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Kinetic mechanism of combustion of hydrogen–oxygen mixtures

Article in Journal of Engineering Physics and Thermophysics · October 2013

DOI: 10.1007/s10891-013-0919-7

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Journal of Engineering Physics and Thermophysics, Vol. 86, No. 5, September, 2013

HEAT AND MASS TRANSFER IN COMBUSTION PROCESSES

KINETIC MECHANISM OF COMBUSTION OF HYDROGEN–OXYGEN MIXTURES

G. Ya. Gerasimov and O. P. Shatalov UDC 541.126:127;536.46

Based on the analysis of the databases published in the scientific literature and concerned with the reaction rate
constants in the H2/O2 system, a new kinetic mechanism is suggested for describing the processes of ignition,
combustion, and detonation in hydrogen–oxygen gaseous mixtures. Attention is mainly focused on consideration of
a low-temperature region (T < 1000 K) where a chain of reactions of the formation and subsequent decomposition
of hydrogen peroxide plays the major role in the system ignition. The proposed mechanism has been tested by
comparing computational results with available data on measurement of the ignition-delay time in shock tubes.

Keywords: hydrogen–oxygen mixtures, combustion, kinetic mechanism, induction time, databases on reaction rate
constants.
Introduction. The study of the ignition of hydrogen–oxygen mixtures is of both theoretical and practical interest.
The creation of hypersonic passenger aeroplanes requires, in particular, the development of new efficient engines that would
operate on hydrogen fuel and be characterized by a short time of combustible mixture residence in a combustion chamber
[1]. With the H2/O2 system being relatively simple, the branched-chain process of its ignition is realized with participation of
various molecules, atoms, and radicals the interaction between which is described by a large number of elementary chemical
reactions. Therefore, the development of reliable detailed kinetic mechanisms of the process plays an important role from the
viewpoint of their application in calculating the parameters of various technical facilities.
At the present time there are several kinetic mechanisms that adequately describe the ignition of the H2/O2 system
under different conditions. The well-known GRI-Mech 3.0 mechanism [2], as well as the mechanisms from [3, 4] based on
the mechanism previously proposed in [5], agree well with a wide spectrum of experimental data obtained in shock tubes
and continuous-flow reactors of complete mixing. In developing the kinetic mechanism in [6], special attention was given
to various channels of reaction between the H atoms and HO2 radicals, as well as to the dependence of the recombination
rate constants of HO2 radicals on pressure and to the abnormal behavior of the rate constant of the reaction between the
OH and HO2 radicals. The results of the testing we carried out reproduce, with a high accuracy, the available experimental
data obtained at temperatures from 950 to 2400 K and pressures up to 87 atm. The mechanism refined in [7] includes recent
experimental data on determining reaction rate constants in shock tubes.
Despite the considerable progress made in the understanding of the process of ignition of the H2/O2 system, a larger
number of uncertainties still remain with respect to the available kinetic mechanisms [8]. The aim of our present study was to
create a generalizing database that would contain the most reliable information on the rate constants of chemical reactions to
be used for describing the processes of ignition, combustion, and detonation in hydrogen–oxygen gaseous mixtures.
Kinetic Mechanism of the Process. The recommended database rests upon the analysis of earlier published databases
and works on simulation of combustion [6, 9–16] in which the recommended values of chemical reaction rate constants were
obtained either by statistical processing of the data of original research, or by adjusting constants for the best description of
modeled processes, or by critically analyzing previous research works. A detailed description of the procedure for choosing
rate constants is given in [17]. In its final form, the kinetic mechanism of the process is presented in Table 1.
All the reactions in the mechanism are reversible. If there is sufficient information, primarily experimental, on rate
constants in the forward and backward directions, both constants are given in the table. Otherwise, the constants of inverse
reactions are calculated from the constants of direct reactions and equilibrium constants with the use of thermodynamic data

Institute of Mechanics at the M. V. Lomonosov Moscow State University, 1 Michurinskii Ave., Moscow, 119192,
Russia; email: gerasimov@imec.msu.ru. Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 86, No. 5, pp. 929–936,
September–October, 2013. Original article submitted April 29, 2013.

0062-0125/13/8605-0987 ©2013 Springer Science+Business Media New York 987

 Fig. 1. Rate constant of the reaction H2O2 + H → HO2 + H2: + and ○) experimental data
of [28] and [29], respectively; 1 and 2) theoretical estimates obtained in [24] and [30],
respectively; 3 and 4) recommendations made in [12] and [11], respectively.

[25]. Dissociation and recombination reactions with participation of various inert partners in collision M are considered as
individual reactions with corresponding rate constants. If there is no kinetic information for some M, it is recommended to
use the following relative efficiencies: Ar:O:H:N2:O2:H2:OH:O3:HO2:H2O:H2O2 = 1:11.7:5.5:1.7:3.3:2.8:2.9:17:17:17:17. The
transition region between the rate constants of the third and second order for recombination reactions (6) and (7) (see Table
1) is described by means of Lindemann–Hinshelwood′s expression. The rate constants in the limit of high pressures k∞ and
the broadening factors at the center of the transition curve Fcent were borrowed from [6], with the value of k∞ for reaction
(7) being increased 1.9 times according to [26]. Table 1 also includes a number of reactions that do not play a material role
in describing the process of combustion (reactions involving ozone, certain dissociation reactions). Information about these
reactions can be found in the literature on atmospheric chemistry [9, 15] and high-temperature kinetics [16].
The recommended kinetic mechanism is analogous in many respects to the mechanism of [6]. The basic difference
consists in the description of the low-temperature region (T < 1000 K) at elevated pressures (p ≥ 1 atm). As a sensitivity
analysis [27] shows, the chain of reactions involving the formation and subsequent decomposition of hydrogen peroxide: HO2
+ H2 → H2O2 + H and H2O2 + M → 2OH + M predominated in ignition of the H2/O2 system in this region. The first reaction
is represented in the table by the rate constant of the reaction reciprocal to the first one (21). The available experimental data
and theoretical estimates of this rate constant within the temperature range from 300 to 2000 K are presented in Fig. 1. It is
seen that at temperatures above 700 K, which are the most interesting from the viewpoint of studying ignition in the system
considered, the theoretical estimates of [24, 30] agree well with the results of measurements made in [29] and with the
recommendations given in [11]. On the other hand, the recommendation given in review [12] that was used in the mechanism
of [6] is much lower in the region of temperatures considered. As shown in what follows, this yields lower values of the
ignition time t calculated in the interval T = 800–1000 K with the use of the proposed model.
The second reaction in the above-considered chain is close to the limit of low pressures at the temperatures and
atmospheric pressure typical of combustion. The results of recent measurements of the rate constant of the given reaction
at M = Ar:H2O2 + Ar → 2OH + Ar [31, 32] agree well with the recommendations given in review [23] that were converted
to an inverse reaction and used in the mechanism proposed in [6]. This value of the rate constant is given in Table 1 for
recombination reaction (7).
Results of Calculations and Discussion. We carried out the testing of the proposed mechanism by comparing the
results of calculations with the available experimental data on measurement of the delay time τ in the ignition of an H2/O2 mixture
in shock tubes. The quantity τ is a function of the initial composition, temperature, and pressure of the mixture. Usually, the
investigated mixtures are highly diluted with an inert gas in order to maximally decrease the influence of the hydrodynamic
effects on the advancement of chemical reactions [33].
The computational procedure is based on the widely used application package CHEMKIN [34]. The calculations
were carried out in the approximation of an adiabatic process at a constant pressure. Applied to simulation of the process of
ignition of a combustible mixture in shock tubes, this approximation overestimates the time t as compared with a constant-

988
TABLE 1. Mechanism of Reactions in the H2/O2 System

Reaction
Reaction M log A n E T⋅10–3 Δ log k Reference
number
1 H2 + M → H + H + M H2 14.96 0 48,350 2.5–8 0.5 [12]
N2 19.66 –1.4 52,530 0.6–2 0.7 [12]
H2O 19.93 –1.1 52,530 0.6–2 0.7 [12]
Ar 14.35 0 48,350 2.5–8 0.3 [12]
–1 H + H + M → H2 + M H2 17.00 –0.6 0 0.2–5 0.5 [16]
N2 18.73 –1.3 0 0.3–2 – [6]
H2O 19.00 –1 0 0.3–2 0.7 [16]
H 15.51 0 0 0.3–5 0.5 [16]
Ar 17.81 –1 0 0.2–2.5 0.5 [12, 13]
2 O2 + M → O + O + M O 25.54 –2.5 59,380 2–8 0.3 [14]
O2 24.99 –2.5 59,380 2–10 0.3 [14]
O3, H2O 19.08 –1 59,380 2–5 1.0 [18]
N2 18.26 –1 59,380 3–8 – [14]
Ar 18.26 –1 59,380 3–8 0.3 [14]
–2 O + O + M → O2 + M O2 17.90 –1 0 0.3–5 0.4 [6]
O 18.46 –1 0 0.3–5 0.3 [6]
N2 17.30 –1 0 0.3–5 0.5 [6]
H2O 17.70 –1 0 0.3-4 0.3 [6]
Ar 17.00 –1 0 0.3–5 0.3 [6]
3 O3 + M → O 2 + M O2 14.19 0 11,600 0.3–3 – [18]
O 15.39 0 11,430 0.2–1 – [18]
O3 14.64 0 11,600 0.2–1 0.2 [18]
N2 14.64 0 11,600 0.2–1 0.6 [14]
Ar 14.39 0 11,430 0.2–1 0.1 [14]
–3 O2 + O + M → O 3 + M O2 20.78 –2.6 0 0.1–0.3 0.1 [9]
O 19.86 –1.9 0 0.2–0.4 – [18]
O3 19.70 –1.9 0 0.2–1 – [18]
N2 20.75 –2.6 0 0.1–0.3 0.1 [9]
Ar 18.86 –1.9 0 0.2–0.4 0.1 [15]
4 O + H + M = OH + M H2 19.30 –1 0 3–3.7 – [19]
O2, N2 19.13 –1 0 3–3.7 – [19]
H2O 20.04 –1 0 3–3.7 0.5
Ar 18.83 –1 0 3–3.7 0.5 [19]
5 H2O + M → H + OH + M O2 15.54 0 52,920 2–6 0.5 [13]
N2 15.54 0 52,920 2–4 0.5 [13]
H2O 16.35 0 52,920 2–6 0.2 [13]
Ar 15.13 0 52,920 2–6 0.3 [12]
–5 H + OH + M → H2O + M H2 22.21 –2 0 0.3–3 0.5 [13]
N2 22.34 –2 0 0.3–3 0.5 [13]

989
TABLE 1. Continued

Reaction
Reaction M log A n E T⋅10–3 Δ log k Reference
number
OH 15.92 0 0 1.7–1.9 – [20]
H2O 23.15 –2 0 0.3–3 0.5 [13]
Ar 21.92 –2 0 0.3–3 0.3 [13]
6 H + O2 + M = HO2 + M H2 19.93 –1.4 0 0.3–2 0.5 [6]
O2 18.76 –1.09 0 0.3–0.7 0.1 [21]
N2 19.42 –1.3 0 0.3–2 0.2 [12]
H2O 19.56 –1.0 0 0.3–2 0.3 [12]
Ar 18.84 –1.2 0 0.3–2 0.2 [12]
7 2OH + M → H2O2 + M Ar 19.38 –0.8 0 0.3–1.4 0.4 [6]
8 H2 + O2 → H + HO2 5.87 2.43 26,926 0.4–2.3 0.5 [22]
–8 H + HO2 → H2 + O2 14.02 0 1030 0.3–1 0.3 [12]
9 HO2 + H = H2O + O 13.48 0 866 0.3–1 0.3 [12]
10 H2 + OH → H + H2O 8.34 1.52 1740 0.3–2.5 0.3 [12]
–10 H2O + H → H2 + OH 8.66 1.6 9030 0.8–2.5 0.2 [12]
11 OH + OH = H2O + O 4.53 2.42 –970 0.3–2.4 0.15 [12]
12 O2 + H → OH + O 14.31 –0.1 7560 0.8–3.5 0.2 [12]
–12 OH + O → O2 + H 14.08 –0.35 –113 0.3–3 0.2 [12]
13 H2 + O = OH + H 4.71 2.67 3165 0.3–2.5 0.2 [23]
14 HO2 + O = OH + O2 13.21 0 –224 0.2–1 0.5 [12]
15 HO2 + H = OH + OH 14.65 0 700 0.25–1 0.15 [12]
16 OH + HO2 = H2O + O2 13.46 0 –250 0.25–2 0.2 [12]
+ 15.97 0 8810 0.25–2 0.2 [12]
17 OH + O3 = O2 + HO2 12.01 0 940 0.2–0.5 0.3 [9]
18 O 3 + O = O 2 + O2 12.68 0 2060 0.2–0.4 0.3 [9]
19 O3 + H = OH + O2 13.93 0 470 0.2–0.4 0.7 [9]
20 HO2 + O3 = OH + O2 + O2 –3.23 4.57 –693 0.3–0.4 – [9]
21 H2O2 + H = HO2 + H2 13.82 0 4200 0.7–1.2 0.2 [24]
22 HO2 + HO2 = H2O2 + O2 14.01 0 5556 0.3–1.2 0.4 [6]
+ 11.29 0 –709 0.3–1.2 0.4 [6]
23 H2O2 + H = H2O + OH 13.01 0 1800 0.3–1 0.3 [10]
24 OH + H2O2 = H2O + HO2 12.29 0 215 0.3–1.7 0.2 [12]
+ 18.23 0 14,800 0.3–1.7 0.5 [12]
25 H2O2 + O = OH + HO2 6.98 2 2000 0.3–2.5 0.5 [11]
26 H2 + O2 = OH + OH 12.31 0.44 34,800 0.3–1 0.5 [6]
Note. The rate constant k = AT n exp (–E/T); the quantity ∆ log k is an error.

990
 Fig. 2. Comparison between calculated and experimental [36] values of induction time
behind the front of an incident shock wave in H2/O2/Ar mixtures at p = 1 atm: (1, + ) H2
= 2%, O2 = 1%, and Ar = 97%; (2, □) H2 = 0.8%, O2 = 4.2%, and Ar = 95%; (3, ○) H2 =
4%, O2 = 4%, and Ar = 92%.

Fig. 3. Effect of pressure on induction time: (1, + ) p = 1 atm; (2, ○) p = 4 atm; (3, □)
p = 16 atm. Points, experimental data of [38]; lines, calculated results.

volume approximation. Nevertheless, as shown in [35], the difference does not exceed several percent, which falls within the
limits of the scatter in experimental data.
In Fig. 2 the values of τ calculated at the pressure p = 1 atm are compared with some results of measurements made
behind the incident wave front in H2/O2 mixtures highly diluted with argon [36]. In the experiments, the induction time was
determined from the delay in the arrival at the maximum level of radiation from the electronically exited OH* radical relative
to the initiating shock wave front. The use of the OH* radical for this purpose is due to the fact that its radiation appears at
an early stage of mixture ignition. Since the excited OH* radical was not included into the considered kinetic mechanism,
the values of t were calculated from the maximum product of the concentrations of O and H atoms that are basic components
leading to the formation of OH* [37]. An analysis of Fig. 2 shows that for all of the mixtures considered there is good
agreement between the measured and calculated values of t. The difference at low temperatures (T < 1000 K) is systematic
in character and is explained by the inability of the homogeneous model to describe the occurrence of the localized zones
of combustion near the shock tube walls and their propagation in the surrounding unreacted mixture [35]. This problem is
considered in more detail in what follows.
To illustrate the influence of pressure on τ, we selected the experimental data that had been obtained in [38] for a
stoichiometric mixture H2/O2 highly diluted with argon. A comparison of these data with those computed is given in Fig. 3. We
see that τ depends in a complex way on p and T, with t in the temperature region from 1000 to 1100 K, attaining a minimum
when the pressure changes from 1 to 16 atm. In the entire region of the considered temperatures and pressures, the computed
values of τ agree well with the measurement results.
Shock-tube experiments concerning the ignition delay in a stoichiometric hydrogen–air mixture at various pressures
were conducted in [39–42]. In Fig. 4 the data from [39–41] at p = 2 atm are compared with the computational results
obtained with the use of various kinetic mechanisms, including the mechanism recommended in the present work. It is seen
that all the mechanisms approximate experimental points well at high temperatures (T ≥ 1100 K). In the intermediate range
of temperatures, the data obtained employing GRI-Mech 3.0 [2] and the mechanism of [4] considerably exceed measured
values. The mechanism recommended in the present work more adequately describes the process of ignition of the given
mixture up to temperatures of the order of 950 K. Nevertheless, at lower temperatures a considerable disagreement exists
between experimental and calculated data for all the mechanisms considered.
In Fig. 5 the experimental data of [42] obtained in a stoichiometric hydrogen–air mixture at higher pressures are
compared with the results of computations based on the present mechanism and that of [6]. The given induction times were

991
 Fig. 4. Delay in ignition calculated for a stoichiometric hydrogen–air mixture at p = 2 atm
with the use of various mechanisms: 1) [2]; 2) [4]; 3) [6]; 4) present mechanism. Points,
experimental data: □) [39]; + ) [40]; ○) [41].

Fig. 5. Induction time vs. inverse temperature in a stoichiometric hydrogen–air mixture:

(1, + ) and (2, ○) calculated results and experimental data [42] obtained at gas densities
6.7·10–4 and 2.8·10–3 g/cm3, respectively; solid lines, calculation by the present mecha-
nism; dashed lines, by the mechanism of [6].

Fig. 6. Results of variation of the rate constant of reaction (21) and comparison with the
experimental data of [43] on ignition of a hydrogen–oxygen mixture at p = 1 atm: 1)
calculation by the present mechanism; 2) calculation with k21 × 10; 3) calculation with
k21 × 100.

measured at gas densities behind a shock wave ρ = 6.7·10–4 and 2.8·10–3 g/cm3; in the considered temperature range this
corresponds to pressures 2.3–3.7 and 9.8–15.4 atm, respectively. On the whole, satisfactory agreement between the calculated
results and experimental data is seen, with the present mechanism providing a better description of the low-temperature
ignition of the mixture than the mechanism of [6]. This is explained by the higher value of the rate constant for the reaction
HO2 + H2 = H2O2 + H, which plays the decisive role in the given temperature range.
To estimate the influence of the rate constant of the given reaction on the induction time τ, we varied the value of k21.
The results are presented in Fig. 6. We see that the 100-fold increase in k21 leads to satisfactory agreement of calculated data
with the measured values of τ for the stoichiometric mixture H2/O2 up to temperatures of the order of 850 K. Nevertheless, an

992
artificial overestimation of the rate constant k21 cannot completely solve the problem of the disagreement between calculated
and experimental data at low temperatures within the framework of the homogeneous model.
Attempts have been made recently to describe the low-temperature ignition of hydrogen–oxygen mixtures by various
hydrodynamic and surface-catalytic effects. In particular, in [44] the process of ignition behind the front of a reflected shock
wave is treated as a formation of local flame sites near the walls and the back flange of a shock tube that subsequently propagate
into the unreacted mixture. In the considered case, it is the velocity of the combustion front propagation that determines the
induction time t, which can be much shorter than the time of the self-ignition of a mixture at the given temperature. To make the
calculated results consistent with experimental data at low temperatures, the authors of [45] introduced, into the computational
scheme, the experimentally observed increase in pressure behind the front of a reflected shock wave, which under the conditions
of adiabatic process raises the mixture temperature and respectively decreases the induction time. In [46], self-ignition in the
low-temperature region is described using modified rate constants of the reactions of formation and subsequent decomposition
of hydrogen peroxide. The constants account for the catalytic properties of the shock tube walls. This procedure also leads to
a reduction in the calculated value of t and correspondingly to its better agreement with measured values.
Conclusions. The recommended kinetic mechanism is based on the analysis of earlier published databases and
works on modeling combustion in a H2/O2 system. The results of testing the mechanism have shown that it can be applied in
describing ignition of both mixtures highly diluted with an inert gas and pure mixtures at temperatures from 950 to 2500 K and
pressures up to 18 atm. We have analyzed the influence of the rate constants for the reaction of hydrogen peroxide formation
on the induction time. It is shown that artificial overestimation of the rate constant cannot completely solve the problem of
the disagreement between calculated and experimental data at low temperatures within the framework of the homogeneous
model of the process.

NOTATION
A, pre-exponential factor in the reaction rate constant, (cm3/mole)m–1·s–1·K–n; E, reaction activation energy, K; Fcent,
broadening factor at the center of transition curve; ki, rate constant of ith reaction, (cm3/mole)m–1·s–1; m, reaction order; n,
power at the temperature in reaction rate constant; p, pressure, atm; T, temperature, K; ρ, gas density, g/cm3; τ, delay in igni-
tion (induction time), μs. Indices: cent, center of transition region; i, reaction number; ∞, limit of high pressures.

REFERENCES
1. D. Cecere, A. Ingenito, E. Giacomazzi, L. Romagnosi, and C. Bruno, Hydrogen/air supersonic combustion for future
hypersonic vehicles, Int. J. Hydrogen Energy, 36, No. 18, 11969–11984 (2011).
2. G. P. Smith, D. M. Golden, M. Frenklach, N. W. Moriarty, B. Eiteneer, M. Goldenberg, C. T. Bowman, R. K. Hanson,
S. Song, W. J. Gardiner Jr, V. V. Lissianski, and Z. Qin, GRI–Mech 3.0 Reaction Mechanism. 2002. http://www.
me.berkeley.edu/gri_mech/.
3. M. O'Conaire, H. J. Curran, J. M. Simmie, W. J. Pitz, and C. K. Westbrook, A comprehensive modeling study of
hydrogen oxidation, Int. J. Chem. Kinet., 36, No. 11, 603–622 (2004).
4. J. Li, Z. Zhao, A. Kazakov, and F. Dryer, An updated comprehensive kinetic model of hydrogen combustion. Int. J.
Chem. Kinet., 36, No. 10, 566–575 (2004).
5. M. Mueller, T. Kim, R. Yetter, and F. Dryer, Flow reactor studies and kinetic modeling of the H2/O2 reaction, Int. J.
Chem. Kinet., 31, No. 2, 113–125 (1999).
6. A. A. Konnov, Remaining uncertainties in the kinetic mechanism of hydrogen combustion, Combust. Flame, 152, No.
4, 507–528 (2008).
7. Z. Hong, D. F. Davidson, and R. K. Hanson, An improved H2/O2 mechanism based on recent shock tube/laser absorption
measurements, Combust. Flame, 158, No. 4, 633–644 (2011).
8. T. Weydahl, M. Poyyapakkam, M. Seljeskog, and N. E. L. Haugen, Assessment of existing H2/O2 chemical reaction
mechanisms at reheat gas turbine conditions, Int. J. Hydrogen Energy, 36, No. 18, 12025–12034 (2011).
9. R. Atkinson, D. L. Baulch, R. A. Cox, et al., Evaluated kinetic and photochemical data for atmospheric chemistry:
Volume I — gas phase reactions of Ox, HOx, NOx, and SOx species, Atmos. Chem. Phys., 4, No. 6, 1461–1738 (2004).
10. J. Warnatz, U. Maas, and R. W. Dibble, Combustion, Springer, Berlin (2003).
11. W. Tsang and R. F. Hampson, Chemical kinetic database for combustion chemistry, Part I. Methane and related
compounds, J. Phys. Chem. Ref. Data, 15, No. 3, 1087–1279 (1986).

993
12. D. L. Baulch, C. T. Bowman, C. J. Cobos, et al., Evaluated kinetic data for combustion modeling: Supplement II, J. Phys.
Chem. Ref. Data, 34, No. 3, 757–1397 (2005).
13. D. L. Baulch, D. D. Drysdale, and D. G. Horne, Evaluated kinetic database for high temperature reactions, in:
Homogeneous Gas Phase Reactions of the H2–O2 System, Vol. 1, Butterworths, London (1972).
14. D. L. Baulch, D. D. Drysdale, J. Duxbury, and S. J. Grant, Evaluated kinetic database for high temperature reactions, in:
Homogeneous Gas Phase Reactions of the O2–O3 System and the CO–O2–H2 System, and Sulfur-Containing Species,
Vol. 3, Butterworths, London (1976).
15. D. L. Baulch, R. A. Cox, P. J. Crutzen, et al., Evaluated kinetic and photochemical data for atmospheric chemistry:
Supplement I, J. Phys. Chem. Ref. Data, 11, No. 2, 327–496 (1982).
16. N. Cohen and K. R. Westberg, Chemical kinetic data sheets for high-temperature chemical reactions, J. Phys. Chem. Ref.
Data, 12, No. 3, 531–590 (1983).
17. L. B. Ibragimova, G. D. Smekhov, and O. P. Shatalov, Comparative analysis of the rates of chemical reactions describing
the combustion of hydrogen–oxygen mixtures (2009), http://www.chemphys.edu.ru/media/files/2009-06-29-001_.pdf.
18. V. N. Makarov and O. P. Shatalov, Gas-dynamical ozone generator, Izv. Ross. Akad. Nauk, Mekh. Zhidk. Gaza, 29, No.
6, 139–148 (1994).
19. S. Javoy, V. Naudet, S. Abid, and C. E. Paillard, Elementary reaction kinetics studies of interest in H2 supersonic
combustion chemistry, Exp. Therm. Fluid Sci., 27, No. 4, 371–377 (2003).
20. M. G. Davis, W. K. McGregor, and A. A. Mason, OH chemiluminescent radiation from lean hydrogen–oxygen flames,
J. Chem. Phys., 61, No. 4, 1352–1357 (1974).
21. J. V. Michael, M. C. Su, J. W. Sutherland, J. J. Carroll, and A. F. Wagner, Rate constant for O2 + H + M → HO2 + M in
seven bath gases, J. Phys. Chem. A, 106, No. 21, 5297–5313 (2002).
22. J. V. Michael, J. W. Sutherland, L. B. Harding, and A. F. Wagner, Initiation in H2/O2: Rate constants for H2 + O2 → H
+ HO2 at high temperature, Proc. Combust. Inst., 28, No. 2, 1471–1478 (2000).
23. D. L. Baulch, C. J. Cobos, R. A. Cox, et al., Summary table of evaluated kinetic data for combustion modeling:
Supplement 1, Combust. Flame, 98, Nos. 1–2, 59–79 (1994).
24. B. A. Ellingson, D. P. Theis, O. Tishchenko, J. Zheng, and D. G. Truhlar, Reactions of hydrogen atom with hydrogen
peroxide, J. Phys. Chem. A, 111, No. 51, 13554–13566 (2007).
25. A. Burcat and B. Ruscic, Third millennium ideal gas and condensed phase thermochemical database for combustion
with updates from active thermochemical tables. ANL-05/20 and TAE 960. Technion-IIT, Aerospace Engineering, and
Argonne National Laboratory, Chemistry Division (2005).
26. J. Troe and V. G. Ushakov, SACM/CT study of the dissociation/recombination dynamics of hydrogen peroxide on an ab
initio potential energy surface, Phys. Chem. Chem. Phys., 10, No. 26, 3915–3924 (2008).
27. D. Li and S. Hochgreb, Hydrogen autoignition at pressures above the second explosion limit (0.6–4.0 MPa), Int. J. Chem.
Kinet., 30, No. 6, 385–406 (1998).
28. R. A. Gorse and D. H. Volman, Photochemistry of the gaseous hydrogen peroxide–carbon monoxide system. II: Rate
constants for hydroxyl radical reactions with hydrocarbons and for hydrogen atom reactions with hydrogen peroxide, J.
Photochem., 3, No. 1, 115–122 (1974).
29. R. R. Baldwin and R. W. Walker, Rate constants for hydrogen + oxygen system, and for H atoms and OH radicals +
alkanes, J. Chem. Soc., Faraday Trans. 1, 75, No. 1, 140–154 (1979).
30. Y. Tarchouna, M. Bahri, N. Jaidane, and Z. Ben Lakhdar, Kinetic study of the hydrogen abstraction reaction H2O2 + H
→ H2 + HO2 by ab initio and density functional theory calculations, J. Mol. Struct.: THEOCHEM, 758, No. 1, 53–60
(2006).
31. Ch. Kappel, K. Luther, and J. Troe, Shock wave study of the unimolecular dissociation of H2O2 in its falloff range and
of its secondary reactions, Phys. Chem. Chem. Phys., 4, No. 18, 4392–4398 (2002).
32. Z. Hong, R. D. Cook, D. F. Davidson, and R. K. Hanson, A shock tube study of OH + H2O2 → H2O + HO2 and H2O2 +
M → 2OH + M using laser absorption of H2O and OH, J. Phys. Chem. A, 114, No. 18, 5718–5727 (2010).
33. E. Schultz and J. Shepherd, Validation of detailed reaction mechanisms for detonation simulation, Technical Report
FM99-5, California Institute of Technology, Pasadena (2000).
34. R. J. Kee, F. M. Rupley, E. Meeks, and J. A. Miller, Chemkin-III: A Fortran chemical kinetics package for the analysis
of gas-phase chemical and plasma kinetics, Technical Report SAND96-8218, Sandia National Laboratories, Livermore
(1996).

994
35. B. L. Wang, H. Oliver, and H. Grönig, Ignition of shock-heated H2–air–steam mixtures, Combust. Flame, 133, Nos. 1–2,
93–106 (2003).
36. V. A. Pavlov and O. P. Shatalov, Measurement of the time of induction of hydrogen–oxygen mixtures behind the
incident shock wave front, Kinet. Katal., 52, No. 2, 1–10 (2011).
37. J. M. Hall and E. L. Petersen, An optimized kinetics model for OH chemiluminescence at high temperatures and
atmospheric pressures, Int. J. Chem. Kinet., 38, No. 12, 714–724 (2006).
38. J. Herzler and C. Naumann, Shock-tube study of the ignition of methane/ethane/hydrogen mixtures with hydrogen
contents from 0% to 100% at different pressures, Proc. Combust. Inst., 32, No. 1, 213–220 (2009).
39. A. D. Snyder, J. Robertson, D. L. Zanders, and G. B. Skinner, Shock tube studies of fuel–air ignition characteristics,
Technical report AFAPL-TR-65-93, Air Force Aero-Propulsion Laboratory, Wright-Patterson (1965).
40. M. W. Slack, Rate coefficient for H + O2 + M = HO2 + M evaluated from shock tube measurements of induction times,
Combust. Flame, 28, No. 1, 241–249 (1977).
41. K. A. Bhashkaran, M. C. Gupta, and T. H. Just, Shock tube study of the effect of unsymmetric dimethyl hydrazine on the
ignition characteristics of hydrogen–air mixtures, Combust. Flame, 21, No. 1, 45–48 (1973).
42. V. V. Martynenko, O. G. Penyazkov, K. A. Ragotner, and S. I. Shabunya, High-temperature of hydrogen and air at high
pressures downstream of the reflected shock wave, Inzh.-Fiz. Zh., 77, No. 4, 100–107 (2004).
43. V. V. Voevodskii and R. I. Soloukhin, Concerning the mechanism and the limits of chain self-ignition of hydrogen with
oxygen in shock waves, Dokl. Akad. Nauk SSSR, 154, No. 6, 1425–1428 (1964).
44. S. P. Medvedev, G. L. Agafonov, S. V. Khomik, and B. E. Gelfand, Ignition delay in hydrogen–air and syngas–air
mixtures: Experimental data interpretation via flame propagation, Combust. Flame, 157, No. 7, 1436–1438 (2010).
45. G. A. Pang, D. F. Davidson, and R. K. Hanson, Experimental study and modeling of shock tube ignition delay times for
hydrogen–oxygen–argon mixtures at low temperatures, Proc. Combust. Inst., 32, No. 1, 181–188 (2009).
46. F. L. Dryer and M. Chaos, Ignition of syngas/air and hydrogen/air mixtures at low temperatures and high pressures:
Experimental data interpretation and kinetic modeling implications, Combust. Flame, 152, Nos. 1–2, 293–299 (2008).

995

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