CHE 625

TOPIC 3.2 : Diffusion and

Reaction
Ref: Fogler (Chapter 12) 4th ed.
Pg 813 onwards

SUBTOPICS

Diffusion and Reaction in Spherical Catalyst Pellets

Effectiveness factor
Estimation of diffusion and Reaction limited regimes
Pore diffusion Resistance and Surface kinetics
Porous catalyst particles
Gas liquid reaction on solid catalyst reaction and its
application

Internal Mass Transfer in Porous Catalysts

Previously, we have examined the potential influence of external mass transfer

on the rate of heterogeneous reactions.
However, where active sites are accessible within the particle, internal mass
transfer (molecular diffusion) has a tremendous influence on the rate of
reaction within the catalyst. Numerous examples exist:
Encapsulated or entrapped enzymes
Microporous catalysts for catalytic cracking (zeolites)
The diffusion rate of reactants and products within the particle often
determines the rate at which a microporous catalyst functions.
22.3

CHEE 323

Concentration Gradients of Diffusing Reactants and Products

In a Uniform Catalyst Particle

CAs

Spherical catalyst particle with diffusing

reactant. CAs is the concentration of
reactant at the particle periphery.

* Concentration at R (pore mouth) should be

higher as compared to concentration at any
point inside the pore
CHE625

Intraparticle Mass Transport

A simple but conceptually useful treatment of intra-particle
mass transfer describes the diffusion of a reactant within a
uniform
catalyst particle.
Assumptions:
Uniform catalytic activity throughout the spherical particle
Uniform properties of solid
Irreversible, first-order kinetics; rate = k CA
Given that mass transfer occurs by molecular diffusion, an
analytical expression for the transport and consumption of
our reactant can be written.

22.5

CAs

Diffusion/Rxn in Porous Catalysts

Pores are tortuous and have varying cross-sectional area
Need to define an effective diffusion coefficient in radial
direction
Effective Diffusivity (De) is a measure of diffusivity that
accounts for the following:
Not all area normal to flux direction is available for molecules to
diffuse in a porous particle (P)
Diffusion paths are tortuous ()
A P
Pore cross-sections vary ()
e
Internal void fraction, s = P

D
D ~

Go thru Example 12-1 pg 815 (Fogler)

STEPS IN INTERNAL DIFFUSION &

REACTION
1. Perform Shell Balance in the radial direction and outward
(increasing r) - in terms of molar flux times area
2. Write the expression for WAr (for EMCD and dilute
concentrations)
3. Write the corresponding rate law (relate rA, -rA and -rA) and
relate with shell balance
4. Set boundary conditions for CA (based on position r)
5. Write the equation in dimensionless form to obtain (Thiele
modulus) in terms of two dimensionless quantities and
6. Obtain W expression with dimensionless quantities included
7. Determine concentration profile for the spherical cat. pellet.

Diffusion/Rxn in Porous Catalysts

Step #1 : Perform Shell balance in radial direction
rate in at r

WAr 4r

rate of generation within shell

rate out at r + r

WAr 4r 2

rA'

r r

R
r + r
r

4rm2 r

reaction rate
catalyst mass
shell volume
catalyst mass
shell volume

steady state mass balance

WAr 4r 2 WAr 4r 2
r

r r

rA' C 4rm2 r 0

d WArr 2
rA' Cr 2 0
dr
cat
A
B

Diffusion/Rxn in Porous Catalysts

Step 2: Write the expression for WAr

d WArr 2
rA' Cr 2 0
dr

Step 3: Write rate laws

rate equation
definitions

substitute Ficks Law

dCA
WAr De
dr
d
dCA 2 '
r rA Cr 2 0
De
dr
dr

d
dCA 2 " n 2 2
r rkAnS
De
CaASCarCr 0 0
dr
dr

rA" k nC2A
rA' Sak nC2A
rA CSak nC2A

Diffusion/Rxn in Porous Catalysts

dC
d2
A 2knSaCRn 2CnAs1 2 n
2d
r k nCA SaCr 0
0
2 De
dr
d ddr

De

d2CA 2 dCA k nSaC n

CA 0


2
dr
r dr De
Step 4: Identify boundary conditions
symmetry

CA r 0 finite

surface

CA r R CAs

Step 5a: Write the equation

in dimensionless form

CA

C As

dCA
C As
d

dr 1

d R
dCA d CAs

dr
d R

Diffusion/Rxn in Porous Catalysts

d2 2 d k nSaCR2CnAs1 n
0

2
d d
De

Step 5b : define Thiele modulus (n)

d2 2 d
2 n

n 0
2
d d

d2CA 2 dCA k nSaC n

CA 0


2
dr r dr De
n1
As

k nSaCR C

De
2

2
n

understand the Thiele modulus

n
k
S

RC
n2 n a C As
De CAs 0 R

reaction rate
diffusion rate

large n - diffusion controls

small n - kinetics control

Diffusion/Rxn in Porous Catalysts

first order
kinetics
(n = 1)

define y =

d2 2 d
2

1 0
2
d d
d 1 dy y
2
d d

d2 1 d2 y 2 dy 2y
2 2 3
2
d
d d
differential has the solution

12

k nS a C 2
R
De

d2 y
2

1y 0
2
d

apply boundary conditions

y A1 cosh1 B1 sinh1

0, is finite

1, 1

A1

cosh1 B1 sinh1

Diffusion/Rxn in Porous Catalysts

first order
kinetics
(n = 1)

d2 2 d
2

1 0
2
d d

1 sinh1 C A


sinh1 C As

differential has the solution

k nS a C 2

R
De
2
1

d2 y
2

1y 0
2
d
apply boundary conditions

y A1 cosh1 B1 sinh1

0, is finite

1, 1

A1

cosh1 B1 sinh1

Thiele Modulus
d 1

CA

C As

1 sinh 1

sinh 1

1
d 1

Refer Figure 12-4 pg 823

for concentration

profile

d 2
0.5

d 5
d 20

0.5

Go thru Example 12-2 pg

823

Internal Effectiveness Factor ()

The internal effectiveness factor () is a measure of the
relative importance of diffusion to reaction limitations:

actual overall reaction rate

rate if entire surface were exposed to CAs, Ts

rA
rA'
rA"
MA

' "
rAs rAs rAs MAs

M mol / time
r mol / time / mass cat

Internal Effectiveness Factor ()

Determine MAs (rate if all surface at CAs)
MAs

surface area
masscatalyst
rate per unit area
masscatalyst

MAs

'
As

k1CAs

MAs k1CAsSa 34 R3c

Sa

VC

Internal Effectiveness Factor ()

Determine MA (actual rate is equal to reactant diffusion
rate at outer surface)

d
MA 4RDeCAs
d 1

MA 4RDeCAs 1 coth 1 1
1 cosh1 1 sinh1
d
1 coth 1 1

2
d 1 sinh1
sinh1 1

Internal Effectiveness Factor ()

Substitute results into definition of

MA

MAs

4RDeCAs 1 coth 1 1

k1CAsSa 34 R3c

De
1 coth 1 1
3
2
k1SaR c

3
2 1 coth 1 1
1

coth 1 ()
Internal Effectiveness Factor
3

1 0
1

small dp

1 2
32 1 1

0.1
0.1

1 20

3
12

3
R

De
k1c Sa

10

3
2 1 coth 1 1
1

100

coth 1

Internal Effectiveness Factor ()

1 0
1

1 2
32 1 1

internal
diffusion
limited

reaction
rate
limited

0.1
0.1

1 20

3
12

3
R

De
k1c Sa

10

3
2 1 coth 1 1
1

100

Effectiveness Factor
Note that internal diffusion resistance decreases with decreasing
. Therefore, the influence of diffusion on the reaction rate
supported by a particle is reduced when particle radius is reduced,
DAB is high and the rate constant is relatively small.

22.21

Revisit and
Thiele modulus -
Derived for spherical particle geometry
Derived for 1st order kinetics
For large , approximately

12

n 1

Internal effectiveness factor -

Assumed =0, correction applied when 0
Assumed isothermal conditions

3
12

Non-Isothermal Behavior
For exothermic reactions, can be > 1 as internal
temperature can exceed Ts.
The rate internally is thus larger than at the surface
conditions where is evaluated.
The magnitude of this effect is dependent on
Hrxn, Ts, Tmax, and kt (thermal conductivity of the pellet)

and are used to quantify this effect:

E
ArrheniusNumber
RTs

Tmax Ts HrxnDeCAs

Ts
k t Ts

can result in mulitple steady states

No multiple steady states exist if Luss criterion is fulfilled

41

Overall Effectiveness Factor

When both internal AND external diffusion resistances are
important (i.e., the same order of magnitude), both must be
accounted for when quantifying kinetics.
It is desired to express the kinetics in terms of the bulk
conditions, rather than surface conditions:

actual overall reaction rate

rate if entire surface were exposed to CA,bulk

Overall Effectiveness Factor

Accounting for reaction both on and within the pellet, the
molar rate becomes:

MA rA" ac Sac 1 V

WAac rA" ac Sab

For most catalyst, internal surface area is significantly higher

than the external surface area:

WA ac rA" Sab

Overall Effectiveness Factor

reaction rate
(internal & external surfaces)

WA ac rA" Sab
internal surfaces not
all exposed to CAs

mass transport rate

WArac V k c CA,bulk CAs ac V

Relation between CAs and CA
defined by the as:

"
rA" rAs
k1CAs

WA ac V k1CAsSab V
k c CA,bulk CAs ac k1CAsSab

Overall Effectiveness Factor

reaction rate
(internal & external surfaces)

WA ac rA" Sab

mass transport rate

WArac V k c CA,bulk CAs ac V

Relation between CAs and CA
defined by the as:

Solving for CAs:

CAs

"
rA" rAs
k1CAs

ack c CA,bulk

ack c k1Sab

Overall Effectiveness Factor

reaction rate
(internal & external surfaces)

WA ac rA" Sab

mass transport rate

WArac V k c CA,bulk CAs ac V

k1k c ac CA,bulk
"
rA
Substitution into the rate law:
ack c k1Sab
Solving for CAs:

CAs

ack c CA,bulk

ack c k1Sab

Overall Effectiveness Factor

summary of factor relationships:

"
rA" rA" ,bulk rAs

"
rAs
k1CAs
"
rAb
k1CAb

Rearranging the expression:

k1k c ac CA,bulk

"
k1CA,bulk rA
1 k1Sab k c ac
ack c k1Sab

r r
"
A

"
A,bulk

1 k1Sab k c ac
Overall Effectiveness Factor ()

Weisz-Prater Criterion
Weisz-Prater Criterion is a method of determining if a given
process is operating in a diffusion- or reaction-limited regime
CWP is the known as the Weisz-Prater parameter. All quantities are
known or measured.

CWP

'
2

r
R
c
A,obs
2
1
DeCAs

CWP << 1, no C in the pellet (kinetically limited)

CWP >> 1, severe diffusion limitations

Go thru Example 12-3 pg 839

Mears Criterion
Mass transfer effects negligible when it is true that

rA' Rbn
0.15
k c C Ab
n is the reaction order, and the transfer coefficients kc and h
(below) can be estimated from an appropriate correlation
(i.e., Thoenes-Kramers for packed bed flow)

Heat transfer effects negligible when it is true that

Hrxn rA' bRE

0.15
2
hRgTb

Application to PBRs Mass Transfer

and Reaction
Shell balance on
volume element Az

Mole flux of A

dWAz '
rA b 0
dz
WAz

First order reaction

dCA
DAB
CAbU
dz

'
rA' rAb
kSaCAb

d CAb
dCAb '
DAB
U
r
0
AbkS
A
aCAb 0
2
dz
dz

Application to PBRs
Axial dispersion negligible
(relative to forced axial
convection) when

rA' b dp
UoC Ab

dp is the particle diameter

Uo is the superficial velocity of the gas
Da is the effective axial dispersion coefficient
Which can be rewritten as:

d2CAb
dCAb
DAB
U
bkSaCAb 0
2
dz
dz

Uo dp
Da

Application to PBRs
Entrance condition:

CAb z0 CAbo

Integrating and applying boundary condtion yields:

CAb

bkSa z
CAbo exp

Which can be rewritten as:

dCAb
bkSa

CAb
dz
U
Go thru Example 12-4 pg 845

Problem in Class (pg 860-Fogler)

THE END of CHAPTER 3