ISSN 0018-151X, High Temperature, 2017, Vol. 55, No. 5, pp. 777–781. © Pleiades Publishing, Ltd., 2017.

Original Russian Text © V.Yu. Gidaspov, N.S. Severina, 2017, published in Teplofizika Vysokikh Temperatur, 2017, Vol. 55, No. 5, pp. 795–799.

HEAT AND MASS TRANSFER

AND PHYSICAL GASDYNAMICS

Numerical Simulation of the Detonation of a Propane-Air Mixture,

Taking Irreversible Chemical Reactions into Account
V. Yu. Gidaspov and N. S. Severina*
Moscow Aviation Institute, Russia
*e-mail: severina@mai.ru
Received June 18, 2016

Abstract⎯This work considers issues related to the numeric simulation of high-speed combustion and deto-
nation of mixtures of carbonic fuel with air. Model problems are used to study the applicability of global
kinetic mechanisms to describe the detonation of a propane-air fuel mixture. Problems of finding equilibrium
adiabatic lines, determining Chapman-Jouguet detonation parameters, and the simulation of the structure of
a stationary detonation wave were considered. Applying global kinetic mechanisms with irreversible chemical
reactions may lead to overestimation of the detonation velocity and temperature of combustion products.

DOI: 10.1134/S0018151X17050078

INTRODUCTION where ρ, u, p, h are density, velocity, pressure, and

There are numerous kinetic mechanisms in the lit- enthalpy, and D is the velocity of detonation wave,
erature related to simulation of high-speed combus- with index “0” marking the initial state of fuel mix-
tion and detonation of carbonic fuel in oxygen and air, ture, elemental composition conservation law
including one to several hundreds of chemical reac- N N
tions [1, 2]. The amount of used gas-phase chemical
reactions is connected to research targets and an advan- ∑ Ai γ i =
k
∑A γ k
i i0 = γ k , k = 1,2,... N e
0
(2)
i =1 i =1
tageous range of initial conditions. Detailed kinetic
mechanisms are often applied to construct global mech- and condition of chemical equilibrium
anisms of chemical transformations, which include less Ne
than ten chemical reactions describing the interesting
properties of a reacting system and allow numeric simu- μ i (ρ,T , γ) = ∑A k
i z k, i = 1,2,... N . (3)
lation of multidimensional flows at reasonable times [1, k =1
3]. Applied kinetic mechanisms must describe the pecu- Here, N e is the number of elements, N is the
liarities of ignition and combustion of fuel mixtures in the amount of components under consideration, γ i , μ i are
conditions under consideration, and exactly ignition mol-mass concentration and chemical potential of ith
delay time, the time for which a system passes to a state
close to equilibrium, parameters characterizing the equi- component, γ 0k are mol-mass concentrations of ele-
librium state, providing correct simulation of the special ments, known quantities defined by initial composi-
propagation mode of detonation waves—Chapman– tion, Aik is the matrix of composition, z k are unknown
Jouguet detonation. parameters. Correlations (2)–(3) set concentrations as
implicitly given functions of density, temperature, and
MODEL PROBLEMS AND NUMERIC element composition:
COMPUTATION RESULTS
In order to compute equilibrium detonation adia- γ i = γ i (ρ,T , γ 0 ). (4)
batic line of fuel gas mixture and Chapman–Jouguet Equivalent transformations applied to (1) can pro-
detonation parameters, it is necessary to solve a set of vide expressions for the Hugoniot adiabat
nonlinear algebraic equations [4–6]: integral laws of
mass, pulse, and energy conservation h − h0 − 1 (V + V 0 )( p − p0 ) = 0, V = 1 , (5)
ρ(D − u) = ρ 0(D − u0 ), 2 ρ
Michelson line
p + ρ(D − u)2 = p0 + ρ 0(D − u0 )2, (1)
(D − u) 2
(D − u0 )
2 (D − u0 ) 2
h+ = h0 + , p − p0 − (V 0 − V ) = 0, (6)
2 2 V 02

777
778 GIDASPOV, SEVERINA

4500 Simulation of Propane Detonation in Oxygen

15 substances
4000 6 substances Let us consider a mixture of propane (partially
15 substances used as model carbonic fuel [1–3]) and oxygen
6 substances
3500 ( x C 3H 8 + (1 − x)O 2). According to works [1, 3], it is
T, K

3000 suggested to apply a five-stage kinetic mechanism,

which includes six substances (С3H8, O2, CO, CO2,
2500 H2, H2O), in order to describe chemical transforma-
D, m/s

2000 tions in a gas phase. It is known from thermodynamic

1500
1000
0.05 0.15 0.25 0.35 0.45
0 0.10 0.20 0.30 0.40
Concentration C3H8, vol %
Fig. 1. Computed dependences of Chapman-Jouguet det-
onation velocity (two lower curves) and temperature (two
upper curves) on mole fraction of С3Н8; markers—expe-
rimental data [10] (p0 = 101325 Pa, T0= 293.15 K).
as well as connection between velocity and thermody-
namic parameters:
p − p0
(D − u) = V
2 2
. (7)
V0 − V
The Chapman–Jouguet point corresponds to the min-
imal value of detonation velocity D, for which set (4)–(6)
has a solution. The values of the parameters of com-
bustion products in the Chapman–Jouguet point are
the most important characteristics of the explosive
mixture and depend only on initial data, which char-
acterize fuel mixture and the thermodynamic proper-
ties of the combustion products. Models of thermody-
namics and chemical kinetics are integral parts of the
multidimensional modeling methodology [7, 8]. Being
built into model problems, they obtain the parameters
of detonation waves, which must be realized in com-
putation, in the data preparation stage.
Thermodynamic properties of combustion prod-
ucts are described using a mixture of perfect gases with
the Gibbs potential [9] as
⎛ ⎞
N
⎜ ⎟
⎜ 0 pγ i ⎟
G ( p,T , γ) = ∑
γ i ⎜G i (T ) + RT ln N ⎟,
⎜ p0 γ j ⎟
i =1
⎜ ⎟
⎝ j =1 ⎠
correspondingly
computations that a list of substances entering pro-
pane combustion products in considerable concentra-
tions in oxygen is wider (the work uses 15 components:
С3H8, O2, CO, CO2, CH4, C2H2, C2H4, H2, OH, H2O,
0.50 C2H6, C*—soot, C, H, O). Let us study the influence
of the accounted components on Chapman–Jouguet
detonation parameters. Figure 1 shows the results of a
comparison between experimental data [10] and com-
puted values of Chapman–Jouguet detonation veloc-
ity (equation set (2), (3), (5), (6), (8) was solved for 6
and 15 substances) as well as corresponding tempera-
ture dependences. According to [8] existence limits of
detonation of propane in oxygen belong to range x =
0.04–0.38 (stoichiometric correlation x = 1/6). In the
neighborhood of stoichiometry Chapman-Jouguet
detonation velocity computed with a shortened list of
substances is 100–150 m/s (5–7%) higher, and the
increment by temperature is 400–500 K (10–12%),
which may have a significant impact on defining ther-
mal effects. The difference of temperatures is condi-
tioned by the presence H, O, as well as radical OH in
combustion products with considerable concentrations
of atomic components. It is necessary to note that the
solution of the system under consideration exists
beyond concentration limits of detonation and that
solid carbon appears in the composition of combustion
products in considerable concentrations for x > 0.4.
Simulation of Propane Detonation in Air
Let us consider fuel mixture of propane and air
x C 3H 8 + (1 − x) × (0.21O 2 + 0.79N 2 ) in normal con-
ditions. Ignition limits: x = 0.023 – 0.095 [10]. Stoichio-
metric correlation x = 0.04031. In this case shortened and
extended lists of substances are complemented by N2 and
NO, N 2, N , respectively. The Table 1 shows the simula-
tion results of Chapman–Jouguet detonation parameters
for four different correlations of propane-air (x =
(8) 0.02057, 0.04031, 0.04988, 0.09502).
∑ The difference of Chapman–Jouguet detonation
parameters for simulation with shortened and
extended sets of substances is essentially smaller (not
greater than 1.5% by detonation velocity and 3% by

( )
temperature) than for the propane-air mixture. This is
⎛ ⎞ ⎛ ⎞
h = G − T ∂G , V = ⎜ ∂G ⎟ , μ i = ⎜ ∂G ⎟ , connected with the dilution of fuel mixture with nitro-
∂T 
p,γ ∂
⎝ ⎠T , γ
p ⎝ ∂γ i ⎠ p,T gen. Propane-air fuel mixtures can be simulated using
a shortened list of substances of seven components.
p0 = 101325 Pa, R is the universal gas constant, G i 0(T ) Consider the model problem on a nonequilibrium
are the known temperature dependences, borrowed flow in a stationary detonation wave [4–6], which is
from [9] for all substances used in numeric simulation. reduced to a solution of the set of differential-algebraic

HIGH TEMPERATURE Vol. 55 No. 5 2017

 NUMERICAL SIMULATION OF THE DETONATION 779

Table 1. Chapman–Jouguet detonation parameters of propane-air fuel mixture (p0 = 101325 Pa, T0 = 293.15 K).
18 substances 7 substances
1 2 3 4 1 2 3 4
D, m/s 1498 1800 1837 1655 1507 1826 1863 1655
T, K 2049 2822 2828 1886 2072 2906 2912 1887
P, Pa 12.32 18.49 19.12 15.24 12.39 18.84 19.39 15.24
U, m/s 633 806 814 694 633 810 815 694
M, g/mol 28.57 27.67 26.73 21.95 28.57 27.77 26.86 21.95
æ 1.271 1.248 1.251 1.295 1.271 1.246 1.248 1.295
O2, mol/kg 3.4162 0.4180 0.0428 – 3.5291 0.7044 0.0885 –
N2, mol/kg 26.429 25.578 25.300 23.596 26.531 25.731 25.349 23.596
CO, mol/kg 0.0038 1.0831 2.6986 8.8575 0.0044 1.1345 2.6544 8.8578
CO2, mol/kg 2.1120 3.0208 2.3551 0.5510 2.1113 2.9695 2.3993 0.5507
H2, mol/kg 0.0011 0.2549 0.9174 9.9574 0.0012 0.2743 0.8918 9.9592
OH, mol/kg 0.0356 0.3491 0.2126 0.0001 – – – –
H2O, mol/kg 2.8021 5.0112 5.6541 2.5852 2.8198 5.1976 5.8464 2.5855
NO, mol/kg 0.2042 0.3051 0.0978 – – – – –
H, mol/kg 0.0001 0.0625 0.1209 0.0039 – – – –
O, mol/kg 0.0030 0.0535 0.0175 – – – – –

equations composed of nonlinear algebraic equation C 3H 8 + 3.5O 2 → 3CO + 4H 2O,

set (1)–(3), (8) and differential equations of chemical
kinetics CO + H 2O → CO 2 + H 2,
CO 2 + H 2 → CO + H 2O, (12)
d γ i W i (ρ,T , γ)
= , i = 1,..., N , 2H 2 + O 2 → 2H 2O,
d ξ ρ 0(D − u0 ) (9)
γ i (0) = γ i 0, i = 1,2,... N . 2CO + O 2 → 2CO 2.
Here, ξ = Dt − X is the distance between the shock In [3], it is recommended to use dependences of
wave and the observation point. The minimal velocity chemical reaction rates on temperature pressure and
of detonation wave D, for which the given set has a concentration of involved components, which provide
solution, corresponds to the Chapman–Jouguet state. agreement of numeric simulation results with experi-
It is necessary to note that conservation laws of elemen- mental data by ignition delay of fuel mixture in a wide
tary composition (2) are the first integrals of set (9). If range of initial parameters. The use of mechanisms
mechanism of chemical reactions is denoted as with irreversible reactions (or reversible ones, whose
rates are not in agreement with thermodynamics
N  (r ) N
  (r ) model) leads to the fact that the limiting state (station-
∑ ⎯⎯⎯→
ν (i r )M i ←⎯⎯⎯ ∑ν M i , r = 1,… , N R, (10)
W
 (r ) i ary point) for the considered equation set depends on
W
i =1 i =1 constants of velocities and knowingly does not coin-
then cide with the thermodynamic equilibrium state. This
may result in differences between equilibrium values
 (r )  (r )  (r )
NR

∑ (ν )( )
and obtained macroparameters, in particular by
Wi = − νi W −W , i = 1,… , N .(11)
(r )
i Chapman–Jouguet detonation velocity, temperature,
r =1 molecular weight of combustion products, and others.
 Let us consider a modification of the mechanism sug-
Here, ν (i r ) are stoichiometric coefficients, M i are gested in [3], which allows counting all the reactions as
symbols of molecules or atoms of chemical compo-
 reversible. The following dependence of gross-reac-
nents, and W (r ) are rates of the (r)-th chemical reac- tion rate of propane expenditure is presented in [3]:
tion in straight and reverse directions.  
W1 = K 1(T , p)(ργ C3H8 )(ργ O2 ). (13)
In order to describe gas-phase chemical transfor-
mations in propane-air fuel mixture, it is suggested in Volume concentrations of propane and oxygen
[1, 3] to use a simplified mechanism consisting of five enter expression (13) in first power. In order to com-
irreversible chemical reactions: pute rate constants of reverse reactions correctly from

HIGH TEMPERATURE Vol. 55 No. 5 2017

780 GIDASPOV, SEVERINA

(a) (b) (c) (d)

1900 3400 ×106
3000 0.029

Mr, kg/mol
1800 2.1
D, m/s
0.027

T, K
1.9

p, Pa
1700 1 2600
1600 2 1 1.7 1 0.025 1
2
2 2
3 2200 3 1.4 3 0.023 3
1500 4 4 4 4
1800 1.1 0.021
0.03 0.07 0.03 0.07 0.03 0.07 0.03 0.07
0.01 0.05 0.09 0.01 0.05 0.09 0.01 0.05 0.09 0.01 0.05 0.09
Concentration C3H8, vol %

Fig. 2. Distribution of mixture parameters depending on mole fraction of propane for initial pressure p0 = 101325 Pa: 1 – irrevers-
ible chemical reactions; 2 – reversible chemical reactions; 3, 4 – equilibrium computation of 7 and 18 substances, respectively.

(a) 3400 (b) ×105 (c) (d)

1900 3200 2.1
3000 0.029
1800

Mr, kg/mol
1.9
D, m/s

2800 0.027
T, K

1700 2600 1.7

p, Pa
1 2400 1 1 0.025 1
1600 2 2 1.5 2
2
3 2200 3 3 0.023
3
4
1500
4
2000 4 1.3 4
1800 1.1 0.021
0.01 0.05 0.09 0.01 0.05 0.09 0.01 0.05 0.09 0.01 0.05 0.09
0.03 0.07 0.03 0.07 0.03 0.07 0.03 0.07
Concentration C3H8, vol %

Fig. 3. Distribution of mixture parameters depending on mole fraction of propane for initial pressure p0 = 10132.5 Pa (designa-
tions are similar to Fig. 2).

the thermodynamical point of view, the given powers ⎛ b (r ) ⎞  (r ')

= min ⎜ i(r ) ⎟ . At the same time K (T , p) =
(r )
must equal stoichiometric coefficients, 1 and 3.5, a
respectively. After equivalent transformations, gross- i =1,N ⎝ ν i ⎠

reaction can be rewritten as [11] νr ≠0
 (r ) i
K (T , p)/ a (r ) and all the stoichiometric coefficient
C 3H 8 + O 2 ⇔ 6 CO + 8 H 2O + 5 C 3H 8. (14) are positive quantities.
7 7 7 As previously stated numeric solution of differen-
In order to compute ignition delay time correctly, tial-algebraic equation set (1), (8), (9) may provide
it is necessary to use a modified rate constant of stationary points of system corresponding to minimal
  velocity of detonation wave, for which the given sys-
gross-reaction K 1'(T , p) = 7 K 1(T , p). Correspond- tem has a Chapman-Jouguet state solution [4–6].
  2
ingly W1' = K 1'(T , p)(ργ CO ) × (ργ H2O ) (ργ C3H8 ) . Figures 2, 3 present the results of a numeric simu-
67 87 57

The rest of the reactions should be assumed as revers- lation for normal and reduced pressures. The model
ible with direct reaction rates recommended in [3] with reversible chemical reactions provides good
agreement with results of equilibrium computation up
CO + H 2O ⇔ CO 2 + H 2, 2H 2 + O 2 ⇔ 2H 2O, to excess fuel of 1.75. The difference from equilibrium
2CO + O 2 ⇔ 2CO 2, at the same time rate constants of values in this case is connected with the fact that the
reverse reactions are computed by standard rules [9]: number of independent chemical reactions yields a
considerable difference in Chapman-Jouguet detona-

K (r ) = exp ⎡ (ν (r ) − ν (r ) ) ⎛G i (T ) + ln RT ⎞⎤ ,
N 0 tion velocity in the stoichiometry vicinity and the dif-
 (r )
K
⎢
⎢⎣ i =1
i ∑ i ⎜
⎝ RT
⎟⎥
p0 ⎠⎦⎥ (15)
ference in temperature and molecular weight of com-
bustion products.
r = 1,… , N R. Figure 4 shows changes of temperature in overcom-
pressed detonation wave (D = 1900 m/s) for various
For an arbitrary r-th chemical reaction of type (10),
  initial pressures and compositions. It can be seen that
∏
N (r )
occurring at rate W (r ) = K (r )(T , p) (ργ i ) bi , for ignition delays in detonation wave, computed using
i =1
models with irreversible and reversible chemical reac-
∑ b
N
case bi(r ) >0 notation (r )
Mi ⇔ tions, coincide, but the level of temperatures reached
i =1 i
  while passing to equilibrium may yield a difference of
∑
N
i =1
(bi(r ) + a (r )(ν (i r ) − ν (i r ) ))M i is valid, where up to 250 K (Fig. 4b).

HIGH TEMPERATURE Vol. 55 No. 5 2017

 NUMERICAL SIMULATION OF THE DETONATION 781

(a) (b) REFERENCES

3200 3200 1-i2-i1-r
2800 1-i2-i1-r
2-r
2800 3-i3-r 1. Basevich, V.Ya. and Frolov, S.M., Khim. Fiz., 2006,
vol. 25, no. 6, p. 54.
T, K

T, K
2-r
3, 4
2400 3-i3-r 1, 2 2400 3, 4
5, 6
1, 2
2. Titova, N.S., Kuleshov, P.S., and Starik, A.M., Com-
2000 5, 6 2000 bust., Explos. Shock Waves (Engl. Transl.), 2011, vol. 47,
1600 1600 no. 3, p. 249.
1e–006 0.01 1e–006 0.01 3. Ivanov, V.S. and Frolov, S.M., Russ. J. Phys. Chem. B,
0.0001 1 0.0001 1 2011, vol. 5, no. 4, p. 597.
ξ ξ
4. Gidaspov, V.Yu. and Severina, N.S., Nekotorye zadachi
fizicheskoi gazovoi dinamiki (Some Problems of Physical
Fig. 4. Dependence of temperature on distance from shock Gas Dynamics), Moscow: Mosk. Aviats. Inst., 2016.
wave: 1, 3, 5—irreversible chemical reactions; 2, 4, 6—
reversible for various initial pressures: 1, 2—0.01; 3, 4— 5. Gidaspov, V.Yu. and Severina, N.S., Combust., Explos.
0.1; 5, 6—1 MPa; (a)—x = 0.04988, (b)—x = 0.03382. Shock Waves (Engl. Transl.), 2013, vol. 49, no. 4, p. 409.
6. Gidaspov, V.Yu. and Severina, N.S., High Temp., 2015,
vol. 53, no. 4, p. 526.
CONCLUSIONS 7. Kotov, D.V. and Surzhikov, S.T., High Temp., 2012,
Research results show that applying kinetic mech- vol. 50, no. 1, p. 120.
anisms with irreversible chemical reactions for 8. Lenkevich, D.A., Golovastov, S.V., Golub, V.V.,
describing combustion and detonation of propane in Bocharnikov, V.M., and Bivol, G.Yu., High Temp.,
air is appropriate, when time of passing of the system 2014, vol. 52, no. 6, p. 890.
to equilibrium state exceeds time of research interest. 9. Gurvich, L.V., Veits, I.V., Medvedev, V.A., et al., Ter-
Otherwise, in numeric simulation it is necessary to use modinamicheskie svoistva individual’nykh veshchestv:
mechanisms with reversible chemical reactions, Spravochnoe izdanie (Thermodynamic Properties of
Individual Substances: Reference Bork), 4 vols., Mos-
whose rate constants are connected by means of equi- cow: Nauka, 1978.
librium constants.
10. Fundamental Data Obtained from Shock-Tube Experi-
ments, Ferri, A., Ed., Oxford: Pergamon, 1961.
ACKNOWLEDGMENTS 11. Gidaspov, V.Yu., Moskalenko, O.A., and Pirumov, U.G.,
This study was performed in accordance with state Vestn. Mosk. Aviats. Inst., 2014, vol. 21, no. 1, p. 169.
task no. 9.7555.2017/BCh and supported by the Russian
Foundation for Basic Research, project no. 15-01-07964. Translated by K. Gumerov

HIGH TEMPERATURE Vol. 55 No. 5 2017