CHE 304:

Chapter 24: Steady-State Molecular

Diffusion
Sagheer Onaizi
 DISCLAIMER!

◼ The materials presented in lecture

presentations are only summaries of the text
materials
◼ The material covered in these presentations
can be incomplete
◼ Students will be examined according to the
text materials presented in the textbook and
handouts
2
 General Differential Equations
for Molar Flux
c A
− .N A + RA =
t
 N A, x N A, y N A, z  c A Rectangular
− + +  + R =
   t
A
 x y z  coordinates

 1  (rN A,r ) 1 N A, N A, z  c A Cylindrical

− + +  + RA = coordinates
 r r r  z  t

− 2
( )
 1  r 2 N A, r
+
1  (N A, sin  )
+
1 N A, 
+ =
c A Spherical
 R coordinates
      t
A
 r r r sin r sin 
3
 General Differential Equations
for Concentration Changes
c A
DAB  c A − v.c A + RA =
2

t
  2 c A  2 c A  2 c A   c A c A c A  c A
Rectangular DAB  2 + 2 + 2  − v x + vy + vz  + RA =
coordinates  x y z   x y z  t
  2 c A 1 c A 1  2 c A  2 c A   c A v c A c A 
DAB  2 + + 2 + 2 
− v
 r r + + v 
     
z
 
2
Cylindrical  r r r r z  r z
coordinates c A
+ RA =
t
 1   2 c A  1   c A  1  2c A 
DAB  2 r + 2  sin  + 2 2 
Spherical  r r  r  r sin       r sin   
coordinates
 c A v c A v c A  c A
− vr + +  + R =
    t
A 4
 r r r sin 
 Steady State Molar Flux of
A
= 0 (SS)

We will cover these topics in this chapter

 N A, x N A, y N A, z  c A
− .N A + RA = − + +  + RA =
 x y z  t
Simplifications:
1. One-dimensional diffusion with no reaction:
i. Unimolecular diffusion
ii. Equimolar countercurrent diffusion of binary
gas systems
2. One-dimensional diffusion with heterogeneous
1st order chemical reaction
3. One-dimensional diffusion with homogeneous
1st order chemical reaction
 One-Dimensional (1D) Mass Transfer
Independent of Chemical Reaction

◼ Consider a binary mixture of A and B

+ y A (N A , z + N B , z )
dy A
N A, z = −cDAB Flux of A along z in a binary
system with no reaction
dz
◼ There are two common cases to consider
for molecular diffusion:
1. Diffusion of A through stagnant B (vB, z = 0) ➔
(unimolecular diffusion, UMD) ➔ NB, z = 0

2. Equimolar Counterdiffusion (EMCD) ➔ NB,z =

– NA,z
6
 Unimolecular Diffusion (1)
Arnold diffusion cell:
◼ Used to measure diffusion coefficients (DAB) of gases.
◼ It consists of a narrow tube which is partly filled with pure
liquid “A”, and is maintained at a constant temperature and
pressure.
◼ Gas “B” flows across the open end of the
cell and has negligible solubility in the
liquid.

Develop the concentration profile of A

Arnold diffusion cell

 Unimolecular Diffusion (2)
Assumptions:
1. B is insoluble in A
2. Gas inside tube is still (stagnant)
3. Liquid level inside the tube is constant → z1 is constant
4. No reaction ➔ RA = 0
5. 1D flux along z
6. Uniform cross sectional area
7. Constant T and P in gas within the tube ➔ Constant c
and DAB
8. Steady state
9. A is volatile and exerts a vapor pressure

8
 Unimolecular Diffusion (3)
◼ Differential equation of mass transfer:
– NA + RA = ∂cA/∂t
0 0 0 0

 1  (rN A,r ) 1 N A, N A, z  c A

− + +  + R =
   t
A
 r r r z 
Similarly, for component B: dNBz/dz = 0
Since B is insoluble in A ➔ NB|z1 = 0

Component B is a stagnant gas in the tube → NB = 0

9
 Unimolecular Diffusion (4)
Flux Equation

+ y A (N A, z + N B , z )
dy A
N A, z = −cDAB
dz If the B gas flow
− cDAB dy A rate is high → A is
N A, z = swept away ➔ yA2
1 − y A dz ~ 0 (very small)

Boundary Conditions:
1: yA= yA1=pA*/P @ z=z1 2: yA= yA2 @ z = z2

z = z2 yA2 dy A cDAB 1 − y A2 
N A, z  dz = −cDAB  N A, z = ln  
z = z1 y A1 1− yA z2 − z1  1 − y A1 
10
 Unimolecular Diffusion (5)
◼ Recall that (yA + yB = 1) ➔ yB changes with z
◼ The average yB is given by the logarithmic-mean
average mole fraction of component B, which is
defined as:
y B = yB ,lm =
yB 2 − yB1
=
1 − y A 2  − 1 − y A1 
=
y A1 − y A 2
ln ( yB 2 yB1 ) ln (1 − y A 2  1 − y A1 ) ln (1 − y A 2  1 − y A1 )

 1 − y A2  y A1 − y A2
 ln  =
 1 − y A1  yB ,lm

Therefore:  DAB   cDAB  ( y A1 − y A 2 )

N A, z =  c ( y A1 − y A 2 ) =  
 yB , lm ( z2 − z1 )   ( z2 − z1 )  yB , lm11
 Unimolecular Diffusion (6)

◼ For ideal gas n P pA

c= =  yA =
V RT P

◼ Therefore:
DAB P ( p A1 − p A 2 ) DAB P
N A, z = = ( p A1 − p A2 )
RT ( z2 − z1 ) pB , lm RT pB , lm

pB 2 pB1 1
− ( pB 2 − pB1 ) p
yB 2 − yB1 P P P
= = = = B ,lm
yB ,lm
ln ( yB 2 yB1 ) p pB1  ln ( pB 2 / pB1 ) y A1 − y A 2 ( p A1 − p A 2 ) / P
ln  B 2 
P
=
 P P  yB ,lm pB ,lm / P
p A1 p A 2  p A1 − p A 2 
y A1 − y A 2 = − = 
P P  P  12
 Unimolecular Diffusion (7)
◼ Concentration Profiles:
BC1:
dN A, z d  − cDAB dy A  cDAB ln (1 − y A1 ) = C1 z1 + C 2
=   = 0 BC2:
dz dz  1 − y A dz 
cDAB ln(1 − y A2 ) = C1 z2 + C 2
− c DAB dy A
Integration → = C1 Solving for C2 from both
1 − y A dz equations and subtracting:
Separation of variables → C 2 = cDAB ln (1 − y A1 ) − C1 z1
dy A
− cDAB = C1dz = cDAB ln (1 − y A2 ) − C1 z 2
1− yA
Integration →  1 − y A2 
0 = cDAB ln  − C1 ( z 2 − z1 )
cDAB ln (1 − y A ) = C1 z + C 2  1 − y A1  13
 Unimolecular Diffusion (8)
cDAB  1 − y A 2 
C1 = ln 
z 2 − z1  1 − y A1 
cDAB  1 − y A 2 
C 2 = cDAB ln (1 − y A1 ) − ln  z1
z 2 − z1  1 − y A1 
Substituting Constants
cDAB  1 − y A2  cDAB  1 − y A2 
cDAB ln (1 − y A ) = 
ln 
 z + cDAB ln (1 − y A1 ) − ln  z1
z2 − z1  1 − y A1  z2 − z1  1 − y A1 
 z − z1 
 
 1 − y A   z − z1   1 − y A 2   1 − y A2   z 2 − z1 
ln  =   ln  = ln 
 1 − y A1   z2 − z1   1 − y A1   1 − y A1 

 z − z1   z − z1 
   
1 − y A  1 − y A2   z 2 − z1   1 − y A2   z 2 − z1 
=   y A = 1 − (1 − y A1 ) 
1 − y A1  1 − y A1   1 − y A1  14
Unimolecular Diffusion (9)
 z − z1 
 
 yB 2   z 2 − z1 
y B = y B1  
 y B1 

15
 Unimolecular Diffusion for
Dilute A (yA<<1)
− cDAB dy A dy A
N A, z = N A, z = −cDAB
1 − y A dz dz

Similar to Equimolar Counterdiffusion

(will be discussed later)
 Concentration Profiles

Concentration profiles of A and

1 B
0.9
Concentration profiles of A and B
0.8 yA 0.06
0.7
Concentrated
0.05
0.6
yA 0r yB

0.5 0.04 Dilute

yA
0.4
0.3
0.03 yA
0.02
0.2 yB yA yB
0.1 0.01
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
z'=(z-z1)/(z2-z1)
z'=(z-z1)/(z2-z1)
 The Convective Mass-Transfer
Coefficients by the “Film Concept” or
Film Theory (1)

◼ The entire resistance to diffusion from the

liquid surface to the main gas stream is
assumed to occur in a stagnant film of
constant thickness δ
18
 The Convective Mass-Transfer
Coefficients by the “Film Concept” or
Film Theory (2)

 DAB   DAB 
N A, z =  c ( y A1 − y A 2 ) =   (c A1 − c A 2 ) = kc (c A1 − c A 2 )
 yB , lm ( z2 − z1 )   yB , lm 

DAB P ( p A1 − p A 2 )
N A, z = =
DAB P
( p A1 − p A2 ) = kc (c A1 − c A2 )
RT ( z 2 − z1 ) pB , lm RT pB , lm

=
kc
( p A1 − p A2 )
RT

DAB P
kc =
pB , lm
19
 Example 1
Vapor degreasers like the one shown in the figure are
widely used for cleaning metal parts. Liquid
solvent rests at the bottom of the degreaser tank. A
cylindrical degreaser tank with a diameter of 2 m
and total height of 5 m is used, and the solvent level
height is kept constant at 0.2 m. The temperatures
of the solvent and headspace of the degreaser are
both constant at 35 °C. The solvent used for vapor
degreasing is trichloroethylene (TCE). Current
regulations require that the degreaser cannot emit more
BCs:
than 1.0 kg TCE per day. Does the estimated
y = y = 0.152 @ z = z1 = 0.2 m
emission rate of the degreaser exceed this limit? A A1
TCE has a molecular weight of 131.4 g/mol and a y A = y A2 = 0 @ z = z2 = 5 m
vapor pressure of 115.5 mmHg at 35°C. The binary-
diffusion coefficient TCE in air is 0.088 cm2/s at 35°C
20
 Solution (1)
This is cylindrical coordinates:
Assume: 1) Flux is only along z; 2) No reaction; 3) Steady state; 4) Ideal gas
0 0 0 0

 1  (rN A,r ) 1 N A, N A, z  c A

− + +  + RA =
 r r r  z  t

N A, z
=0
z
This is 1-D flux along z. As we found previously:
cDAB 1 − y A2 
N A, z = ln  
z2 − z1  1 − y A1  21
Solution (2)

22
Solution (3)
 Pseudo-Steady-State
Diffusion (1)
◼ If the changes in the length of the diffusion path over a long
period of time is small, a pseudo-steady-state might be
assumed. In such case:
cDAB ( y A1 − y A 2 )
N A, z =
Z y B , lm
Where Z is the length of the
diffusion path, which is a function
of time t.
◼ Unsteady state balance
on A gives:
Density of A
 A, L dZ
in the liquid N A, z =
phase M A dt
 Mass balance on A
Input – Output + Generation – Consumption =Accumulation

– Output =Accumulation
 dm A, L Z
− m A, L , z =
dt
d ( A, LVA, L )
Liquid
dVA, L d (Sh ) dh
− N A, z .M A .S = =  A, L =  A, L =  A, L S A
dt dt dt dt
dh
h
− N A, z .M A =  A, L
dt
dh dZ
=− t0 tf
dt dt
dZ  A, L dZ
− N A, z .M A = −  A, L  N A, z =
dt M A dt
 Pseudo-Steady-State
Diffusion (2)
◼ Under pseudo-steady-state conditions:
 A, L dZ cDAB ( y A1 − y A 2 )
= N A, z =
M A dt Z y B , lm

◼ Separating variables:
y B , lm  A, L
ZdZ = dt
M AcDAB ( y A1 − y A 2 )

◼ Integrate:
y B , lm  A, L Z t

M AcDAB ( y A1 − y A 2 ) 
Z0
ZdZ =  dt
t0
 Pseudo-Steady-State
Diffusion (3)
◼ Integration gives:
 A, L y B , lm
 Z 2 − Z 02 
t = t0 +  
M AcDAB ( y A1 − y A 2 )  2 

◼ For the pseudo-steady-state diffusion process,

the plot of Z 2 − Z 02 vs t will be linear with a slope of:
 A, L y B , lm
2M A cD AB ( y A1 − y A2 )

◼ Rearrange:
Commonly used to evaluate
 A, L y B , lm  Z 2 − Z 02 
D AB =   the gas-diffusion coefficient
M A c( y A1 − y A2 )(t − t 0 ) 
 2 
 from Arnold cell experimental data
 Example 2
Molecular O2 dissolves into the SiO2 solid
(i.e., diffuses through the SiO2 film) and
then reacts with Si at the Si/SiO2 interface,
as shown in the Figure. Assuming that the
diffusion of O2 through the SiO2 film limits
the oxidation process, Develop a model to
predict the thickness of the SiO2 layer (δ)
as a function of time at 1000°C. The
density of solid SiO2 (ρB) is 2.27 g/cm3, and
the molecular weight of SiO2 (MB) is 60 BCs:
g/mol. The molecular diffusion coefficient
of O2 in SiO2 (DAB) is 2.7 x 10-9 cm2/s at c A = c As @z =0
1000°C, and the maximum solubility of O2
in SiO2 (cAs) is 9.6 x 10-8 mol O2/cm3 solid
cA = 0 @z =
at 1000°C and 1 atm O2 partial pressure.
28
 Solution (1)
Assumptions:
1. The O2 in the gas phase above the wafer represents an infinite source for
O2 transfer.
2. The rate of SiO2 formation is controlled by the rate of molecular diffusion
of O2 (species A) through the solid SiO2 layer (species B) to the unreacted
Si layer (i.e., the reaction is very rapid).
3. There are no mass-transfer resistances in the gas film above the wafer
surface
4. The flux of O2 through the SiO2 layer is one dimensional along the z
coordinate only.
5. The thickness of the film will still increase with time. Consequently, this is
a ‘‘pseudo-steady-state’’ process.
6. The overall thickness of the wafer does not change as the result of the
formation of the SiO2 layer.
7. Temperature and pressure are constants
 Solution (2)
Based on the previous assumptions, the general differential
equation for mass transfer reduces to:
For 1 cm:
Solution (3)
 Input – Output + Generation – Consumption =Accumulation

Balance on O2 (A)
Input – Output + Generation – Consumption =Accumulation

Input – Consumption =0 → Input = Consumption → Input = N A, z .S

Balance on SiO2 (B)
Input – Output + Generation – Consumption =Accumulation

dmB d (  BV ) dV d
Generation = Accumulation → Generation = = = B =  B .S
dt dt dt dt
From the reaction stoichiometry: Consumption of A= Generation of B = N A, z .S
dmB d (  BV ) dV d
N A, z .S .M B = = = B =  B .S
dt dt dt dt
Solution (4)

OR
 Equimolar Counterdiffusion (1)
NB
◼ Assumptions: yA2 z2
1. Steady state
yA1 z1
2. 1-D flux (e.g., along z) NA
3. Uniform cross-sectional area
4. Constant T and P ➔ constant c & DAB
5. No chemical reaction → RA = 0
6. Binary mixture of A and B

35
 Equimolar Counterdiffusion (2)

◼ Differential equation of mass transfer:

No reaction,
- NA + RA =∂cA/∂t Steady state

N A, x N A, y N A, z
N A = + + =0 Flux along z only
x y z

N B , x N B , y N B , z
Similarly, for component B: N B = + + =0
x y z
Since EMCD → NB = - NA
36
 Equimolar Counterdiffusion (3)

Flux Equation =0 since NA, z, =-NB, z

+ y A (N A, z + N B , z )
dy A
N A, z = −cDAB
dz

dy A
N A, z = −cDAB
dz
Boundary Conditions:
1: yA= yA1 @ z=z1 2: yA= yA2 @ z = z2
z = z2 yA2
N A, z  dz = −cDAB  dy A
z = z1 y A1

N A, z =
cDAB
 y A1 − y A2  = DAB
c A1 − c A2 
z 2 − z1 z 2 − z1 37
 Equimolar Counterdiffusion (4)
nA p A
If the gas behaves ideally cA = =
V RT

N A, z =
DAB
 p A1 − p A2 
RT (z 2 − z1 )

38
 Equimolar Counterdiffusion (5)

◼ Concentration Profiles:
BC1:
dN A, z d  dy A  y A1 = C1 z1 + C 2
=  − cDAB =0 BC2:
dz dz  dz 
y A2 = C1 z2 + C 2
dy A
Integration → = C1 Solving for C2 from both
dz equations:
Separation of var.s →
C 2 = y A1 − C1 z1
dy A = C1dz
= y A2 − C1 z 2
Integration → y A = C1 z + C 2 0 = ( y A2 − y A1 ) − C1 (z2 − z1 )
39
 Equimolar Counterdiffusion
(6)
y A 2 − y A1 y A 2 − y A1
C1 = ; C 2 = y A1 − z1
z 2 − z1 z 2 − z1
Substituting Constants y A2 − y A1 y A 2 − y A1
yA = z + y A1 − z1
z 2 − z1 z 2 − z1
y A2 − y A1
 y A − y A1 = (z − z1 )
z 2 − z1
 z − z1 
y A = y A1 + ( y A 2 − y A1 )   z − z1 
c A = c A1 + (c A 2 − c A1 ) 
 z 2 − z1   z 2 − z1 
y A − y A1 z − z1 and c A − c A1 z − z1
= =
y A 2 − y A1 z 2 − z1 c A 2 − c A1 z 2 −40z1
Concentration profiles
 Unimolecular Diffusion for
Dilute A (yA<<1)
− cDAB dy A dy A
N A, z = N A, z = −cDAB
1 − y A dz dz

Similar to Equimolar Counterdiffusion

Profiles

42
 Film Concept for Molecular
Mass Transfer
cA (and yA) =
constant in bulk gas
Flow of gas B
Flow of gas B
z = ,
NA yA
Slowly moving
Liquid A  gas film
z = 0,
yA0
Liquid A

Assume that concentration gradient is

contained in the gas film →  is the
resistance to molecular diffusion

43
 Generalization of Mass
Transfer Forms
EMCD UMD

c ( y A0 − y A )
DAB
c ( y A0 − y A )
DAB N A, z =
N A, z =
  . y B , lm
N A, z = kc c ( y A0 − y A )
0
N A, z = kc c ( y A0 − y A )
kc0 and kc = film mass transfer coefficients for EMCD and
UMD, respectively 0
kc = kc . y B ,lm
• If yA is very small → yB ~ 1 → yB,lm ~ 1
➔ At low concentrations of A, UMD ≈ EMCD 44
 Chemical Reactions
Two types of Chemical Reactions:
1. Heterogeneous Reactions consist of:
◼ Reactant(s) which is consumed
◼ Product(s) which is formed
◼ Solid catalyst which promotes reaction(s) of
component(s) but it is neither consumed nor formed

2. Homogeneous Reactions: Reactions which occur

within a single phase where the reactant(s) are
consumed and the product(s) are formed within
the same phase
45
 Steady State Mass
Transfer with Reaction
= 0 (SS)
 N A, x N A, y N A, z  c A
− .N A + RA = − + +  + RA =
 x y z  t

 1  (rN A,r ) 1 N A, N A, z 

= 0 (SS)
c A
− + +  + RA =
 r r r  z  t
= 0 (SS)

− 2
( )
 1  r 2 N A, r
+
1  (N A, sin  )
+
1 N A,  c A
 + RA =
r r r sin   r sin    t

46
 Simultaneous Diffusion and 1st Order
Heterogeneous Reactions: Diffusion
with Varying Area
◼ Both the diffusion rate and the reaction rate can
be important
◼ When the reaction rate >> diffusion rate → the
process is diffusion-controlled
◼ When the reaction rate << diffusion rate → the
process is reaction-controlled
◼ For cylindrical and spherical coordinates, cross-
sectional area for flux might vary along the
direction of diffusion
◼ Knudsen diffusion might play an important role
 Example
A catalyst particle is suspended in a gas stream of A c A
mixture A and B that is maintained at constant
B
A
( )
concentration c A . A radial cross section of the
cAs B
particle is shown in the figure. The following
reaction occurs at the coated surface (i.e., at r = R1= Porous
inert
0.3 cm): A ⎯⎯→ ks
B layer
ɛ = 0.60
Consider both a cylindrical and spherical core A
particle, where r=R1 represent the radial position of
the catalyst and r=R2 represents the outer radius of
the porous layer. The length of the cylindrical A
particle is L. B
Nonporous catalyst
Develop equations to predict the flux of A at the coating
catalyst surface (r=R1) and then compare the flux r = R2 = 0.5 cm
for a reaction carried out at 300°C and 1 atm r = R1 = 0.3 cm
with ks = 2 cm/s.
DAB = 0.3 cm2/s and 50 mole% of A is maintained in
the gas phase
 Solution (1)
◼ Assumptions:
1. Steady state
2. 1-D flux of A and B along r
3. No homogeneous reaction taking place
within the noncatalytic porous layer → RA=0
(for r ≠ R1)
4. Assume large pore size (i.e., D Ae   2 D AB )
5. Constant T and constant total P
6. The catalyst material is impermeable 49
 Solution (2): Spherical
Catalyst Particle
For spherical catalyst particle:

− 2
(
 1  r 2 N A, r)+
1  (N A, sin  )
+
1 N A,  c A
 + RA =
r r r sin   r sin    t
For any value of r
except when r = R1

1
− 2
 (
r 2
)
N A, r
=0
(
 r 2 N A, r )=0 r 2 N A,r = C1
r r r
N A,r = C1 / r 2
We also have:
+ (N A,r + N B ,r )
dc A c A
N A, r = − DAe 50
dr c
 Solution (3): Spherical
Catalyst Particle
A and B are fluxing in opposite direction and, therefore, NA,r = - NB,r

dc A
N A, r = − DAe = C1 / r 2
dr
The molar flowrate of A (WA,r)= Flux × area of flux
Area of flux in case of sphere = surface area of sphere = 4r 2

W A, r dc A
WA,r = 4r N A,r
2
 = N A,r = − DAe
4r 2
dr

W A, r
2
dr = −4DAe dc A
r 51
Solution (4): Spherical
Catalyst Particle
Since WA,r is constant
R2 A c
dr
WA,r  2 = −4DAe  dc A
R1
r c As

 1 1
WA,r  −  = 4DAe (c A − c As )
 R2 R1 

4DAe (c A − c As )
W A, r =
 1 1
 − 
 R2 R1 

52
 Solution (5): Spherical
Catalyst Particle
4DAe (c A − c As )
W A, r = = 4r 2 N A,r
 1 1
 − 
 R2 R1 
Negative because A is
DAe (c A − c As ) consumed in the reaction
For r = R1 N A, r =
r = R1
 1 1 2
 −  R1
 R2 R1 
At the particle surface (i.e., R1): N A, r r = R1
= −k s c As

− N A, r r = R1
c As =
ks 53
 Solution (6): Spherical
Catalyst Particle
4DAe (c A − c As ) − c A
W A, r = = 4r 2 N A,r N A, r =
 1
 − 
1 r = R1 (1 / R1 − 1 / R2 )R12 + 1
 R2 R1  DAe ks

c A = y A c =
y A P
=
(0.5)  (1 atm )P = 1 . 06  10 −5
mol / cm 3
RT  82.06 cm 3 . atm 
 (573 K )
 mol. K 
 
DAe =  2 DAB = 0.6 2  0.3 = 0.108 cm 2 / s k s = 2 cm / s R1 = 0.3 cm R2 = 0.5 cm

Substituting these values into the above equation gives:

N A, r r = R1
= −6.6 10 −6 mol / cm 2 .s Negative sign means
the flux is opposite
− N A, r r = R1
to increasing radial
y As = = 0.155 position
ksc
 Solution (7): Cylindrical
Catalyst Particle
For cylindrical catalyst particle:
 1  (rN A,r ) 1 N A, N A, z  c A
− + +  + RA =
 r r r  z  t
For any value of r
except when r = R1

1  (rN A,r )  (rN A,r )

− =0 =0 rN A,r = C1
r r r

N A,r = C1 / r
We also have:
+ (N A,r + N B ,r )
dc A c A
N A, r = − DAe 55
dr c
 Solution (8): Cylindrical
Catalyst Particle
A and B are fluxing in opposite direction and NA,r = - NB,r
Excluding the term
dc A 2r 2 because there
N A, r = − DAe = C1 / r is no flux along z
dr
The molar flowrate of A (WA,r)= Flux × area of flux
Area of flux in case of sphere = surface area of cylinder = 2rL

W A, r dc A
WA,r = 2rLN A,r  = N A,r = − DAe
2rL dr

W A, r
dr = −2LD Ae dc A
r 56
Solution (9): Cylindrical
Catalyst Particle
Since WA,r is constant
R2 cA
dr
W A, r  = −2LD Ae  dc A
R1
r c As

 R2 
WA,r ln  = −2LD Ae (c A − c As )
 R1 

−2 LDAe ( c A − c As )
WA , r =
 R2 
ln  
 R1 
57
 Solution (10): Cylindrical
Catalyst Particle
− 2LD Ae (c A − c As )
W A, r = = 2rLN A,r
 R2 
ln 
 R1 

Negative because A is
For r = R1 DAe (c A − c As ) consumed in the reaction
N A, r =
r = R1
R 
ln 1  R1
 R2 
At the particle surface (i.e., R1): N A, r r = R1
= −k s c As

− N A, r r = R1
c As =
ks 58
 Solution (11): Cylindrical
Catalyst Particle
DAe (c A − c As ) − c A
= =
R1 ln (R2 / R1 ) 1
N A, r N A, r
r = R1
 R1  r = R1
+
ln  R1 DAe ks
 R2 
c A = y A c =
y A P
=
(0.5)  (1 atm )P = 1 . 06  10 −5
mol / cm 3
RT  82.06 cm 3 . atm 
 (327 K )
 mol. K 
 
DAe =  2 DAB = 0.6 2  0.3 = 0.108 cm 2 / s k s = 2 cm / s R1 = 0.3 cm R2 = 0.5 cm

Substitute these values into the above equation gives:

N A, r = −5.52  10 −6 mol / cm 2 .s Negative sign means
r = R1 the flux is opposite
− N A, r to increasing radial
r = R1
y As = = 0.130 position
ksc
 Solution (12): Effect of
Reaction Rate Constant (ks)
− N A, r r = R1
c As =
ks
As ks increases → cAs approaches zero
→ the process becomes controlled by diffusion
 Simultaneous Diffusion and 1st
Order Homogeneous Reactions (1)
◼ For very little fluid motion and/or dilute systems:
dN A, z d  dc A 
− + RA =  DAB  + RA = 0
dz dz  dz 
◼ For 1st2 order reactions:RA = −k1cA
d cA d 2cA k1
 DAB 2
− k1c A = 0 Or: − cA = 0
dz dz 2
DAB
◼ The general solution is:
( ) (
c A ( z ) = A exp z k1 / D AB + B exp − z k1 / D AB )
( ) (
= C1 cosh z k1 / D AB + C 2 sinh z k1 / D AB ) Pure B
61
 Simultaneous Diffusion and 1st
Order Homogeneous Reactions (2)
Boundary Conditions:
1: cA=c A0 @ z=0 2: cA=0 @ z = 

C1 = c A0

c A0
C2 = −
( )
and
tanh  k1 / DAB

( )
 c A ( z ) = c A0 cosh z k1 / DAB −
(
c A0 sinh z k1 / DAB )
(
tanh  k1 / DAB )
62
 Simultaneous Diffusion and 1st
Order Homogeneous Reactions (3)
dc A
(
= c A0 k1 / DAB sinh z k1 / DAB − )
c A0 k1 / DAB cosh z k1 / DAB ( )
dz tanh  k / DAB ( )
dc A c A0 k1 / DAB c A0 k1 / DAB
= 0− =−
dz z =0 (
tanh  k / DAB ) (
tanh  k / DAB )

dc D AB c A0   k1 / D AB 
 N A, z = − D AB A  N A, z =
z =0 dz z =0
z =0 

(
 tanh  k1 / D AB )



 N A, z =0 If there is no flux at z = 
z =
 Simultaneous Diffusion and 1st
Order Homogeneous Reactions (4)
◼ In the absence of chemical reaction:
DAB c A0
N A, z =

~ 1 if reaction-rate controlled
◼ Hatta number:
 k1 / D AB
(
tanh  k1 / D AB ) >> 1 if diffusion-rate controlled

Hatta number shows the effect of chemical

reaction on the process.
64
 Example 4
It is desired to treat 0.1 m3/h of
wastewater containing 0.1 mol/m3 of
the toxic substance phenol. If the
biofilm thickness is 2.0 mm, what is
the required surface area of the
biofilm necessary to achieve the
desired outlet concentration of 0.02
mol/m3?

The kinetic and mass-transport

properties for the biofilm are:
KA=0.3 mol/m3, RA,max= 5.7×10-3 The rate of degradation of the toxic solute
mol/m3.s, and DAB = 2.0×10-10 m2/s at per unit volume of the biofilm is described
the process temperature of 25°C by a kinetic rate equation of the form:

Read the assumptions in the textbook

 Solution (1)

Input = Consumption
 Solution (2)

(24-37)

dN A, z d  dc 
− + RA =  DAB A  + RA = 0
dz dz  dz 
 Solution (3)
dc A
=0 @ z =
c A = c A0 @ z = 0 Boundary Conditions dz
Boundary Condition 1:
cA=c A0 @ z=0
c A0 = C1 cosh (0 ) + C2 sinh (0 ) = C1
Boundary Condition 2:
dc A
=0 @ z =
dz
dc A
dz
( ) (
= 0 = c A0 k1 / DAB sinh  k1 / DAB + C2 k1 / DAB cosh  k1 / DAB )
z =

C2 =
(
− c A0 sinh  k1 / DAB )
(
cosh  k1 / DAB )
 Solution (4)
(
c A ( z ) = c A0 cosh z k1 / DAB − ) (
c A0 sinh  k1 / DAB )sinh (z )
(
cosh  k1 / DAB ) k1 / DAB

cA ( z) =
( ) ( ) ( ) (
c A0 cosh z k1 / DAB cosh  k1 / DAB − c A0 sinh  k1 / DAB sinh z k1 / DAB )
(
cosh  k1 / DAB )
From hyperbolic functions prosperities
cosh( x) cosh( y ) − sinh( x) sinh( y ) = cosh( x − y )

cA ( z) =
(
c A0 cosh ( − z ) k1 / DAB )
cosh ( k1 / DAB )
 Solution (5)
cA ( z) =
(
c A0 cosh ( − z ) k1 / DAB )
cosh ( k1 / DAB )
dc A
dz
(
= −c A0 k1 / DAB tanh  k1 / DAB )
z =0

N A, z z =0
= − DAB
dc A
dz
= DAB c A0 k1 / DAB tanh  k1 / DAB( )
z =0

=
DAB c A0

( ) (
k1 / DAB tanh  k1 / DAB )
Equation (24-43)
 Solution (6)

Equation (24-43) can be also expressed in terms of the Thiele modulus as

 tanh ( )
DAB c A0
N A, z =
z =0

The Thiele modulus represents the ratio of reaction rate to diffusion rate.
When  is less than 0.1, tanh ( ) approaches  and
DAB c A0 DAB c A0 2
N A, z =  =
z =0
 
 Solution (7)
The situation arises when the rate of reaction is low relative to the rate
of diffusion, so that the process is reaction-rate controlling.
When  is greater than 5, tanh ( ) ≈1 and

N A, z z =0
=
DAB c A0

( )
k1 DAB (1) =
DAB c A0

( )(1) = DAB c A0

This situation arises when the rate of diffusion is low relative to the rate
of reaction, so that the process is diffusion-rate controlling.
The flux of phenol into the biofilm is

N A, z z =0
 Solution (8)
The required surface area of the biofilm is
End of Chapter 24

74