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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
C
Ai

Ai CAi

G/L/S
phase

Liquid phase
Bulk
B

Diffusion
film

Condition for validity of Regime 1:


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

Volumetric rate of kmol


mass transfer
s m3

Volumetric rate kmol


of homogeneous
chemical reaction s m 3

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

Regime 2: slow reactions


C
B0

G/L/S
Liquid phase
phase C
Ai Diffusion
film

C
B0

Bulk
B
C
=0
Ab

Condition for validity of Regime 2:


k aC << k Cm Cn ... ( 5 )
L Ai
L mn Ai Bb

Volumetric rate of kmol


mass transfer
s m3

Volumetric rate kmol


of homogeneous
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
9
L

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

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

1
Ai = 1 +
... ( 9 )
R a k a k Cn
A
L
L 1n Bb
If R a = k aC ... ( 10 )
A
LR Ai
then,

1
k

LR

1
k a
L

1
k Cn
L 1n Bb

... ( 11)

12

Plot of

1
k

LR

versus

with slope =

1
k

1
Cn
L Bb

will be a straight line

and Y-intercept =

1n

1
k a
L

For m = n = 1:
1

... ( 12 )

k a k C
LR
L
L 1n Bb
1
1
Plot of
versus
will be a straight line
C
k a
LR
L Bb
1
1
and Y-intercept =
with slope =
k
k a
13
2
L
k

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

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


Equation (8) gives,
k C2 Cn
R a
= C A = C L 2n Ab Bb ... ( 15 )
C
k a
Ab
Ai k a
Ai
L
L
2
n
k C C C

L 2n Ai Bb Ab + Ab 1 = 0 ... ( 16 )
k a
C
C
Ai
Ai
L

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
=

of homogeneous
3
chemical reaction s m
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


Liquid phase C
C
Bb
G/L/S Bb
phase
Diffusion
film
C
Bulk
Increase
in
Ai
B
reaction rate

dC

Ab

=0

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

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

where k

=k

Cn
mn Bb

Boundary conditions:
dC
B = 0 ... ( 21)
at x = 0, C = C ,
A
Ai dx
at x = , C

= 0 ... ( 22 )
21

Solution:
dC
R = D A
A
A dx

x = 0
12
2

m 1
= C
k
D
C

+
m
1
Ai
A m Ai
12
2

n Cm 1
= C
... ( 23 )
D
k
C

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
A = k C ... ( 32 )
D
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

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

d 2C

A = c2C ; c =
1
D
A
dx 2
A

cx
cx

C =h e +h e
A
1
2
B.C. ( 1) : at x = 0, C
C

=C

Ai

gives :

= h +h h = C h
Ai
1
2
2
Ai
1
25

B.C. ( 2 ) : at x = , C
C

=C

Ab

gives:

= h ec + h e c
Ab
1
2
C

h =
1

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

e c

Ab
Ai
ec e c

h =
2

ec C

Ai
Ab
ec e c

Now, [ A ] = h ecx + h e cx
1
2
26

dC

dC

A = c h ecx h e cx
A
1

dx
dx
2

dC

A
A dx

=D
x=0

x=0

= c h h
1
2

1 h h
A D 2 1
A

= D k h h
A
A 1 2 1

C ec C
C e c
C
Ai

Ab
Ab
Ai
R = D k

c
c
A
A 1 ec e c

e e
27

C ec C

C
+C e

Ab
Ab
Ai
R = D k Ai

c
c
A
A 1

e e
C ec + e c 2C

Ab
R = D k Ai

A
A 1
ec e c
C

ec + e c
Ab

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

28

C
C

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

Substituting c =

k
D

1 , and =

D
k

A gives:

C
C

Ab
Ai

R = D k
D k
D k
A
A 1
A 1 sinh
A 1
tanh
k

L
L

29

Ai

tanh

D k
C
D k
A 1 Ab
A 1 ... ( 33 )
D k
D k
A 1 sinh
A 1

L
L

Under different appropriate conditions, Equation (33)


reduces to Regime 1, 2, or 3.

30

Rearranging Equation (33):

C
C
M
M

R = k Ai
Ab
A
L tanh [ M ] sinh [ M ]
D k
A reacted in film
A
1

where, M =
= Hatta number =
k

A diffused

L
As M

( M  1) , limit ( tanh [ M ] ) 1

As M

M
M  1) , limit
0
sinh [ M ]

which gives :
31

Rearranging Equation (33):


C

M
C ( 0)
R = k Ai

1
A
L
Ab
R

=k C
M
A
L Ai

D k
A 1
R =k C
A
L Ai k
L
R

=C

D k ... ( 23 )
Ai
A 1

... Regime 3 [ All A reacts within the diffusion film ]


32

C
C
M
M

R = k Ai
Ab
A
L tanh [ M ] sinh [ M ]
As M 0

As M 0

which gives: R

M
M  1) , limit
1
tanh [ M ]

M
M  1) , limit
1
sinh [ M ]
=k

C C ) ... Regime 1-2


(
L Ai
Ab

No A reacts within the diffusion film


0 < C

C

Ab
Ai
33

Ai ... Regime 1-2


R = k C

A
L Ai k
L 1 + 1

k a

L
1

R = k C 1
;

k
A
L Ai

L 1 + 1

k a

Ab

Ai
k
L 1 +1
k a
L

k a

L
L
1
R = k C 1
=k C

A
L Ai k + k a
L Ai k + k a

L 1
L 1
L
L
34

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

a
L 1
L
A
L Ai k a
Ai
L
R a = k C ... Regime 1
A
L 1 Ai
Regime controlled by pure kinetics; C
=C

Ab
Ai

35

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

Ab

0, then

M
R = k Ai
0
A
L tanh [ M ]
k C
M
... Regime 2-3
R = L Ai
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
C
plane
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 )

Z( )
A

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
1

A
Ai
B
Bb
L
=

ZD C
D

A
A Ai
k

41

D C
R = A Ai

A
Z D C + D C

A
Ai
B
Bb
L
R =

D C
ZD C
A D
A Ai

A
A Ai
k

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 )
ZC D
a
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
Bb
If m + 1 A mn Ai
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

A = k CmCn ... ( 44 )
A dx 2
mn A B

d 2C
B = Z k CmCn ... ( 45 )
D
B dx 2
mn A B
The boundary conditions are,
dC
B = 0 ... ( 45a )
at x = 0, C = C , C = C ,
A
Ai B
Bi dx
at x = , C = 0, C = C
... ( 45b )
A
B
B0
45

Eliminating k

mn

from (44) and (45),

d 2C

d 2C
A =D
B ... ( 46 )
ZD
A dx 2
B dx 2
Integration of (46) gives,
dC

dC
A =D
B Z R ... ( 47 )
ZD
A dx
B dx
A
Second integration gives,
D
ZR
A
A ... ( 48 )
C = C + ZC
D
Bi
B0
Ai D
B
B
46

Equation (48) gives "interfacial" concentration


of B in terms of R

and C are two variables,


A
Bi
hence we must have another equation.
R

d 2C

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
A = k CmCn ... ( 49 )
D
A dx 2
mn A Bi
48

Integrating (49) as usual,

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

Bi B0

C
When M Bi
C
B0

n2
> 3, DENOMINATOR 1
1

2
2

m
1
n
R = C
C
... ( 51)
D k C
A
Ai m + 1 A mn Ai
Bi
49

C
R
A ,
Let Bi = 2 , and = enhancement factor =
k C
C
B0
L Ai
which gives,
M. ( )n
=
... ( 52 ) ; 0 < < 1
tanh M. ( )n

For m = 1 and n = 1, Equation (48) becomes,


M
1
2
+
1 + = 0 ... ( 53 )
q
q

C
D
B0 . B ... ( 54 ) ;
where, q =
ZC
D
Ai A

50

Solution of (53):

M
+
q

M
1

+ 4 1 +
q

q2
2

... ( 55 )

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

51

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

When

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

E = n M = M a
1
a

n2
... ( 57 )

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
r
AS
dC
P
A =0
dx
Reaction occurring on the inside surface of catalyst
pore is first order w.r.t. A, irreversible, isothermal:
k
1
A
product
catalyst
56

With reference to the cylindrical pore, the following


differential mass (mole) balance can be written:

dC
dC

A D
A
= 2r dx k C
r 2 D
P eA dx eA dx
P
1 A


x
x + dx

dC
dC
A
A
D
D

eA
eA
dx
dx 2k


x + dx
x = 1 C

A
dx
r
P

d 2C

2k

A =
1 C
A
D r
dx 2
eA P

d 2C

A = c 2C ; c =
A
dx 2

2k

1
D r
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

B.C. 2: At x = L ( pore's closed end ) ,


= h ecx + h e cx
A
1
2
B.C. 1: At x = 0 ( pore inlet ) , C

AS
dC

A =0
dx

General solution: C

=C

AS

gives :

= h + h h = A h
AS
1
2
2 s 1

58

= h ecx + h e cx
A
1
2
dC

cx
cx
A
= c h e h e

1
2
dx

B.C. 2: At x = L ( pore's closed end ) ,

dC

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

e2cL

AS h = AS
h =
1 e2cL + 1
2
e 2cL + 1
Now,

dC

A = c h ecx h e cx
1
2
dx
dC
A

= c h h
2
1
dx
x=0
dC

A
D
eA dx
R

2k

1 h h
= D
eA D r 1
2
eA P
x=0

2D k
eA 1 h h
2 1
r
P

60

2D k
eA 1
r
P

C e2cL

C
AS
AS

e2cL + 1 e 2cL + 1

2D k
eA 1
r
P

C e2cL C

AS
AS

2cL
+
e
1

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

e2cL 1

e2cL + 1

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

ecL e cL

ecL + e cL
61

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

2k
1
tanh L

D r

eA P

2k

1 = Thiele modulus =
1
D r
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
eA 1 tanh L
1
r C
P AS
r
D r

P
eA P

=
2r L k C
P
1 AS

( )

2k
1
tanh L
r
P
D r

eA P

=
( 2L ) k
1

2k
1
tanh L
D r tanh

eA P
1

=
=

2k
1
1
L
D r
eA P

( )

2D k
eA 1
r
P

( )

63

( ) 1

tanh
1

As 0, limit
1

=1

( )) 1

As , limit tanh
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:

1
2k C
n
AS
=L
1
D r
eA P

Squaring both sides:

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

65

2r L k Cn
n AS
P
2 =
1
C

2
AS
r D

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 )

OBSERVED reaction rate


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

eA

1 = Thiele modulus =
1
D
eA

68

k
1
r 2 C
D k tanh L
P AS
eA 1
D

eA

=
r 2 k C
P 1 AS

( )

( )

k
1
tanh L
D

eA

k
1
L
D

eA

tanh

1
=

( )

69

Cylinder


volume of pellet

= exterior surface available ... any particle shape


for reactant penetration

thickness flat slab pellet


Flat slab
=
... open ONLY on
two sides
2

thickness

L=

R
cylindrical
pellet

R
= ... open ONLY on
two sides
2

R
R
= ...spherical pellet
3
Sphere
70

A
area through which
reactant penetrates

thickness

area through which


reactant penetrates


volume of pellet

= exterior surface available ...any particle shape


for reactant penetration

area ( thickness ) flat slab pellet


L = =
... open ONLY on
two sides
2 area

thickness
=

2
71

A
A
A

Area
through
which
reactants
penetrate

A
A
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
=
72
2


volume of pellet

= exterior surface available ...any particle shape


for reactant penetration


4
3
R

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

porous
4 R2

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,

1 dN A
mol A reacted
Based on Void
= kC ,

Volume in reactor rA = V
A
3
dt
s ( m void )
V

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

1 dN A
Based on Volume r
=k C ,
of catalyst Pellets vA = V
v A
dt
P

mol A reacted

3
s ( m cat )

dN
Based on total r '''' = 1
A = k ''''C ,
Reactor Volume
A V
A
dt
R

mol A reacted

3
s ( m reactor )

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 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,

(
(

)
)

v = Thiele modulus for 1st order kinetics


=L
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
=k C ,
of catalyst pellets vA
v A

mol A reacted

3
s ( m cat )

77

Effectiveness factor versus Thiele modulus


1

=1
1

Flat plate
No
resistance
to
0.5 pore diffusion
Cylinder
0.4
Sphere
0.3

Strong pore
diffusion effects

0.2

0.1

0.05
0.1

0.2 0.3 0.4


1
2
3 4 5
Thiele modulus = L k D

1
v eA

10

20
78

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.

actual rate
intrinsic rate
2
2
=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

Effectiveness factor
(isothermal reaction)

Thiele
Weisz
1<0.4
2<0.15

Kinetic control

1,2>4.0

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)],
=
1

( rvAS ) L
C

AS
2D

r
dC

eA
vA
A
C

Ae

12

= 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

v
=L
1
D X
eA Aeq
for nth order irreversible reactions:
n1
k
C
n + 1 v AS
=L
1
2
D
eA

84

Combining the nth order rate with the generalised


Thiele modulus gives:
1
n
k Cn
r
= k C
=
vA
v AS v AS
1
D
1
2
eA
k Cn
r
=
vA L n + 1 k Cn 1
v AS
v AS
12
2 k D
( n + 1) 2
v
eA
C
r
=

vA n + 1 L2
AS

C
r
=k
v,observed AS
vA

( n + 1) 2
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
k
D
2

v
eA
k
=

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

( )

d ln D
1 d ln k v
v, observed
eA
=
+
dT
2 dT
dT

87

The Arrhenius temperature dependence for reaction


and diffusion are expressed as:
E

true and D = D
Diffu
k =k
exp
exp
v
v, 0
eA
eA,0
RT
RT
E

+E

Diffu
E
= true
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
true
observed
2
88

Best wishes for end-semester


examinations,
and
timely DECLARATION OF
RESULTS !
89