hydrocarbon and Oxygenated Fuels

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Studies of reactions of atoms in a discharge flow stirred reactor. Part 2.—O+H2+CO system

Abstract: A discharge-flow stirred reaction system has been used to measure the rate constant for the reaction O(3P) + Hz -+ OH + H over the temperature range 315-490K. Below 350K, carbon monoxide (< 5 %

Cited by 24 publications

References 0 publications

The kinetics of gas phase reactions studied in a "homogeneous reactor"

The kinetics of gas phase reactions studied in a "homogeneous reactor"

A comprehensive kinetic mechanism for CO, CH2O, and CH3OH combustion

A Hierarchical and Comparative Kinetic Modeling Study of C1 − C2 Hydrocarbon and Oxygenated Fuels

Contact Info

Product

Resources

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A comprehensive kinetic mechanism for CO, CH₂O, and CH₃OH combustion

A Hierarchical and Comparative Kinetic Modeling Study of C₁ − C₂ Hydrocarbon and Oxygenated Fuels