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, rapid compression
machine, single-zone HCCI, well-stirred and plug flow reactors.

Use CHEMKIN to solve each of the above problems with detailed chemical 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. Variable Volume, Fixed Mass Reactor: Rapid Compression Machine
A rapid compression machine (RCM) is an instrument designed to simulate the compression
stroke of a single engine cycle thereby allowing auto-ignition phenomena to be studied in a
much more controllable environment than would be possible in an actual engine. The device
functions by rapidly compressing a homogeneous premixed volume of fuel and air. The rapid
compression is accompanied by rapid heating of the mixture and the process results in an
elevated final temperature and pressure with negligible heat loss. Since only the test gas is
heated and not the vessel walls, wall reactions are avoided and the reactions that occur inside
the cylinder are nearly homogeneous. The figure below shows the Rapid Compression
Machine currently installed at EECL along modeling results of temperature, pressure and NO
mole fraction vs. time for the homogeneous compression ignition of methyl butanoate/O 2/N2 at a
compression ratio of 20 and initial temperature of 315 K.
2000
100
Temperature (K)
Pressure (PSIA)
80
1500
60
1000
40
500
0
0.000
20
NO (ppm)
0.005
0.010
0.015
0
0.020
time (s)
The figure below predicted temperature vs. time history for n-heptane/iso-octane mixtures
(PRF0 to PRF100) in a RCM in HCCI mode at  = 0.4 and compression ratio of 16. As the
figure shows, the fuel-air mixtures are initially compressed adiabatically over a period of 5 ms.
After a subsequent induction period, which depends on the low temperature reactivity of the
mixture, hot ignition occurs and the temperature rapidly rises. During the induction period, the
moderately reactive mixtures (PRF 75 and 90) exhibit low temperature heat release, as signified
by the temperature rise during this period.
NO (ppm)
Temperature (K) and Pressure (psia)
2500
MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 5
Text: Ch.6
To simulate an RCM using CHEKMIN, it is possible to use the same “fixed volume” reactor
model described above, wherein a given Volume vs. time curve is supplied as an input to
CHEMKIN as shown below:
4. 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
MECH 558
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Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 6
Text: Ch.6
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.
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)
MECH 558
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Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 7
Text: Ch.6
Conservation of x-momentum
(6.40)
Conservation of Energy
(6.41)
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)
MECH 558
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Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 8
Text: Ch.6
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)
5. Single Zone, Homogeneous Charge Compression Ignition 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
autoignition 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)
MECH 558
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Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 9
Text: Ch.6
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:
(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) as follows:
(n7.5)
It is also possible to model the heat transfer to the walls of the cylinder using the following
model:
(n7.6)
Where Twall is the wall temperature and h the wall heat transfer coefficient.
Combining Equations (n7.5) and (n7.6) results in the following energy equation:
(n7.5a)
MECH 558
notes08
Combustion
0-Dimensional Chemical Reacting Systems
Class Notes - Page: 10
Text: Ch.6
The wall heat transfer coefficient can be approximated using the following Nusselt number
correlation:
(n7.7)
Where Reynolds number is approximated as follows:
(n7.8)
Where Sp is the mean piston speed.