ChE 231

Advanced Chemical Reaction Engineering II

Internal diffusion effects ChE 231
Adv Chem Rxn Engg II
• A diffusion of the reactants or products from the external pellet surface (pore
mouth) to the interior of the pellet.
• When the reactants diffuse into the pores within the catalyst pellet, the
concentration at the pore mouth will be higher than that inside the pore and the
entire catalytic surface is not accessible to the same concentration.

CAs Porous catalyst

particle
CAb CA(r)

External Internal External surface

diffusion diffusion
 ChE 231
Adv Chem Rxn Engg II

Of pore
constriction
and tortuosity
Effective diffusivity, De or Deff ChE 231
Adv Chem Rxn Engg II

• Describes the average

diffusion at any position r
in the pellet.
• Considers only radial
variations in the Dr
concentration r+Dr
• Lumps together the effect r
of pore tortuosity, pore
interconnections,
variance in pore cross-
sectional areas.
 Differential balance ChE 231
Adv Chem Rxn Engg II

Consider an irreversible reaction A → B occurs on the surface

of pore walls within a spherical pellet of radius R:
IN − OUT + REACTION = 0

(W Ar 4 r
2
) − (W r Ar 4 r
2
) r + Dr
 ( )
+ rA 4 rm Dr c = 0
2

(W
Ar 4 r 2
) − (W
r Ar 4 r 2
) r + Dr
+
r  ( 4 r D r ) 
A m
2
c
=0
4 D r 4Dr
Derive the differential
equation in War , r and rA’
Differential balance ChE 231
Adv Chem Rxn Engg II

Consider an irreversible reaction A → B occurs on the surface

of pore walls within a spherical pellet of radius R:

IN − OUT + REACTION =0

(W Ar 4 r
2
) − (W
r Ar 4 r
2
) + r  ( 4  r Dr ) 
r + Dr A
2
c =0

(
1 d WAr r
− 2
2
) + (r )(  ) = 0
A c
r dr
Differential balance ChE 231
Adv Chem Rxn Engg II

Steady state assumption for A → B implies equimolar counter

diffusion and using the effective diffusivity:
dC A
WA = −Deff
dr

Derive the differential

equation in terms of
CA, r and rA’
Differential balance ChE 231
Adv Chem Rxn Engg II

Steady state assumption for A → B implies equimolar counter

diffusion and using the effective diffusivity:
dC A
WA = −Deff
dr
 g cat 
 3 
 m 
1 d  dC A  2 
2 dr  Deff  r  + ( rA )( c ) = 0
r  dr  
 mol 
 g cat  s 
 
Differential balance ChE 231
Adv Chem Rxn Engg II

If the rate law were based on the catalyst surface area and
what is know is:
rA = knC A
n

 mol 
 2 
 m cat  s 

Write the differential

equation in terms of
the CA, r, Sa and Deff
Differential balance ChE 231
Adv Chem Rxn Engg II

If the rate law were based on the catalyst surface area:

rA = knC A
n
→ rA = k nC AS a
n

 mol   m2 surface area 

 2   
 m cat  s   g catalyst 
What would be
1 d  dC A  2  the boundary
 r  + knC AS a c = 0
n
2 dr  Deff conditions?
r  dr  
Differential balance ChE 231
Adv Chem Rxn Engg II

If the rate law is based on the catalyst surface area:

rA = knC A
n
→ rA = k nC AS a
n

 mol   m2 surface area 

 2   
 m cat  s   g catalyst 

Boundary Conditions:
d  2 dC A  2
 + r cS ak nC A = 0
n C A finite at r = 0
 r Deff
dr  dr  C A = C As at r = R
 ChE 231
d  2 dC A  2 Adv Chem Rxn Engg II
 r Deff 
 + r  cS a k n C A = 0
n
dr  dr 
We wish to generalize the above DE and therefore define the
following dimensionless variables
r CA
=  =
R C As

Carry out the differentiation of the first term and

then write the differential equation and
boundary conditions in terms of the above
dimensionless variables
d  2 dC A  2 ChE 231
 + r cS ak nC A = 0
n
 r Deff Adv Chem Rxn Engg II
dr  dr 
2 n −1
r CA knS a cRC As
n
knS a cR C As
=  = n =
2
=
R C As  C As − 0  De
De  
 R 
Boundary Conditions:
d
2
2  d 
 − n  = 0
2 n
+   = 1 at  = 1
d 2   d   finite at  = 0
Thiele modulus ChE 231
Adv Chem Rxn Engg II
2 n −1

k nS a cR C As reaction rate
n 2
= =
De diffusion rate
n = 1:
small 1
d 2
2  d  CA
 − 1  = 0
2
+  C As
d 2   d  medium 1

CA 1  sinh 1  large 1

 = =  
C As   sinh 1  R r=0
Thiele modulus ChE 231
Adv Chem Rxn Engg II

CA 1  sinh 1 
 = =  
C As   sinh 1 

n is small: surface reaction is rate limiting

- significant amount of reactant diffuses into pellet
interior without reacting
n is large: internal diffusion is rate limiting
- surface reaction is rapid, reactant is consumed very
closed to the external surface of pellet
Internal effectiveness factor ChE 231
Adv Chem Rxn Engg II

• the relative importance of diffusion and reaction limitations

• a measurement of how far the reactant diffuses into the
pellet before reacting
actual ( observed ) overall rate of reaction
=
rate of reaction if entire interior surface
were exposed to C As and Ts

−rA −rA −rA ( mass of catalyst )

= = =

−rAs −rAs  ( mass of catalyst )
−rAs
 −rA −rA −rA ( mass of catalyst ) ChE 231
= = =
 ( mass of catalyst )
Adv Chem Rxn Engg II

−rAs −rAs −rAs
ChE 231
Adv Chem Rxn Engg II
 ChE 231
Adv Chem Rxn Engg II
actual ( observed ) overall rate of reaction
=
rate of reaction if entire interior surface
were exposed to C As and Ts

Plot the effectiveness factor as a

function of Thiele Modulus for a first
order reaction in a spherical particle
 First Order
Reaction in a
Spherical
Catalyst
Internal diffusion vs overall reaction ChE 231
Adv Chem Rxn Engg II

 quantifies how internal diffusion affects the overall

reaction rate:
Effectiveness factor vs n
1
−rA =  ( −rAs
 )
0.8 Reaction limited

 0.4
0.2
Internal diffusion limited
0.1
0.2 1 2 4 6 8 10
1
 ChE 231
Adv Chem Rxn Engg II

Thiele modulus for Thiele modulus for

zero, first, second different catalyst
order reactions shapes
 Seatwork #4.1 ChE 231
Adv Chem Rxn Engg II

1. For the reaction A→B occurring in a spherical catalyst, plot

the internal effectiveness factor as a function of catalyst
diameter R (0.01, 0.1, 1) if the reaction were first order and
the Thiele modulus is 40 when R = 1.
2. For reactions of order n,
If one wants to increase the effective factor, discuss
would you decrease/increase the following :
a) Pellet radius
b) Concentration for Case 1 (n>1) and Case 2(n<1)
c) Temperature for isothermal case and for
exothermic non-isothermal case
d) Internal surface area
Example ChE 231
Adv Chem Rxn Engg II

3 De 3 De
−rA =  ( k1C As ) S a  −rA = ( k1C As ) S a
R k1cS a R k1cS a

When the overall rate of reaction is limited by internal diffusion, which

of the following would decrease the internal diffusion limitation?
(a)decreasing the radius R of the particle
(b)increasing the concentration of the reactant
(c) increasing the temperature
(d) increasing the internal surface area
(e) Both a and b
Total rate of consumption ChE 231
Adv Chem Rxn Engg II

At steady state, net flow of A into pellet at the external surface

completely reacts within the pellet
The overall molar reaction rate is equal to the total molar flow
of A into catalyst pellet
MA = (external surface area of pellet) x (molar flux of A into
pellet at external surface)
MA = the net rate of reaction on and within the catalyst pellet
MA = −4 R WAr
2 ChE 231
r =R Adv Chem Rxn Engg II

 CA 
d 
2 dC A   C As   C As 
M A = 4 R  D e  = 4 R D e 
2

 dr   R  r
r =R d 
 R  r =R
d
MA = 4 RDeC As
d  =1
 ChE 231
Advanced Chemical Reaction Engineering II
 ChE 231
Adv Chem Rxn Engg II

Objective: Derive a new rate equation that accounts for

internal and external diffusion
• (-r’A) is a function of reactant concentration
• Reactant concentration is affected both by internal
and external diffusion
• Must express reactant concentration in terms of
diffusion-related constants & variables
Mole balance ChE 231
Adv Chem Rxn Engg II

At steady-state: transport of
reactants from bulk fluid to external CAs CAb
catalyst surface is equal to net rate of
reactant consumption in/on the pellet
Molar rate of mass transfer from bulk C(r)
fluid to external surface:
MA = WAr ( ac ) Vr
external surface
area per unit
reactor volume
Mole balance ChE 231
Adv Chem Rxn Engg II

This molar rate of mass transfer to surface is equal to net

reaction rate on AND in the pellet:

MA = ( −rA )( external area + internal area )

At the pellet surface:
external 
 flux  external   actual   and 
 bulk to    reaction rate   
external    surface  =  per unit    internal 
 surface   area   surface area   surface 
   area 
 
Mole balance ChE 231
Adv Chem Rxn Engg II

This molar rate of mass transfer to surface is equal to net

reaction rate on AND in the pellet:

MA = ( −rA )( external area + internal area )

At the pellet surface:

( WAr )r =R  ( ac Vr ) = ( −rA )  ( ac Vr + Sa b Vr )
catalyst mass
bulk density, b = = c (1 − E )
reactor volume
Mole balance ChE 231
Adv Chem Rxn Engg II

( WAr )r =R  ( ac Vr ) = −rA  ( ac Vr + S a b Vr )
external area internal area: a c S a b

( WAr )r =R ( ac ) = ( −rA )(Sa b )

Since internal diffusion resistance is also ChE 231
significant, the reactant concentration at the Adv Chem Rxn Engg II
internal surface is lower that the reactant
concentration at the external surface:
−rA
= → − rA =  ( −rAs
 ) =  ( k1C As )

−rAs
 actual ( observed ) 
overall rate of reaction 
internal effectiveness factor: =
 reaction rate if entire 
 interior surface were 
exposed to C As and Ts 
Overall molar rate of reaction ChE 231
Adv Chem Rxn Engg II

 
 overall  reaction rate 
flux to
reaction  = surface
=  out AND in 
 rate   the pellet 

MA = WAr
r =R
( ac ) = ( −rA )( S a b )

For external mass transport: WAr = k c ( C Ab − C As )

r =R
Overall molar rate of reaction ChE 231
Adv Chem Rxn Engg II

 
 overall  reaction rate 
flux to
reaction  = surface
=  out AND in 
 rate   the pellet 

k c ( C Ab − C As )  ( ac ) = ( k1C As )(S a b )
 

k cC Ab ac − k cC As ac =  k1C AsS a b
Overall molar rate of reaction ChE 231
Adv Chem Rxn Engg II

 
 overall  reaction rate 
flux to
reaction  = surface
=  out AND in 
 rate   the pellet 

k c ( C Ab − C As )  ( ac ) = ( k1C As )(S a b )
 

k cC Ab ac =  k1C AsS a b + k cC As ac
Overall molar rate of reaction ChE 231
Adv Chem Rxn Engg II

 
 overall  reaction rate 
flux to
reaction  = surface
=  out AND in 
 rate   the pellet 

k c ( C Ab − C As )  ( ac ) = ( k1C As )(S a b )
 

k cC Ab ac = C As ( k1S a b + k c ac )
Overall molar rate of reaction ChE 231
Adv Chem Rxn Engg II

 
 overall  reaction rate 
flux to
reaction  = surface
=  out AND in 
 rate   the pellet 

k c ( C Ab − C As )  ( ac ) = ( k1C As )(S a b )
 

k cC Ab ac
C As =
 k1S a b + k c ac
 −rA =  k1C As ChE 231
Adv Chem Rxn Engg II

 k1k cC Ab ac
−rA = Overall reaction rate with
 k1S a b + k c ac internal and external diffusion

Is this the overall reaction rate that we ALWAYS use for a surface
reaction that has both internal and external?
(a) Yes, we should always use this rate equation for a surface reaction
(b) No, we should only use this rate equation for processes that use spherical pellets
(c) No, we should only use this rate equation for processes that involve catalyst
particles that have a constant density and even catalyst loading on the surface
(d) No, we should only use this rate equation for 1 st order irreversible reactions
(e) b, c, & d
 Parametric analysis ChE 231
Adv Chem Rxn Engg II

External diffusion-limited:

DAB
−rA  k c = Sh → − rA = k c ( C Ab − C As )
dp
In what manner is the rate
 12
 Udp    
13 affected by the following:
DAB 2 + 0.6  
• Superficial velocity U
kc =    • Particle diameter dp
dp      DAB   • temperature
 
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Internal diffusion-limited:
−rA =  k1C AsS a

3   kS  ck1S a  
= R c 1 a
coth  R  − 1
2  c k1S a  De  D  
R  e  
De
In what manner is the rate affected by the
following:
• Superficial velocity U
• Particle diameter dp
• temperature
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Surface reaction-limited:
−rA = k1C A

In what manner is the rate

affected by the following:
• Superficial velocity U
• Particle diameter dp
• temperature
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Variation of reaction rate with

Type of
Limitation Superficial
Particle size Temperature
velocity

External U1/2 dp-3/2 Linear

Internal Independent dp-1 Exponential

Surface
Independent Independent Exponential
reaction
Question ChE 231
Adv Chem Rxn Engg II

According to these equations, if we increase the flow rate without

increasing the concentration of reactants in the feed, the observed
reaction rate will increase if the reaction is limited (slowed down) by:
a. External diffusion
b. Internal diffusion
c. The surface reaction
d. Either external and internal diffusion
e. Any of these (external diffusion, internal diffusion, or surface
reaction)
 ChE 231
Adv Chem Rxn Engg II

actual ( observed ) overall rate of reaction 

=  
reaction rate if entire interior surf ace w ere 
 exposed to the external surface conditions 

actual ( observed ) overall rate of reaction 

=  
reaction rate if entire interior s urface were 
 exposed to the bulk conditio ns 
 actual ( observed ) overall rate of reaction 
ChE 231
=   Adv Chem Rxn Engg II

reaction rate if entire interior s urface were 

 exposed to the bulk conditio ns 

−rA Derive expression for  in terms of

= , Sa, bulk density, k1, kc, ac

−rAb
 actual ( observed ) overall rate of reaction 
ChE 231
=   Adv Chem Rxn Engg II

reaction rate if entire interior s urface were 

 exposed to the bulk conditio ns 

 k1k cC Abac
−rA  k1S a b + k c ac
= =

−rAb k1C Ab

→ =
 k1S a b
1+
k c ac
 ChE 231
Adv Chem Rxn Engg II

Objective: Derive a new rate equation that accounts for

internal and external diffusion
• (-r’A) is a function of reactant concentration
• Reactant concentration is affected both by internal
and external diffusion
• Must express reactant concentration in terms of
diffusion-related constants & variables
 ChE 231
Adv Chem Rxn Engg II

−rA =  k1C As

 k1k cC Ab ac
−rA = Overall reaction rate with
 k1S a b + k c ac internal and external diffusion
Parametric analysis ChE 231
Adv Chem Rxn Engg II

External diffusion-limited:

DAB
−rA  k c = Sh → − rA = k c ( C Ab − C As )
dp

 12
 Udp    
13
DAB 2 + 0.6  
kc =   
dp      DAB  
 
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Internal diffusion-limited:

−rA =  k1C AsS a

3   kS  ck1S a  
= R c 1 a
coth  R  − 1
2  c k1S a  De  D  
R  e  
De

Surface reaction-limited: −rA = k1C A

Parametric analysis ChE 231
Adv Chem Rxn Engg II

Variation of reaction rate with

Type of
Limitation Superficial
Particle size Temperature
velocity

External U1/2 dp-3/2 Linear

Internal Independent dp-1 Exponential

Surface
Independent Independent Exponential
reaction
 ChE 231
16

Example 14

12 Adv Chem Rxn Engg II

The graph herein

-rA (mol/g cat-h)

10

shows the reaction 8

rates obtained when 6

the irreversible, 4

liquid-phase, 2
catalytic reaction A 0
→ B was carried out 0.0 0.1 0.2 0.3 0.4 0.5
dp (cm)
0.6 0.7 0.8 0.9

in a catalytic reactor
using the indicated
FT0=4000 mol/h, T=400K
FT0=4000 mol/h, T=300K
Which, if any, of the conditions
catalyst dp, T, and FT0. FT0=3500 mol/h, T=400K
shown illustrate a reaction that
CA0 was the same in FT0=3500 mol/h, T=300K
FT0=1000 mol/h, T=400K is limited by external diffusion?
each trial. FT0=1500 mol/h, T=400K
FT0=2000 mol/h, T=400K
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Variation of reaction rate with

Type of
Limitation Superficial
Particle size Temperature
velocity

External U1/2 dp-3/2 Linear

Internal Independent dp-1 Exponential

Surface
Independent Independent Exponential
reaction
 ChE 231
16

Example 14

12 Adv Chem Rxn Engg II

The graph below

-rA (mol/g cat-h)

10
* internal
shows the reaction 8 diffusion
external
rates obtained when 6
limited
diffusion
the irreversible, 4 limited
liquid-phase, 2
catalytic reaction A 0
→ B was carried out 0.0 0.1 0.2 0.3 0.4 0.5
dp (cm)
0.6 0.7 0.8 0.9

in a catalytic reactor
using the indicated
FT0=4000 mol/h, T=400K
FT0=4000 mol/h, T=300K
Which, if any, of the conditions
catalyst dp, T, and FT0. FT0=3500 mol/h, T=400K
shown illustrate a reaction that
CA0 was the same in FT0=3500 mol/h, T=300K
FT0=1000 mol/h, T=400K is limited by external diffusion?
each trial. FT0=1500 mol/h, T=400K
FT0=2000 mol/h, T=400K
 ChE 231
16

Example 14

12 Adv Chem Rxn Engg II

The graph below

-rA (mol/g cat-h)

10

shows the reaction 8

rates obtained when 6

the irreversible, 4

liquid-phase, 2
catalytic reaction A 0
→ B was carried out 0.0 0.1 0.2 0.3 0.4 0.5
dp (cm)
0.6 0.7 0.8 0.9

in a catalytic reactor
using the indicated
FT0=4000 mol/h, T=400K
FT0=4000 mol/h, T=300K
Which, if any, of the conditions
catalyst dp, T, and FT0. FT0=3500 mol/h, T=400K
shown illustrate a reaction that
CA0 was the same in FT0=3500 mol/h, T=300K
FT0=1000 mol/h, T=400K is limited by internal diffusion?
each trial. FT0=1500 mol/h, T=400K
FT0=2000 mol/h, T=400K
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Variation of reaction rate with

Type of
Limitation Superficial
Particle size Temperature
velocity

External U1/2 dp-3/2 Linear

Internal Independent dp-1 Exponential

Surface
Independent Independent Exponential
reaction
 ChE 231
16

Example 14

12 Adv Chem Rxn Engg II

The graph below

-rA (mol/g cat-h)

10

shows the reaction 8 internal diffusion

limited
rates obtained when 6

the irreversible, 4

liquid-phase, 2
catalytic reaction A 0
→ B was carried out 0.0 0.1 0.2 0.3 0.4 0.5
dp (cm)
0.6 0.7 0.8 0.9

in a catalytic reactor
using the indicated
FT0=4000 mol/h, T=400K
FT0=4000 mol/h, T=300K
Which, if any, of the conditions
catalyst dp, T, and FT0. FT0=3500 mol/h, T=400K
shown illustrate a reaction that
CA0 was the same in FT0=3500 mol/h, T=300K
FT0=1000 mol/h, T=400K is limited by internal diffusion?
each trial. FT0=1500 mol/h, T=400K
FT0=2000 mol/h, T=400K
 ChE 231
16

Example 14

12 Adv Chem Rxn Engg II

The graph below

-rA (mol/g cat-h)

10

shows the reaction 8

rates obtained when 6

the irreversible, 4

liquid-phase, 2
catalytic reaction A 0
→ B was carried out 0.0 0.1 0.2 0.3 0.4 0.5
dp (cm)
0.6 0.7 0.8 0.9

in a catalytic reactor
using the indicated
FT0=4000 mol/h, T=400K
FT0=4000 mol/h, T=300K
Which, if any, of the conditions
catalyst dp, T, and FT0. FT0=3500 mol/h, T=400K
shown illustrate a reaction that
CA0 was the same in FT0=3500 mol/h, T=300K
FT0=1000 mol/h, T=400K is limited by surface reaction?
each trial. FT0=1500 mol/h, T=400K
FT0=2000 mol/h, T=400K
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Variation of reaction rate with

Type of
Limitation Superficial
Particle size Temperature
velocity

External U1/2 dp-3/2 Linear

Internal Independent dp-1 Exponential

Surface
Independent Independent Exponential
reaction
 ChE 231
16

Example 14

12 surface Adv Chem Rxn Engg II

The graph below reaction

-rA (mol/g cat-h)

10
limited
shows the reaction 8

rates obtained when 6

the irreversible, 4

liquid-phase, 2
catalytic reaction A 0
→ B was carried out 0.0 0.1 0.2 0.3 0.4 0.5
dp (cm)
0.6 0.7 0.8 0.9

in a catalytic reactor
using the indicated
FT0=4000 mol/h, T=400K
FT0=4000 mol/h, T=300K
Which, if any, of the conditions
catalyst dp, T, and FT0. FT0=3500 mol/h, T=400K
shown illustrate a reaction that
CA0 was the same in FT0=3500 mol/h, T=300K
FT0=1000 mol/h, T=400K is limited by surface reaction?
each trial. FT0=1500 mol/h, T=400K
FT0=2000 mol/h, T=400K
 ChE 231
16

Example 14

12 Adv Chem Rxn Engg II

The graph below

-rA (mol/g cat-h)

10

shows the reaction 8

rates obtained when 6

surface reaction
the irreversible, 4
limited
liquid-phase, 2
catalytic reaction A 0
→ B was carried out 0.0 0.1 0.2 0.3 0.4 0.5
dp (cm)
0.6 0.7 0.8 0.9

in a catalytic reactor
using the indicated
FT0=4000 mol/h, T=400K
FT0=4000 mol/h, T=300K
Which, if any, of the conditions
catalyst dp, T, and FT0. FT0=3500 mol/h, T=400K
shown illustrate a reaction that
CA0 was the same in FT0=3500 mol/h, T=300K
FT0=1000 mol/h, T=400K is limited by surface reaction?
each trial. FT0=1500 mol/h, T=400K
FT0=2000 mol/h, T=400K
Example ChE 231
Adv Chem Rxn Engg II
The catalytic reaction
A → B takes place in a
reactor containing

-r’A (mol/g cat·s)

spherical porous
catalyst X22. The
overall reaction rates at
a point in the reactor
are shown in the graph.
For which, if any, of the
conditions shown is the
reaction limited by
internal diffusion?
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Variation of reaction rate with

Type of
Limitation Superficial
Particle size Temperature
velocity

External U1/2 dp-3/2 Linear

Internal Independent dp-1 Exponential

Surface
Independent Independent Exponential
reaction
Example ChE 231
Adv Chem Rxn Engg II
The catalytic reaction
A → B takes place in a
reactor containing

-r’A (mol/g cat·s)

spherical porous
catalyst X22. The
overall reaction rates at
a point in the reactor
are shown in the graph.
For which, if any, of the
conditions shown is the
reaction limited by
internal diffusion?
Example ChE 231
Adv Chem Rxn Engg II
The catalytic reaction
A → B takes place in a
reactor containing

-r’A (mol/g cat·s)

spherical porous
catalyst X22. The
overall reaction rates at
a point in the reactor
are shown in the graph.
For which, if any, of the
conditions shown is the
reaction limited by
external diffusion?
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Variation of reaction rate with

Type of
Limitation Superficial
Particle size Temperature
velocity

External U1/2 dp-3/2 Linear

Internal Independent dp-1 Exponential

Surface
Independent Independent Exponential
reaction
Example ChE 231
Adv Chem Rxn Engg II
The catalytic reaction
A → B takes place in a
reactor containing

-r’A (mol/g cat·s)

spherical porous
catalyst X22. The
overall reaction rates at
a point in the reactor
are shown in the graph.
For which, if any, of the
conditions shown is the
reaction limited by
external diffusion?
Parametric analysis ChE 231
Adv Chem Rxn Engg II

Variation of reaction rate with

Type of
Limitation Superficial
Particle size Temperature
velocity

External U1/2 dp-3/2 Linear

Internal Independent dp-1 Exponential

Surface
Independent Independent Exponential
reaction
Example ChE 231
Adv Chem Rxn Engg II
The catalytic reaction
A → B takes place in a
reactor containing

-r’A (mol/g cat·s)

spherical porous
catalyst X22. The surface
reaction
overall reaction rates at limited
a point in the reactor
are shown in the graph.
For which, if any, of the
conditions shown is the
reaction limited by
surface reaction?
Example ChE 231
Adv Chem Rxn Engg II
The catalytic reaction
A → B takes place in a
reactor containing

-r’A (mol/g cat·s)

spherical porous
catalyst X22. The
overall reaction rates at
a point in the reactor
are shown in the graph.
For a flow rate of 10
mol/h, determine the
overall effectiveness
factor  at 360 K.
 ChE 231
actual ( observed ) overall rate of reaction 
Adv Chem Rxn Engg II

=  
reaction rate if entire interior surf ace w ere 
 exposed to the external surface conditions 

actual ( observed ) overall rate of reaction  

=   =
reaction rate if entire interior s urface were   k1Sa b
 exposed to the bulk conditio ns  1+
k c ac
 Example ChE 231
Adv Chem Rxn Engg II
The catalytic reaction A → B

-r’A (mol/g cat·s)

takes place in a reactor containing
spherical porous catalyst X22.
The overall reaction rates at a
point in the reactor are shown in
the graph. For a flow rate of 10
mol/h, determine the overall
effectiveness factor  at 360 K.

actual ( observed ) overall rate of reaction  0.25

=   = = 0.38
reaction rate if entire interior surface were  0.66
 exposed to the bulk conditions 