Auto-ignition of hydrogen-air mixture at elevated

pressures

A.N. Derevyago, O.G. Penyazkov, K.A. Ragotner, and K.L. Sevruk

Physical and Chemical Hydrodynamic Laboratory, Luikov Heat and Mass Transfer Institute,
National Academy of Sciences of Belarus, ul. P.Brovki, 15, 220072, Minsk, (Belarus’)

Summary. Ignition times and auto-ignition modes of hydrogen-air mixtures have been studied
behind reflected shock waves. Experiments were performed at temperatures 830 − 1450 K,
pressures 2−21 atm, and equivalence ratio of φ = 1.0. Ignition delay times were determined using
OH emission profiles, pressure and ion current measurements. Different auto-ignition modes of
the mixture (strong, transient, and weak) were identified by comparing velocities of reflected
shock wave at different distances from the reflecting wall. The influence of the interaction of the
reflected shock wave with the dynamic boundary layer on the ignition time measurements in a
shock tube has been examined.

1 Introduction
The critical conditions and mechanisms of hydrogen oxidation are explained in the theory
of chain reactions by the competition of the reactions of branching and termination of
chains [1-4]. One of the most important consequences of this theory is the existence of
hydrogen -oxygen explosion limits in a temperature-pressure plane [2] and the complex
functional dependence of the ignition delay time on the pressure and temperature of the
reaction mixture [5].
The reaction rates of hydrogen oxidation (T > 800 K) at low post-shock pressures
(> 0.2 M P a) has been thoroughly studied and validated with the use of a large amount of
shock-tube experiments behind incident and reflected shock waves in mixtures highly di-
luted with argon. At these conditions, the ignition delay usually is inversely proportional
to the oxygen partial pressure and fast chain branching reactions [1-4] are dominating in
reaction mechanism of hydrogen oxidation.
The growing of initial pressures (> 0.2 M P a) increases the role of the chain branching
reactions with the participation of HO2 molecules formed due to trimolecular reaction
H +O2 +M = HO2 +M , which favors the removal of active hydrogen atoms from the fast
chain branching cycle and increase the characteristic time of hydrogen oxidation. The
functional behavior of induction time on temperature and pressure at elevated pressures
is usually established by using detailed numerical simulations [6, 7], or from empirical ap-
proximations based on low-pressure measurements. Moreover, existing reaction schemes
of hydrogen oxidation are not validated extensively by experimental measurements at
high pressures. Only few works [8-11] were devoted to studies of high-temperature hy-
drogen auto-ignitions at elevated pressures of 2 − 9 atm. At the same time, the prospects
of hydrogen applications in power engineering and industry call for a knowledge of hy-
drogen auto-ignitions at high pressures.
The present work gives results of experimental studies on auto-ignition of stoichiomet-
ric hydrogen-air mixtures at pressures of up to 21 atm and temperatures of 830 − 1450 K.
734 A.N. Derevyago, O.G. Penyazkov, et. al.

2 Experimental setup

The experimental configuration and cross-section of the test section is illustrated in

Fig. 1. A stainless steel shock tube of 50 mm diameter and 8.5 m length was used in
the experiments. The runs were performed in stoichiometric hydrogen-air mixtures at
mean post-reflected shock pressures of 2 − 21 atm. The ranges of post-shock conditions
studied in this work are summarized in Table 1. Commercial grade hydrogen of 99.9%
purity and compressed air were used for mixture preparations. An electronic pressure
meter controlled the initial pressure in the shock tube with accuracy of ±0.2 mm Hg.
Gas parameters behind incident and reflected shock waves were computed by using the
shock-adiabatic curve assuming frozen chemistry, known temperature dependence of heat
capacity, and shock wave velocity measurements with accuracy ±0.5% at different loca-
tions along the tube.

Fig. 1. Test section of the shock tube: 1-4 - high-frequency pressure transducers; 5 - quartz
reflecting wall; 6 - lens (f = 40 cm); 7 - interference filters; 8 - diaphragms; 9 - ring diaphragm;
10 - beam-splitter; 11 - photomultipliers.

Mixture P, atm. T, K
1 2.1-3.86 890-1433
2 5.1-7.72 989-1385
3 5.1-7.72 989-1385
4 5.1-7.72 989-1385
5 5.1-7.72 989-1385
6 5.1-7.72 989-1385

Table 1. The experimental conditions of hydrogen-air mixtures

Pressure variations at different cross-sections of the shock tube were measured by

high-frequency P CB pressure sensors, Model 113A24, with response time less than 1.5
μs and with a 1.5 mm spatial resolution (Fig.1). Light emission measurements were made
 Auto-ignition of hydrogen-air mixture at elevated pressures 735

by imaging the gas column (φ 5 mm) along the tube axis onto the first photomultiplier
detector. The 0.5 mm aperture ensured the angle selection of transmitted radiation and
passed only light beams propagating along the tube axis. To identify the influence of the
shock wave bifurcation on the hydrogen auto-ignition in the boundary layer, the emission
from an annular gas volume of outside diameter 44 mm and inside diameter 38 mm
selected by means of the annular diaphragm was imaged onto the second photomultiplier
(Fig. 1). The beam splitter divided the output spectrum in two optical paths to provide
the simultaneous observations of the gas luminosity in selected directions. The luminosity
from OH (λ = 306.2 nm; Δ = 2.4 nm) radicals was used to measure autoignition
of the mixture. Ignition-delay times were compared with the pressure measurements at
reflecting wall. The ignition time was defined as the time difference between shock arrival
at the end wall and the onset of emission at required intensity levels from the selected
gas columns along the tube axis. The optical setup was calibrated for ignition-delay time
measurements in both spectral paths.

Fig. 2. Velocities of reflected shock wave at 81.2, 181.2 and 155 mm from reflecting wall vs.
post-shock temperature in stoichiometric hydrogen-air mixtures and corresponding position of
the strong ignition limit. Post-shock density is 1.4 ± 0.02 kg/m3 .

Three distinct autoignition modes of the gas mixture namely strong, transient, and
weak [12-14] were identified based on velocity measurements of the reflected shock wave
relative to the gas flow behind the incident shock at different locations from the reflecting
wall [15]. Visible speed was calculated by processing shock-arrival times at pressure sen-
sors along the tube. Figure 2 illustrates the typical dependence of reflected shock-wave
velocity on post-shock temperature. On the basis of pressure and emission observations
the inflection point of velocity curve at low temperatures for distances of 81.2 mm was
used for determining the position of the strong explosion limit.
736 A.N. Derevyago, O.G. Penyazkov, et. al.

3 Result

The results of induction time measurements for two selected post-shock densities are pre-
sented in Fig. 3. At high temperatures of T > 1100 K, the strong ignition of hydrogen-air
mixtures was realized in the experiments. Because the detonation onset occurs near the
reflecting wall the arrival time of reaction front to ion sensor located at a distance of 31.2
mm from is almost independent on the temperature. For strong auto-ignitions, the induc-
tion time measurements along the tube axis and boundary layer gives the same results
within the experimental error, which indicates that the gas ignition is quite homogeneous.

Fig. 3. Induction time vs. the reciprocal temperature in a stoichiometric hydrogen-air mixture
for post-shock density of 0.67±0.02 kg/m3 (a) and 2.8±0.03 kg/m3 (b): 1, 2 - OH emissions along
the tube axis and in a boundary layer; 3 - pressure measurements; 4 - ion current measurements;
5 - reaction mechanism [16]; 6 - reaction mechanism [17]; 7 - reaction mechanism [15].

The predictions of detailed reaction mechanisms [16, 18] correlate well with experi-
ments at temperatures of T > 1100 K. The best agreement is observed for low pressures
mixtures (2.1 − 3.86 atm). At temperatures of T > 1250 K and pressures of 7 − 15 atm,
the reaction mechanisms [16, 18] give 1.2 − 1.5 times shorter induction times. In this case,
the mechanism [18] exhibits better agreement with the experimental data (Fig. 3). Thus,
predictions of the detailed hydrogen reaction mechanisms at elevated pressures P > 7
atm and temperatures of T > 1250 K are not sufficiently adequate.
A significant discrepancy between the measurements and calculations is observed
at temperatures of T < 1100 K. Experiments show that at high pressures and low
temperatures the induction time remains practically independent on the temperature. As
the temperature decreased, the strong regime of hydrogen ignition changed to a mild one
[13-15]. Under these conditions, the pressure recording becomes insensitive to the instant
of the onset of ignition and gives overestimated values for induction times (Fig. 3). The
emission measurements have shown that both the ignition mode and the temperature
dependence of the ignition time are changed at T < 1200 K. Emissions of OH radicals in
the periphery of the tube start to be earlier than at the tube axis. Thus, when the regime
changes the hydrogen auto-ignition becomes inhomogeneous. This tendency becomes the
most pronounced in high-density mixtures (Fig. 3).
 Auto-ignition of hydrogen-air mixture at elevated pressures 737

An analysis shows that at elevated pressures and low temperatures (T < 1200 K),
the interaction of reflected shock-wave with a dynamic boundary layer affect strongly
on the nonuniformity of the flow and the autoignition of hydrogen-air mixture. Under
these conditions, comparisons of experimental and numerical results become difficult
and require knowledge of both the reaction kinetics and the local flow parameters behind
incident and reflected shock waves. Domains of different autoignition modes in stoichio-
metric hydrogen-air mixtures are presented in Fig. 4. As seen in the figure, weak ignitions
have been observed only in a narrow range of post-shock conditions at low temperatures.
Strong initiations and transient regimes, resulting to deflagration to detonation transition
upstream the reflecting surface, occupy the major part of the diagrams.

Fig. 4. Autoignition domain in stoichiometric hydrogen-air mixture in a P-T plane: 1 - strong

ignition; II - transient ignition; III - weak ignition; IV - no ignition.

4 Conclusion
The autoignition of a stoichiometric hydrogen-air mixture at pressures of 2 − 21 atm and
temperatures of 840 − 1430 K has been investigated numerically and experimentally.
It has been established that the reaction mechanism of A. A. Konnov (version 4.0)
[16] and the GRIMECH 3.0 [18] provide a good qualitative agreement with experimental
data at temperatures of T > 1200 K; however, they should be somewhat refined to
improve the quantitative agreement with the experimental data at elevated pressures.
It was shown that the interaction of the reflected shock wave with the boundary
layer significantly influences on the results of induction time measurements and hydrogen
autoignitions at temperatures of T < 1100 K.
738 A.N. Derevyago, O.G. Penyazkov, et. al.

The data obtained can be used for analysis of combustion in engines and gas-turbines,
improvement of the reaction mechanism of hydrogen oxidation, and predictions of the
detonability limits and explosion safety of hydrogen-air mixtures.

Acknowledgement. This work was sponsored by State Research Programs of the Republic of
Belarus “Hydrogen 18, “Hydrogen 36” and “Thermal Processes 56”.

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