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Procedia Engineering 62 (2013) 786 790

The 9th Asia-Oceania Symposium on Fire Science and Technology

Comparison of the maximum gas combustion pressure of

hydrogen/oxygen/nitrogen-between chemical equilibrium calculations
and experimental data
Gang Taoa, Daniel A. Crowlb,*
a

College of urban construction and safety engineering, Nanjing University of Technology, Nanjing 210009, China
b
Department of Chemical Engineering, Michigan Technological University, Houghton, MI 49931, USA

Abstract
A study was completed comparing equilibrium combustion pressures obtained using constant volume and internal energy constraints to
maximum combustion pressures from an existing experimental data base for hydrogen / oxygen and nitrogen mixtures (Jo and Crowl,
2006). We found that the experimental and calculated combustion pressures were close near the stoichiometric combustion point. At other
compositions, particularly near the flammable limits, the calculated equilibrium pressures were much higher. Since the maximum pressure
is of interest in insuring the design of process equipment and vents, the equilibrium calculation approach can be used instead of
experimental data.
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Keywords: Maximum combustion pressure; Equilibrium calculation; Explosion; Hydrogen

1. Introduction
The maximum pressure of gas combustion, Pmax, is a very important parameter in a closed vessel for risk assessment
(AIChE/CCPS, 1989) [1] and relief vent design (NFPA, 2007) [2]. It is difficult to theoretically predict the maximum
pressure because of the complicated mechanism of combustion.
The pressure of gas combustion is measured experimentally by placing a flammable gas in a spherical pressure vessel,
igniting it, and measuring the pressure vs. time. The maximum pressure recorded during the experiment is the maximum
pressure of gas combustion. The results are dependent on the apparatus, procedure, gas composition, initial pressure and
temperature. Previous studies have shown some connection between the experimental maximum pressure of gas combustion
and the equilibrium pressure calculated at the same composition and initial conditions. This study will use a very detailed
data set [10-13] to compare the experimental and equilibrium values.
Several studies have been completed on this. In this previous work, explosion properties of an explosive mixture can be
divided into equilibrium and dynamic (non-equilibrium) parameters. Equilibrium parameters are based on thermodynamics
and can easily be determined from standard computer codes (e.g. STANJAN, GASEQ, CEA, etc.). Crowl [3] presented a
method to calculate the change in thermodynamic availability due to the combustion of gas mixture. Melhem [4] presented a
general method for the estimation of flammability envelops for chemical mixtures based on chemical equilibrium. Fan and
Crowl [5] presented a semi-empirical method to predict the maximum pressure for fuel/air deflagrations over the entire
flammable range. Experimental data sources about flammability and deflagration include Bartknecht [6], Senecal and

* Corresponding author. Tel.: +1 906 487 3221; fax: +1 906 487 3213.
E-mail address: crowl@mtu.edu.

1877-7058 2013 International Association for Fire Safety Science. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of the Asian-Oceania Association of Fire Science and Technology
doi:10.1016/j.proeng.2013.08.126

Gang Tao and Daniel A. Crowl / Procedia Engineering 62 (2013) 786 790

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Beaulieu [7], Mashuga and Crowl [8], and Cashdollar [9].

2. Apparatus and experimental procedures
2.1. Apparatus
The combustion experimental data was obtained from our previous studies [10-13]. The experimental apparatus consists
of a closed 20 L sphere with initially quiescent mixtures at an initial temperature and pressure of 298 K and 101.3 kPa. This
experimental device is composed of the following parts: The first part is the 20 L spherical vessel which is constructed of
6.35 mm stainless steel with a MAWP of 2.068 MPa. The second part is a gas purging and loading system which includes
vacuum pumps, gas cylinders and an internal magnetic driven stirrer. The third part is a fuse wire igniter located at the
center of sphere which can achieve 10 J. The fourth part is the transducers which include temperature transducers and
pressure transducers. The apparatus is controlled by an interactive LabVIEW computer program.
2.2. Experimental procedures
The experimental procedures are composed of the following: First, the spherical vessel is purged with ultra high purity
nitrogen with a concentration of at least 99.99%. The vessel is evacuated several times to remove previous combustion
impurities in the reactor. Then ultra high purity oxygen, nitrogen and hydrogen are filled sequentially to the desired partial
pressures. The process of gas filling is controlled by a high precision pressure transducer with feedback function and
solenoid valves which are controlled by the LabVIEW software. Two Sensotec TJE pressure transducers are used. The first
transducer is used to mix the gas mixture with a max pressure of 172 kPa and a precision of +/0.05% full scale. The second
transducer is used to record the combustion pressure with a max pressure of 1.37 MPa and a precision of +/0.1% full scale.
Both transducers have a response of 3 kHz. The error in gas mixing is about 0.034% because of the precision of the pressure
transducer. The maximum concentration deviation is less than 0.4%. The combustion pressure measurement precision is
about +/2 kPa.
After the gas filling the gases must be mixed to a homogeneous level. At the same time a temperature requirement must
also be satisfied. Then the gas mixture is ignited by a fuse wire positioned in the center of the vessel. The fuse wire provides
10 J at ignition. An alternating current electric source is used to heat the fusing wire, and stabilize the flame kernel in the
gas mixture. The time uncertainty of the ignition by the fusing wire is less than about 10 msec.
When the ignition is finished the high pressure transducer located on the vessel wall monitors the pressure signal and
characterizes the explosion of the flammable gas mixture. The operator is able to visually observe through two sight glasses.
The pressure and temperature time history are saved to a data file on the computer, as well as the maximum temperature and
pressure achieved during the combustion.
3. Chemical equilibrium calculations
Complex equilibrium analysis has been widely studied in chemical engineering. In this paper, an on-line chemical
equilibrium calculator was used to calculate the chemical equilibrium state of an ideal gas mixture, subject to necessary
constraints on two intrinsic variables. Depending on the constraint chosen, the calculation invokes STANJAN to minimize
the derived property - Gibbs energy, Helmholz energy, internal energy, enthalpy - or maximize entropy for the user-supplied
gas mixture [14].
Table 1. The chemical equilibrium results of parameters
Parameters

Initial State

Equilibrium State

Pressure (atm)

1.0000E+00

7.3179E+00

Temperature (K)

2.9982E+02

2.4765E+03

Specific Volume (cm3/g)

1.1056E+03

1.1056E+03

Enthalpy (erg/g)

2.2435E+07

7.1002E+09

Internal Energy (erg/g)

-1.0978E+09

-1.0978E+09

Entropy (erg/g K)

8.3595E+07

1.0052E+08

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Gang Tao and Daniel A. Crowl / Procedia Engineering 62 (2013) 786 790

The initial temperature is 26.7 C. The initial pressure is 101.3 kPa. The estimated equilibrium temperature is 649 C.
The estimated equilibrium pressure is 689.5 kPa. The reaction is with the condition of constant volume and internal energy.
Because the mixture system is composed of hydrogen, oxygen and nitrogen the elements in the reaction are H, O and N. The
species that may be present at equilibrium include H, H2, H2O (g), OH, N, N2, N2O, NH3, NH2, NH, O, O2, NO, NO2 and
H2O (L). The chemical equilibrium results of parameters and species at 24% hydrogen, 12% oxygen and 64% nitrogen are
listed in Table 1 and Table 2.
Table 2. The chemical equilibrium results of species
Species

Initial State

Equilibrium State

Mole fraction

Mass fraction

Mole fraction

Mass fraction

N2

6.4000E-01

8.0570E-01

7.2110E-01

8.0431E-01

O2

1.2000E-01

1.7256E-01

2.6416E-03

3.3656E-03

H2

2.4000E-01

2.1743E-02

9.8325E-03

7.8923E-04

0.0000E+00

0.0000E+00

8.2563E-04

3.3136E-05

H2 O

0.0000E+00

0.0000E+00

2.5840E-01

1.8535E-01

OH

0.0000E+00

0.0000E+00

4.4666E-03

3.0247E-03

0.0000E+00

0.0000E+00

7.3070E-08

4.0751E-08

N2 O

0.0000E+00

0.0000E+00

3.2174E-07

5.6382E-07

NH3

0.0000E+00

0.0000E+00

6.7512E-08

4.5779E-08

NH2

0.0000E+00

0.0000E+00

1.8563E-08

1.1843E-08

NH

0.0000E+00

0.0000E+00

2.8195E-08

1.6855E-08

0.0000E+00

0.0000E+00

2.4264E-04

1.5457E-04

NO

0.0000E+00

0.0000E+00

2.4847E-03

2.9685E-03

NO2

0.0000E+00

0.0000E+00

6.2644E-07

1.1475E-06

H2O(L)

0.0000E+00

0.0000E+00

9.1684E-19

6.5765E-19

4. Results and discussions

4.1. Type of pressure-time curves
A typical pressure rise history in the vessel for a gas composition in a non-flammable region is shown in Fig. 1(a). In
this case a small flame is possible after ignition. This flame propagates upward but does not last very long. The pressure in
the vessel increases after ignition and has a maximum explosion pressure. The pressure after the maximum point decreases
because of the heat transfer from the gas mixture to the wall of the 20 L sphere. If the flame of the gas mixture is
extinguished during upward propagation, the production rate of burned gas is decreased and hence the pressure rise rate in
the vessel is decreased. For self-extinguished conditions, the pressure-time curve from the ignition point to the maximum
explosion pressure has a convex curve, as shown in Fig. 1(a). This case is not considered flammable since the pressure
increase is less than 7% of the initial pressure, as per ASTM E 918-83 (2011) [15].
Consider the case where the concentration is within the downward flammable concentration range. If the burning
velocity of the gas mixture is lower than the bulk velocity of the burned gas rising up by buoyancy, the pressure-time curve
has three sections. First, the pressure rise rate increases as the flame travels upward from the ignition point to the top of the
spherical explosion vessel. Second, as the flame travels from the top to the center of the vessel, the pressure-time curve also
has a concave curve due to the increasing area of the flame front. During downward propagation the shape of the flame front
seems like the cross-section area of the spherical vessel. Finally, as the flame travels from the center to the bottom of the
vessel, the surface area of the flame front decreases and the pressure-time curve is convex as shown in Fig. 1(b).

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15.6

40

15.4

35

15.2

30

Pressure(psia)

Pressure(psia)

Gang Tao and Daniel A. Crowl / Procedia Engineering 62 (2013) 786 790

15.0

20

14.8

14.6

25

15

500

1000

1500

500

Time(msec)

(a) Not ignited

1500

(b) Pessure time curve with complex behavior

70

80

60

70

60

Pressure(psia)

50

Pressure(psia)

1000

Time(msec)

40

30

50

40

30

20

10

20

50

100

150

200

250

300

350

10

400

20

40

60

80

Time(msec)

100

120

140

160

180

Time(msec)

(c) Classical pressure time curve

(d) Combustion with noise at high pressure

Fig. 1. Typical pressure rise history for mixtures of hydrogen at 64% N2.

Fig. 1(c) shows a classical pressure time recording from our apparatus. Fig. 1(d) shows the instability that can result in
the combustion pressure due to acoustic noise. The noise in this figure makes the determination of the maximum pressure
more difficult.
4.2. Comparison of equilibrium data and experimental data
Pressure of Hydrogen at 64%N2
800

800
Equilibrium Line Fit

700

700

Equilibrium Calculated Points

Pressure(kPa)

Experimental Data
600

600

500

500

400

400

300

300

200

200

100

100

0
0

10

15

20

25

O2 Percentage

Fig. 2. Pressure of hydrogen at 64%.

30

35

40

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Gang Tao and Daniel A. Crowl / Procedia Engineering 62 (2013) 786 790

The equilibrium curve is obtained by using the on-line chemical equilibrium calculator [14]. The experimental data and
the equilibrium calculated points are also shown in Fig. 2. The equilibrium curve shows that even at very low oxygen
concentrations there is still an equilibrium pressure much higher than the experimental pressure. At the right part of the
equilibrium curve at very low hydrogen concentrations there is also an equilibrium pressure near atmosphere pressure.
The experimental data begins at the lower flammable limit and ends at the upper flammable limit. The shape of the
experimental data looks more abrupt than the equilibrium curve. There is an obvious difference between the experimental
data and the equilibrium calculated points at both low pressure areas. This difference decreases gradually when the pressure
is more than 448 kPa. Above 448 kPa the shape of experimental data is similar to the equilibrium curve. The difference
between the experimental and equilibrium pressure is less than 3% at the peak pressure.
5. Conclusions
1) Several types of pressure time curves are observed, depending upon whether the flame is growing or extinguishing, and
whether the flame is propagating upward or downward.
2) The Pmax from experimental data is close to the equilibrium data at pressures of more than 448 kPa.
3) We have compared lots of different data sets at other concentrations and found the same behavior. Thus, the
equilibrium calculation is a very useful tool for predicting maximum combustion pressures near the stoichiometric point.
Acknowledgements
Financial support for this work was provided by Jiangsu Government scholarships and Michigan Technological
University.
References
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Process Safety, New York.
[2] NFPA 68. Standard on Explosion Protection by Deflagration, National Fire Protection Association, Quincy, MA, 2007.
[3] Crowl, D. A., 1992. Calculating the Energy of Explosion Using Thermodynamic Availability, Journal of Loss Prevention in the Process Industries 5, p.
109.
[4] Melham, G. A., 1997. A Detailed Method for Estimating Mixture Flammability Limits Using Chemical Equilibrium, Process Safety Progress 16, p.
203.
[5] Fan, Y., Crowl, D. A., 2000. Predicting the Maximum Gas Deflagration Pressure over the Entire Flammable Range, Journal of Loss Prevention in the
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