Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

CHAPTER 6

SIMPLIFIED CONSERVATION EQUATIONS FOR REACTING

FLOWS
Our discussion so far has been focused on chemical equilibrium and reaction kinetics, which are
essential but only two of the many aspects of a practical combustion problem. The objective of this
chapter is to present a more complete description of the physical and chemical processes for
combustion. As will be noted, the discussion will be still limited to simplified cases where the principles
can be demonstrated without heavy involvement of mathematical derivations.

Practical combustion processes are different from the idealized reactors discussed in Chap. 5, mainly
in terms of the flow field and mass transfer. Considering the non-uniformity of flow and concentration
fields requires two major revisions to our previous models.

1. Variables now are not only temporal functions, but also spatial functions. For example, to solve
the molar concentration of the ith species, [Xi], we need to solve four partial differential equations
∂[ X i ] ∂[ X i ] ∂[ X i ] ∂[ X i ]
(PDE) in a Cartesian system, , , , , rather than one ordinary differential
∂t ∂x ∂y ∂z
d[ X i ]
equation (ODE) as discussed in Chap. 5, (for constant-pressure or constant-volume closed
dt
d[ X i ]
reactors), or (for plug-flow reactor).
dx
2. Mass diffusion must be considered for each species in species conservation and energy
conservation equations, which substantially increases the complexity of the problem. Inclusion of
mass diffusion also poses challenges for solving the problem, e.g. determining mass diffusion
coefficients of each species in the mixture.

In the following, we will first discuss the principle of mass transfer, and then present the complete
conservation equations for steady reacting flows occurring at a one-dimensional planar geometry,
from which we will develop an analysis of premixed laminar flames in Chap. 7. The concept of
“conserved scalar” will be present in the end which is useful to simplify the analysis of certain
combustion problems.

1. Mass Transfer Rate Law

Mass transfer occurs in two modes, convective and diffusive. Convective mass transfer is due to the
bulk motion of the flow (advection) which is included in the conservation equations. Diffusive mass
transfer is due to molecular diffusion which is discussed here.

With the inclusion of diffusive mass transfer, the total mass flux of species A can be expressed as
follows (in a scalar form)
 A" m
m
=  "YA + m
 A" ,diff
 YA , and
Which states that the total mass flux is the sum of the mass flux associated with bulk flow, m
"

 A ,diff .
the mass flux associated with molecular diffusion, m
"

The diffusive mass transfer can be described by Fick’s law. For one-dimensional binary diffusion,
Fick’s law on a mass basis is

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 Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

dYA
 A" ,diff = − ρ DAB
m .
dx
where DAB is the binary diffusivity, in the unit of m2/s, and depends on both A and B, as well as the
mixing conditions.

The Fick’s law indicates that the diffusion rate is proportional to the gradient of the mass fraction, and
diffusion proceeds preferentially in the direction from a region of high concentration to a region of low
concentration. The rate constant is ρ DAB . The negative sign indicates positive mass flux for “diffuse-
out” and negative mass flux for “diffuse-in”.

Binary diffusivity, DAB, can be obtained from the kinetic theory of gases and is a function of
temperature and pressure,
DAB ∝ T 3/2P −1
P
Given ρ= , the mass diffusion rate is only a weak function of temperature,
RT
 A" ,diff ∝ ρ DAB ∝ T 1/2
m

Note that the Fick’s law of diffusion is in a similar form to the Fourier’s law of conduction, which for a
one-dimensional system can be written as
dT
Q x" = −k
dx
where Q  x is the heat flux in the x-direction, k is the thermal conductivity of the material, and dT/dx is
"

the temperature gradient. The similarity between mass diffusion and thermal conduction can be used
to simplify conservation equations, as shown in later discussions.

For binary diffusion of species A and B, one can prove that the sum of diffusion fluxes of A and B is
zero.
dYA dY
 A" ,diff + m
m − ρ DAB
 B" ,diff = − ρ DBA B =
0 eq. 6-1
dx dx
This is understandable in that when consider a control volume containing A and B, the total (net)
mass flux flow into and out of the control surfaces should not depend on the internal mass exchange
between A and B.

This conclusion can be extended to mixtures containing N species,

N

∑ m
i =1
"
i ,diff =0 eq. 6-2

dYA dY
It is important to note from eq. 6-1 that DAB and DBA are equal because YA + YB =
1 , so = − B.
dx dx
As the number of species increases in a mixture, the number of mass diffusivity required for solving
the problem increases dramatically. This greatly increases the complexity of the problem. A commonly
used approximate method is to assume a binary mixture consisting of species i and the mixture which
lumps all the rest species. With this approximation Fick’s law can be written for multi-component
mixtures in the following one-dimensional form,
dYi
 i",diff = − ρ Dim
m for i = 1, 2, …, N
dx
where Dim is the effective binary diffusivity for species i in the mixture m.

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 Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

To ensure eq. 6-2 is still satisfied after such approximation, the mass diffusion of the Nth species,
which for many cases is nitrogen, is determined by balance, rather than by the Fick’s law.

It is also important to note that in discussing one-dimensional systems we ignored the vector nature of
mass diffusion. A vector form for mass diffusion can be written as
− ρ Dim∇Yi
 i",diff =
m
where the vectors are in bold font.

Our discussion on mass diffusion here focuses ordinary diffusion, which is resulted from
concentration gradient. Other types of mass diffusion can be resulted from temperature gradient
(thermal or Soret diffusion), pressure gradient (pressure diffusion), and unequal body forces
among the species (forced diffusion). The mass fluxes associated with each diffusion mode are
additive. In the vector form, it can be written
 i",diff = m
m  i",diff , X + m
 i",diff ,T + m
 i",diff ,P + m
 i",diff,f
where the subscript X, T, P, and f stands for concentration, temperature, pressure, and force,
respectively. Pressure and forced diffusions are usually small in typically combustion systems, but
thermal diffusion can be important in some special cases.

2. Conservation Equations for One-Dimensional Reacting Flow

Mass Conservation (Continuity)
dmCV
 ]x − [m
= [m  ]x +∆x
dt
= ρVCV
With mCV = ρ A∆x , and m  = ρυ x A , the above equation becomes
d (ρ A∆x)
= [ ρυ x A]x − [ ρυ x A]x +∆x
dt
Dividing both sides by A∆x and taking the limit as ∆x → 0,
∂ρ ∂(ρυ x )
= −
∂t ∂x
For steady flow, ∂ρ / ∂t =0 ,
d (ρυ x )
=0
dx
Or
ρυ x = constant

Species Conservation
dmi ,CV
=  i" A]x − [m
[m  i" A]x +∆x + m i'"V
dt
where the species mass flux m  i" can be written by applying the Fick’s law to a mixture
dYi
m
=  "Yi − ρ Dim
 i" m for i = 1, 2, …, N
dx
Substitute this into the species conservation equation, and use m=
i ,CV ρYV
i=
CV ρYi A∆x , and
V = A∆x

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 Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

∂(ρYi )  " ∂Y   " ∂Y 

A∆x = A m Yi − ρ Dim i  − A m Yi − ρ Dim i   i'" A∆x
+m
∂t  ∂x  x  ∂x  x +∆x
Divide both side by A∆x, and take the limit as ∆x → 0,
∂(ρYi ) ∂  " dY
− m
=  Yi − ρ Dim i  +m
 i'"
∂t ∂x  dx 
For steady flow where ∂( ρYi ) / ∂t =0

d  " dY
  Yi − ρ Dim i  =
m  i'"
m
dx  dx 
Or
 "Yi ) d 
d (m dY 
−  ρ Dim i  =
 i'"
m
dx dx  dx 
Or
dm i"
 i'"
=m
dx
The last equation is a more general form of species conservation for one-dimension steady reacting
flow with no assumptions about binary diffusion coefficient (e.g. Dim) being imposed.

Momentum Conservation
ΣF = (υout - υin )
m
For 1-D steady flow system,
 [(υ x )x +∆x − (υ x )x ]
(PA)x − (PA)x +∆x= m
 / A = ρυ x we obtain
Divide both sides by A∆x, take the limit as ∆x → 0, and recognize m
dP dυ
− ρυ x x
=
dx dx

For 1-D laminar premixed flame, we can assume that kinetic energy change across the flame is small,
i.e.,
d (υ x2 / 2) dυ
= υx x ≈ 0
dx dx
Hence the momentum equation simplifies to the trivial result that
dP
=0
dx
which implies that the pressure is constant throughout the flow field.

Energy Conservation
For 1-D steady state, steady flow system, the first law of thermodynamics can be written as
 υ 2   υ2  
(Q x" − Q x" +∆x )A − W
 CV m
=  " A  h + x + gz  −  h + x + gz  
 2  x +∆x  2  x 
Assume no work being done by the control volume and no change in potential energies of the inlet
and outlet streams, the energy conservation equation then becomes
 υ x2   υ x2  
−(Q x" +∆x − Q=
"
x ) A 
m "
A   h +  − h +  
 2  x +∆x  2  x 

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 Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

Divide both sides by A∆x, and take the limit as ∆x → 0, we obtain

dQ x"  dh dυ 
− = m "  + υx x  eq. 6-3
dx  dx dx 
Unlike the special cases for the idealized reactors in Chap. 5 where the heat flux was considered as a
prescribed parameter, heat fluxes through control surfaces generally are variable and in the form of
radiation, conduction, and mass-diffusion associated heat transfer. If radiation is negligible, the heat
flux for a 1-D planar control volume can be written as
dT N "
Q x" =
−k + ∑m  i ,diff hi eq. 6-4
dx i =1
 i ,diff , can be expressed in terms of the velocity of the ith
where the diffusion flux of the ith species, m
"

species and the bulk flow velocity as discussed below.

At the beginning of this chapter, we discussed that the total mass flux of species A can be expressed
as the sum of the mass flux associated with bulk flow and the mass flux associated with molecular
diffusion. In the vector form, it can written as

 "i m
=
m  "Yi + m
 "i,diff

So the eq. 6-4 can be written as

dT N "
Q x" =
−k + ∑ (mi −m  "Yi )hi
dx i =1
dT N " N
−k
= + ∑ (m i hi ) − ∑ (m  "Yi hi )
= dx i 1=i 1
dT N "
−k
= + ∑ (m i hi ) − m "h
dx i =1
N
where h = ∑Y h is the mixture enthalpy.
i =1
i i

 x" expression into eq. 6-3 yields (canceling m

Substituting the Q  "dh / dx on both sides of the
equations)
d  dT  d  N "  dυ
 k  −  ∑m  "υ x x
 i hi  =
m eq. (6-3’)
dx  dx  dx  i =1  dx

d  N " 
Further deriving the ∑ m i hi  term obtains
dx  i =1
d   dm i" dh
 ∑
=
dx  i
 i"hi 
m

∑i hi dx +∑i m i" dxi

Recognizing from the species conservation

dm i"
 i"'
=m
dx
So the eq. (6-3’) becomes

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 Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

dhi d  dT  dυ
∑ m "
i
dx dx  dx 
 "υ x x =
+  −k  + m
dx
−∑ m
 i"'hi eq. 6-5

This equation is obtained for steady 1-D flow, neglecting shaft work, radiation heat transfer, viscous
dissipation, and potential energy changes.

Shvab-Zeldovich Energy Equation

The energy conservation equation (eq. 6-5) can be simplified into a form called Shvab and Zeldovich
equation. This form is particularly useful, as will be seen in later chapters, in that the first term at LHS
of eq. 6-5 is eliminated and replaced with terms having temperature as the only dependant variable.

Development of the Shvab-Zeldovich equation involves two key assumptions:

1) Lewis number is unity.
2) Fick’s law can be applied to describe the species mass fluxes.

Lewis number is defined as the ratio of the thermal diffusivity and mass diffusivity
α
Le ≡
D
where the thermal diffusivity is
k
α=
ρ cP
where k is the thermal conductivity.

Lewis number is an important dimensionless number (both α and D are in the unit of m2/s) for many
combustion problems. Lewis number essentially compares the rate of energy transport (α) and the
rate of mass transport (D) of a species or a mixture of species. For many species of interest in
combustion, Lewis numbers are of the order of unity. The unity Le assumption is frequently invoked to
simplify the analysis of combustion problems.

By applying Fick’s law to eq. 6-4, it becomes

dT N  dY 
Q x" =
−k − ∑  ρ D i hi 
dx i =1  dx 
The summation term can be derived as
 dYi  d (hY
 i i) dh 
∑=
 ρD
i
h
dx 
i
i 
ρD∑ 
dx
− Yi i 
dx 
dh  dh dT 
= ρ D − ρ D ∑  Yi i 
dx i  dT dx 
dh dT
= ρ D − ρ D ∑ (Yi cp ,i )
dx dx i
dh dT
= ρ D − ρ Dcp
dx dx
where a single diffusivity, D, is assumed to characterize the mixture.

Therefore,
dT dT dh
Q x" =
−k + ρ DcP − ρD
dx dx dx

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 Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

Applying Le = 1 , k / ρ cp = D , the first and second terms at the RHS is cancelled, so

dh
Q x" = − ρ D eq. 6-6
dx
Substituting eq. 6-6 back to the energy conservation equation (eq. 6-3) yields
d  dh  dh dυ
 ρ D= "
 m  "υ x x
+m eq. 6-7
dx  dx  dx dx

Now employing the definition of the standardized enthalpy of a mixture,

T
Σh0f ,iYi + ∫ cP dT
h=
Tref

and with further manipulation, plus neglecting the kinetic energy changes, the final Shvab-Zeldovich
energy equation is obtained as

d ∫ cP dT d  d cP dT 
"
m + − ρD ∫  =− ∑ m
 i"'h0f ,i
dx dx  dx 
 
Rate of sensible enthalpy Rate of sensible enthalpy Rate of sensible enthalpy
transport by convection transport by diffusion production by chemical
(advection) (W/m2) (W/m2) reaction (W/m2)
eq. 6-8
Note that sensible enthalpies are expressed in terms of temperature, ∫ c dT .
P

This equation has the simple physical interpretation that the combined rates of convection (advection)
and diffusion of sensible enthalpy (thermal energy) equal the rate at which chemical energy is
converted to thermal energy by chemical reaction.

3. The Concept of Conserved Scalar

As has been repeatedly demonstrated, the target of solving a combustion problem is to determine the
fields of velocity, species, and temperature etc. The conserved scalar concept can help us greatly in
this regard by simplifying the solution, in particular for non-premixed flames.

Conserved scalar is any scalar property that does not have a source term (either source or sink)
associated with it throughout the flow field, i.e. it is not being produced or consumed. The total mass
is obviously a conserved scalar. Other conserved scalars include element mass fractions, since
elements are neither created or destroyed by chemical reactions, and mixture enthalpy, which can be
considered conserved when there is no sources (or sinks) of thermal energy such as radiation into or
out of the flow or viscous dissipation.

Conservation of mixture fraction

For a combustion reaction written in the form below

1 kg fuel + ν kg oxidizer → (ν + 1) kg products R. 1

Mixture fraction, f , is defined as

Mass of material having its origin in the fuel stream
f=
Mass of mixture

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 Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

which applies to any control volume in the flow field.

Mixture fraction is nothing new physically; it is just a special kind of mass fraction, formed as a
combination of the mass fractions of fuel, oxidizer, and product. The mixture fraction is unity in the fuel
stream and zero in the oxidizer stream; and within the flow field, it takes on values between unity and
zero. That is,
 1 
f =(1)YF + (0)YOx +  YPr
ν + 1 
Or
 1 
f= YF +  YPr
ν + 1 
The utility of the mixture fraction is that it can be used to generate a species conservation equation
that no reaction rate terms appearing, i.e. the equation is “sourceless”.

For the 1-D steady reacting flow with planar geometry, we can write the species conservation
equation for the fuel and product
dYF d  dY   '"
"
m −  ρD F =mF eq. 6-9
dx dx  dx 
and
dYPr d  dY 
"
m −  ρ D Pr  =
 Pr'"
m eq. 6-10
dx dx  dx 

The stoichiometry of the combustion reaction (R. 1) dictates that the mass production rates of the fuel
and product are related as
1
 F'" = m
−m  '"
ν + 1 Pr
Dividing eq. 6-10 by (ν+1) and add the resultant equation to eq. 6-9 yields

d[YF + YPr / (ν + 1)] d  d 

"
m −  ρ D [YF + YPr / (ν + 1)]  =
0
dx dx  dx 
We note that this equation is sourceless, i.e. the RHS is zero, and the term in the derivatives is the
mixture fraction, that is

df d  df 
"
m −  ρD  = 0
dx dx  dx 
which indicates that f is a conserved scalar.

Mixture fraction as a conserved scalar is particularly useful in dealing with diffusion flames where the
fuel and oxidizer streams are initially segregated. For premixed combustion, the mixture fraction is
essentially uniform everywhere; hence, a conservation equation for mixture fraction provides no new
information.

Mixture enthalpy as a conserved scalar

Subject to all the assumptions underlying the Shvab-Zeldovich energy equation, the mixture enthalpy,
h, is also a conserved scalar:

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 Advanced Thermodynamics - Semester 2 2016 - Lecture Notes

T
Σh0f ,iYi + ∫ cP dT
h=
Tref

This can be seen directly from energy conservation in eq. 6-7 when the kinetic energy term,
dυ x
 "υ x
m , is assumed to be negligible. So we have
dx
dh d  dh 
"
m −  ρD  = 0
dx dx  dx 
which indicates that h is a conserved scalar.