On the rate constants of OH + HO2 and HO2+ HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Hong, Zekai; Lam, King-Yiu; Sur, Ritobrata; Wang, Shengkai; Davidson, David F.; Hanson, Ronald K.

doi:10.1016/j.proci.2012.06.108

Cited by 90 publications

(92 citation statements)

References 24 publications

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“…Each elementary reaction in a H 2 -O 2 system is tightly coupled with significant sensitivities of global flame phenomena. The challenges associated with the determination of the R6 rate constants stem from the lack of consistent experimental results and its unusual apparent temperature dependence (e.g., [71,72]). To parameterize correctly the non-Arrhenius expression for R6 over a wide range of conditions, additional experimental data are needed.…”

Section: Pressure Effects On Extinction Limits Of Non-premixed H 2 Flmentioning

confidence: 99%

Studies of premixed and non-premixed hydrogen flames

Park

Veloo

Burbano

et al. 2015

Combustion and Flame

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a b s t r a c tThe hydrogen oxidation chemistry constitutes the foundation of the kinetics of all carbon-and hydrogencontaining fuels. The validation of rate constants of hydrogen-related reactions can be complicated by uncertainties associated with experimental data caused by the high reactivity and diffusivity of hydrogen. In the present investigation accurate experimental data on flame propagation and extinction were determined for premixed and non-premixed hydrogen flames at pressures between p = 1 and 7 atm. The experiments were designed to sensitize the three-body H + O 2 + M ? HO 2 + M reaction, whose rate is subject to notable uncertainty. This was achieved by increasing the pressure and by adding to the reactants H 2 O and CO 2 whose collision efficiencies are high compared to other species. In the present study, directly measured flame properties were compared against computed ones, in order to eliminate uncertainties associated with extrapolations, as is the case for laminar flame speeds. The measured extinction strain rates exhibit both a positive and negative dependence on pressure with and without weighting with the density, and this non-monotonic behavior is caused by the competition between the H + O 2 ? O + OH and H + O 2 + M ? HO 2 + M reactions as well as HO 2 kinetic pathways as pressure increases. The various kinetic models considered in this investigation did not reproduce equally well the non-premixed flame extinction data with added H 2 O. On the other hand, the predicted extinction strain rates were consistent between the various models in the case of added CO 2 . Finally, it was shown that the formulation of binary diffusion coefficient pairs including H-N 2 and H 2 -N 2 has a first order effect on the prediction of extinction strain rates of non-premixed H 2 flames.

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Section: Pressure Effects On Extinction Limits Of Non-premixed H 2 Flmentioning

confidence: 99%

Studies of premixed and non-premixed hydrogen flames

Park

Veloo

Burbano

et al. 2015

Combustion and Flame

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“…Their analysis guided by ab initio calculations showed that the rate constant of reaction (15) does exhibit weak temperature dependence with a shallow minimum around 1000 K. Simultaneously Hong et al [67] performed dedicated experiments between 1070 and 1280 K and came to the same conclusion. The expression of Hong et al [67] is adopted in the model of Alekseev et al [40] and in the present work. This rate constant of reaction (15) is shown in Fig.…”

Section: Reactions Of Singlet Oxygenmentioning

confidence: 80%

“…Most recently Burke et al [119] re-interpreted experimental measurements for the H 2 O 2 decomposition including those indicating deep rate constant minimum [66,121]. Their analysis guided by ab initio calculations showed that the rate constant of reaction (15) does exhibit weak temperature dependence with a shallow minimum around 1000 K. Simultaneously Hong et al [67] performed dedicated experiments between 1070 and 1280 K and came to the same conclusion. The expression of Hong et al [67] is adopted in the model of Alekseev et al [40] and in the present work.…”

Section: Reactions Of Singlet Oxygenmentioning

confidence: 88%

“…The rate expression for reaction (16) proposed by Kappel et al [66] and recently reconfirmed by Hong et al [67] was adopted by Konnov [56], Alekseev et al [40], and kept in the present work. Yield of hydrogen in reaction (-X3) was experimentally found negligible and below 1E−4 [68], while the branching ratio of the reaction path (X4) forming O 3 was determined to be less than 1E−3 [69] thus both channels can be safely ignored.…”

Section: Reactions Of Initiationmentioning

confidence: 95%

“…Until recent studies of Hong et al [67,118] and of Burke et al [119] there was a controversy between the rate constant of reaction (15) measured within 250-400 K [120] and anomalous deep and unusually narrow rate constant minimum observed around 1250 K [66,121]. Srinivasan et al [122] found no evidence for temperature dependence of the rate constant from 1237 to 1554 K. Hong et al [118] measured this rate constant in the range 1600-2200 K and concluded that the expression of Keyser [120] can be extended from room up to these high temperatures.…”

Section: Reactions Of Singlet Oxygenmentioning

confidence: 99%

See 2 more Smart Citations

On the role of excited species in hydrogen combustion

Konnov

2015

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Harnessing the Combined Power of Theoretical and Experimental Data through Multiscale Informatics

Burke

2016

Int J of Chemical Kinetics

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Monumental, recent and rapidly continuing, improvements in the capabilities of ab initio theoretical kinetics calculations provides reason to believe that progress in the field of chemical kinetics can be accelerated through a corresponding evolution of the role of theory in kinetic modeling and its relationship with experiment. The present article reviews and provides additional demonstrations of the unique advantages that arise when theoretical and experimental data across multiple scales are considered on equal footing, including the relevant uncertainties of both, within a single mathematical framework. Namely, the multiscale informatics framework simultaneously integrates information from a wide variety of sources and scales: ab initio electronic structure calculations of molecular properties, rate constant determinations for individual reactions, and measured global observables of multireaction systems. The resulting model representation consists of a set of theoretical kinetics parameters (with constrained uncertainties) that are related through elementary kinetics models to rate constants (with propagated uncertainties) that in turn are related through physical models to global observables (with propagated uncertainties). An overview of the approach and typical implementation is provided along with a brief discussion of the major uncertainties (parametric and structural) in theoretical kinetics calculations, kinetic models for complex chemical mechanisms, and physical models for experiments. Higher levels of automation in all aspects, including closed‐loop autonomous mixed‐experimental‐and‐computational model improvement, are advocated for facilitating scalability of the approach to larger systems with reasonable human effort and computational cost. The unique advantages of combining theoretical and experimental data across multiple scales are illustrated through a series of examples. Previous results demonstrating the utility of simultaneous interpretation of theoretical and experimental data for assessing consistency in complex systems and for reliable, physics‐based extrapolation of limited data are briefly summarized. New results are presented to demonstrate the high predictive accuracy of multiscale informed models for both small (molecular properties) and large (global observables) scales. These new results provide examples where the optimization yields physically realistic parameter adjustments and where physical model uncertainties in experiments are larger than kinetic model uncertainties. New results are also presented to demonstrate the utility of the multiscale informatics approach for design of experiments and theoretical calculations, accounting for both theoretical and experimental existing knowledge as well as relevant parametric and structural uncertainties in interpreting potential new data. These new results provide examples where neglecting structural uncertainties in design of experiments results in failure to identify the most worthwhile experiment. Further progress in the c...

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On the rate constants of OH + HO2 and HO2+ HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Cited by 90 publications

References 24 publications

Studies of premixed and non-premixed hydrogen flames

Studies of premixed and non-premixed hydrogen flames

On the role of excited species in hydrogen combustion

Harnessing the Combined Power of Theoretical and Experimental Data through Multiscale Informatics

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