Measurement of the reaction rate of H + O2 + M → HO2 + M, for M= Ar, N2, CO2, at high temperature with a sensitive OH absorption diagnostic

Choudhary, Rishav; Girard, Julian J.; Peng, Yuzhe; Shao, Jiankun; Davidson, David F.; Hanson, Ronald K.

doi:10.1016/j.combustflame.2019.02.017

Cited by 23 publications

(13 citation statements)

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“…More generally and despite some systematic experimental studies (eg, Refs. [42][43][44][45][46][47][48][49][50][51][52][53][54], it remains difficult to anticipate how collision efficiencies vary with the temperature and identity of the bath gas M as well as the size and chemical structure of the unimolecular reactant A.…”

Section: Introductionmentioning

confidence: 99%

“Third‐body” collision parameters for hydrocarbons, alcohols, and hydroperoxides and an effective internal rotor approach for estimating them

Jasper

2020

Int J of Chemical Kinetics

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Collision rate constants and third-body collision efficiencies are calculated for more than 300 alkanes, alcohols, and hydroperoxides, for the bath gases He, Ar, H 2 , and N 2 , and from 300 to 2000 K. The data set includes highly branched species and species with as many as 16 nonhydrogen atoms N, and it is analyzed to develop strategies for estimating collision properties more generally. Simple analytic formulas describing the Lennard-Jones collision parameters and are obtained for each of the three classes of systems as a function of N. Trends in the collision efficiency range parameter = ⟨ΔE d ⟩ are more complicated, and a method is developed and validated for estimating based on the numbers and types of internal rotors and oxygen-containing groups. Specifically, the approach maps the expected value of for a branched alkane, alcohol, or hydroperoxide onto those for the corresponding normal (linear) series via an effective number of nonhydrogen atoms N eff . The prescription for N eff is based on counting internal rotor types and is shown to be insensitive to temperature and fairly insensitive to the identity of the bath gas. Together, these strategies allow for the ready estimation of the collision parameters , , and so long as results for the associated linear series are available. K E Y W O R D Sclassical trajectories, Lennard-Jones parameters, third-body collision efficiencies, unimolecular kinetics, automation Int J Chem Kinet. 2020;52:387-402. wileyonlinelibrary.com/journal/kin

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Section: Introductionmentioning

confidence: 99%

“Third‐body” collision parameters for hydrocarbons, alcohols, and hydroperoxides and an effective internal rotor approach for estimating them

Jasper

2020

Int J of Chemical Kinetics

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“…These tools use sensitivity analysis to determine the experimental conditions that yield the most useful information about reaction rates. Two case studies were performed to compare experimental conditions to those identified in Choudhary et al (2019) and Santner et al (2015). These case studies were used in order to explain, validate, and improve our method.…”

Section: S Ijmentioning

confidence: 99%

“…These case studies were used in order to explain, validate, and improve our method. In Choudhary et al (2019), OH concentration was measured in a shock tube for H 2 /O 2 /inert mixtures at 1,450-2,000 K in order to measure the reaction rate of H + O 2 (+M) → HO 2 (+M), where the third-body collider is argon, nitrogen, and carbon dioxide. In Santner et al (2015), laminar burning rates of 1,3,5-trioxane/O 2 /N 2 mixtures were measured in a spherical, heated, high pressure, constant volume chamber in order to measure the flame properties of formaldehyde (CH 2 O) and formyl radical (HCO).…”

Section: S Ijmentioning

confidence: 99%

“…In order to measure H + O 2 (+N 2 )→HO 2 (+N 2 ), Choudhary et al (2019). performed 9 experiments with 0.1% H 2 /2%O 2 /N 2 with temperatures from 1552-1908 K, and pressures from 9.35 to 21.68 atm.…”

Section: Stanford Case Studymentioning

confidence: 99%

“…performed 9 experiments with 0.1% H 2 /2%O 2 /N 2 with temperatures from 1552-1908 K, and pressures from 9.35 to 21.68 atm. These conditions were chosen to improve the sensitivity of OH concentration to the target reaction rate [see Figure 7 in (Choudhary et al, 2019)]. The present software is applied over a broader range of conditions, as shown in Table 1.…”

Section: Stanford Case Studymentioning

confidence: 99%

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Computational Design of Sensitized Combustion Chemistry Experiments

Ising¹,

Rodríguez

Lopez

et al. 2021

Front. Mech. Eng.

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In combustion chemistry experiments, reaction rates are often extracted from complex experiments using detailed models. To aid in this process, experiments are performed such that measurable quantities, such as species concentrations, flame speed, and ignition delay, are sensitive to reaction rates of interest. In this work, a systematic method for determining such sensitized experimental conditions is demonstrated. An open-source python script was created using the Cantera module to simulate thousands of 0D and hundreds of 1D combustion chemistry experiments in parallel across a broad, user-defined range of mixture conditions. The results of the simulation are post-processed to normalize and compare sensitivity values among reactions and across initial conditions for time-varying and steady-state simulations, in order to determine the “most useful” experimental conditions. This software can be utilized by researchers as a fast, user-friendly screening tool to determine the thermodynamic and mixture parameters for an experimental campaign. We demonstrate this software through two case studies comparing results of the 0D script against a shock tube experiment and results of the 1D script against a spherical flame experiment. In the shock tube case study we present mixture conditions compared to those used in the literature to study H + O2 (+M)→HO2(+M). In the flame case study, we present mixture conditions compared to those in the literature to study formyl radical (HCO) decomposition and oxidation reactions. The systematically determined experimental conditions identified in the present work are similar to the conditions chosen in the literature.

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Calculation of strong‐collision dissociation rate constants from NASA thermodynamic polynomials

Смирнов

2020

Int J of Chemical Kinetics

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A new method for calculating low‐pressure strong‐collision rate constants of dissociation and recombination reactions was proposed. The method is based on determining the density of states of the internal degrees of freedom of the reactant molecule by applying the inverse Laplace transform to the respective partition function, which, in turn, is calculated from the thermodynamic properties in the form of NASA polynomials. The proposed model is universal in the sense that the required NASA polynomials can be calculated using molecular properties obtained by various methods, both theoretical and experimental or a combination thereof. In the present study, the NASA polynomials were taken from the available databases or calculated from thermodynamic functions, either tabulated or determined by statistical mechanics in the rigid‐rotor harmonic‐oscillator approximation, with a simple anharmonicity correction introduced when necessary. In addition, a model for calculating the rotational factor is developed and tested. It is based on determination of the centrifugal barrier as a function of the dissociating bond length at a given rotational energy through calculating the principal moments of inertia of the molecule at each step of elongation of the bond. The proposed approach is exemplified for the dissociation of the H2O, HO2, and H2O2 molecules and the corresponding reverse reactions. A comparison with the available experimental data made it possible to estimate the weak‐collision efficiency. At high temperatures, for all the reactions studied, the weak collision efficiency appears to be quite reasonable, whereas, at low temperatures, the situation is unsatisfactory, except perhaps for H2O dissociation. Given that the energy threshold E0 of dissociation reactions is typically well known, the calculated and measured dissociation rate constants are represented and handled in terms of the preexponential factor A(T) in the expression k(T) = A(T)exp(−E0/RT). A new formula for fitting A(T) was proposed: log A(T) = a + b(1000/T) + c(1000/T)p, which turned out to be a good approximation for the preexponential factors of not only the rate constants but also the equilibrium constants.

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Measurement of the reaction rate of H + O2 + M → HO2 + M, for M= Ar, N2, CO2, at high temperature with a sensitive OH absorption diagnostic

Cited by 23 publications

References 50 publications

“Third‐body” collision parameters for hydrocarbons, alcohols, and hydroperoxides and an effective internal rotor approach for estimating them

“Third‐body” collision parameters for hydrocarbons, alcohols, and hydroperoxides and an effective internal rotor approach for estimating them

Computational Design of Sensitized Combustion Chemistry Experiments

Calculation of strong‐collision dissociation rate constants from NASA thermodynamic polynomials

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Measurement of the reaction rate of H + O2 + M → HO2 + M, for M= Ar, N2, CO2, at high temperature with a sensitive OH absorption diagnostic

Cited by 23 publications

References 50 publications

“Third‐body” collision parameters for hydrocarbons, alcohols, and hydroperoxides and an effective internal rotor approach for estimating them

“Third‐body” collision parameters for hydrocarbons, alcohols, and hydroperoxides and an effective internal rotor approach for estimating them

Computational Design of Sensitized Combustion Chemistry Experiments

Calculation of strong‐collision dissociation rate constants from NASA thermodynamic polynomials

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Product

Resources

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Measurement of the reaction rate of H + O2 + M → HO2 + M, for M= Ar, N2, CO2, at high temperature with a sensitive OH absorption diagnostic