Reaction Kinetics of CO + HO<sub>2</sub> → Products:  Ab Initio Transition State Theory Study with Master Equation Modeling

You, Xiaoqing; Wang, Shuangfeng; Goos, Elke; Sung, Chih-Jen; Klippenstein, Stephen J.

doi:10.1021/jp067597a

Cited by 97 publications

(68 citation statements)

References 54 publications

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“…The objective of the present work is to determine k 1 from a reinterpretation of the experimental data of Baldwin et al [11], combined with ab initio calculations for the reaction. Baldwin Their value has been considered to be the most reliable experimental determination of k 3 , but it has been questioned by recent studies, such as the high-level theoretical work of You et al [12]. In the present work, the experimental results from Baldwin et al are re-interpreted in terms of a detailed chemical kinetic model with a recent value of k 3 .…”

Section: Introductionmentioning

confidence: 79%

“…This expression has been widely accepted as the best way to estimate k 3 [15,16]. However, recently the reaction has received considerable attention [4,12,[17][18][19]. Even though some scatter is observed among experimental and theoretical determinations, there are strong indications that reaction (R6) is considerably slower than indicated by the analysis of Baldwin et al The most reliable value for the rate constant presumably comes from the theoretical work by You et al [12].…”

Section: Experimental Interpretationmentioning

confidence: 99%

“…However, recently the reaction has received considerable attention [4,12,[17][18][19]. Even though some scatter is observed among experimental and theoretical determinations, there are strong indications that reaction (R6) is considerably slower than indicated by the analysis of Baldwin et al The most reliable value for the rate constant presumably comes from the theoretical work by You et al [12]. Calculations of the potential energy surface for CO+HO 2 revealed barrier heights of 17.9 and 18.9 kcal/mol for initial trans-and cis-adduct formation respectively.…”

Section: Experimental Interpretationmentioning

confidence: 99%

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The rate constant for the CO+H2O2 reaction

Glarborg

Marshall

2009

Chemical Physics Letters

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The reaction CO+H 2 O 2 → HOCO+OH (R1) has been proposed as an important oxidation step for CO in CO/H 2 mixtures at low temperatures. In this paper the rate constant for the reaction at 713 K is determined based on the batch reactor experiments of Baldwin, Walker and Webster [Combust. . The results show that the reaction is significantly slower than indicated by an earlier rough estimate and it is probably of minor importance in combustion. The present analysis reconciles the batch reactor data of Baldwin et al. with recent highlevel theoretical work on the CO+HO 2 reaction.

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Section: Introductionmentioning

confidence: 79%

Section: Experimental Interpretationmentioning

confidence: 99%

Section: Experimental Interpretationmentioning

confidence: 99%

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The rate constant for the CO+H2O2 reaction

Glarborg

Marshall

2009

Chemical Physics Letters

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“…Davis et al [15] applied uncertainty parameter f=0.3. We use the rate expression of Kéromnès et al [47] as the mean, which is based on the theoretical determination of You et al [70]. Apart from the You et al…”

Section: Reaction R22: Co + Ho2 → Co2 + Ohmentioning

confidence: 99%

Uncertainty of the rate parameters of several important elementary reactions of the H2 and syngas combustion systems

Nagy

Valkó

Sedyó

et al. 2015

Combustion and Flame

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Re-evaluation of the temperature-dependent uncertainty parameter f(T) of elementary reactions isproposed by considering all available direct measurements and theoretical calculations. A procedure is presented for making f(T) consistent with the form of the recommended Arrhenius expression. The corresponding uncertainty domain of the transformed Arrhenius parameters (ln A, n, E/R) is convex and centrally symmetric around the mean parameter set. The f(T) function can be stored efficiently using the covariance matrix of the transformed Arrhenius parameters.The calculation of the uncertainty of a backward rate coefficient from the uncertainty of the forward rate coefficient and thermodynamic data is discussed. For many rate coefficients, a large number of experimental and theoretical determinations are available, and a normal distribution can be assumed for the uncertainty of ln k. If little information is available for the rate coefficient, equal probability of the transformed Arrhenius parameters within their domain of uncertainty (i.e. uniform distribution) can be assumed. Algorithms are provided for sampling the transformed Arrhenius parameters with either normal or uniform distributions. A suite of computer codes is presented that allows the straightforward application of these methods. For 22 important elementary reactions of the H2 and syngas (wet CO) combustion systems, the Arrhenius parameters and 3 rd body collision efficiencies were collected from experimental, theoretical and review publications. For each elementary reaction, kmin and kmax limits were determined at several temperatures within a defined range of temperature. These rate coefficient limits were used to obtain a consistent uncertainty function f(T) and to calculate the covariance matrix of the transformed Arrhenius parameters.2

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“…Klippenstein employed transition state theory and a two barrier model to produce the correlation recommended in . Adopting the rate expression for (R12) derived by You et al (2007) into the model of Li et al (2007) considerably improves its predictions of RCM ignition delay at high pressures. It should be stated again, however, that reaction (R12) is only important during the chemical induction period, principally through its impact on the initial build-up of HO 2 .…”

Section: Update On Co+ho 2 Reaction Rate Correlationmentioning

confidence: 99%

Chemical Kinetics in Support of Syngas Turbine Combustion

Dryer¹

2007

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Executive SummaryThis document is the final report on an overall program formulated to extend our prior work in developing and validating kinetic models for the CO/hydrogen/oxygen reaction by carefully analyzing the individual and interactive behavior of specific elementary and subsets of elementary reactions at conditions of interest to syngas combustion in gas turbines. A summary of the tasks performed under this work are: 1. Determine experimentally the third body efficiencies in H+O 2 +M = HO 2 +M (R1) for CO 2 Results are summarized in this document and its appendices. Three archival papers which contain a majority of the research results have appeared. Those results not published elsewhere are highlighted here, and will appear as part of future publications. Portions of the work appearing in the above publications were also supported in part by the Department of Energy under Grant No. DE-FG02-86ER-13503.As a result of and during the research under the present contract, we became aware of other reported results that revealed substantial differences between experimental characterizations of ignition delays for syngas mixtures and ignition delay predictions based upon homogenous kinetic modeling. We adjusted emphasis of Task 2 to understand the source of these noted disparities because of their key importance to developing lean premixed combustion technologies of syngas turbine applications. In performing Task 3, we also suggest for the first time the very significant effect that metal carbonyls may have on syngas combustion properties. This work is fully detailed in Appendix C. The work on metal carbonyl effects is entirely computational in nature. Pursuit of experimental verification of these interactions was beyond the scope of the present work.3 Results over this Progress Period ApproachThe present research further extended our prior work in developing and validating kinetic models for the CO/hydrogen/oxygen principally studied under Department of Energy Grant No. DE-FG02-86ER-13503, by providing additional experimental data using a Variable Pressure Flow Reactor (VPFR) on the collisional efficiencies of water and carbon dioxide in the reaction H+O 2 +M = HO 2 + M (R1) by carefully analyzing the individual and interactive behavior of specific elementary and subsets of elementary reactions at the conditions of interest, and by extending computational model comparisons with data obtained in this program and those appearing in the literature since 2004 to further test and refine the model at conditions relevant to gas turbine applications. Additionally, syngas contaminant species such as small hydrocarbons (e.g., methane) and other combustion gas components (e.g. NO x ) have been identified and it is suspected that these contaminants may affect syngas chemistry in gas turbine applications, particularly in mixing regions of entering fuel and air. These contaminants can have significant influence on some of the kinetic behavior. The initial research plan was to investigate only the effects of small local amo...

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Reaction Kinetics of CO + HO₂ → Products: Ab Initio Transition State Theory Study with Master Equation Modeling

Cited by 97 publications

References 54 publications

The rate constant for the CO+H2O2 reaction

The rate constant for the CO+H2O2 reaction

Uncertainty of the rate parameters of several important elementary reactions of the H2 and syngas combustion systems

Chemical Kinetics in Support of Syngas Turbine Combustion

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Reaction Kinetics of CO + HO2 → Products: Ab Initio Transition State Theory Study with Master Equation Modeling

Cited by 97 publications

References 54 publications

The rate constant for the CO+H2O2 reaction

The rate constant for the CO+H2O2 reaction

Uncertainty of the rate parameters of several important elementary reactions of the H2 and syngas combustion systems

Chemical Kinetics in Support of Syngas Turbine Combustion

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Product

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Reaction Kinetics of CO + HO₂ → Products: Ab Initio Transition State Theory Study with Master Equation Modeling