Chapter 12

Diffusion and Reaction

in Porous Catalysts
Diffusion and Reaction in Spherical Catalyst Pellets
In a heterogeneous sequence, a) mass transfer from C Ab CAs CA (r)
bulk fluid to external surface, b) diffusion from external
Internal
surface into and through the pores to catalytic surface External
diffusion
diffusion

Effective Diffusivity
Only radial variations in the concentration will be considered; the radial flux WAr will
be based on the total area (voids and solids) normal to diffusion transport rather
than void area alone. This basis for WAr is made possible by proper definition of the
effective diffusivity De.

The effective diffusivity accounts for the fact that:

1. Not all of the area normal to the direction of the flux is available for the
molecules to diffuse
2. The paths are tortuous
3. The pores are of varying cross-sectional areas

actual distance a molecule travels between two points

τ = tortuosity =
shortest distance between those two points
D A φp σ volume of void space
De = ~ ϕ p = pellet porosity =
total volume (voids and solids)
τ
σ = constriction factor
Differential Equation Describing Diffusion and Reaction
A→B
R
rate of A in at r = WAr .area = WAr 4πr 2
r

rate of A out at (r + Δr ) = WAr .area = WAr 4πr 2

r + Δr
r + Δr
⎛ rate of generation ⎞
⎜ ⎟ ⎛ rate of reaction ⎞ ⎛ mass of catalyst ⎞
⎟ (volume of shell)
r
⎜ of A within a shell ⎟ = ⎜⎜ ⎟⎟ ⎜
⎜ thickness of Δr ⎟ ⎝ mass of catalyst ⎠ ⎝ volume ⎠
⎝ ⎠
= rAʹ′ ρc 4πrm2 Δr
The mole balance over a shell thickness Δr
(
d WAr r 2 ) − rʹ′ ρ r 2
=0
WAr 4πr 2 - WAr 4πr 2 + rAʹ′ ρc 4πrm2 Δr = 0 dr
A c
r r + Δr

dy A dC
We have EMCD at const. total conc. WAr = −cD e = −De A
dr dr
⎛ dCA 2 ⎞
d⎜ − De r ⎟
⎝ dr ⎠ − rʹ′ ρ r 2 = 0
A c
dr
We have to incorporate the rate law

−rA [ = ] ( mol / dm s ) 3

− rA" [ = ] ( mol / g cat.s )

− rA""[ = ] ( mol / m s ) 2 − rAʹ′ = − rAʹ′ʹ′ Sa A→B

Sa [ = ] ( m / g cat )
2

At high temperatures denominator of the catalytic rate law approaches 1.

It is reasonable to assume that the surface reaction is of nth order in the
gas phase concentration of A within the pellet
n −1
⎛ m 3 ⎞ m
− rAʹ′ʹ′ = k n C nA k n [=] ⎜⎜ ⎟
⎟
⎝ kmol ⎠ s
n −1 n −1
⎛ m 3 ⎞ m3 ⎛ m 3 ⎞ 1
- rAʹ′ : Sa k n [=] ⎜⎜ ⎟
⎟ - rA : ρcSa k n [=] ⎜⎜ ⎟
⎝ kmol ⎠ kg.s ⎟
⎝ kmol ⎠ s
 " dC % " dC %
d $ −De A r 2 ' d $ −De A r 2 '
# dr & # dr &
− rA( ρc r 2 = 0 substituting rate law − knC An Sa ρc r 2 = 0
dr dr

d 2C A 2 dC A kn S a ρc n
2
+ − CA = 0
dr r dr De
Boundary conditions
1. The concentration remains finite at the center of the pellet: CA is finite at r = 0

1. At the external surface of the pellet, the concentration is CAs: CA=CAs at r = R

CA r
Dimensionless variables ϕ and λ must be introduced ϕ= and λ=
C As R
With the transformation of variables boundary
conditions
C
CA=CAs at r = R becomes ϕ = A =1 at λ =1
C As
CA is finite at r = 0 becomes ϕ is finite at λ=0
d 2 C A 1 dC A k n S a ρ c n
2
+ − CA = 0
dr r dr De
dϕ
Using chain rule
dC A dC A dλ dϕ dC A dλ
dλ = =
dr dλ dr dλ dϕ dr
dC A
= CAs
dϕ dC A dϕ C As d 2CA d ⎛ dC A ⎞ d ⎛ dϕ CAs ⎞ dλ d 2ϕ ⎛ CAs ⎞
= 2
= ⎜ ⎟ = ⎜ ⎟ = 2 ⎜ 2 ⎟
dλ 1 dr dλ R dr dr ⎝ dr ⎠ dλ ⎝ dλ R ⎠ dr dλ ⎝ R ⎠
=
dr R
d 2ϕ 2 dϕ k n R 2Sa ρc C nAs−1 n
2
+ − ϕ =0
dλ λ dλ De

d 2ϕ 2 dϕ 2 n 2 k n R 2Sa ρc C nAs−1
+ − φn ϕ = 0 φ =
n
2
dλ λ dλ De
 Thiele Modulus: φn

k n R 2Sa ρc C nAs−1
φn =
De

k n R 2Sa ρc C nAs−1 k n Sa ρc C nAs R " a" surface reaction rate

φ2n = = =
De D e [(C As − 0) / R ] " a" diffusion rate

φn2 is a measure of the ratio of “a” surface reaction rate to “a” reaction
rate of diffusion through the catalyst pellet

When φn is large, internal diffusion usually limits the overall rate of reaction;
when φn is small, surface reaction is usually rate limiting

For the reaction A → B the surface reaction is rate limiting with respect
to the adsorption of A and desorption of B, and if A and B are weakly
adsorbed and present in very dilute concentrations,
 − rA"" ≈ k1C A k1 $% m3 / m2 s &'

d 2ϕ 2 dϕ 2 k1Sa ρc
2
+ − φ1 ϕ = 0 φ1 = R
dλ λ dλ De

ϕ1 = m
( m / s)( m 2
)(
/ g g / m3 ) (dimensionless)
2
m /s

Boundary conditions: ϕ = 1 at λ =1
ϕ is finite at λ=0

Variable transformation: Let y = ϕλ

dϕ 1 dy y d 2ϕ 1 d 2 y 2 dy 2y
= − 2 and 2
= 2
− 2 + 3
dλ λ dλ λ dλ λ dλ λ dλ λ

d2y 2
2
− φ1 y = 0
dλ
 d2y 2
2
− φ1 y = 0
dλ
Operators can be used to solve the differential equation

dy d
my = where m is elementary operation
dx dx
2 d2y
m( my ) = m y = 2
dx

d2y 2
dλ2
− φ1 y = m (
2
− φ1
2
y=0 ) m2 − φ12 = 0 m = ± φ1

y = A1e − φ1λ + A 2 e φ1λ or y = A cosh(φ1λ) + B sinh(φ1λ)

ex + e−x ex − e−x
cosh( x ) = sinh(x ) =
2 2
A B
in terms of ϕ ϕ= cosh(φ1λ) + sinh(φ1λ)
λ λ
 A B
ϕ= cosh(φ1λ) + sinh(φ1λ)
λ λ
at λ = 0 cosh(φ1λ) → 1, (1/λ) → ∞ and sinh(φ1λ) → 0

Boundary conditions: ϕ = 1 at λ =1
ϕ is finite at λ=0

Because the 2.B.C. requires ϕ to be finite at the center, A must be zero

Evaluating B from 1. B.C., using in the equation, the dimensionless
concentration profile is
C 1 ⎛ sinh(φ1λ) ⎞
ϕ = A = ⎜⎜ ⎟⎟
CAs λ ⎝ sinh(φ1 ) ⎠

Small values of φ is the indication of surface reaction

control. Large amount of reactant diffuses into the pellet
without reacting
Large values of φ is the indication of rapid surface
reaction. Reactant consumed very close to the external
surface and very little penetrates into the pellet
Internal Effectiveness Factor: η
The effectiveness factor indicates the relative importance of diffusion and
reaction limitations

actual overall rate of reaction − rA − rAʹ′ − rAʹ′ʹ′

η= η= = =
rate of reaction that would result if entire interior surface − rAs − rAs − rAs
ʹ′ ʹ′ʹ′
were exposed to the external pellet surface conditions C As , Ts

To derive the effectiveness factor for a first order reaction it is easier to

work in reaction rates of (moles per unit time)

− rAʹ′ − rʹ′ × mass of catalyst M A

η= = A =
− rAs
ʹ′ − rAs
ʹ′ × mass of catalyst M As

! surface area $
M As = ( rate per unit surface area ) # & ( mass of catalyst )
" mass of catalyst %

!4 $ !4 $
= ( 1 As a ) #"
k C S π R 3
ρ c&
%
= − r *
As #
"3
π R 3
ρ c&
%
3
The actual rate of reaction is the rate at which the reactant diffuses into
the pellet at the outer surface.
The actual rate of reaction MA can be obtained by multiplying the molar
flux at the outer surface by the external surface area of the pellet
dC A dϕ
M A = −4πR 2 WAr r =R = 4πR 2 De = 4πRDeCAs
dr r =R dλ λ=1

CA 1 ⎛ sinh φ1λ ⎞
ϕ= = ⎜⎜ ⎟⎟ Differentiating and evaluating the result at λ1
CAs λ ⎝ sinh φ1 ⎠

dϕ ⎛ φ cosh φ1λ 1 sinh φ1λ ⎞

= ⎜⎜ 1 − 2 ⎟⎟ = (φi coth φ1 − 1)
dλ λ =1 ⎝ λ sinh φ1 λ sinh φ1 ⎠λ =1

M A = 4πRDeCAs (φ1 coth φ1 − 1)

M A 4πRD e C As (φ1 coth φ1 − 1) 1

η= = =3 2
(φ1 coth φ1 − 1)
M As 4 k1Sa ρc R / D e
ʹ′ ⎛⎜ πR 3ρc ⎞⎟
− rAs
⎝ 3 ⎠
 3 3
η= 2
(φ1 coth φ1 − 1) = 2
(φ1 coth φ1 − 1)
k1Sa ρc R / De φ1

3
η = 2 (φ1 coth φ1 − 1)
φ1

ηʹ′
η
 3 dp ↓ φ1 ↓ ⇒ η ≈ 1 ∴ surface reaction limited
η= 2
(φ1 coth φ1 − 1)
φ1 φ1 ↑ (≈ 30) ⇒ η↓ ∴ diffusion limited

3
If φ1 > 2 η≈ 2
(φ1 − 1)
φ1
3 3 De For large values of
If φ1 > 20 η≈ =
φ1 R k1Sa ρc the Thiele modulus

# Actual reaction rate &

−rA" = % ( ) ( ) (
( Reaction rate at C As = η -rAs" = η k1C As Sa
$ Reaction rate at C As '
)
The overall rate of reaction for a first 3 k1Sa De
− rAʹ′ = C As
order, internal diffusion limited reaction R ρc
To increase the overall rate of reaction: − rAʹ′

1. decrease dp
2. increase temperature
3. increase concentration
4. increase the internal surface area
For reactions of order n
2 k n R 2Sa ρc C nAs−1
φ =
n
De
For large values of the Thiele
modulus, η
1/ 2 1/ 2
⎛ 2 ⎞ 3 ⎛ 2 ⎞ 3 De
η = ⎜ ⎟ = ⎜ ⎟ C(As1−n ) / 2
⎝ n + 1 ⎠ φn ⎝ n + 1 ⎠ R k nSa ρc

η decreases with increasing Cas for n>1

Effectiveness factor can be greater than 1 for exothermic and nonisothermal

reactions.
E
γ = Arrhenius number =
RTs
ΔTmax Tmax − Ts ΔH Rx D e C As Prater Number
β=
Ts
=
Ts
=
k t Ts
For multiple
steady state Luss
6.5 < γ < 29.4
(β = 0.025, φ1 = 0.22) (β = 6 ×10 −5 , φ1 = 1.2) 4(1 + β) > βγ
Falsified Kinetics − rAʹ′ = kʹ′n CnAsʹ′

ʹ′ ) = η(k nSa CnAs )

− rAʹ′ = η(−rAs

for large Thiele modulus φn

3 2 3 2 De
− rAʹ′ = k nSa CnAs = k nSa CnAs
φn n +1 R n + 1 ρcSa k n

3 2DeSa 1 / 2 ( n +1) / 2 3 2DeSa 1 / 2 ( n +1) / 2

− rAʹ′ = k n CAs − rAʹ′ = k n CAs = kʹ′n CnAsʹ′
R (n + 1)ρc R (n + 1)ρc

3 2De Sa 1/2 (n +1)/2 n!

n +1
kn = kn" C As = C As n! =
R (n + 1)ρc 2
There is also an apparent activation energy, Eapp

kʹ′n = A app exp(−E app / RT ) k n = A T exp(−E T / RT )

3 2DeSa
− rAʹ′ =
R (n + 1)ρc
[ ]
[AT exp(−ET / RT)]1/ 2 C(Asn +1) / 2 = Aapp exp(−Eapp / RT) CnAsʹ′

Taking the natural logarithm of both side

⎧⎪ 3 2DeSa 1/ 2 ( n +1) / 2 ⎫⎪ E T E app

ln⎨
⎪⎩ R (n + 1)ρc
AT CAs ⎬ −
⎪⎭ 2RT
[ nʹ′
= ln A appCAs −]RT

E T = 2E app
Overall Effectiveness Factor C Ab CAs CA
External Internal
resistance resistance

The molar rate of mass transfer from the bulk fluid to the external surface
is
molar rate = ( molar flux ) ( external surface area )
M A = WAr ( surface area/volume ) ( reactor volume )

M A = WAr a c ΔV
The molar rate of mass transfer to the surface is equal to the
net (total) rate of reaction on and within the pellet

MA = −rAʹ′ʹ′ (external area + internal area)

! external area $
external area = # & reactor volume = a c ΔV
" reactor volume %
 ( )
internal area = Saρc 1− φ ΔV = Saρb ΔV

( ) (
MA = −rA"" external area + internal area = −rA"" ac ΔV + Saρb ΔV )
M A = WAr a c ΔV (
WAr ac = −rA"" ac + Saρb )
For most catalysts Sa>>ac WAr ac = −rA""Saρb
The rate of mass transport is (
M A = WAr ac ΔV = k c C Ab − C As ac ΔV )
Effectiveness factor is a measure of surface − rAʹ′ʹ′ = η(−rAs
ʹ′ʹ′ )
accessibility
For a first order surface reaction − rAʹ′ʹ′ = η(k1CAs )

Net rate of reaction is equal to the rate of

mass transfer of A from the bulk fluid to WAr ac = η k1C AsSaρb
the external surface
 η k1CAsSa ρb = k c (CAb − CAs )a c

k c C Aba c ηk1k c C Ab a c
C As = − rAʹ′ʹ′ =
k c a c + η k1Sa ρ b k c a c + η k1Sa ρ b
actual overall rate of reaction
η=
rate of reaction that would result if entire interior surface
were exposed to the external surface concentration C As

actual overall rate of reaction

Ω=
rate of reaction that would result if entire surface
were exposed to the bulk concentration, C Ab

η
− rAʹ′ʹ′ = kC Ab − rAʹ′ʹ′ = Ω(− rAb
ʹ′ʹ′ ) = Ωk1CAb
1 + η k1Sa ρ b / k c a c
η
Ω=
1 + η k1Sa ρ b / k c a c
 −rA"" = Ω −rAb(
"" = η −rAs
"" ) ( )
-rAs!! =k1!!C As
-rAb
!! =k1!!C Ab

Actual rate of reaction

−rA = −rA" ρb = −rA""Saρb

−rA = rAbΩ = rAb

# ρbΩ = −rAb
## SaρbΩ = k1##C AbSaρbΩ
" m3 %
k1!! $ 2 '
# m .s &
 Estimation of Diffusion- and Reaction-Limited Regimes
Weisz-Prater Criterion for Internal Diffusion

Weisz-Prater Criterion uses measured values of the rate of reaction to

determine if internal diffusion is limiting the reaction

ηφ12 = 3(φ1 coth φ1 − 1) CWP = ηφ12

2 observed (actual) reaction rate reaction rate evaluated at C As

C WP = ηφ =
1 ×
reaction rate evaluated at C As a diffusion rate

2 observed (actual) reaction rate

C WP = ηφ =
1
a diffusion rate
− rAʹ′ (obs ) − r ʹ′
ʹ′ S ρ R 2
− r ʹ′ ρ R 2
η= and φ12 = As a c = As c
− rAsʹ′ De C As De C As
 ʹ′ ρc R 2 ⎞
− rAʹ′ (obs ) ⎛ − rAs
C WP = ⎜⎜ ⎟⎟
− rAsʹ′ ⎝ De C As ⎠

− rAʹ′ (obs)ρc R 2
C WP =
D e C As

If CWP << 1: There are no diffusion limitations and no

concentration gradient exists within the pellet

If CWP >> 1: Internal diffusion limits the reaction severely

Example: The first order reaction A→B was carried out over two different-
sized pellets. The pellets were contained in a spinning basket reactor that
was operated at sufficiently high rotation speed that external mass transfer
resistance was negligible. The results of two experimental runs made under
identical conditions are given in table. Estimate the Thiele modulus and
effectiveness factor for each pellet. How small the pellets be made to virtually
eliminate all internal diffusion resistance ?

Measured Rate Pellet Radius

× -5
(mol/g-cat.s) 10 (m)
Run 1 3.0 0.01
Run 2 15.0 0.001

− rAʹ′ (obs)ρc R 2
C WP = = 3(φ1 coth φ1 − 1)
D e C As
Let the subscripts 1 and 2 refer to runs 1 and 2. Taking the ratio
2
− rA 2 R 2 φ12 coth φ12 − 1
ʹ′
2
=
− rAʹ′ 1R1 φ11 coth φ11 − 1
 − rAs
ʹ′ ρc Taking the ratio of Thiele φ11 R 1
φ1 = R =
De CAs moduli for runs 1 and 2 φ12 R 2

R1 0.01
φ11 = φ12 = φ12 = 10φ12
R2 0.001

− rAʹ′ 2 R 22 φ12 coth φ12 − 1 (15)(0.001) 2 φ12 coth(φ12 ) − 1

2
= 2
= = 0.05
− rAʹ′ 1R1 φ11 coth φ11 − 1 (3)(0.01) 10φ12 coth(10φ12 ) − 1

Solving φ12 = 1.65 and φ11 = 16.5

3(φ12 coth φ12 − 1) 3(1.65 coth(1.65) − 1)

η2 = 2
= 2
= 0.856
φ12 1.65
3(16.5 coth(16.5) − 1)
η1 = 2
= 0.171
16.5
For the particle radius needed to virtually eliminate internal diffusion,
let η = 0.95

3(φ1 coth(φ13 ) − 1) φ13 = 0.9

η= 2
= 0.95
φ13

φ13 0.9
R3 = R1 = (0.01) = 5.5 ×10 −4 m
φ11 16.5

Particle size of 0.55 mm is necessary to virtually eliminate diffusion

control
Mears’ Criterion for External Diffusion

Mears criterion uses the measured rate of reaction (-rʹ′A) to learn if

mass transfer from the bulk phase to catalyst surface can be
neglected.
n = reaction order
R = catalyst particle radius, m
− rAʹ′ ρ b Rn ρb = bulk density of catalyst bed, kg/m3
< 0.15 = (1-φ) ρc
k c C Ab
CAb= bulk concentration, kmol/m3
kc = mass transfer coefficient, m/s

No concentration gradients between bulk gas and external surface

Bulk fluid T will be virtually the same as the temperature at the

external surface of the pellet when
h = heat transfer coefficient, kJ/m2.s.K
−ΔH Rx ( − rA# ) ρb RE Rg = gas constant, kJ/molK
2
< 0.15
hT Rg ΔHRx = heat of reaction, kJ/mol
E = activation energy, kJ/kmol
Mass Transfer and Reaction in a Packed Bed
Consider the isomerization taking place in a packed bed of catalyst pellets
rather than on a single pellet

Ac WAz z − Ac WAz z+Δz + rAʹ′ ρb Ac Δz = 0

dWAz
− + rAʹ′ ρb = 0
dz
dC Ab
WAz = −D AB + y Ab ( WAz + WBz )
dz
d 2CAb dC Ab
BAz = y Ab (WAz + WBz ) = y AbcU = UCAb D AB 2
−U + rAʹ′ ρb = 0
dz dz
The overall reaction rate, rʹ′A, is the function of concentration within the
catalyst It can be related to the reaction of A that would exist if the entire
surface were exposed to the bulk concentration CAb through the overall
effectiveness factor Ω
 − rAʹ′ = −rAb
ʹ′ Ω
For the first order reaction − rAb
ʹ′ = −rAb
ʹ′ʹ′ Sa = kSa CAb
− rAʹ′ = ΩkSa CAb
d 2CAb dC Ab
Da 2
− U + ΩkSa ρbCAb = 0
dz dz
for the case in which the flow rate through the bed is very large and the
axial diffusion can be neglected when
− rAʹ′ ρb d p U 0d p U0: superficial velocity
<< dp : particle diameter
U 0CAb Da
Da: effective axial dispersion coefficient
Neglecting axial dispersion
dC Ab d 2CAb
with respect to forced axial U >> Da
convection dz dz 2
dC Ab ΩkSa ρb
=− CAb
dz U
Boundary conditions:

Cab = Cab0 at z=0

$ ΩzkSaρb '
C Ab = C Ab0 exp & − )
% U (

The conversion at the reactor’s exit, z = L

C Ab $ ΩLkSaρb '
X = 1− = 1− exp & − )
C Ab0 % U (
Example: It is propose to reduce the concentration of NO in an effluent stream
from a plant by passing it through a packed bed of spherical porous
carbonaceous solid particles. A 2 % NO-98 % air mixture flows at a rate of 10-6
m3/s through a 2 in.-ID tube packed with solid at a temperature of 1173 K and
a pressure of 101.3 atm. The reaction NO + C → CO + 1 / 2N2
is first order in NO − rNO
ʹ′ = kSa C NO
occurs primarly in the pores inside the pellet where
Sa = 530 m2 / g and k = 4.42 ×10-10 m3 / m2 .s
Calculate the weight of porous solid necessary to reduce the NO concentration
to a level of 0.004 %.

At 1173 K, the fluid properties : Catalyst and bed properties :

ν = kinematic viscosity = 1.53 ×10 -8 m 2 / s ρc = density of catalyst particle = 2.8 g/cm 3
D AB = gas − phase diffusivity = 2.0 ×10 -8 m 2 / s φ = bed porosity = 0.5
De = effective diffusivity = 1.82 ×10 -8 m 2 / s ρ b = bulk density of bed = ρc (1 - φ)
= 1.4 × 10 6 g/m 3
R = pellet radius = 3 × 10 -3 m
γ = 1.0
Solution
C NO from 2 percent to 0.004 percent
C Ab0 − C Ab 2 − 0.004
X= = = 0.998
C Ab0 2

the variation of NO down the dC Ab ΩkSa ρb

=− CAb
length of reactor dz U
dC Ab ΩkSa
=− C Ab
dW v
NO present in dilute concentrations, ε << 1 ⇒ v = v0. Integrating and
using boundary conditions
C Ab # ΩkSa W &
C Ab = C Ab0 @ W = 0 X = 1− = 1− exp % − (
C Ab0 $ v 0 '

η v0 1
Ω= W= ln
1+ ηkSaρc / k c ac ΩkSa 1− X
 3
Internal effectiveness factor (
η = 2 φ1 cothφ1 − 1
φ1
)
k1ρc Sa 4.42 × 10 −10 × 530 × 2.8 × 10 6
Thiele modulus φ1 = R = 0.003 = 18
De 1.82 × 10 −8

Because φ1 is large 3 3
η= =
φ1 18

To calculate the external mass transfer coefficient, The Thoenes-Kramer

correlation is used 1/ 2 1/ 3
Sh! = Re! Sc
For a 2-in ID pipe Ac=2.03×10-3 m2
v0 Udp ν
U= = 4.93 × 10 −4 m / s Re! = = 386.7 Sc = = 0.765
Ac (1− φ )ν D AB

1/ 2 1/ 3 1− φ # D AB &
Sh! = 386.7 0.765 = 18 kc = % ( Sh) = 6 × 10 m / s
−5

φ $ dp '
External area per mass of solids 6(1− φ)
ac = = 500 m 2 / m3
dp
η
Effectiveness factor Ω= = 0.059
1+ ηkSaρc / k c ac

Weight of solid necessary to achieve 99.8 % conversion

v0 1 10 −6 m3 / s 1
W= ln = 3 2 2
ln
ΩkSa 1− X (0.059)(4.42 × 10 m / m .s)(530m g) 1− 0.998
−10

W = 450 g
Reactor length

W 450 g
L= = -3 2 6 3
= 0.16 m
A c ρb (2.03 × 10 m )(1.4 × 10 g / m )
Determination of Limiting Situations from Reaction Data

1/ 2
−rA" = k c ac C A
U
k c ∝ 1/ 2
dp
1
−rA" ∝ 3 / 2
1 dp
ac ∝
dp
Variation of Reaction Rate with:
Type of Limitation Velocity Particle Size Temperature
External Diffusion U1/2 d −p3 / 2 ≈ Linear

Internal Diffusion independent d −p1 Exponential

Surface Reaction independent independent Exponential