Rate Determining Step

Heat Exchanger
1 1 1
i o
U h h
= +
What will be the rate controlling step:
If inside heat transfer is by condensation
and outside by convection ????
h
i
= O(1000-10000)
h
o
= O(10-1000)
Gas-Solid Reaction
Design Problem
To emphasize the importance of rate
controlling step
Design Problem
In a process of combustion, flue gases contain
carbon dioxide and unreacted air
Flow rate: 10 m
3
/s
Pressure: 1 atm
composition of flue gases

mol %
CO2 5
N2 85
O2 10
We can not send these gases to atmophere, the norms say
CO2 content should be below 100 ppm
Reaction

CO2 + 2 NaOH --------> Na2CO3 + H2O
A (g) + B (l) -----> Products
Steps
1. What experiments I should carry out to find the
kinetics (i.e. order and rate constant) of the
reaction?
2. What is the heat of reaction? Is it an endothermic
or exothermic reaction?
3. What should be the temperature of the reaction?
4. Whether the liquid phase (Aq. NaOH solution) is
in batch or it is should be continuous ?
5. What is the amount of NaOH solution I will use
for this reaction?

Steps
6. What should be the concentration of NaOH
solution?
7. what kind of reactor, I will use?
8. What should be the height to diameter ratio for
the reactor selected?
9. If I make a choice of CSTR type reactor, which
impeller I should use and at what speed I should
rotate?
10. What provisions I will make to either provide or
remove heat from the system?
11. What should be the material of construction of
the reactor?
Lab Scale Studies
Kinetics
order with respect to A m 1
order with respect to B n 1
k2 (rate const for reaction) 0.002 m/(mol.s)
Thermodynamics
Reaction exothermic
Heat of reaction 100 kJ/mol of A reacted
Process Conditions
isothermal reaction
T 330 K
Mode of operation
Gas Phase obviously continuous
Liquid Phase continuous
Hw 0.000282 kmol/(m.kN/m)
Equilibrium solubility of A 0.002451 kmol/m3
Diffusivity of CO2 1.96E-09 m2/s
Preliminary Calculation
Flow rate of flue gases 10 m3/s
Pressure 1 atm
Temperature 330 K
R 8.314

To find total molar flow rate, we will use ideal gas law

PV = n (total) R T

N (total) 369.31135 mol/s

Overall Balance
Composition of flue gases
IN OUT mol wt
mol % mol/s gm/s mol/s gm/mol gm/s mol/s mol %
CO2 5.00 18.47 849.42 ? 46.00 1.00 0.02 0.00
N2 85.00 313.91 8789.61 313.91 28.00
8789.6
1 313.91 0.89
O2 10.00 36.93 1181.80 36.93 32.00
1181.8
0 36.93 0.11

total 100.00 369.31
10820.8
2 total 350.87
inlet ppm 78498
Overall Balance
Total moles of CO2 reacted per unit time in - out
18.44389

NaOH moles required per unit time
stiochiometric coeff x moles of CO2 reacted 36.88778

Taking 20 % excess of NaOH flow
NaOH moles required per unit time 44.26534

Liquid phase concentration [Bo] 1 1000 mol/m3

Liquid phase flow rate 0.044265

outlet concentration of liquid phase 200

from experiments he found out that

concentration of CO2 in liquid phase 0.00098 0.98049 mol/m3
material balance across the reactor

[Bo]in*Q-[Bo]out*Q = 2 * (-rA) V

volume of liquid phase 45.14615 m3

let the gas phase hold up is 0.2
hence liquid phase hold up is 0.8


volume of dispersion 56.43268
provide 20 % excess for gas dispersion
total volume of reactor 67.71922
Sizing of the reactor
D 4.35 m
H 4.35 m
Design is further continued for impeller
selection, heat transfer aspects. Reactor is
fabricated and sent for actual operation
Actual Plant Operation
outlet [Bo] 800.62 mol/m3
moles of [Bo] reacted 8.83 mol/sec

moles of CO2 reacted 4.41 mol/sec
so outlet moles of CO2 14.05 mol/sec

outlet composition in actual operation
mol/s gm/s
CO2 14.05 646.43
N2 313.91 8789.61
O2 36.93 1181.80

outlet PPM = 60881
What we did not consider
Mass Transfer Rate

Variables of importance
Rate constant (intrinsic kinetics)
Order with respect to all the reactants
Liquid phase concentration
Gas phase concentration
Equilibrium solubility
Gas holdup, bubble size, interfacial area, mass
transfer coefficient
Diffusion coefficient
Reason
mol/m3sec

Rate of reaction (intrinsic kinetics) 0.78


Rate of reaction (plant operation) 0.0977



Rate controlling step
* *
2
3
1 1 1
1 1 1
[ ] [ ][ ]
1 1 1
0.001 2.45 0.002 0.8 200 2.45
0.0977 /
L L o
overall rate mass transfer rate intrinsic kinetic rate
overall rate
k a A k B A
overall rate
overall rate mol m s
c
= +
= +
= +

=
Slowest step controls the process,
Similar to Heat exchangers (inside and outside HTC
and wall resistance)
Three Phase Reaction
GAS Liquid Solid
Heterogeneous reaction regimes
Heterogeneous reactions
( ) ( )
A l ZB l products +
Transfer of solute A from dispersed phase to
continuous phase
Dispersed phase may be gas / liquid / solid
Continuous phase may be gas / liquid
Reaction of dissolved A with non-volatile liquid phase
reactant B
The rate of transfer depends upon the relative rates of
diffusion and reaction.
Heterogeneous reactions
Mass Transfer
Rate
Reaction Rate
Regime 1 very slow
reactions
High Low
Regime 2 slow reactions Comparable
Slightly low
Comparable
Slightly high
Regime 3 fast reactions Low High
Regime 4 Instantaneous
reactions
Low High
Notations
[C] : concentration of species, mol/m
3
[A*] : equilibrium solubilty, mol/m
3
R
A
: specific rate of absorption, mol/m
2
s
a : interfacial area, m
2
/m
3
k
L
: true liquid side mass transfer coefficient, m/s
H
A
: Henrys constant
p
A
: partial pressure of gas A, Pa
D
A
: Diffusion coeff of A in liquid, m
2
/s

L
: liquid hold-up
k
mn
: intrinsic kinetics rate constant

Regime 1
Pure gas (gas side resistance absent)
| |
o
B
A
p
| |
* A
Gas
side film
Liquid
side film
Interface
| | | |
*
o
A A =
GAS
LIQUID
VERY SLOW REACTION
REGIME 1: VERY SLOW REACTIONS
The rate of reaction between the dissolved A and B is
very much slower than the rate of transfer of A from gas
to liquid phase. The liquid phase will be saturated with
solute A at any moment and the rate of formation of the
products will be determined by kinetics of homogeneous
chemical reaction. The diffusional factors are unimportant
in this regime.
Regime 1
| |
| |
*
* *
1:
1
m
n
A l mn o
m
n
L l mn o
R a k A B
criterion for regime
k a A k A B
volumetric rateof mass transfer
rateof homogeneous chemical reaction
(
=

( (

c
c
A A
r R a =
Reaction between isobutylene and acetic acid
Reaction temperature = 30
o
C
First order with respect to isobutylene and acetic
acid
Rate constant = 1.2 cm
3
/mol sec
Catalyst concentration = 10 % w/w
[B
o
] = [AcOH]=15 x 10
-3
mol/cm
3
Liquid phase hold up = 0.75
k
L
a = 0.15 to 0.4 s
-1

Regime 1
Liquid phase air oxidation of ethyl benzene
Reactor: Stirred vessel
Temperature: below 130
0
C
Industrial range: 115 125
0
C

0.0E+00
4.0E-06
8.0E-06
1.2E-05
1.6E-05
2.0E-05
0 200 400 600 800 1000
Stirring Speed, rpm
R
a
t
e

o
f

A
b
s
o
r
p
t
i
o
n
,

m
o
l
/
c
m
3
s
Liquid-Liquid reaction (Oils)
Alkylation of Benzene, first step in manufacture of
alkyl benzene sulphonates, used as detergents

0.0E+00
1.0E-06
2.0E-06
3.0E-06
4.0E-06
0 500 1000 1500 2000 2500
Stirring Speed, rpm
R
a
t
e

o
f

A
b
s
o
r
p
t
i
o
n
,

m
o
l
/
c
m
3
s
REGIME 2: SLOW REACTIONS
The rate of reaction between the dissolved A and B is
much faster than the rate of transfer of A from gas to
liquid phase. The liquid phase concentration of A will be
almost zero at any moment and the rate of formation of
the products will be determined by rate of transfer of A
from gas phase to liquid phase. The diffusional factors
are important in this regime.
Regime 2
| |
*
* *
2:
1
A L
m
n
l mn o L
R a k a A
criterion for regime
k A B k a A
rateof homogeneous chemical reaction
volumetric rateof mass transfer
(
=

( (

c
A A
r R a =
Regime 2
Pure gas (gas side resistance absent)
A
p
| |
* A
Gas
side film
Liquid
side film
Interface
| |
0
o
A =
GAS
LIQUID
| |
o
B
SLOW REACTION
WHAT IF
| |
*
*
1
L
m
n
l mn o
k a A
k A B c
(

~
(

Between Regime 1 and 2
Pure gas (gas side resistance absent)
BETWEEN VERY SLOW AND SLOW REACTION
A
p
| |
* A
Gas
side film
Liquid
side film
Interface
| |
0
o
A =
GAS
LIQUID
| |
o
B
| |
0
o
A =
Between Regime 1 and 2
| | | |
| |
( )
| |
| |
*
*
1
*
1
1 1
1 1 1
m n
A l mn o o
L o
n
A L
l n o
A LR
n
LR L
l n o
R a k A B
k a A A
A
R a k a
k B
R a k a A
k a k a
k B
c
c
c
=
(
=

(

= +
(
=

= +
1 1 1
i o
U h h
= +
Regime ??? (Polymers)
Absorption of phosphine in an aqueous solution of
formaldehyde and hydrochloric acid
The product (Tetrakis(hydroxymethyl) phosphonium
chloride) is an important intermediate in manufacture of
flame-resistant ploymers
T = 27
0
C
Kmn = 1.84 x 10
3
[A*] = 1 x 10
-5
mol/cm
3
[HCHO] = 0.001 mol/cm
3
[HCl] = 0.0005 mol/cm
3

Liquid hold up = 0.8
k
L
a = 0.2 s
-1

Pollution control
Absorption of CO
2
in carbonate solution
k
2
[B
o
]=1.2 s
-1
a = 200 m
2
/m
3
k
L
a = 0.08 s
-1
First order with respect to both A and B
D
A
k
2
[B
o
]=1.6 x 10
-5
(cm/sec)
2
Regime ?? (Oils)
Hydrochlorination of olefins (C
12
-C
18
):
manufacturing of biodegradable detergents
Temperature : 25 55
0
C
First order w.r.to olefin and half order w.r.to HCl
Rate constant: 0.017
[A*] = 1.2 x 10
-4
mol/cm
3

[B
o
] = 3.5 x 10
-3
mol/cm
3
Liquid hold up = 0.8
k
L
a = 0.03 s
-1
Depending on the k
L
a, reaction belongs to either
regime 2 or between 2 and 3.

Dyestuff, Pharma and polymers
Nitration of aromatic compounds like benzene,
toluene, phenol and naphthhalene, for
manufacture of intermediates in dyestuff, pharma
and polymers
Two phases, organic and aqueous
Experimentally it has been found that rate of
nitration is diffusion controlled,

means Regime ???

Between regime 1 and 2
n-butylacetate + NaOH ------------> Sodium Acetate + Butanol
This is liquid liquid reaction. N-butylacetate is pure liquid and NaOH is 1 N solution.
The product butanol goes to organic phase and Sodium acetate remains in aquaous phase
Time (s) Normality RAa [A*] [Bo] 1/[Bo] [A*]/Ra
gmol/lit gmol/cm3sgmol/cm3 (gmol/cm3)(cm3/gmaol)
0 1.01 2.93E-06 3.41E-05 1.01E-03 990 1.16E+01
100 0.76 2.19E-06 3.31E-05 7.56E-04 1323 1.51E+01
200 0.57 1.64E-06 3.23E-05 5.66E-04 1768 1.97E+01
300 0.42 1.23E-06 3.17E-05 4.23E-04 2363 2.58E+01
400 0.32 9.18E-07 3.13E-05 3.17E-04 3158 3.41E+01
500 0.24 6.87E-07 3.10E-05 2.37E-04 4220 4.51E+01
600 0.15 4.32E-07 3.07E-05 1.49E-04 6713 7.11E+01
Between regime 1 and 2
| |
*
1
1 1
n
A L
l n o
A
R a k a
k B
(

= +
c
y = 0.0104x + 1.3266
R
2
= 1
0
20
40
60
80
0 2000 4000 6000 8000
1/[Bo]
[
A
*
]
/
R
A
a
1
0.72
100
L
n
k a
k
=
=
Regime 1
gaseous mixture (gas side resistance present)
| |
*
A A
A H p =
| |
o
B
A
p
| |
* A
Gas
side film
Liquid
side film
Interface
| | | |
*
o
A A =
GAS
LIQUID
VERY SLOW REACTION
Liquid side
Gas side
A
I
A
A
A
A
A
A
I
I I I
I
I
I
I
I
I
Regime 2
gaseous mixture (gas side resistance present)
A
p
| |
* A
Gas
side film
Liquid
side film
Interface
| |
0
o
A =
GAS
LIQUID
| |
o
B
SLOW REACTION
| |
*
A A
A H p =
REGIME 1 and 2
One more criterion
The amount of dissolved solute that reacts in the
diffusional film adjacent to the phase boundary compared
to that which reaches the liquid bulk in the unreacted state
should be negligible. Practically no reaction occurs in the
liquid side film.
| |
1
*
2
1
1
m
n
mn A o
L
k D B A
m
M
k

(

+
=
Regime 3
Pure gas (gas side resistance absent)
A
p
| |
* A
Gas
side film
Liquid
side film
Interface
| |
0
o
A =
GAS
LIQUID
| |
o
B
FAST REACTION
Regime 3
| |
1
*
*
2
1
1
m
n
mn A o
L
A L
k D B A
m
M
k
R k A M

(

+
=
(
=

1. The expression for regime 3 is similar to regime 2, but in
regime 3, one extra term appears which is higher than 1.
2. The rate of absorption of solute A is enhanced due to chemical
reaction occuring in the film.
3. So in some cases, reactions are forced to regime 3, to get an
advantage of the enhanced level of mass transfer, so that total
volume of the reactor/separator can be brought down.

Regime 3
gaseous mixture (gas side resistance present)
A
p
| |
* A
Gas
side film
Liquid
side film
Interface
| |
0
o
A =
GAS
LIQUID
| |
o
B
FAST REACTION
| |
*
A A
A H p =
Regime 4
The reaction is potentially so fast that the solute
A and reactant B can not co-exist.
At a certain distance from the interface, a
reaction plane is formed at which the solute and
the reactant are consumed instantaneously.
Regime 4
Pure gas (gas side resistance absent)
A
p
| |
* A
Gas
side film
Liquid
side film
Interface
| | | |
0
o o
B A = =
GAS
LIQUID
| |
o
B
Reaction
plane
VERY FAST REACTION
Regime 4
| |
| |
| |
| |
| |
| |
*
1
*
*
*
* 1
2
1
1
*
o
B
A L
A
m
n
mn A o
o
B
L A
o
A B
L A
B
D
R k A
D
Z A
criterion
k D B A
B
D
m
k D
Z A
B
R D
enhancement factor
k A D
Z A

= +
`
(


)
(

+
(

| = = + =
(

Regime 4
gaseous mixture (gas side resistance present)
A
p
| |
* A
Gas
side film
Liquid
side film
Interface
| | | |
0
o o
B A = =
GAS
LIQUID
| |
o
B
Reaction
plane
VERY FAST REACTION
| |
*
A A
A H p =
Regime 3 revisited
| |
| |
| |
*
1
*
1
*
*
2
1
1
2
1
A L
m
n
mn A o
L
m
n
mn A o
o
B
L A
R k A M
k D B A
m
M
k
k D B A
B
D
m
k D
Z A

(
=

(

+
=
(

+
(

Alkaline hydrolysis of formate
HCOOR + OH
-
HCOO
-
+ROH
Alkaline hydrolysis of isobornyl formate, step in
manufacture of camphor
First order w. r. to each reactant
[A*] = 5 x 10
-5
mol/cm
3
[B
o
] = 2 x 10
-3
mol/cm
3

k
L
= 0.003 cm/s
D
A
= 8 x 10
-6
cm
2
/s
D
B
= 2.12 x 10
-5
cm
2
/s
k
2
= 3 x 10
4
cm
3
/mol.s

Human body
Absorption of oxygen in red cells of the blood
D
O2
= 7.0 x 10
-6
cm
2
/s
D
Hb
= 7.5 x 10
-8
cm
2
/s
PP
O2
= 0.21 atm
H
O2in Hb
= 9.4 x 10
-7
mol/cm
3
atm
k
L
= 0.01 cm/s
[Hb] = 2 x 10
-5
mol/cm
3
k2 = 1.8 x 10
9
cm3/mol s

Regimes 1- 4
| |
o
B
A
p
| | * A
Gas
side film
Liquid
side film
Interface
| | | | *
o
A A =
GAS LIQUID
| |
o
B
A
p
| | * A
Gas
side film
Liquid
side film
Interface
| | | | *
o
A A =
| |
o
B
A
p
| | * A
Gas
side film
Liquid
side film
Interface
| | | | *
o
A A =
GAS LIQUID
A
p
| | * A
Gas
side film
Liquid
side film
Interface
| | 0
o
A =
GAS LIQUID
| |
o
B
A
p
| | * A
Gas
side film
Liquid
side film
Interface
| | 0
o
A =
GAS LIQUID
| |
o
B | |
o
B
A
p
| | * A
Gas
side film
Liquid
side film
Interface
| | 0
o
A =
GAS LIQUID
| |
o
B
A
p
| | * A
Gas
side film
Liquid
side film
Interface
| | 0
o
A =
GAS LIQUID
| |
o
B | |
o
B
A
p
| | * A
Gas
side film
Liquid
side film
Interface
| | | | 0
o o
B A = =
GAS LIQUID
| |
o
B
Reaction
plane
A
p
| | * A
Gas
side film
Liquid
side film
Interface
| | | | 0
o o
B A = =
GAS LIQUID
| |
o
B | |
o
B
Reaction
plane
Heterogeneous reactions
Regime 4
Regime 3
Regime 2
Regime 1
Regime 4
Regime 3
Regime 2
Regime 1
| |
*
m
n
A l mn o
R a k A B c ( =

*
A L
R a k a A
(
=

| |
1
*
2
1
m
n
mn A o
L
k D B A
m
M
k

(

+
=
*
A L
R k A M ( =

| |
| |
*
* 1
o
B
A L
A
B
D
R k A
D Z A


= +
`
(


)
What is required

Kinetics of gas-liquid reaction
Diffusivity of gas and liquid reactant
Solubility of the gas or the gases



Interfacial area
Mass transfer coefficient
Factors affecting overall rate of absorption
Factor Regime 1 Regime 2 Regime 3 Regime 4
[Bo]
+ - + +
[A*]
+ + + / - +
Interfacial area
- + + +
Liquid hold up
+ - - -
MTC (liquid side)
- + - +
MTC (gas side)
- + + +
Rate constant
+ - + -
Effect of k
L
and holdup

Regime Effect on the specific rate of absorption (R
A
) of
[A*] [B
o
] Speed of
stirring
Phase hold up
Regime 1 [A*]
m
[B
o
]
n
No Yes
Regime 2 [A*]
1
[B
o
]
0
Yes No
Regime 3 [A*]
(m+1)/2
[B
o
]
n/2
No No
Regime 4 [A*]
0
[B
o
]
1
Yes No