MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 1
Text: Ch.6
Technical Objectives:

Derive the governing equations for constant pressure, constant volume, well-stirred and plug
flow reactors.

Use Chemkin to solve each of the above problems with detailed kinetic mechanisms.
1. Motivation
Now that we have finished learning about detailed chemical kinetic mechanisms for some
practical fuel/oxidizer systems, we can actually begin to solve some chemically reacting
systems. We will begin by looking at homogenous (i.e. 0-dimensional) systems.
The major assumption in these models is that the diffusion of species is ignored. This
assumption is acceptable if the system is well-stirred (i.e. infinite mixing rate of all species as
they are produced) or if the chemical reaction occurs very quickly and simultaneously over a
large homogenous volume.
These systems are of interest in studying combustion because it is possible to perform
numerical simulations of these systems even with very large detailed chemical kinetic
mechanisms (100’s of species, 1000’s of reactions). Thus, they are used to validate and test
chemical kinetic mechanisms without having to worry about the difficult fluid mechanics and
mass transport present in real flames.
1.1 Examples of 0-Dimensional Chemically Reacting Systems are as follows:
Constant Pressure, Fixed Mass Reactor
Constant Volume, Fixed Mass Reactor
Well Stirred (or Longwell) Reactor
Plug Flow Reactor
MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 2
Text: Ch.6
2. Constant Volume, Fixed Mass Reactor
Consider the following closed system, filled initially with a reacting gas mixture at a specified
temperature and pressure. The volume is fixed:
Lets assume that we have developed a detailed chemical kinetic mechanism for this
fuel/oxidizer system that considers N species and L reactions. (Recall the H2 mechanism
considered 8 approximately species and 20 reactions). The unknowns in this problem are as
follows:
Thus, for N species, there are N + 2 unknowns that needs to be solved as a function of time.
Therefore we need to solve N+2 equations. The N+2 equations are:
Net Production Rate for Each Species
The first N equations are the differential equations that are developed by applying the Law of
Mass Action for each the N species for all L reactions:
(4.28a)
(4.28b)
Where
 i is the net production rate of the ith species in the mechanism in mol/cm3-s,

[Ci] the concentration of the ijth species in mol/cm3
MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 3
Text: Ch.6
The (N+1)th equation can be derived by applying the First Law of Thermodynamics for a
transient, fixed mass system:
(6.18)
The total internal energy, U, is the equal to:
(6.18a)
Substituting and taking the derivative of the internal energy term in (6.18) yields;
(6.18b)
Recalling that du = cvdT and u = h – Pv, and substituting, yields:
(6.20)
Equations (4.28) and (6.20) can be used to solve for the concentration of each of the N species
vs. time and the temperature vs. time.
Since the volume is constant, any change in temperature will be accompanied by a change in
pressure, which can be calculated from the ideal gas equation:
(6.21)
MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 4
Text: Ch.6
Taking the derivative with respect to time yields the following:
(6.24)
Differential equations (4.28), (6.21) and (6.24) can be used to solve a constant volume,
homogenous, transient system, with detailed chemistry, such as the hydrogen-oxygen system
from your previous homework problem set. In fact, these equations are virtually identical to the
differential equations solved by Chemkin for this same type of system.
3. Plug Flow Reactor
A plug flow reactor is a system that can be used to study chemical kinetics, since it enables the
experimentalist to sample at various distances along the reactor, thereby allowing the
measurement of species as a function of distance in a chemical reaction. By using dilute
mixtures of fuel and oxidizer, it is possible to slow down the chemical reaction, which stretches
out the chemical reaction zone over a distance of approximately 1 meter (vs. approx. 1 mm in a
flame).
Electric Resistance
Heater
Evaporator
Fuel Inlet
Wall Heaters
Sample Probe
Slide T able
Oxidizer Injector
Optical Access Ports
The schematic diagram above shows the Princeton Variable Pressure Flow Reactor. This
system can be solved theoretically by making the following assumptions:
1.
2.
3.
4.
5.
MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 5
Text: Ch.6
Note that the only derivatives in this case are d/dx. If one were to “ride along with the plug flow”
it would appear that all of the species were varying with respect to time (d/dt), so this problem is
really very similar to the homogeneous problem discussed in the previous section.
Consider the flow tube in the flow reactor above:
In this case, the unknowns are (x), v(x), T(x), P(x) and Yi(x) for i = 1, N. These N+4 equations
can be solved using the conservation of mass, momentum, energy, equation of state and the N
species equations.
Assuming that heat transfer to the wall Q”(x) is zero and the cross sectional area A(x) = A =
constant, the following are the governing equations:
Equation of State
(6.47)
In differential form:
(6.48)
Conservation of Mass
(6.39)
Which can be rewritten as:
(6.43)
Conservation of x-momentum
(6.40)
Conservation of Energy
(6.41)
MECH 558
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Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 6
Text: Ch.6
Which can be rewritten as:
(6.44)
But, dh/dx can be evaluated based on the mass fractions:
(6.46)
Resulting in the following energy equation:
(6.44a)
Species Equations
The net production rate of the ith species can be converted from d/dt to d/dx and the
concentrations can be converted to mass fractions as follows:
(6.42)
Equations (6.48), (6.43), (6.40), (6.41), (6.44a) and (6.42) can be combined into the following
three differential equations in x, which can now be solved:
(6.51)
(6.52)
(6.53)
MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 7
Text: Ch.6
5. Internal Combustion Engine Simulation
It is also possible to simulate the closed compression-ignition process of an internal combustion
engine as a 0-dimensional, transient system, in which volume varies with time based on the
geometry of the piston-cylinder assembly. These simulations are useful for studying engine
knock in IC engines and also for studying a new class of engines called Homogeneous Charge
Compression Ignition (HCCI) engines.
Consider the following engine cylinder:
Where D is the cylinder diameter, Lc is the length of the connecting rod, LA the crank arm radius,
Vc the clearance volume and Vs the swept volume.
The maximum swept volume is given by:
(n7.1)
The engine compression ratio is defined as follows:
(n7.2)
Given these geometrical parameters of an engine-cylinder it is possible to derive the following
relationship for volume vs. time within the engine combustion chamber:
(n7.3)
Where R is the ratio of the connecting rod to crank arm radius (Lc/LA) and C is the compression
ratio.
The time rate of change of volume is given by the following:
MECH 558
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Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 8
Text: Ch.6
(n7.4)
Where  is the angular velocity of the crank arm (d/dt).
Equation (n7.4) can be solved along with the equation of state, species equations (4.28a) and
conservation of energy (with variable volume and pressure).
It is also possible to model the heat transfer to the walls of the cylinder using the following
model:
(n7.5)
Where Twall is the wall temperature and h the wall heat transfer coefficient. The wall heat
transfer coefficient can be approximated using the following Nusselt number correlation:
(n7.6)
Where Reynolds number is approximated as follows:
(n7.7)
Where Sp is the mean piston speed.
MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 9
Text: Ch.6
HW Assignment
1. Thermal DeNOx. The engine-out conditions of the untreated exhaust gas of a heavy duty,
on-road diesel school bus engine are measured to be the following:
P = 1.0 atm
T = 900
K
v = 560 cm/s
Exhaust Pipe Diameter: 10 cm
Exhaust Pipe Length: 1000 cm
Mole Fractions
CO
0.01368
CO2
0.110289
H2
0.003024
H2O
0.134434
NO
0.001000 (1000 ppm)
N2
0.727048
O
OH
H
O2
0.000330
0.003545
0.000461
0.006189
One method of reducing NOx (called the Thermal DeNOx process) is to inject small quantities of
ammonia (NH3) into an exhaust stream. Use the CHEMKIN plug flow reactor model to
determine the effect of NH3 injection in the exhaust stream.
a) For exhaust inlet temperature of 900 K plot mole fraction of NO and NH3 vs. distance
in the exhaust pipe for injected NH3 mole fractions of 0, 250, 500, 750, 1000 and 1250
ppm.
b) For inlet temperature of 900 K, plot of % reduction in exhaust outlet NO vs. mole
fraction of injected NH3. Comment on results.
c) For an injected NH3 mole fraction of 1000 ppm, plot mole fraction of NO and NH3 vs.
distance in the exhaust pipe for exhaust inlet temperature of 700, 800, 900, 1000, 1100
and 1200 K.
d) For an injected NH3 mole fraction of 1000 ppm, plot of % reduction in exhaust outlet
NO vs. exhaust inlet temperature. Comment on results.
2. Methane Number. Methane Number (MN) is defined as the percentage by volume of
methane blended with hydrogen that exactly matches the knock intensity of an unknown gas
mixture under specified operating conditions in a variable compression ratio knock testing
engine. For example, a gaseous fuel/air mixture with a methane number of 80 will knock at the
same compression ratio as a mixture of 80% CH4 and 20% H2. For the range beyond 100 MN,
methane-carbon dioxide mixtures are used as reference mixtures. For example, a gaseous
fuel/air mixture with a methane number of 120 will knock at the same compression ratio as a
mixture of 80% CH4 and 20% CO2.
The following methane number data were acquired using a variable compression ratio engine at
the Engines and Energy Conversion Laboratory at CSU.
Gas
Mixture
%CH4
%C2H6
%C3H8
1
2
3
69
93
49
20
4.3
19
11
2.7
32
Measured MN
(Malenshek,
2008)
50.8
76.2
42.2
MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 10
Text: Ch.6
Use the CHEMKIN 4.1 IC Engine Model to calculate a theoretical Methane Number for each of
these gas mixtures using two different chemical kinetic mechanisms: GRIMECH 3.0 and the
Marinov/Pitz Mechanism. Use the following procedure:
i.
For each of the gas mixtures above, determine the appropriate stoichiometric fuel/air
mixture required for complete combustion.
ii. Run the CHEMKIN IC engine model with this mixture and determine the compression
ratio at which the mixture just barely autoignites.
iii. Using the same compression ratio as part ii, run the CHEMKIN IC engine model with
stoichiometric mixtures of CH4 and H2 and vary the percentage of H2 in the mixture
so that the mixture just barely autoignites at the same compression ratio as part ii.
iv. The theoretical Methane Number will be equal to 100 - %H2 in part iii.
Use the following parameters to model the EECL CFR engine:
Engine Crank Revolutions = 1
Engine Compression Ratio: 4 to 18
Displacement Volume= 611 cm3
R = 3.714286
 = 900 RPM
o = -180
To = 450 K, Po = 1 atm
t = 1e-5
tprint = 0.001666
tsave = 0.000166
ATOL = 1e-20
RTOL = 0.0001
heat transfer: adiabatic