CH6701 CHEMICAL REACTION ENGINEERING – II Overall Rate (Global rate) for heterogeneous reaction:

UNIT II HETEROGENEOUS REACTORS 10 When component of A fluid reactor on the catalytic surface:
The flux of component A to the catalytic surface by diffusion is
Rate equations for heterogeneous reactions, adsorption
isotherms, rates of adsorption and desorption, surface reaction r A =k m ( C A −C AS ) −−−−−−−−(1)
analysis of rate equation and rate controlling steps
Where, CA – the concentration of A in the bulk fluid.kmol/m3
In Homogenous reaction, only one phase, either a gas or a
liquid, is present throughout the course of reaction. CAS – the concentration of A in catalytic surface. kmol/m3

Heterogeneous reactions - two or three phases are present t km – Mass transfer coefficient m3/m3.S
during the course of reaction.
If the reactant A disappears by a first –order reaction on the
Types:
catalytic surface, then the rate of reaction is
1. Catalytic type heterogeneous reactions
2. Non-catalytic type heterogeneous reactions 1 dN A '
−r 'A =− =k C AS−−−−−−−(2 )
S dt
Catalytic Type Heterogeneous Reactions
NA- Number of moles of A
1.Gas-Solid reactions Eg.1. Ammonia synthesis2.Oxidation
of SO2 to SO3 using V2O5 catalyst (manufacture of H2SO4) S – Surface area of catalyst

2.Gas-Liquid-Solid Reactions Eg. Catalytic hydrogenation t – Reaction time

of acetone to propanol
Since at steady –state, these two rates must be equal,
Non-catalytic type heterogeneous reactions
k m ( C A −C AS ) =kC ' −−−−−−−−( 3)
AS or
1.Gas –Solid reactions: Eg. Combustion of Coal
km
2.Gas-Liquid rections:Eg. 1. Purification of gas mixtures 2. C AS = C A −−−−−−−( 4 )
k m +k '
Chlorination of liquid hydrocarbons

3.Liquid-liquid reactions Eg.Soap preparation Substituting Equation (4) in (2), we get,

4.Liquid-Solid reactions Eg. Calcium

carbide+H2O.==>Acetelyene

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 1
−r 'A = C A =k o C A −−−−−(5)
1 1
+
km k'

1 1 1
= + ' −−−−−−−(6 )
Steps in a Catalytic Reaction:
Where k o k m k

ko-Over all rate coefficient(1/ko- over all resistance)

Note that addition of resistances gives overall resistance when

the rate is lineal functions of driving force with mass transfer
and reaction steps occurring in series.

Case I: Reaction Controlling:

When the mass transfer step is much more rapid than the
surface reaction step.i.e

km >> k’ and equation (6) gives

1-External diffusion of reactants towards the external surface
k 0 ≃k ' ∧C AS=C A of the catalyst pellet

So the reactant concentration at the catalytic surface is the 2-Internal diffusion of reactants into the pores of the catalyst
same as that measured in the bulk. The observed rate pellet
corresonds to the actual reaction. This situation is termed
“reaction controlling” 3- Adsorption of reactants on the active sites

Case II: DiffusionControlling: 4- Surface reaction (Eg. AÞB)

When km << k’ 5- Desorption of products from active sites into the pore
volume of the catalyst pellet
k 0 ≃k m ∧C AS≃0
6- Internal diffusion of products through the pores of the
The observed rate corresponds to the mass transfer step. This catalyst pellet towards the external surface of the catalyst pellet
situation is termed “diffusion controlling”
7- External diffusion of products to the bulk of the fluid
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The overall rate of reaction is equal to the rate of the slowest It does not require any It requires activation
step in the mechanism. activation energy. energy.
Adsorption decreases with It first increases with
increase of temperature. increase of temperature.
Step 3 Adsorption Isotherms
It is not specific in nature It is specific in nature
Adsorption-Process in which a gas, liquid, or solid adheres to i.e. all gases are adsorbed
the surface of a solid but does not penetrate it.Eg. adsorption on all solids to some extent.
of gases by activated carbon (charcoal).  It forms multi-molecular It forms unimolecular layer.
layer.
Adsorbent-The solid that takes up a gas or vapor or a solute
from a solution is called adsorbent Isotherms: “The amount of a gas adsorbed on a solid at
Adsorbate-The gas or vapor or solute which is held to the different pressures but at one temperature”.
surface of the solid is called the adsorbate
LangmuirIsotherm:
 Associative Adsorption: A gas molecule adsorbs
without fragmentation. Irving Langmuir was awarded the Nobel Prize in 1932 for his
investigations concerning surface chemistry. Langmuir’s
 Dissociative Adsorption: A gas molecule adsorbs and isotherm describing the Adsorption of Adsorbate (A) onto the
fragmentation occurs. surface of the Adsorbant (S) requires following assumptions:

Assumptions:

Types: 1. The adsorbed gas behaves ideally is the vapor phase

i. Physical Adsorption, ii.Chemisorption
Physical Adsorption Chemisorption 2. Only a monolayer is formed by the adsorbed gas.

The forces operating in The forces operating in 3. The surface of the solid is homogeneous
these are weak    vander these cases are similar to
Waal’s forces. those of a chemical bond. 4. There is no lateral interaction between adsorbate
molecules
No compound formation Surface compounds are
takes place in these cases. formed. 5. The adsorbed gas molecules are localized.
Reversible by desorption Irreversible.
The chemical reaction for monolayer adsorption can be
represented as follows:
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 Substitute above equation in (2)

C A.S K A PA
= −−−−−(5)
Ct 1+ K A P A

Net rate of adsorption of A: θ-The fraction of surface sites occupied by the gas molecules

[ The net rate ¿ ] ¿ ¿ ¿ θ=

No. of adsorption sites occupied
¿ No. of adsorption sites available

1 C A.S V K A PA
[
r A =k A P A C V −
K A A.S ]
C −−−−−−−−(1)
Ct
=
Vm
=θ=
1+ K A P A
−−−−−(6 )

At equilibrium, net rate=0 This is called Langmuir adsorption isotherm.

Vm 1
1
[
0= P A CV − C A . S
KA ] , C A . S =K A P A CV −−−−−(2)
V
=1+
KP

Multiply with P/Vm to get Langmuir in linearized form

The site balance
p p 1
= +
ν ν m Kν m
Where, p- pressure,

V- Volume of the gas adsorbed at the pressure (p)

Ct =CV +C A . S −−−−−(3 ) vm-volume of one mono-layer
By equation (2), above equation become
P0- vapor pressure,
Ct =CV +K A P A C V
C-constant for given gas
Therefore

Ct
C v= −−−−(4 )
1+K A P A
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 quantity of gas adsorbed by unit mass of solid adsorbent with
pressure. This equation is known as Freundlich Adsorption
Isotherm or Freundlich Adsorption equation or simply
Freundlich Isotherm.

X
=KP( 1/n)
m

Where

x/m - adsorption per gram of adsorbent which is obtained be

dividing the amount of adsorbate (x) by the weight of the
adsorbent (m).

At low pressure KP<<1 P - Pressure, k and n are constants whose values depend upon
1
θ=KP ,i . e θ=K [ P ] adsorbent and gas at particular temperature.

At high pressure KP>>1 Though Freundlich Isotherm correctly established the

0 relationship of adsorption with pressure at lower values, it
θ=1 , i. e θ=K [ P ]
failed to predict value of adsorption at higher pressure. This
relation is called as the Freundlich adsorption isotherm.
For intermediates pressure, the following expression should
hold good As see the following diagram. The value of x/m is increasing
n
θ=K [ P ] −−−−−−−−−(5 ) with increase in p but as n>1 it does not increase suddenly.
a ∝θ This curve is also called the Freundlich isotherm curve.
n
a=k 1 θ=k 1 K [ P ]

Take k=k1K
n
a=k [ P ] −−−−−−−−−−−−−−−(6)

This Freundlich Isotherm

Freundlich adsorption isotherm

In 1909, Freundlich expressed an empirical equation for

representing the isothermal variation of adsorption of a
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 Type of isotherms

Type I isotherms:(Langmuir type)

1. The above graph depicts Monolayer adsorption.

2. This graph can be easily explained using Langmuir

Adsorption Isotherm.

3. If BET equation, when P/P0<<1 and c>>1, then it leads

to monolayer formation and Type I Adsorption
Isotherm is obtained.

4. Eg. Adsorption of Nitrogen (N2) or Hydrogen (H2) on

charcoal at temperature near to -1800°C
Taking the logarithms of a first equation

x 1
log( )=log K + log P
m n

Hence, if a graph of log x/m is plotted against log p, it will be a

straight line in the following diagram.

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Type II isotherms: (typical physical adsorption on 2. The saturation level reaches at a pressure below the
nonporous solid) saturation vapor pressure .This can be explained on the
basis of a possibility of gases getting condensed in the
1. It shows large deviation from Langmuir model of tiny capillary pores of adsorbent at pressure below the
adsorption. saturation pressure (PS) of the gas.
2. The intermediate flat region in the isotherm 3. Eg. adsorption of Benzene on silica gel at 500oC
corresponds to monolayer formation.
Type V isotherm 
3. In BET equation, value of C has to be very large in
comparison to 1. 1. Explanation of Type V graph is similar to Type IV.

4. Eg. Nitrogen Nitrogen (N2 (g)) adsorbed at -195oC on 2. Example of Type V Adsorption Isotherm is adsorption
silica gel. of Water (vapors) at 1000oC on charcoal.

Type III isotherm: (typical autocatalytic process) 3. Type IV and V shows phenomenon of capillary
condensation of gas.
1. Type III Adsorption Isotherm also shows large
deviation from Langmuir model. Uses of Adsorption Isotherms

2. In BET equation value if C <<< 1 Type III Adsorption Adsorption isotherms are most commonly used to select the
Isotherm obtained. adsorbent or even the adsorption process as a unit operation for
the adsorptive separation of gases.
3. This isotherm explains the formation of multilayer.
If the adsorption isotherm shape is Type I, II or IV,
4. There is no flattish portion in the curve which indicates adsorption can be used to separate the adsorbate from the
that monolayer formation is missing. carrier gas.
5. Eg. Iodine (I2) at 790oC on silica gel. If it is Type III or V, adsorption will probably not be
Type IV isotherm:  economical for the separation.

1. At lower pressure region of graph is quite similar to Applications of Adsorption

Type II. This explains formation of monolayer followed The process of adsorption is very important as it has many
by multilayer. applications in domestic as well as in industrial processes.
Some of them are as follows:

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1. In heterogeneous catalysis: Surface active materials are 3. Eley-Rideal mechanism
widely used as catalysts mostly due to adsorption processes.
Single site Mechanism:
2. In removal of coloring material: Many colored materials or
The surface reaction may be a single –site mechanism in which only
impurities are removed through adsorption by suitable surface
the site on which the reactant is adsorbed. It is involved in the
active materials like charcoal. Activated charcoal has been
reaction.
extensively used for this purpose.
For example, an adsorbed molecule of A may isomerizes (or perhaps
3. In ion exchange resins: Several polymeric materials are
decompose) directly on the site to which it is attached:
used for the separation of ionic substances in chromatography
through ion-exchange.

4. In adsorption indicators: Several dyes like resin and

fluoresein are used as indicators in the titrations of Cl - , Br -
etc., against Ag +(Fajan’s method).
2. Duel site Mechanism:
5. In gas masks : Activated charcoal is used to remove toxic
The adsorbed reactant interacts with another site(either
gases in gas masks
unoccupied or occupied) to form the product.
. 6. In dyeing of cloth: Many substances work as mordants for
i.Foreg., adsorbed A may react with an adjacent-vacant site to yield
dyeing of cloths. Several metal cyanogen complexes and alums
a vacant site and a site on which the product is adsorbed
work as efficient mordants in dyeing cloths.

7. In de humidizers: Many substances, when they adsorb

water, change their colour. Silica and alumina gels are used as A . S+ S ⇔ B . S+ S
adsorbents for removing moisture. Silica is colourless but after
adsorbing water becomes blue. ii. Another example of a dual-site mechanism is the reaction
between two adsorbed species.
Surface Reaction: Once a reactant has been adsorbed onto the
surface, it is capable of reacting in a no. of ways to form the
reaction product.

Three of these ways are:

1. Single site Mechanism iii.A third dual –site mechanism is the reaction of two species
2. Duel site Mechanism adsorbed on different types of sites S and S’
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 [ The net rate ¿ ] ¿ ¿ ¿
¿
Reaction involving either single-or dual-site mechanisms described 1
above are sometimes referred to as following Langmuir-
Hinshelwood kinetics.
[
r A =k A P A C V −
]
C −−−−−−−−(1)
K A A.S

At equilibrium, net rate=0

Eley-Rideal mechanism:
1
A third mechanism is the reaction between an adsorbed molecule
and a molecule in the gas phase. [
0= P A CV − C
K A A.S ] , C A . S =K A P A CV −−−−−(2)

Net rate of adsorption of B:

[ The net rate ¿ ] ¿ ¿ ¿

¿
1
Solid Catalyzed reactions: (Langmuir-Hinshelwood
kinetics)
[
r B =k B P B C V −
]
C −−−−−−−−(3 )
KB B.S

Derivation: At equilibrium, net rate=0

Equations are developed for the rate, for various 1

controlling steps, for the reaction system. [
0=k B P B C V − C
KB B.S ] ,
C B . S =K B PB CV −−−−−(4 )

Net rate of Surface reaction:

Since the reaction is between adsorbed A and adsorbed B,the

net rate of surface reaction is given by :

kS 1
Net rate of adsorption of A: rs=
Ct [ ]
C A . S C B . S − C C. S C v −−−−−(5)
KS

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At equilibrium, net rate=0 C C. S K C K C
K p= . B V. A V
K C .C V C B . S C A . S
1
[ C A . S C B . S− C C =0
K S C .S v ] ,
K K C C
¿ A B C .S v
KC C A.SCB.S
CC .S Cv
K S= −−−−−(6 ) In view of equation 6, the previous equation becomes,
C A.S CB.S
K A KB
Net rate of desorption: K p= K S −−−−(9)
KC
r c =k −c C C .S −k c P c C v )
The concentration of vacant sites can be expressed in terms of
1 the total concentration of sites, Ct.
[
r c =−k C Pc C v − C −−−−(7 )
KC C .S ]
At eqm, net rate=0

1
[
0= Pc C v− C
KC C .S ] , CC . S =K C PC C V −−−−−(8 )
Ct =CV +C A . S +C B . S + CC . S

In view of equation 2,4,and 8 the previous equation becomes

Note:
Ct =CV +K A P A C V + K B PB CV +K C PC C V
Equilibrium constants for each steps

kA kB kC Ct =CV (1+K A P A +K B P B+K C PC ) or

K A= , KB= , K C=
k− A k−B k −C
Ct
CV = −−−−(10 )
If the equilibrium constant for the overall reaction, ( 1+ K A P A +K B PB +K C P C ) -------X------

Adsorption of A controlling: Then the adsorption of B, the

surface reaction and the desorption of C will occur at equation
PC
K p= 1
P B . PC
[
r A =k A P A C V −
]
C −−−−−−−−(1)
K A A.S
In view of equation 2,4 and 8 the previous equation becomes
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 C B . S =K B PB CV −−−−−(4 ) 1 PC

CC .S Cv rA=
[
k A C t P A−
K p PB ]
K S=
C A.S CB.S
−−−−−(6 ) [ 1+K A P A +K B P B+ K C PC ]
Surface reaction controlling:
CC . S =K C PC C V −−−−−(8 )
Then the adsorption of ‘A’,adsorption of ‘B’,and the desorption
K A KB of ‘C’ will occur at equilibrium.
K p= K S −−−−(9)
KC
kS 1
CV =
Ct
( 1+ K A P A +K B PB +K C P C )
−−−−(10 )
rs=
Ct [ C A . S C B . S−
]
C C −−−−−(5)
K S C. S v

From equation 6,

CC .S Cv
C A . S=
K SCB.S C A . S =K A P A CV −−−−−(2)
In view of equation 4, 8, 9 the previous equation becomes C B . S =K B PB CV −−−−−(4 )
K A KB 1 K P C
C A . S =K C PC C v .C V . K = A C V −−(11) CC . S =K C PC C V −−−−−(8 )
KC . K B PBCv KP B E
quation 11 in equation 1 gives K A KB
K p= K S −−−−(9)
KC
1 K A PC C V
[
r A =k A P A C V −
K A KP B ] CV =
Ct
( 1+ K A P A +K B PB +K C P C )
−−−−(10 )

1 PC
r A =k A CV P A−
[ K p PB ]
−−−−(12) In view of equation 2,3,8 and 9 , equation 5 becomes

Equation 10 in equation 12 gives

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 kS KA KB −k C . Ct [ Pc −K p P A PB ]
rs=
Ct [ K A P ACV KB PBCV −
KC K
K C PC CV CV
] rc =
[ 1+ K A P A + K B P B + K C PC ]
2
k C 1 Nomenclature:
Ct [
r s = S V K A K B P A PB − PC −−−−−(11)
Kp ] Equation 10 Ct-Total molar concentration of active sites per unit mass of
in equation 11 gives catalyst

1 Cv- Molar concentration of vacant sites per unit mass of

rs=
[
k S C t K A K B P A PB − P
Kp C
2
] catalyst

[ 1+K A P A +K B PB +K C P ] A,B –reactant, C- Product

Desorption of C controlling:T KA,KB,KC- Adsorption equilibrium constant for A, B and C

Then the adsorption of A, the adsorption of B and the surface Ks- Equilibrium constant for surface reaction
reaction will at equilibrium.
PA,PB,PC-Partial Pressure of A,B and C respectively
1
[ ]
r c =−k C Pc C v − C C . S −−−−(7 )
KC rA, rB- Net rate of adsorption of A and B

rC- Net rate of desorption, rs- Net rate of surface reaction

C A . S =K A P A CV −−−−−(2)
C- Concentration
C B . S =K B PB CV −−−−−(4 )
A.S- One unit of species A will be adsorbed on the site S.
CC .S Cv
K S= −−−−−(6 ) The Rate Limiting Step:
C A.S CB.S
When heterogeneous reactions are carried out at steady state,
K A KB the rates of each of the three reaction steps in series
K p= K S −−−−(9)
KC (adsorption, surface reaction and desorption) are equal to one
another.
Ct
CV = −−−−(10 ) If we could make the rate-limiting step go faster, the entire
( 1+ K A P A +K B PB +K C P C )
reaction would proceed at an accelerated rate.
Result can be obtained with the same procedure as adsoption.
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We wish to determine which step is rate-limiting. We first 6. Compare with data. Compare the rate law derived in
assume one of the steps to be rate-limiting and then formulate step5 with experimental data. If they agree, there is a
the reaction rate law in terms of the partial pressures of the good chance that you have found the correct
species present. mechanism and rate-limiting step. If your derived rate
law does not agree with the data:
a) Assume a different rate-limiting step and repeat steps 2
through 6.
b) If, after assuming that each step is rate-limiting, none of
the derived rate laws agree with the experimental data,
select a different mechanism and then proceed through
steps 2 through 6.

Below table gives the forms of rate laws for different reaction
From this expression we can determine the variation of the mechanisms that are irreversible and surface-reaction limited.
initial reaction rate with the initial total pressure.

If the predicted rate varies with pressure in the same manner as

the rate observed experimentally, the implication is that the
assumed mechanism and rat-limiting step are correct.

Algorithm for determining reaction mechanism and rate-

limiting step

1. Select a mechanism
2. Assume a rate-limiting step. Choose the surface
reaction first, since more than 75% of all heterogeneous
reactions that are not diffusion limited are surface –
reaction limited.
3. Find the expression for concentration of adsorbed
species (like CA.S). Use other steps that are not limited
to solve CA.S.
4. Write a site balance (Ct = Cv + CA.S + CB.S)
5. Derive the rate law. Combine steps 2,3 and 4 to arrive
For cumene derivation refer page 671 in Fogler 4th edition.
at the rate law

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University questions Part-A
1. What are the physical and chemical steps involved
1. The following data were obtained at 70°C for the in fluid-solid catalytic reaction.(MJ-2011)
equilibrium adsorption on m-hexane on silica gel 2. Write the Langmuir adsorption isotherm equation?
particles. (MJ-2011)
3. State three application of physical adsorption?(MJ-
2013,ND-2008)
Partial Hexane 4. Distinguish physical and chemisorptions?(AM-
Pressu adsorbe 2015,MJ-2014,(ND-2013,MJ-2012,ND-2012,ND-
re of d, 2010,ND-2009)
hexane (gmole/ 5. What are the assumptions of Langmuir’s approach
in gas, g. gel) x for adsorption?(MJ-2009)
atm 105 6. What is Eley-Rideal Mechanism of surface
0.002 10.5 reaction?(MJ-2009)
0.004 16
0.008 27.2
0.0113 34.6
0.0015 43
0.0206 47.3

Determine how well the Langmuir isotherm fits these

data. Calculate the values of the constants in the Langmuir
isotherm equation. (MJ-2013,MJ-2011)

2. .Discuss in detail the different adsorption theories .

(AM-2017,AM-2015,MJ-2014,MJ-2013,ND-2010)
3. For a bimolecular reaction A+B-->C+D when all the
species are adsorbed onto the catalytic surface and if
surface reaction is rate controlling derive the rate
expression for the formation of the product c. (ND-
2014)

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