AdvancedThermodynamicsSemester22015LectureNotes

CHAPTER 5
IDEAL REACTORS FOR COMBUSTION KINETICS
In the previous adiabatic flame temperature calculations, we dealt only with the initial and final states
of the system. The process connecting the initial and final states was unknown. In this chapter, we
couple the knowledge of chemical kinetics with fundamental conservation equations, e.g. mass and
energy conservation, to solve various idealized thermodynamic systems. This coupling allows us to
describe the detailed evolution of the system from it initial reactant state to its final product state. In
other words, we will be able to calculate the system temperature and species concentrations as
functions of time as the system proceeds from reactants to products, i.e. we will be able to solve

d[ X i ]
dT
, and
for i = 1,2, , N
dt
dt
Once these are solved, we can then obtain enthalpy, internal energy, pressure, volume, etc as
functions of time.
Four reactors are studied in this chapter, including constant-pressure closed reactor, constant-volume
closed reactor, well-stirred flow reactor, and plug-flow reactor. The first three reactors ignore mass
diffusion by assuming perfectly-mixed, homogeneous reaction, and the plug-flow reactor assumes
perfect mixedness in the radial direction and no diffusion along the flow (axial) direction. We will
develop mathematical description for each of these reactors, but will not attempt to solve them.
Computer programs will do the job for us.
The assumptions of ignoring mass diffusion and flow dynamics make these reactors ideal for studying
chemical kinetics. A complete set of conservation equations will be presented in Chap. 6 to take into
account all aspects of a combustion problem.

1.

Constant Pressure Closed Reactor

For a perfectly-mixed closed system at constant pressure, we want to solve the temperature (or
enthalpy) and species concentrations as functions of time, i.e.,

d[ X i ]
dT
and
.
dt
dt

Write the energy conservation (First Law of Thermodynamics) in the rate form

du
Q W m
dt
Differentiating h u Pv with respect to time gives
dP
du dh
dv
(v
0 for constant pressure)

P
dt
dt dt
dt
Assume only boundary work Pdv/dt is done, so

W
dv
P
m
dt
Then

Q dh

m dt

eq. 5-1

AdvancedThermodynamicsSemester22015LectureNotes
For a chemical reacting system including multiple species
N

n h
i 1

i i

Differentiating this equation with respect to time

dn
dh
dh 1
hi i ni i
dt m i
dt
dt
i

eq. 5-2

For ideal gases, we can write

dhi dhi dT
dT

cp ,i
dt dT dt
dt
where

cp ,i is molar-based constant-pressure specific heat of ith species. So we express dhi / dt in the

form of dT / dt which is directly measurable.

Also dni / dt is related to the net production rate of ith species, i , by the following definition

dni
V i
dt
where i can be calculated from the equations in Chap. 3 regarding the net production rate of
multiple-step mechanisms, as repeated below.
L

i (ij" ij' )q j

for ith species.

j 1

ij'

where

q j k fj [ X i ]
i 1

Substituting the

ij"

krj [ X i ]

, the rate-of-progress variable for jth reaction.

i 1

dhi / dt and dni / dt in eq. 5-2, and then into eq. 5-1, we can obtain the rate of

temperature change for this system.

dT

dt

(Q / V ) hi i
i

([ X ]c
i

P ,i

where the enthalpy of ith species can be obtained via

T

hi hfo,i cP ,i dT
Tref

For the rate of species concentration change, we can write

d[ X i ] d (ni / V ) 1 dni
1 dV

ni 2
dt
dt
V dt
V dt
or

d[ X i ]
1 dV
i [ X i ]
dt
V dt
where the first term on the RHS is the chemical production term and the second term accounts for the
changing volume (due to constant pressure).
The ideal gas law can be used to eliminate the dV/dt term. Differentiating the following with respect to
time,

AdvancedThermodynamicsSemester22015LectureNotes

PV ni RuT
i

and rearranging for the case of constant pressure, yields

1 dV
1

V dt ni

dni

dt

1 dT
T dt

Substitute this term into the above

d[ X i ]
dni
equation and use the relation
V i , we obtain
dt
dt

d[ X i ]
1 dT

i
i [ X i ]

[ X ] T dt
dt
i
i

With the knowledge of initial temperature and species concentrations, these equations can be solved
via integration routines which are capable of handling stiff equations (referring to a set of equations in
which some variables change very rapidly, while others change very slowly). This can be done by
computer software such as CHEMKIN.

2.

Constant Volume Closed Reactor

Similar to the constant-pressure case, from the First Law, the energy conservation for constantvolume reacting system can be written as

Q du

m dt
Internal energy here is essentially the same role as enthalpy in the constant-pressure analysis, we
then have

dT

dt

(Q / V ) ui i
i

([ X i ]cv ,i )
i

For ideal gases, cV cP Ru , and replacing ui

hi Pv hi RuT , we can rewrite the above

equations in terms of enthalpy and constant-pressure specific heats.

dT

dt

(Q / V ) RuT i (hi i )
i

[ X ](c
i

P ,i

Ru )

For species concentrations as a function of temperature, it is simple due to no change in volume,

d[ X i ] 1 dni

i
dt
V dt
With the knowledge of initial temperature and species concentrations, these equations can be solved
via integration routines capable of handling stiff equations, such as CHEMKIN.

3.

Well Stirred Flow Reactor

The well-stirred, or perfectly-stirred, reactor is an ideal reactor in which perfect mixing is achieved
inside the control volume, as shown in the figure below. Experimental reactors employing highvelocity inlet jets approach this ideal condition and have been used to study many aspects of
combustion, such as reaction kinetic parameters.

AdvancedThermodynamicsSemester22015LectureNotes
With the control volume, we consider mass conservation or continuity equation

dmcv
in m
out
m
dt
For each species in the control volume, we have the mass conservation equation

dmi ,CV
i"'V m
i ,in m
i ,out
m
dt
i"' is the generation term for ith species in [kg/m3/s], resulting from chemical reactions. A
where m
positive generation rate indicates formation of a species and is called a source, and a negative
generation rate indicates destruction of a species and is called a sink.
Control volume

Q CV

Yi,in
hi,in
Yi
T
P
V

Control
surface

Yi,out
hi,out
Schematic of a well-stirred reactor

i"' , in the unit of kg/m3/s, is related to the net production

The mass generation term of a species, m
rate, i , as follows,

i"' i MWi
m
dmi ,CV
0 , the mass conservation for ith species becomes
dt

for i = 1,2,,N species

eq. 5-3
i MWV
i m(Yi ,in Yi ,out ) 0

For steady-state condition,

i
where m

i because the homogeneous mixture.

mY

Furthermore, since the composition within the reactor is the same everywhere, the composition at the
outlet of the control volume must be the same as the interior. With this knowledge, the species
production rates can be written as

i f ([ X i ]CV ,T ) f ([ X i ]out ,T )
And the mass fraction and molar concentration are related by

Yi

X i MWi
[ X ]MWi
N i
MWmix
[ X j ]MWj
j 1

Write the eq. 5-3 for each species will provide N equations and N+1 unknowns (n species
, Yi,in, and V are known. An energy
concentrations, [Xi] or Yi, plus temperature), assuming that m
conservation equation provides the additional equation needed for closure.
The energy equation for an open system (control volume) can be written as,

(hout hin )
Q cv W cv m

AdvancedThermodynamicsSemester22015LectureNotes
For a steady-state, steady-flow, well-stirred reactor, no work is done by the control volume, therefore

(hout hin )
Q cv m
which can be written in terms of individual species,
N
N

Yi ,out hi (T ) Yi ,in hi (Tin )

Q m
i 1
i 1

where
T

hi (T ) h0f ,i cp ,i dT
Tref

Solving for the temperature, T, and species mass fractions, Yi,out, is quite similar to our computation of
equilibrium flame temperature in Chap. 2; however, now the product composition is constrained by
chemical kinetics, rather than by chemical equilibrium.
Well-stirred reactors are often characterized by a mean residence time for the gases in the reactor:

tR V / m
where the mixture density is calculated from the ideal gas law

PMWmix / RuT
And the molecular weight of the mixture can be readily calculated from a knowledge of the mixture
composition, i.e. MWmix [ X i ]out MWi . Note that for steady-state, steady-flow, well-stirred reactor,
MWmix and are constant so that a characteristic residence time can be defined for the gases.
Because a well-stirred reactor is assumed to operate at steady state, there is no time dependence in
the mathematical model. The equations describing the reactor are a set of coupled non-linear
algebraic equations, rather than a system of ordinary differential equations as for the previous two
examples. The i term here depends only on Yi (or [Xi]) and temperature, not on time.

4.

Plug Flow Reactor

A plug-flow reactor represents an ideal reactor that has the following attributes:
1. Steady state and steady flow.
2. No mixing in the axial direction. This implies that molecular and/or turbulent mass diffusion is
negligible in the flow direction.
3. Uniform properties in the direction perpendicular to the flow, i.e. one dimensional flow with single
velocity, temperature and composition.
4. Ideal gas behavior and ideal frictionless flow.
With reference to the fluxes and control volumes illustrated in the figure below, we can derive the
following conservation relationship along the flow (x-) direction.

Mass conservation

d ( x A)
0
dx
where x is the velocity in x-direction, A is the cross-section area of the flow reactor which can be a
variable, A(x), to represent practical devices such as a nozzle or a diffuser.
Apply the chain rule to expand the term in the parenthesis, and divide both sides with
obtain

1 d 1 d x 1 dA

0
dx x dx A dx

x A , we

AdvancedThermodynamicsSemester22015LectureNotes

x
Flow

CV
x

(PA)x
( x A )x

(PA)x x

( x A)x x

(2x A)x
Mass

( x2 A) x x
x-Momentum

Q "x

2x

m
(
h
)

2 x x

x2

m
(
h
)

2 x

i"' Ax
m

i )x
(mY

Energy

i ) x x
(mY
Species

Schematic of a plug-flow reactor, and mass, x-momentum, energy, and species conservations

Momentum conservation in x-direction

( x )x x m
( x )x 0
(PA)x x (PA)x m
/ A x we obtain
Divide both sides by Ax, let x 0, and with m

dP
d
x x 0
dx
dx
Energy conservation
(h
[m

x2

(h
)]x x [m

x2

)]x Q "x

2
2
"

where Q is the heat flux, in the unit of W/m2, which can vary along x-direction, and P is the local
perimeter of the reactor.

x , and let x 0, we obtain

Divide both sides by m
d (h x2 / 2) Q "

dx
m

or

d x Q "
dh
x

dx
dx
m

AdvancedThermodynamicsSemester22015LectureNotes
For ideal gas mixtures, the following relation is valid

h h(T ,Yi ) hi (T )Yi

i

Differentiate h with respect to dx and apply the chain rule

dh

dx

d hY
i i
i

dx

dY
dh
Yi i hi i
dx
dx
i

eq. 5-4

where

dhi dhi dT
dT

c p. i
dx dT dx
dx
So eq. 5-4 can be rewritten as

dY
dh
dT
cp
hi i
dx
dx
dx
i
where cp

Y is the mass-based cp of the mixture.

P ,i i

And the energy conservation equation now becomes

hi dYi x d x Q "
dT

0
P
dx
cP dx mc
i cP dx
Species conservation

i )x x (mY
i )x m
i"' Ax
(mY

eq. 5-5

i"' is the mass generation rate for ith species, in the unit of kg/m3/s.
where m
x ( A x )x , and let x 0,
i i MWi into eq. 5-5 and divide the both sides by m
Substitute m
"'

we obtain

dYi i MWi

0
x
dx
Note that there are N such equations for the N species.
The above conservation equations (enclosed in boxes) for a plug flow reactor are in a form of linear
combination of d/dx, dx/dx, dP/dx, dT/dx, dYi/dx (i = 1,2,,N). The number of equations (and
derivatives) can be reduced by eliminating some of the derivatives by substitution. For example we
can use d/dx, dT/dx, and dYi/dx, to describe the plug-flow reactor as follows,

Ru
1
d cP MWmix

dx

N
2 2 1 dA

Ru
MWmix

MWi i hi
cPT

x
MWi
A dx x cP MWmix i 1

P 1 x x2
cPT

dT x2 d x2 1 dA
1

dx cP dx cP A dx x cP
dYi i MWi

x
dx

hi i MWi
i 1

Q "
x AcP

AdvancedThermodynamicsSemester22015LectureNotes
In obtaining these equations, the ideal gas law has been differentiated with respect to x in order to
relate dP/dx with d/dx, dT/dx, and dYi/dx.
In summary we see that the mathematical description of the plug-flow reactor is similar to the
constant-pressure and constant-volume reactor models in that all three result in a coupled set of
ordinary differential equations. For the plug-flow reactor, however, the variables are expressed as
functions of a spatial coordinate rather than time.