IV-Heterogeneous Catalysis:

Internal Diffusion and Reaction

Internal resistance to diffusion

Thiele modulus
CAS

Internal effectiveness factor

r+r
r

1
Attendance monitoring
 After completing this section, you will
be able to:

• Describe diffusion and reactions in porous catalyst.

• Define the Thiele modules and the effectiveness factor to design

and use the precious catalysts in the most efficient way.

• Describe
• the regions of reaction limitations
• internal diffusion limitations & the conditions that affect them.
• Develop internal effectiveness factor
3
 Learning Outcomes for this section

A2.4.6- Be able to apply their knowledge of these principles to complex

problems with conflicting requirements
 Consider a porous catalyst sphere. Plots for CA in the catalyst pellet
vs. distance into the pellet are shown.

Which plot is most likely corresponding to a very fast

reaction?

A
CAb
B
R
r CA C

r=R r=0
 Let’s focus on step 2 & 6

1. Mass transfer (diffusion) of the reactant(s) from the bulk fluid to the
external surface of the catalyst pellet.

2. Diffusion of the reactant from the pore mouth through the catalyst
pores to the immediate vicinity of the internal catalytic surface.

3. Adsorption of reactant A onto the catalytic surface.

4. Reaction on the surface of the catalyst.

5. Desorption of the products from the surface.

6. Diffusion of the products from the interior of the pellet to the pore
mouth at the external surface.

7. Mass transfer of the products from the external pellet surface to the
bulk fluid.
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 Internal Diffusion Effects in Spherical
Catalyst Particles

• Internal diffusion: diffusion of the reactants or products from

the external pellet surface (pore mouth) to the interior of the
pellet. (Chapter 12-Fogler)
• 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
CAb CA(r) particle

External Internal External surface

diffusio diffusio
n n
 Basic Molar Balance for Differential Element-
to derive equation for diffusion and reaction

An irreversible rxn A→B occurs on the

CAs surface of pore walls within a spherical
pellet of radius R:
r Rate of A in at r = WAr · area =
R
r+Dr
Rate of A out at r - r = WAr · area =

Spherical shell of
inner radius r &
outer radius r+Dr

The mole balance over the shell thickness r is:

IN - OUT + GEN =ACCUM
 Diffusion Equation (Step 2)

Steady state assumption implies equimolar

CAs counter diffusion, WB = -WA (otherwise A or
B would accumulate)
r
R
r+Dr

Must use effective diffusivity, De, instead of DAB to account for:

1) Tortuosity of paths
2) Void spaces
3) Pores having varying cross-sectional areas
DA bulk diffusivity
 ppellet porosity (Vvoid space/Vvoid & solid) (typical ~ 0.4)
 constriction factor (typical ~ 0.8)
~ tortuosity (distance molecule travels between 2
pts/actual distance between those 2 pts) (typical
~ 3.0)
 Diffusion & Rxn in a Spherical Catalyst
dy A dC
Diffusion: WA  cDe  De A
dr dr
 Dimensionless Variables

d dC A 2  2 n
 D r  r C a n A 0
S k " C
dr  e dr 

 The solution for a 1st order rxn

Fn ≡ Thiele modulus for rxn of nth order "a" surface rxn rate
n2 
Subscript n = reaction order "a" diffusion rate

fn is small: surface reaction is rate limiting

fn is large: internal diffusion is rate limiting

The solution for a 1st order

CA 1  sinh 1 
  
rxn: CAs   sinh 1 

small 1
CA
CAs medium 1
large 1
R r=0
• small 1: surface rxn control, significant amount of reactant diffuses
into pellet interior w/out reacting
• large 1: surface rxn is rapid, reactant is consumed very closed to the
external surface of pellet (A waste of precious metal inside of pellet)
 Internal Effectiveness Factor, h

rnal effectiveness factor:

he relative importance of diffusion and reaction limitations
measurement of how far the reactant diffuses into the pellet before rea
actual observed overall rate of rxn

rate of reaction if entire interior surface were exposed to C As & Ts
 rA  r ''A  r 'A mass of catalyst 
  
 rAs  r ''As  r 'As mass of catalyst 

For example, when n=1 (1st order kinetics, -r’’As )

 Internal Diffusion & Overall Rxn Rate
 r '' A   r ''As 
h quantifies how internal diffusion affects the overall rxn r
Effectiveness factor vs fn
1
0.8 Reaction limited
0.6
h 0.4

0.2
Internal diffusion limited
0.1
0.2 1 2 4 6 8 10
f1
As particle diameter ↓, fn ↓, h→1, rxn is surface rxn limited
As particle diameter ↑, fn ↑, h→0, rxn is diffusion limited
This analysis was for spherical particles. A similar approach can
be used to evaluate other geometries, non-isothermal rxn, & more
complex rxn kinetics
Internal effectiveness factor for nth order reaction kinetic-sphere
Internal effectiveness factor for various geometries-
1st order reaction
 Example: A zero‐order isothermal reaction

A zero‐order isothermal reaction takes place in a porous

catalyst slab that is 4‐mm thick and has essentially infinite
dimensions in the other two directions. The effectiveness
factor for the reaction is 0.60. Another slab of the same
catalyst has a thickness of 8 mm. What is the effectiveness
factor in this new slab?

4 mm
8 mm

A. 1.2
B. 0.6
C. 0.3
D. Not enough data 17
 Rxn Rate Variation vs Reactor Conditions

 12 13 
D AB DAB  Udp   
External diffusion  r ' A  k c  Sh  k c   2  0.6     
dp dp 
      DAB  

3  ck1Sa  c k1Sa  
Internal diffusion  rA k r C AsSa    R coth  R   1

kS De De 
R2 c 1 a   
De

Surface reaction -r’A=kCA

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
 A zero-order isothermal reaction takes place in a porous catalyst
slab of thickness L.

The reactant concentration is only non-zero for a

distance b into the slab. For a slab twice as thick, what
distance does the reactant penetrate into the slab?

CAs
b
L

CAs

2L
 Example:
The catalytic reaction A  B takes place within a fixed bed reactor containing spherical
porous Zeolite 5A. Figure 1 shows the overall rates of reaction, at a point in the reactor,
as a function of particle size for two reaction temperatures. Total flow rate (F To) is
constant and there are no external diffusion limitations.

(a)Which range of temperature and particle size are “internal diffusion-limited”? Explain
briefly.

(b) Which range of temperature and particle size are “reaction-rate-limited”? Explain
Rate (mol.g-1.s-1)

20
briefly.
15

400 oC
10

5 300 oC

Particle diameter (cm)

The concentration of a reactant is plotted as a function of radius in three
porous catalyst spheres. The diffusivity is the same for each catalyst.
Which catalyst converts the largest amount of reactant in a given time?
Explain your answer.

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 What did you learn?

I can define the regions in a

given data with external
diffusion limitations.

I confidently explain external/internal

diffusion and reaction rate limited areas
in plot.

A
CAb
B
R
C C
r
I can explain which plot is to
A

D
describe very fast/slow
r= r=
reaction R 0
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