1-23

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

(19.49) tanh(19.49) = 3.910

-8
mol/(m
2
s)

The required surface area of the biofilm is finally

S =
,
A
A z
W
N
=
3
8
8.0 10
(3.9 10 )(3600)

= 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)