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
C
Bb
C
Ai
Ai CAi
G/L/S
phase
Liquid phase
Bulk
B
Diffusion
film
G/L/S
Liquid phase
phase C
Ai Diffusion
film
C
B0
Bulk
B
C
=0
Ab
m 1Cn
D
k
C
m + 1 A mn Ai
Bb
<< 1 ... ( 6 )
k
9
L
R a = k Cm Cn ... ( 7 )
A
L mn A0 Bb
R a = k a C C
... ( 8 )
A
L
Ai
A0
10
and R a
Ab
A
k Cm Cn = k a C C
L mn Ab Bb
L
Ai
A0
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
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
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
L 2n Ai Bb Ab + Ab 1 = 0 ... ( 16 )
k a
C
C
Ai
Ai
L
15
k Cm Cn = k a C C
L mn Ab Bb
L
Ai
Ab
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
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
dC
Ab
=0
A =0
dx
19
D k Cm 1Cn
C
D
m + 1 A mn Ai
Bb
<< Bb B ... ( 19 )
k
ZC D
L
Ai A
20
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
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
30
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
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
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
Ab
Ai
33
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
38
39
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:
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
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
44
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
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
d 2C
A = k CmCn ... ( 44 )
A dx 2
mn A B
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
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
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
= a
for m = 1, n = 1 ... ( 56 )
1
a
52
E = n M = M a
1
a
n2
... ( 57 )
53
54
55
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
=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
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
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
1
2k C
n
AS
=L
1
D r
eA P
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 )
67
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
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
volume of pellet
thickness
=
2
71
A
A
A
Area
through
which
reactants
penetrate
A
A
A
volume of pellet
2
R Length cylindrical pellet
L = =
... open ONLY
2 R Length on curved side
R
=
72
2
volume of pellet
4
3
R
spherical pellet
3
L = =
... with all surface
porous
4 R2
R
=
3
73
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 )
( )
tanh
1 ... flat slab pellet
=
1 I 2
1
1 ... cylindrical pellet
=
= 1 I 0 21
1
1
1
= tanh 3 3 ... spherical pellet
1
1
1
where,
(
(
)
)
Based on volume r
=k C ,
of catalyst pellets vA
v A
mol A reacted
3
s ( m cat )
77
=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
1
v eA
10
20
78
actual rate
intrinsic rate
2
2
=L
=L
2
D C
D C
eA AS
eA AS
Effectiveness factor
(isothermal reaction)
Thiele
Weisz
1<0.4
2<0.15
Kinetic control
1,2>4.0
Diffusion control
( 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
81
= f + f + f + ...
mean 1 1 2 2 3 3
82
( 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
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
vA n + 1 L2
AS
C
r
=k
v,observed AS
vA
( n + 1) 2
85
86
v
eA
k
=
v,observed n + 1 L2
d ln k
( )
d ln D
1 d ln k v
v, observed
eA
=
+
dT
2 dT
dT
87
true and D = D
Diffu
k =k
exp
exp
v
v, 0
eA
eA,0
RT
RT
E
+E
Diffu
E
= true
observed
2
E
true
observed
2
88