Introduction to Multiphase Reactors

Basics of mass transfer with chemical reaction

Dr. Anand V. Patwardhan

Professor of Chemical Engineering
Institute of Chemical Technology
Nathalal M. Parikh Road
Matunga (East), Mumbai-400019

av.patwardhan@ictmumbai.edu.in; avpuict@gmail.com; avpiitkgp@gmail.com

1
Objective: to ascertain the effect of chemical reaction on
specific rate (flux) of mass transfer

Consider G-L, L-L, S-L reactions (absorption+reaction,

extraction+reaction, leaching+reaction, respectively)

Assumptions:
Reaction occurs exclusively in liquid phase (B
phase)
Solute A (gas or liquid) slightly soluble in B phase
Mass transfer resistance confined to B phase
Reactive species B considered nonvolatile
2
 IRREVERSIBLE REACTIONS:
A + ZB products ... (1)
mth order w.r.t. A, nth order w.r.t. B

Depending on the relative rates of diffusion and

chemical reaction, four regimes:
Regime 1: very slow reactions
Regime 2: slow reactions
Regime 3: fast reactions
Regime 4, instantaneous reactions

3
 REGIME 1: VERY SLOW REACTIONS

Reaction rate << rate of transfer of A into B phase

B phase saturated with A at any given moment

Rate of formation of products determined by true

kinetics of homogeneous chemical reaction

Diffusional factors are unimportant in this regime

The transfer rate of A, is given by

R a = k Cm Cn ... ( 2 )
A L mn Ai Bb

4
 Regime 1: very slow reactions
C
Bb C
Bb
p
Ai CAi C
Ai
G/L/S Liquid phase
phase
Diffusion Bulk
film B
0
5
 Condition for validity of Regime 1:

k aC >> k Cm Cn ... ( 3 )
L Ai L mn Ai Bb

{ }
Volumetric rate of kmol Volumetric rate kmol
mass transfer of homogeneous
s m3 chemical reaction s m 3

6
 REGIME 2: SLOW REACTIONS

Reaction rate faster than rate of transfer of A into B

phase

Reaction occurs uniformly throughout B phase, but,

Rate determined by rate of transfer of A into B phase.

The concentration of dissolved A in the bulk of phase B

is zero.
R a = k aC ... ( 4 )
A L Ai

7
 Regime 2: slow reactions
C
B0 C
B0
G/L/S Liquid phase
phase C
Ai Diffusion Bulk
film B
C =0
Ab
0
8
 Condition for validity of Regime 2:
k aC << k Cm Cn ... ( 5 )
L Ai L mn Ai Bb

{ }
Volumetric rate of kmol Volumetric rate kmol
mass transfer of homogeneous
s m3 chemical reaction s m 3
Also, the amount of unreacted dissolved A that
reacts in the diffusion film compared to that which
reaches the bulk of B phase should be negligible.
The condition for this to happen is,
12
2 m 1Cn
D k C
m + 1 A mn Ai Bb << 1 ... ( 6 )
k
L 9
 REGIME BETWEEN 1 and 2 (Regime 1-2)

For some systems condition (6) satisfied but condition

(5) is not satisfied

Dissolved A concentration in bulk phase, CA0 is finite,

and CA < CAi

In such a case,
R a = k Cm Cn ... ( 7 )
A L mn A0 Bb

A L (
R a = k a C C
Ai A0 )
... ( 8 )

10
Simultaneous solution of Equations (7) and (8) gives
C and R a
Ab A

k Cm Cn = k a C C
L mn Ab Bb L Ai A0 ( )
for m = 1 (if reaction is 1st order w.r.t. A)

k aC C
C = L Ai = Ai
A0 k Cn + k a k Cn
L mn Bb L L mn Bb + 1
k a
L
11
SPECIAL CASES:
For m = 1, Equations (7) and (8) are linear in [A].
Eliminating [A0] gives,
C
Ai = 1 + 1
... ( 9 )
R a k a k Cn
A L L 1n Bb
If R a = k aC ... ( 10 )
A LR Ai
1 1 1
then, = + ... ( 11)
k
LR
a k a
L k Cn
L 1n Bb

12
 1 1
Plot of versus will be a straight line
k
LR
a Cn
L Bb
1 1
with slope = and Y-intercept =
k k a
1n L
For m = n = 1:
1 1 1
= + ... ( 12 )
k ak a k C
LR L L 1n Bb
1 1
Plot of versus will be a straight line
k a C
LR L Bb
1 1
with slope = and Y-intercept =
k k a
2 L 13
Zero order reaction w.r.t. A (m = 0):

Volumetric rate of reaction (Equation (7)):

R a = k Cn ... ( 13 )
A L 0n Bb
Provided there is sufficient amount of dissolved A in
the bulk of liquid !
Equation (8) gives,

R a k Cn
C = C A = C L 0n Bb ... ( 14 )
Ab Ai k a Ai k a
L L

14
Second order reaction w.r.t. A (m = 2):

Equation (8) gives,

R a k C2 Cn
C = C A = C L 2n Ab Bb ... ( 15 )
Ab Ai k a Ai k a
L L
n
k C C C 2
C
L 2n Ai Bb Ab + Ab 1 = 0 ... ( 16 )
k a C C
L Ai Ai

15
 For a general order reaction (mth order) w.r.t. A, the
concentration of A in the bulk (A0) is found by trial or
error method or any suitable numerical method, from
the following equations:

k Cm Cn = k a C C
L mn Ab Bb L Ai Ab ( )
Volumetric rate kmol Volumetric rate kmol
of homogeneous = of
chemical reaction s m 3 mass transfer s m 3

k Cm Cn + k aC = k aC
L mn Ab Bb L Ab L Ai

16
ENHANCEMENT FACTOR FOR MASS TRANSFER:

The enhancement factor for mass transfer (or

simply, enhancement factor), , is defined as:

Actual rate of mass transfer with chemical reaction

=
Rate conforming to Regime 2 ( slow reaction regime )

R a
= A ... ( 17 )
k aC
L Ai

17
 FAST REACTIONS
(Regime 3 and Regime between 2 and 3)

Under certain condition, diffusion and reaction are

parallel steps. This condition is given by:
12
2 m 1Cn
D k C
m + 1 A mn Ai Bb >> 1 ... ( 18 )
k
L

18
 Regime 3: fast reactions

C Liquid phase C
G/L/S Bb Bb
phase Diffusion
film
C Bulk
Ai Increase in
B
reaction rate
C =0
Ab
0
dC
A =0
dx
19
 Under certain conditions, there is no depletion of
reactive species B in the film; the condition is given by,

12
2
D k Cm 1Cn C D
m + 1 A mn Ai Bb << Bb B ... ( 19 )
k ZC D
L Ai A

The experimental data are better correlated through

(DB/DA), rather than (DB/DA).

20
REGIME 3 (A reacts entirely in the Film) ...

d 2C
D A = k CmCn = k Cm ... ( 20 ) ,
A dx 2 mn A Bb m A

where k =k Cn
m mn Bb
Boundary conditions:
dC
at x = 0, C = C , B = 0 ... ( 21)
A Ai dx
at x = , C = 0 ... ( 22 )
A

21
Solution:
dC
R = D A
A A dx
x = 0

12
2 m 1
= C D k C
Ai m + 1 A m Ai
12
2 n Cm 1
= C D k C ... ( 23 )
Ai m + 1 A mn Bb Ai

22
For example:

Kinetics of absorption of carbon monoxide in aqueous

solutions of sodium hydroxide and aqueous calcium
hydroxide slurries. Anand V. Patwardhan; Man
Mohan Sharma, Industrial & Engineering Chemistry
Research 1989, 28, 5-9.

Kinetics of reactive absorption of carbon dioxide with

solutions of aniline in non-aqueous aprotic solvents.
Srikanta Dinda; Anand V. Patwardhan; Narayan C.
Pradhan, Industrial & Engineering Chemistry Research
2006, 45, 6632-6639.

23
Regime Overlapping 1, 2, & 3 (Generalised Derivation):

Reaction occurs partly in Film, partly in Bulk, and yet

there may be a finite concentration of A in the bulk of
the liquid phase (B-phase).
2
d C
D A = k C ... ( 32 )
A dx 2 1 A
Boundary conditions:
B.C. ( 1) : at x = 0, C =C
A Ai
B.C. ( 2 ) : at x = , C = C
A Ab

24
 d 2C d 2C k
D A =k C A= 1 C
A dx 2 1 A dx 2 D A
A

d 2C k
A = c2C ; c = 1
dx 2 A D
A
cx
C =h e +h e cx
A 1 2

B.C. ( 1) : at x = 0, C =C gives :
A Ai
C = h +h h = C h
Ai 1 2 2 Ai 1
25
B.C. ( 2 ) : at x = , C =C gives:
A Ab

C = h ec + h e c
Ab 1 2

C = h ec + C h e c
( )
Ab 1 Ai 1

C C e c C ec C
h = Ab Ai h = Ai Ab
1 ec e c 2 ec e c

Now, [ A ] = h ecx + h e cx
1 2
26
 dC dC
A = c h ecx h e cx A = c h h
dx 1 2 dx 1 2
x=0

dC k
D A =D 1 h h
A dx A D 2 1
x=0 A

R = D k h h
A A 1 2 1
C ec C C C e c
Ai Ab Ab Ai
R = D k
A A 1 ec e c c
e e c
27
 C ec C C +C e c

R = D k Ai Ab Ab Ai

A A 1 c
e e c

C ec + e c 2C

R = D k Ai Ab
A A 1 ec e c

ec + e c C
R = D k C Ab
A A 1 Ai ec e c ec e c


2

28
 C C
R = D k Ai Ab
A A 1 tanh ( c ) sinh ( c )

k D
Substituting c = 1 , and = A gives:
D k
A L

C C
R = D k Ai Ab
A A 1 D k D k
tanh A 1 sinh A 1
k k
L L

29
 C D k C D k
R = Ai A 1 Ab A 1 ... ( 33 )
A D k D k
tanh A 1 sinh A 1
k k
L L

Under different appropriate conditions, Equation (33)

reduces to Regime 1, 2, or 3.

30
 Rearranging Equation (33):
C M C M
R = k Ai Ab
A L tanh [ M ] sinh [ M ]
D k
A 1 A reacted in film
where, M = = Hatta number =
k A diffused
L
As M ( M  1) , limit ( tanh [ M ] ) 1
M
As M ( M  1) , limit 0
sinh [ M ]
which gives :
31
 Rearranging Equation (33):

C M
R = k Ai C ( 0)
A L 1 Ab
R =k C M
A L Ai
D k
R =k C A 1
A L Ai k
L
R =C D k ... ( 23 )
A Ai A 1
... Regime 3 [ All A reacts within the diffusion film ]

32
 C M C M
R = k Ai Ab
A L tanh [ M ] sinh [ M ]
M
As M 0 ( M  1) , limit 1
tanh [ M ]
M
As M 0 ( M  1) , limit 1
sinh [ M ]
which gives: R
A
=k ( C C ) ... Regime 1-2
L Ai Ab
No A reacts within the diffusion film
0 < C C
Ab Ai

33
 C
R = k C Ai ... Regime 1-2
A L Ai k
L 1 + 1
k a
L
C
1 Ai
R = k C 1 ; C =
A L Ai k Ab k
L 1 + 1 L 1 +1
k a k a
L L
k a k
L L 1
R = k C 1 =k C
A L Ai k + k a L Ai k + k a
L 1 L L 1 L
34
 k k
L 1 L 1C
If k  k a, then R = k C =
L 1 L A L Ai k a a Ai
L

R a = k C ... Regime 1
A L 1 Ai

Regime controlled by pure kinetics; C =C

Ab Ai

35
 k

If k  k a, then R = k C L 1
L 1 L A L Ai k
L 1
R =k C
A L Ai

R a = k aC ... Regime 2
A L Ai

Regime controlled by pure mass transfer;

C =0
Ab

36
If C 0, then
Ab
C M
R = k Ai 0
A L tanh [ M ]

k C M
R = L Ai ... Regime 2-3
A tanh [ M ]

Most A reacts within the diffusion film,

and the rest reacts in the bulk of liquid;

A
0 = 0

37
REGIME 4: INSTANTANEOUS REACTIONS

Reaction potentially so fast that A and B cannot

coexist !

At a certain distance from the interface, reaction

plane formed

The mass transfer rate (& hence reaction rate)

governed by rate at which dissolved A and reactant
B supplied to reaction plane.

38
Regime 4: instantaneous reactions
Reaction
plane C
Bb
G/L/S Liquid phase
phase
C Bulk
Ai No B B

No A
0

39
 Condition for validity for Regime 4:
12
2 m 1Cn
D k C C D
m + 1 A mn Ai Bb >> Bb B ... ( 38 )
k ZC D
L Ai A
At steady state:

diffusion rate of dissolved A through region 0 < x <

= diffusion rate of B through region > x >

40
 D C D C
R = A Ai = B Bb ... ( 39 )
A Z( )
Z D C +D C
A Ai B Bb ... ( 40 )
=
ZD C
A Ai
Z D C + D C
1 1 A Ai B Bb
=
ZD C
A Ai
Z D C + D C
k
1 L A Ai B Bb
=
D ZD C
A A Ai
41
 D C
R = A Ai
A
Z D C + D C
k
L A Ai B Bb
R = D C
A D ZD C A Ai
A A Ai

D C

R = k C 1 + B Bb ... ( 41)
A L Ai D ZC
A Ai

C D
Asymptotic enhancement factor = = 1 + Bb B ... ( 42 )
a ZC D
Ai A
42
For example:

Kinetics of absorption of oxygen in aqueous alkaline

solutions of polyhydroxybenzenes. Anand V.
Patwardhan; Man Mohan Sharma, Industrial and
Engineering Chemistry Research 1988, 27, 36-41.

43
 Transition between Regime 3 and Regime 4)
(regime overlapping R3 and R4):
12
2 m 1Cn
D k C C D
If m + 1 A mn Ai Bb Bb B ... ( 43 )
k ZC D
L Ai A

R3 4

( Depletion of reactant B in the diffusion film )

44
The relevant differential equations are,
2
d C
D A = k CmCn ... ( 44 )
A dx 2 mn A B

d 2C
D B = Z k CmCn ... ( 45 )
B dx 2 mn A B
The boundary conditions are,
dC
at x = 0, C = C , C = C , B = 0 ... ( 45a )
A Ai B Bi dx
at x = , C = 0, C = C ... ( 45b )
A B B0
45
 Eliminating k from (44) and (45),
mn
d 2C d 2C
ZD A =D B ... ( 46 )
A dx 2 B dx 2
Integration of (46) gives,
dC dC
ZD A =D B Z R ... ( 47 )
A dx B dx A
Second integration gives,
D ZR
C = C + ZC A A ... ( 48 )
Bi B0 Ai D D
B B

46
 Equation (48) gives "interfacial" concentration
of B in terms of R
A

R and C are two variables,

A Bi
hence we must have another equation.

d 2C
D A = k CmCn ... ( 44 )
A dx 2 mn A B
... non-linear, hence, analytical solution is NOT possible.

47
 Simplifying assumption:
B.C. (45a) : C = constant = C in the IMMEDIATE
B Bi
neighbourhood of interface.

So, restricting the solution of (44) in the IMMEDIATE

neighbourhood of interface, C can be replaced by C .
B Bi

Equation (44) then becomes,

d 2C
D A = k CmCn ... ( 49 )
A dx 2 mn A Bi
48
 Integrating (49) as usual,

( )
k C M C C n2
R = L Ai Bi B0 ... ( 50 )
tanh M C ( )
A C n 2
Bi B0

n2
C
When M Bi > 3, DENOMINATOR 1
C
B0
1
2 m 1 n 2
R = C D k C C ... ( 51)
A Ai m + 1 A mn Ai Bi
49
 C R
Let Bi = 2 , and = enhancement factor = A ,
C k C
B0 L Ai
which gives,
M. ( )n
= ... ( 52 ) ; 0 < < 1
tanh M. ( )n

For m = 1 and n = 1, Equation (48) becomes,
2 M 1
+ 1 + = 0 ... ( 53 )
q q
C D
where, q = B0 . B ... ( 54 ) ;
ZC D
Ai A 50
Solution of (53):

M M 1
+ + 4 1 +
q q2 q
= ... ( 55 )
2

When M  q, 1 Regime 3
(NO depletion of B in liquid film)

51
 When M  q, 0 Regime 4
(COMPLETE depletion of B in liquid film)
C D
Since = 1 + B0 B = 1 + q
a ZC D
Ai A

and, for M > 3, = M ,

Equation (53) can be solved to give,
12

= a for m = 1, n = 1 ... ( 56 )
1
a

52
 Hikita and Asai (J. of Chemical Engineering of Japan

1964, vol. 2, p.77)

have shown that the following equation holds

for a GENERAL order reaction

n2

E = n M = M a ... ( 57 )
1
a

53
 Role of diffusion within the catalyst pellet
(internal diffusion)
Reaction within a solid catalyst: reactant must first
diffuse into it lowering of reactant concentration in
the inner regions of catalyst.
As A diffuses inward, it is also reacting to form the
product, but at a progressively diminishing rate.
Observed rate = true or intrinsic rate multiplied by an
effectiveness factor, which is a function of the true rate
constant, diffusivity, and pellet shape and size.

54
 Effectiveness factor is a co-determinant of the actual
reaction rate, it is very important in the analysis and
design of catalytic reactors.

Effectiveness factor () is defined as,

actual reaction rate inside catalyst
=
rate based on surface (bulk) concentration

55
Isothermal effectiveness factors (single pore model):
Consider a first-order reaction in a cylindrical catalyst
pore, which is closed at one end (for example).
L
dx
C
AS r dC
P A =0
dx

Reaction occurring on the inside surface of catalyst

pore is first order w.r.t. A, irreversible, isothermal:
k
A 1 product
catalyst 56
 With reference to the cylindrical pore, the following
differential mass (mole) balance can be written:
dC dC

r 2 D A D
P eA dx eA dx

A
(
= 2r dx k C
P 1 A )
x x + dx

dC dC
D A D A
eA dx eA dx 2k
x + dx x = 1 C
dx r A
P

d 2C 2k d 2C 2k
A = 1 C A = c 2C ; c = 1
dx 2 D r A dx 2 A D r
eA P eA P

57
 The above differential equation can be solved for the
following two boundary conditions:
B.C. 1: At x = 0 ( pore inlet ) , C =C
A AS
dC
B.C. 2: At x = L ( pore's closed end ) , A =0
dx
General solution: C = h ecx + h e cx
A 1 2
B.C. 1: At x = 0 ( pore inlet ) , C =C gives :
A AS
C = h + h h = A h
AS 1 2 2 s 1

58
 C = h ecx + h e cx
A 1 2

( )
dC
A cx
= c h e h e cx
dx 1 2
dC
B.C. 2: At x = L ( pore's closed end ) , A = 0 gives,
dx

(
0 = c h ecL h ecL
1 2 )
h = h e2cL
2 1
C h = h e2cL
AS 1 1

59
 C C e2cL
h = AS h = AS
1 e2cL + 1 2 e 2cL + 1

( )
dC
Now, A = c h ecx h e cx
dx 1 2
dC
A = c h h
dx 1 2
x=0
dC 2k
D A = D 1 h h
eA dx eA D r 1 2
x=0 eA P
2D k
R = eA 1 h h
A r 2 1
P
60
 2D k C e2cL C
R = eA 1 AS AS
A r e2cL + 1 e 2cL + 1
P

2D k C e2cL C
R = eA 1 AS AS
A r 2cL +
P e 1
2D k e2cL 1
R =C eA 1
A AS r e2cL + 1
P
2D k ecL e cL
R =C eA 1
A AS r
P ecL + e cL

61
 2D k 2k
R =C eA 1 tanh L 1
A AS r D r
P eA P

2k
L 1 = Thiele modulus =
D r 1
eA P

An effectiveness factor () for pore is defined as,

actual reaction rate within catalyst pore

=
rate based on surface concentration throughout pore

62
 2D k
( )
2k
2
r C eA 1 tanh L 1
P AS r D r
P eA P
=
(
2r L k C
P 1 AS )

( )
2D k 2k
r eA 1 tanh L 1
P r D r
P eA P
=
( 2L ) k
1
2k
tanh L 1

=


D r tanh
eA P
=
( ) 1
2k
L 1 1
D r 63
eA P
As 0, limit
( ) 1
tanh
1
1
1
=1

( ( )) 1
As , limit tanh
1 1
1
=

1

64
 Expression for Thiele modulus (single pore model) for
an irreversible reaction, which nth order w.r.t. A is
given by:
2k C n 1
=L n AS
1 D r
eA P
Squaring both sides:

2k Cn 1 2r L k Cn 1C
( )
2 = L2 n AS = P n AS AS
1 D r r D r C L
eA P P eA P AS

65
 2 =
( P )
2r L k Cn
n AS
1 C
2
r D AS
P eA L

maximum possible surface reaction rate

( in absence of any Diffusion resistance )
2 =
1 maximum possible diffusion rate
( in absence of any Reaction )

2 OBSERVED reaction rate

=
1 maximum possible diffusion rate

66
Porous Catalyst Particles
The results for a single pore can approximate the
behavior or particles of various shapes spheres,
cylinders, etc. For these systems:
1. Use of the proper diffusivity: Replace the effective
diffusivity for single pore by the effective
diffusivity of fluid in the porous structure.
2. Use of proper measure of particle size: To find the
effective distance penetrated by reacting fluid to
get to all the interior surfaces, a characteristic size
of particle is defined as:

67
 If the reaction rate in the single pore is based on the
pore volume (volumetric rate) instead of inner pore
surface area, then we get following expressions:

k
R =C D k tanh L 1
A AS eA 1 D
eA

k
L 1 = Thiele modulus =
D 1
eA

68

( )
k
r 2 C D k tanh L 1
P AS eA 1 D
eA
=
( )
r 2 k C
P 1 AS
k
tanh L 1

=




D
eA
=
( )
tanh
1
k
L 1 1
D
eA

69
 volume of pellet
= exterior surface available ... any particle shape
for reactant penetration


thickness flat slab pellet Flat slab
= ... open ONLY on
2 two sides
L= thickness
R
R cylindrical pellet
= ... open ONLY on
2 two sides

Cylinder

R
= ...spherical pellet R
3 Sphere
70
 A A
area through which thickness area through which
reactant penetrates reactant penetrates
volume of pellet
= exterior surface available ...any particle shape
for reactant penetration


area ( thickness ) flat slab pellet
L = = ... open ONLY on
2 area two sides

thickness
=
2

71
 R
A A
Area
A through A
which
reactants
A penetrate A
volume of pellet
= exterior surface available ...any particle shape
for reactant penetration

2
R Length cylindrical pellet
L = = ... open ONLY
2 R Length on curved side

R
=
2 72
 R

volume of pellet
= exterior surface available ...any particle shape
for reactant penetration

4 3
3 R spherical pellet
L = = ... with all surface

4 R2 porous
R
=
3
73
 3. Measure of reaction rate: In catalytic systems the
rate of reaction can be expressed in many
equivalent ways. For example, for FIRST-ORDER
KINETICS,
Based on Void
}
Volume in reactor rA = V
1 dN A

V
dt A
mol A reacted
= kC ,
s ( m void )
3

}
dN
Based on Weight r ' = 1 A = k 'C , mol A reacted
of catalyst pellets A W dt A s ( kg cat )

}
dN
Based on catalyst r '' = 1 A = k ''C , mol A reacted
Surface area A S dt A ( 2 )
s m cat surf

74
Based on Volume r
}
of catalyst Pellets vA = V
1 dN A

P
dt
=k C ,
v A
mol A reacted
s ( m cat )
3

}
dN mol A reacted
Based on total r '''' = 1 A = k ''''C ,
s ( m reactor )
Reactor Volume A V dt A 3
R
For porous catalyst particles: rates based on unit mass
and on unit volume of particles, (r and r) are the
useful measures.

4. Similar to a single cylindrical pore, Thiele (1939)

and Aris (1957) related (pellet effectiveness
factor) with (pellet Thiele modulus) for various
pellet shapes as:
75
 tanh
=
( ) 1 ... flat slab pellet

1
1 I 2
=
(1 )
1 ... cylindrical pellet
(
= 1 I 0 21 )

( )
I1 & I 0 = Bessel functions

1 1 1
= tanh 3 3 ... spherical pellet
1 ( 1 ) 1
where,
k
=L v = Thiele modulus for 1st order kinetics
1 D
eA 76
 For a first order irreversible isothermal reaction given
by A R, then actual rate is then given by:
Based on volume r
}
of catalyst pellets vA
=k C ,
v A
mol A reacted
s ( m cat )
3

77
 Effectiveness factor versus Thiele modulus
1 =1
1

No resistance to Flat plate

0.5 pore diffusion Strong pore
Cylinder diffusion effects
0.4
Sphere
0.3

0.2

0.1

0.05
0.1 0.2 0.3 0.4 1 2 3 4 5 10 20
Thiele modulus = L k D 78
1 v eA
 5. Finding pore resistance effects from experiments:
another modulus is defined which includes only
observable and measurable quantities. This is
known as the Weisz modulus 2.

2 actual rate 2 intrinsic rate

=L =L
2 D C D C
eA AS eA AS
Pore resistance limits: When reactant fully penetrates
the pellet and covers all its surfaces, then pellet is in
the diffusion-free (kinetic) regime (1<0.4 or 2<0.15).
When the pellet is starved for reactant and is unused
then the particle is in the strong pore resistance regime
(diffusion regime) (1>4 or 2>4).
79
 Thiele
Effectiveness factor Weisz
(isothermal reaction)

1<0.4 1,2>4.0
2<0.15

Kinetic control Diffusion control

Thiele modulus 1 and Weisz modulus 2

Doraiswamy (2001) 80
 6. Particles of different sizes: Comparing the
behavior of particles of size R1 and R2, the
diffusion-free regime is found out.

}
Based on weight r' = k 'C , mol A reacted
of catalyst pellets A A s ( kg cat )

( r'A )1 1k 'CA 1
= = =1
( r'A ) 2 2k 'CA 2
In the regime of strong diffusion resistance:
( r'A )1 1 ( 1 ) 2 L2
= = =
( r'A ) 2 2 ( 1 )1 L1
Rate is inversely proportional to the particle size. 81
7. Mixture of particles of various shapes and sizes:
For a catalyst bed consisting of a mixture of
particles of various shapes and sizes, Aris (1957)
proved the correct mean effectiveness factor as:

= f + f + f + ...
mean 1 1 2 2 3 3

82
8. Arbitrary reaction kinetics: If the Thiele modulus
is generalised as follows [Froment and Bischoff
(1962)],

=
( rvAS ) L
1 12
C
2D AS
eA
(
r
vA
dC )
A
C
Ae
C = equilibrium concentration
Ae
then the versus 1 curves for all forms of rate
equation closely follow the curve for the 1st order
reaction. This generalised modulus becomes:
83
for first-order reversible reactions:
k
=L v
1 D X
eA Aeq

for nth order irreversible reactions:

k C n1
n + 1 v AS
=L
1 2 D
eA

84
 Combining the nth order rate with the generalised
Thiele modulus gives:
n 1
r = k C = k Cn
vA v AS v AS
1
1 2 D
r = eA k Cn
vA L n + 1 k Cn 1 v AS
v AS
12
2 k D ( n + 1) 2
r =
vA n + 1 L2
v eA ( C
AS )
( n + 1) 2
r
vA
=k C
v,observed AS ( )
85
 That is, in strong pore diffusion regime, an nth order
reaction behaves like a [(n+1)/2]th order reaction.

86
 Also, the temperature dependency of reactions is
affected by strong pore resistance (diffusion resistance).
12
2 k D
k = v eA
v,observed n + 1 L2

Taking logarithms and differentiating w.r.t.

temperature and (reaction rate and to a lesser extent
the diffusional process are T-dependent):

(
d ln k )
v, observed ( )
1 d ln k v
= +
(
d ln D )

eA
dT 2 dT dT

87
 The Arrhenius temperature dependence for reaction
and diffusion are expressed as:
E E
k =k exp true and D = D exp Diffu
v v, 0 RT eA eA,0 RT

E +E
E = true Diffu
observed 2
Etrue for gas-phase reactions is high (~ 80-240 kJ/mol),
and Ediff is small (~ 5 kJ/mol at room temperature or 15
kJ/mol at 1000 0C). Therefore,
E
E true
observed 2
88
Best wishes for end-semester
examinations,
and
timely DECLARATION OF
RESULTS !

89