Chapter 1
1.4 Diffusion with Chemical Reaction
Example 1.4-1 ------------------------------------------------------------------------------
A fluidized coal reactor operates at 1145
K and 1 atm. The process will be limited by the
diffusion of oxygen countercurrent to the carbon dioxide, CO
2
, formed at the particle surface.
Assume that the coal is pure solid carbon with a density of 1280 kg/m
3
and that the particle is
spherical with an initial diameter of 1.510
-4
m. Air (21% O
2
and 79% N
2
) exists several
diameters away from the sphere. The diffusivity of oxygen in the gas mixture at 1145
K is
1.310
-4
m
2
/s. If a quasi-steady state process is assumed, calculate the time necessary to
reduce the diameter of the carbon particle to 5.010
-5
m.
(Ref. Fundamentals of Momentum, Heat, and Mass Transfer by Welty, Wicks, and Wilson, 4
th
Edition, 2001,
pg. 496.)
Solution ----------------------------------------------------------------------------------------------
The reaction at the carbon surface is
C(s) + O
2
(g) CO
2
(g)
We have diffusion of oxygen (A) toward the surface and diffusion of carbon dioxide (B)
away from the surface. The molar flux of oxygen is given by
N
A,r
= cD
Amix
A
dy
dr
+ y
A
(N
A,r
+ N
B,r
)
In this equation, r is the radial distance from the center of the carbon particle. Since N
A,r
=
N
B,r
, we have
N
A,r
= cD
Amix
A
dy
dr
The system is not at steady state, the molar flux is not independent of r since the area of mass
transfer 4r
2
is not a constant. Using quasi steady state assumption, the mass (mole) transfer
rate, 4r
2
N
A,r
, is assumed to be independent of r at any instant of time.
W
A
= 4r
2
N
A,r
= 4r
2
cD
Amix
A
dy
dr
= constant
R
r
y
A,R
y
A,inf
1-24
At the surface of the coal particle, the reaction rate is much faster than the diffusion rate to
the surface so that the oxygen concentration can be considered to be zero: y
A,R
= 0.
Separating the variables and integrating gives
W
A
2
R
dr
r
= 4 cD
Amix
,
0
A
y
A
dy
W
A
1
R
r
= 4 cD
Amix
y
A,
=> W
A
= 4cD
Amix
y
A,
R
Since one mole of carbon will disappear for each mole of oxygen consumed at the surface
W
C
= W
A
= 4cD
Amix
y
A,
R
Making a carbon balance gives
C
C
M
3
4
3
d
R
dt
| |
|
\
=
C
C
M
4R
2
dR
dt
= 4cD
Amix
y
A,
R
Separating the variables and integrating from t = 0 to t gives
0
t
dt
=
Amix ,
C
C A
M cD y
f
i
R
R
RdR
t =
Amix ,
2
C
C A
M cD y
(R
i
2
R
f
2
)
The total gas concentration can be obtained from the ideal gas law
c =
P
RT
=
1
(0.08206)(1145)
= 0.0106 kmol/m
3
Note: R = 0.08206 m
3
atm/kmol
o
K
The time necessary to reduce the diameter of the carbon particle from 1.510
-4
m to 5.010
-5
m is then
t =
( ) ( )
2 2
5 5
4
(1280) 7.5 10 2.5 10
2(12)(0.0106)(1.3 10 )(0.21)
(
(
= 0.92 s
1-25
Example 1.4-2 ------------------------------------------------------------------------------
Pulverized coal pellets, which may be approximated as carbon spheres of radius R = 1 mm,
are burned in a pure oxygen atmosphere at 1450
K and 1 atm. Oxygen is transferred to the
particle surface by diffusion, where it is consumed in the reaction C(s) + O
2
(g) CO
2
(g).
The reaction rate is first order and of the form " R
= k
1
C
O2
|
R
where k
1
= 0.1 m/s. This is
the reaction rate per unit surface area of the carbon pellets. Neglecting change in R,
determine the steady-state O
2
molar consumption rate in kmol/s. At 1450
K, the binary
diffusion coefficient for O
2
and CO
2
is 1.7110
-4
m
2
/s.
(Ref. Fundamentals of Heat Transfer by Incropera and DeWitt.)
Solution ----------------------------------------------------------------------------------------------
We have diffusion of oxygen (A) toward the surface and diffusion of carbon dioxide (B)
away from the surface. The molar flux of oxygen is given by
N
A,r
= cD
AB
A
dy
dr
+ y
A
(N
A,r
+ N
B,r
)
In this equation, r is the radial distance from the center of the carbon particle. Since N
A,r
=
N
B,r
, we have
N
A,r
= cD
AB
A
dy
dr
The system is not at steady state, the molar flux is not independent of r since the area of mass
transfer 4r
2
is not a constant. Using quasi steady state assumption, the mass (mole) transfer
rate, 4r
2
N
A,r
, is assumed to be independent of r at any instant of time.
W
A
= 4r
2
N
A,r
= 4r
2
cD
AB
A
dy
dr
= constant
R
r
y
A,R
y
A,inf
The oxygen concentration at the surface of the coal particle, y
A,R
, will be determined from the
reaction at the surface. The mole fraction of oxygen at a location far from the pellet is 1.
Separating the variables and integrating gives
W
A
2
R
dr
r
= 4 cD
AB
,
,
A
A R
y
A
y
dy
W
A
1
R
r
= 4 cD
AB
(y
A,
y
A,R
) => W
A
= 4cD
AB
(1 y
A,R
)R
1-26
The mole of oxygen arrived at the carbon surface is equal to the mole of oxygen consumed
by the chemical reaction
W
A
= 4R
2
" R
= 4R
2
k
1
C
O2
|
R
= 4R
2
k
1
c y
A,R
4cD
AB
(1 y
A,R
)R = 4R
2
k
1
c y
A,R
D
AB
(1 y
A,R
) = Rk
1
y
A,R
=> y
A,R
=
1
"
AB
AD
D
D Rk +
y
A,R
=
4
4 3
1.71 10
1.71 10 10 .1
+
= 0.631
The total gas concentration can be obtained from the ideal gas law. (Note: R = 0.08206
m
3
atm/kmolK)
c =
P
RT
=
1
(0.08206)(1450)
= 0.008405 kmol/m
3
The steady-state O
2
molar consumption rate is
W
A
= 4cD
AB
(1 y
A,R
)R = 4(0.008405)( 1.7110
-4
)(1 0.631)(10
-3
)
W
A
= 6.6610
-9
kmol/s
Example 1.4-3 ------------------------------------------------------------------------------
A biofilm consists of living cells immobilized in a gelatinous matrix. A toxic organic solute
(species A) diffuses into the biofilm and is degraded to harmless products by the cells within
the biofilm. We want to treat 0.1 m
3
per hour of wastewater containing 0.1 mole/m
3
of the
toxic substance phenol using a system consisting of biofilms on rotating disk as shown
below.
Waste water
feed stream
Treated
waste water
biofilm
Well-mixed contactor
biofilm
z=0
C (z)
A
C
A0
C
A0
Inert
solid
surface
Determine the required surface area of the biofilm with 2 mm thickness to reduce the phenol
concentration in the outlet stream to 0.02 mole/m
3
. The rate of disappearance of phenol
(species A) within the biofilm is described by the following equation
1-27
r
A
= k
1
c
A
where k
1
= 0.019 s
-1
The diffusivity of phenol in the biofilm at the process temperature of 25
o
C is 2.010
-10
m
2
/s.
Phenol is equally soluble in both water and the biofilm.
(Ref. Fundamentals of Momentum, Heat, and Mass Transfer by Welty, Wicks, and Wilson, 4
th
Edition, 2001,
pg. 496.)
Solution ----------------------------------------------------------------------------------------------
The rate of phenol processed by the biofilms, W
A
, is determined from the material balance on
the process unit
W
A
= 0.1 m
3
/h(0.1 0.02) mol/m
3
= 8.010
-3
mol/h
W
A
is then equal to the rate of phenol diffused into the biofilms and can be calculated from
W
A
= SN
A,z
= S
0
A
AB
z
dc
D
dz
=
| |
|
\
In this equation, S is the required surface area of the biofilm and N
A,z
is the molar flux of
phenol at the surface of the biofilm. The molar flux of A (phenol) is given by
N
A,z
= cD
AB
A
dy
dz
+ y
A
(N
A,z
+ N
B,z
)
Since the biofilm is stagnant (or nondiffusing), N
B,z
= 0. Solving for N
A,z
give
N
A,z
(1 y
A
) = cD
AB
A
dy
dz
The mole fraction of phenol in the biofilm, y
A
, is much less than one so that c can be
considered to be constant. Therefore
N
A,z
= cD
AB
A
dy
dz
= D
AB
A
dc
dz
z
Solid surface
Biofilm
N
A,z
Making a mole balance around the control volume Sz gives
1-28
SN
A,z
|
z
SN
A,z
|
z+z
+ Szr
A
= 0
Dividing the equation by Sz and letting z 0 yields
, A z
dN
dz
= r
A
= k
1
c
A
(E-1)
Substituting N
A,z
= D
AB
A
dc
dz
into equation (E-1) we obtain
D
AB
2
2
A
d c
dz
= k
1
c
A
=>
2
2
A
d c
dz
=
1
AB
k
D
c
A
(E-2)
The solution to the homogeneous equation (E-2) has two forms
1) c
A
= C
1
exp
1
AB
k
z
D
| |
|
\
+ C
2
exp
1
AB
k
z
D
| |
|
\
2) c
A
= B
1
sinh
1
AB
k
z
D
| |
|
\
+ B
2
cosh
1
AB
k
z
D
| |
|
\
The first exponential form (1) is more convenient if the domain of z is infinite: 0 z
while the second form using hyperbolic functions (2) is more convenient if the domain of z is
finite: 0 z . The constants of integration C
1
, C
2
, B
1
, and B
2
are to be determined from
the two boundary conditions. We use the hyperbolic functions as the solution to Eq. (E-2).
c
A
= B
1
sinh
1
AB
k
z
D
| |
|
\
+ B
2
cosh
1
AB
k
z
D
| |
|
\
(E-3)
At z = 0, c
A
= c
As
= c
A0
= B
2
At z = ,
A
dc
dz
= 0 = B
1
1
AB
k
D
cosh
1
AB
k
D
| |
|
\
+ B
2
1
AB
k
D
sinh
1
AB
k
D
| |
|
\
Therefore
B
1
= B
2
1
1
sinh
cosh
AB
AB
k
D
k
D
| |
|
\
| |
|
\
= c
A0
1
1
sinh
cosh
AB
AB
k
D
k
D
| |
|
\
| |
|
\
Equation (E-3) becomes
1-29
c
A
= c
A0
1
1
sinh
cosh
AB
AB
k
D
k
D
| |
|
\
| |
|
\
sinh
1
AB
k
z
D
| |
|
\
+ c
A0
cosh
1
AB
k
z
D
| |
|
\
c
A
= c
A0
1 1 1 1
1
cosh cosh sinh sinh
cosh
AB AB AB AB
AB
k k k k
z z
D D D D
k
D
| | | | | | | |
| | | |
\ \ \ \
| |
|
\
Using the identity cosh(A B) = cosh(A)cosh(B) sinh(A)sinh(B) we have
c
A
= c
A0
1
1
cosh ( )
cosh
AB
AB
k
z
D
k
D
| |
|
\
| |
|
\
0
A
z
dc
dz
=
= c
A0
1 1
1
0
sinh ( )
cosh
AB AB
AB
z
k k
z
D D
k
D
=
| |
|
\
| |
|
\
= c
A0
1 1
tanh
AB AB
k k
D D
| |
|
\
The molar flux of phenol at the biofilm surface is given by
N
A,z
=
0
A
AB
z
dc
D
dz
=
=
0 A AB
c D
1 1
tanh
AB AB
k k
D D
| |
|
\
The dimensionless parameter
1
AB
k
D
represents the ratio of reaction rate to diffusion rate.
For this problem we have
1
AB
k
D
= 0.002 m
2
10
1
0.019
s
m
2 10
s
= 19.49
This value indicates that the rate of reaction is very rapid relative to the rate of diffusion. The
flux of phenol into the biofilm is then
1-30
N
A,z
=
10
(0.02)(2 10 )
0.002
= 57.0 m
2
Example 1.4-4. ----------------------------------------------------------------------------------
Consider a spherical organism of radius R within which respiration occurs at a uniform
volumetric rate of r
A
= k
1
C
A
. That is, oxygen (species A) consumption is governed by a
first-order, homogeneous chemical reaction.
(a) If a molar concentration of C
A
(R) = C
A,0
is maintained at the surface of the organism,
obtain an expression for the radial distribution of oxygen, C
A
(r), within the organism.
(b) Obtain an expression for the rate of oxygen consumption within the organism.
(c) Consider an organism of radius R = 0.10 mm and a diffusion coefficient for oxygen
transfer of D
AB
= 10
-8
m
2
/s. If C
A,0
= 510
-5
kmol/m
3
and k
1
= 20 s
-1
, what is the molar
concentration of O
2
at the center of the organism? What is the rate of oxygen
consumption by the organism?
Solution ------------------------------------------------------------------------------------------
(a) If a molar concentration of C
A
(R) = C
A,0
is maintained at the surface of the organism,
obtain an expression for the radial distribution of oxygen, C
A
(r), within the organism.
R
r r+dr
Figure E-1 Illustration of a spherical shell 4r
2
dr
The one-dimensional molar flux of A is given by the equation
"
A
N = D
A
dr
dC
A
(E-1)
Applying a mole balance on the spherical shell shown in Figure E-1 yields for steady state
4r
2
r
A
N
"
4r
2
dr r
A
N
+
"
+ R
A
4r
2
dr = 0
1-31
Dividing the equation by the control volume (4r
2
dr) and taking the limit as dr 0, we
obtain
2
1
r dr
d
(r
2 "
A
N ) + R
A
= 0 (E-2)
For a first order reaction, R
A
= k
1
C
A
and substituting the molar flux from equation (E-1)
into the above equation, we have
2
1
r dr
d
|
\
|
dr
dC
r
A
A
D
2
k
1
C
A
= 0
D
A
2
1
r dr
d
|
\
|
dr
dC
r
A 2
1
kC
A
= 0 (E-3)
In this equation, D
A
and k
1
are constants independent of r. We want to transform this
equation into the form
2
2
dr
y d
2
y = 0 (E-4)
Let
2
=
1
A
k
D
, we can transform equation (4.6-3) into the form of equation (E-4) by the
following algebraic manipulations
r
1
dr
d
|
\
|
dr
dC
r
A 2
2
rC
A
= 0
r
1
|
|
\
|
+
2
2
2
2
dr
C d
r
dr
dC
r
A A
2
rC
A
= 0
2
dr
dC
A
+
2
2
dr
C d
r
A
2
rC
A
= 0
Since
dr
d
|
\
|
) (
A
rC
dr
d
=
dr
d
|
\
|
+
dr
dC
r C
A
A
=
dr
dC
A
+
dr
dC
A
+
2
2
dr
C d
r
A
, the above equation
becomes
dr
d
|
\
|
) (
A
rC
dr
d
2
rC
A
= 0
Let y = rC
A
, the equation has the same form as equation (E-4) with the solution
y = B
1
sinh(r) + B
2
cosh(r)
or rC
A
= B
1
sinh(r) + B
2
cosh(r), where
2
=
1
A
k
D
1-32
The two constants of integration B
1
and B
2
can be obtained from the boundary conditions
At r = 0, C
A
= finite or
dr
dC
A
= 0
At r = R, C
A
= C
A0
(a known value)
Applying the boundary at r = 0 yields
0 = B
2
Applying the boundary at r = R yields
RC
R
= B
1
sinh(R) B
1
=
0
sinh( )
A
RC
R
Therefore the concentration profile for species A within the organism is
C
A
= C
A0
r
R
) sinh(
) sinh(
R
r
(E-5)
At the center of the organism, the concentration is given by C
A
(r = 0) = C
A0
) sinh( R
R
(b) Obtain an expression for the rate of oxygen consumption within the organism.
Rate of oxygen consumption within the organism. = 4R
2
(D
A
A
r R
dC
dr
=
)
The oxygen concentration within the organism is given by equation (E-5)
C
A
= C
A0
r
R
) sinh(
) sinh(
R
r
(E-5)
A
dC
dr
=
0
sinh( )
A
C R
R
(
+ ) cosh( ) sinh(
1
2
r
r
r
r
A
r R
dC
dr
=
=
0
sinh( )
A
C R
R
(
) sinh(
1
) cosh(
2
R
R
R
R
A
r R
dC
dr
=
=
0 A
C
R
[ ] ) 1 ) coth( ) ( R R
1-33
Let = R =
1/ 2
2
1
A
k R
D
| |
|
\
= Thiele modulus for a first order reaction. Ignoring the minus sign,
the rate of oxygen consumption within the organism is then
Rate of oxygen consumption = 4 R
2
D
A
0 A
C
R
( coth - 1)
Rate of oxygen consumption = 4 RD
A
C
A0
( coth - 1)
(c) Consider an organism of radius R = 0.10 mm and a diffusion coefficient for oxygen
transfer of D
AB
= 10
-8
m
2
/s. If C
A,0
= 510
-5
kmol/m
3
and k
1
= 20 s
-1
, what is the molar
concentration of O
2
at the center of the organism? What is the rate of oxygen consumption by
the organism?
At the center of the organism, the concentration is given by C
A
(r = 0) = C
A0
) sinh( R
R
=
1/ 2
1
A
k
D
| |
|
\
=
1/ 2
8
20
10
| |
|
\
= 4.472110
4
m
R =
1/ 2
2
1
A
k R
D
| |
|
\
=
( )
1/ 2
2
4
8
20 10
10
| |
|
|
\
= 4.4721
C
A
(r = 0) = C
A0
) sinh( R
R
= 510
-5
4.4721
sinh(4.4721)
= 5.1110
-6
kmol/m
3
Rate of oxygen consumption = 4 RD
A
C
A0
( coth - 1)
Rate = 4(10
-4
)(10
-8
)( 510
-5
) [4.4721 coth(4.4721) - 1] = 2.1810
-15
kmol/s
The following Matlab program plots the concentration of oxygen within the organism as a
function of position.
% Example 1.4-4
%
alfa=4.4721e4; % m
R=1e-4; % m
alfaR=4.4721;
CA0=5e-5; % kmol/m3
roR=(1:50)/50;
r=R*roR;
1-34
CA=CA0*sinh(alfa*r)./(roR*sinh(alfaR));
plot(roR,CA)
grid on
xlabel('r/R');ylabel('C_A(kmol/m^3)')
Figure E1.4-4 Oxygen concentration profile in a spherical organism.
We now consider the diffusion of species A into a spherical catalyst particle where
homogeneous first order chemical reaction occurs. The concentration profile for species A
within the spherical catalyst particle is then
C
A
= C
R
r
R
) sinh(
) sinh(
R
r
(1.4-1)
In this equation C
R
is the concentration of species A at the surface of the catalyst particle and
is defined by the expression
2
=
A
k
D
, where k is the first order rate constant and D
A
is the
diffusivity of A in the particle. At the center of the bead, the concentration is given by
C
A
(r = 0) = C
R
) sinh( R
R
(1.4-2)