36.

Adsorption
After studying this lecture, you will be able to
Distinguish between physisorption and chemisorption
Distinguish between monolayer adsorption and multiplayer adsorption
Outline the main ingredients of the major isotherms
Distinguish quantitatively between the adsorption isotherms of Gibbs, Freundlich and
Langmuir
haracterise a multiplayer adsorption through the !"# isotherm
Determine the heat of reaction using an adsorption
Distinguish between the characteristics of bul$ reactions and reactions at surfaces
Outline the mechanisms of unimolecular and bimolecular reactions at surfaces
List the applications of adsorption
36.1Adsorption :
#he molecules at a surface of a material e%perience imbalanced forces of intermolecular
interaction which contribute to the surface energy& 't causes accumulation of molecules of
a solute or gas in contact with the substance& #his preferential accumulation of substrate
molecules at the surface is called adsorption which is purely surface phenomenon&
#he surface active material is refered to as the adsorbent and the molecules which are
accumulated on the adsorbent called adsorbate molecules& #he strength by which adsorbate
molecules are attached with the adsorbents determines the nature of adsorption& (ormally,
release of energy in the range of ) to *+ $,-mole due to adsorption is termed as
physisorption whereas a much larger energy comparable to chemical bonding energy leads
to chemisorption& #here are always some e%ceptions to these values& #he prescribed value
of energy differentiating physisorption and chemisorption are based on general e%perience&
.hen an adsorbed molecule receives energy equal to or greater than the energy of
adsorption, it will leave the surface& #his phenomenon is the reverse of adsorption and is
called as desorption& .hen the number of molecules stri$ing the surface and staying there
is equal to the number of molecules that are leaving /evaporating0 the surface is called to
be in equilibrium&
All the atoms or molecules adsorbed on the surface do not have identical environment as
distribution of free energy on the surface is not always smooth because of the difference in
the energy of the molecular orbitals of the adosrbent and also due to other internal
interactions&
36.2 Adsorption Isotherms
A relation between the amount of adsorbate adsorbed on a given surface at constant
temperature and the equilibrium concentration of the substrate in contact with the
adsorbent is $nown as Adsorption 'sotherm& #wo types of typical adsorption isotherms are
shown in the following Figures A 1 !& Figure A shows adsorption with monolayer
formation at saturation point& Figure ! shows a situation when several layers of adsorbate
molecules are formed on the surface of the adsorbent /multilayer adsorption0&
e 2
3
e 2
3

4
x x
m x
A. Monolayer adsorption B. Multilayer adsorption
5
m
is the amount of the substrate required to ma$e a monolayer where as 2
o
is the
saturation equilibrium concentration of the substrate&
Arrangement of adsorbed molecules on the surface of the adsorbent could normally be
monolayer in nature& (ormally, chemisorption leads to monolayer adsorption whereas
multilayer arrangement of substrate molecules is observed due to physisorption only&
6ultilayer formation is also possible due to chemisorption followed by physisorption
36.2.1 Gibbs Adsorption Isotherm:
#his isotherm normally considers the case when adsorbents are liquid and
adsorbates are soluble or partially soluble in it e&g&, surfactants - water or organic liquid -
water system&
onsidering a system having a plane interface between them the Gibb7s free energy
of a system containing two components could be written as follows8
* * 4 4
n n G + =

/9:&*&40
.here
4
n and
*
n are the number of moles and
4
and
*
are the chemical potentials of the
two components respectively& .hile dealing with the adsorption of one of the components
on the surface of another, an additional term of surface energy has to be introduced, and
hence, equation /9:;*;40 modifies to
+ + =
* * 4 4
n n G /9:&*&*0
where

is the surface energy per unit area and

is the surface area& 't is now clear that

equation /9:;*;40 is for bul$ while equation /9:;*;*0 will be applicable for the surface of
the absorbent liquid& #he complete differential of /9:;*;*0 may be written as
d d dn d n dn d n dG + + + + + =
* * * * 4 4 4 4
/9:&*&90
.e find that the total free energy G of the whole system depends on independent
variables , namely , #,2,n
4
,n
*
and <, thus,
0 , , , , /
* 4
n n P T f G =
and complete differential of G will be,
*
xm
, , ,
* 4
n n p
dT
T
G
dG

=
, , ,
* 4
n n T
dP
P
G

+
, , ,
4
4 *
n P T
dn
n
G

+
, , ,
*
* 4
n P T
dn
n
G

+
* 4
, , , n n P T
d
G

+
or d dn dn Vdp SdT dG + + + + =
* * 4 4
/9:&*&=0
At constant temperature and pressure, above equation reduces to ,
d dn dn dG + + =
* * 4 4
/9:&*&+0
omparing equation /9:;*;90 and /9:&*&+0, we get
3
* * 4 4
= + + d d n d n /9:&*&:0
A corresponding equation for the bul$ of the system may be,
3
*
3
* 4
3
4
= + d n d n /9:&*&>0
.here
3
4
n and
3
*
n are the number of moles of adsorbent liquid and solute in the bul$&
From the equation /9:;*;:0 and /9:;*;>0, we get
*

d
d

0 - /
3
4
3
* 4 *
n n n n
/9:&*&)0
@ere, the term

0 - /
3
4 4 *
n n n n
represents the corresponding e%cess moles of solute per
unit area on the surface of the adsorbent and now be represented by
*

*
*

d
d

=

#he chemical potential of solute + =
3
* *
A# ln a
2
or =
*
d A#d ln a
2
.hen solution is very dilute activity a
*
of solute could be replaced by its concentration&

*
*
*
T
c d
RT c

=

or, in general for any solute and liquid adsorbent,
9

T
c
RT c

=

/9:&*&B0

'n the above equation

is essentially surface energy per unit area, which may easily be

replaced by surface tension /force-length0&
#he application of the above equation is as follows& 'f the detergent /solute or adsorbate0
tends to accumulate at the interface its surface e%cess is positive, and so
dc
d
is negative &
#his means surface tension decreases when a solute accumulates at the surface&
Example: the surface tension of the dilute solution of phenol in water at C
o
*> were the
following8
6ass C phenol 3&3*= 3&3+ 3&4*+ 3&*+
3&=3

% 43
9
-/(m
;4
0 >*&> >*&* >4&9 >3&9
:B&9
alculate surface e%cess concentration / D0 at a concentration of 3&4+ mass of phenol&
omment on the significance of the observed value of D&
olution 8 A plot of

us mole of phenol gives a curvature with negative slope for 3&4+

mol of phenol slope is
4)>+ & 3
> & 4

, putting values in equation,

T
C
RT c

=

.e get,
3
3&4+ 4&>
)&94 933 3&4)>+ x k

=



? +&=+ % 43
;=
mol m
;*
#he positive value of signifies that phenol is
surface active and accumulates at the interface&
36.2.2 !reundli"h Adsorption Isotherm
't is an empirical relation between the amount of an adsorbate adsorbed per unit weight
/%-m,mg g
;4
0 of adsorbent and the adsorbate equilibrium concentration /
e,molesL
;40 in the
fluid as follows8
%-m ? E
e
n
/9:&*&430
=
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45
69.0
69.5
70.0
70.5
71.0
71.5
72.0
72.5
73.0

x

1
0
3
(
N

m
-
1
)
Mass % phenol
.here, E and n are Freundlich coefficients
% ? weight of adsorbate adsorbed on m unit weight of adsorbent

e
? equilibrium concentration of adsorbate
From equation , we get
log/%-m0 ? logE F n log
e
/9:&*&440
#he coefficients E and n can be determined from the intercept and slope of a plot of
log/%-m0 versus log
e
&
From the appearance of the type ' isotherm /Figure A0 it is seen that for low values of
concentration the amount adsorbed /%-m0 is nearly proportional to
e
, whereas for large
values it is nearly constant /or proportional to
e
o
0& Go it is reasonable that for intermediate
values of
e
, %-m should be proportional to some power of
e
lying between 3 and 4& #his
is the motivation behind the empirical Freundlich adsorption isotherm&
Freundlich adsorption isotherm may be verified by performing a simple e%periment for the
adsorption of o%alic acid on charcoal& Gupposing m gram of charcoal is added in +3 mL
i

6 solution of o%alic acid& After adsorption is established equilibrium concentration of
o%alic acid was determined as
f&
@ence, amount of o%alic acid adsorbed per unit weight of
charcoal,
%-m /mg g
;4
0 ? /
i
H
f
0 % :9 % +3 /9:&*&4*0
'n a series of such e%periment with different initial concentration of o%alic acid, values of
%-m /mg g
;4
0 is determined& A plot of log %-m versus
f
is made and Freundlich coefficients
E and n are determined&

36.2.3 #an$muir Adsorption Isotherm
'n the Langmuir model the adsorbent surface is considered to possess a number of active
interaction sites for adsorption& Langmuir derived a relation between adsorbed material and
its equilibrium concentration& @is assumption are8
4& #here are fi%ed adsorption sites on the surface of the adsorbent& At a given #12 some
fraction of these sites are occupied by adsorbate molecules& Let this fraction be &
*& "ach site on the surface of the adsorbent can hold one adsorbate molecule&
9& #he heat of adsorption is the same for each site and is independent of &
=& #here is no interaction between molecules on different sites&
onsidering the processes of adsorption and desorption of the molecules on the surface, the
Langmuir adsorption isotherm may be obtained as follows8
Aate of adsorption of molecules on the surface of the adsorbent ? $
a

e
/4 ; 0
Aate of desorption ? $
d

+
At equilibrium
( ) = 4
e a d
C k k
/9:&*&490
L
, where E is the adsorption coefficient
4
a e L e a
d a e L e d
k C K C k
k k C K C k
= = =
+ +
Gince,
m
x
x
=

e L
e L
m
C K
C K
x
x
+
=
4


/9:&*&4=0
where x and X
m
are the amount of the adsorbent adsorbed at equilibrium concentration
e
and ma%imum amount of adsorbate for the formation of monolayer, respectively&
rearranging equation /9:&*&*0, we get

m
e
m L
e
x
C
x K x
C
+ =
4
/9:&*&4+0
'f we plot
x
C
e
vs e
C
, we will get a straight line& Glope of which will be
m
x
4
and
intercept as
m L
X K
4
&
#herefore, from values of intercept and slope of the plot values of X
m
and E
L
could be
calculated& 'n the case for the adsorption of gaseous substrate C
e,
,X, and X
m
will be
replaced by p.V, and V
m
, respectively&
For chemisorptions Langmuir7s equation wor$s very well but fails for the cases where
multilayer formation ta$es place&
Example: the volume of @
=
/corrected to G#20 adsorbed per gram of charcoal at *=3 E
various pressures of @
=
is8
2-/#orr0 9) ++ >) 43= 499 4>9 *4)
I-/cm
9
&g
;4
0 4=&4= 4>&+* *4&9) *=&>* *)&33 94&9+ 9=&+3
Ierify that the data obey Langmuir adsorption isotherm& Also determine Langmuir
constant K
L
and the volume corresponding to complete surface coverage& alculate the
fraction of charcoal surface which is covered by @
=
molecules at 2?4+3 torr&
2lot of p-v vs p as shown below is linear which shows that the data verify the Langmuir
monolayer adsorption isotherm&
:
m L m
V K V
p
V
p 4
+ =
Glope of the curve ?3&3* cm
;9
&g
4 9
9
3 & +3
3* & 3
4 4

= = = g cm
g cm slope
V
m

intercept ?*&3+ torr cm
;9
g ?
m L
V K
4
intercept
=
m
L
V
K
4

0 3+ & * 0/ 3 & +3 /
4
9 4 9
g g cm
K
L
=
cm torr

?B&>+ % 43
;9
torr
;4
Fraction of the surface covered / 0
at 2?4+3 torr,

p K
p K
L
L
+
=
4

?
0 4+3 0/ 43 >+ & B / 4
0 4+3 0/ 43 >+ & B /
4 9
4 9
torr torr x
torr torr x


+
? 3&+B9 +B&9C of the surface is covered by @
=
molecules&
36.2.% #an$muir adorption isotherm &or se'eral non(disso"iati'ely adsorbed spe"ies:
'f two species A and ! are adsorbed on the surface& #hen applying Langmuir hypothesis
for species A, we have,
( ) ( )
( ) 4
A A
A A
a a
! k p =
/9:&*&4:0
( ) ( )
( )
A A
d d
A
! k =
/9:;*;4>0
( ) 4
A
A A A A d
k ka p =
( )
( )
A A
A d
A a
A
p
k
k

= 4
0 /
>
20 40 60 80 100 120 140 160 180 200 220 240
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
P
/

V

(

T
o
r
r
.
c
m
-
3
.
g
)
P (torr)
( )
A A A A
p K = 4

=
0 /
0 /
A
A a
A
kd
k
k /9:&*&4)0
Gimilarly for species !,
( )
A
p K = 4 /9:&*&4B0
or,
A
p K p K p K =
( )
A
p K p K p K = + 4

A

p K
p K p K
+

=
4

/9:&*&*30
(ow, patting the value

from /9:;*;*30 into equation /9:;*;4)0, we get

=

A
A A A A
p K
p K p K
p K
4
4



A
A A A A A A
p K
p K p K
p K p K
+

=
4



A A A A A
A
p K
p K p K
+

=
4

/9:&*&*40

A A
A A
A
p K p K
p K
+ +
=
4


/9:&*&**0
Gimilarly, we can obtain

A A

p K p K
p K
+ +
=
4


/9:&*&*90
'n general, Langmuir adsorption isotherm for species A under conditions of several non;
dissociatively adsorbed species could be derived as,

( )
( )
" " "
A A
A m
A
p K
p K
x
x
+
=
4

/9:&*&*=0
where sum runs over all species&

)
36.2.) Multilayer Adsorption
'mportant assumption of Langmuir theory is the formation of monolayer& !ecause of
monolayer formation a saturation in adsorption would reach at higher equilibrium
concentration of the adsorbate& #his type of adsorption occurs due to short range chemical
forces which do not allow penetration through the primary adsorbed molecules& 6ultilayer
formation has been observed when molecules are adsorbed through wea$ forces /long
range forces normally under physical adsorption0 due to cohesive forces e%erted by the
molecules of the adsorbate&
At high pressure multilayer adsorption ta$es place& #he theory of multimolecular
/multilayer0 adsorption was developed by Gtephen !runauer, 2aul "mmet and "dward
#eller and is called !"# isotherm& #his isotherm derived by them successfully accounts for
all types of adsorption&
36.2.6 BE* Isotherm
't assumes that the surface possess uniform, localised sites and that adsorption on one site
does not affect adsorption on neighbouring sites just as in Langmuir theory& Also,
molecules can be adsorbed in second, third,J and n
t#
layers with the surface available for
layer equal to the coverage of the ne%t lower layer&
#he rate constants for adsorption and desorption of the primary layer are k
a
and k
d
and
those of the subsequent layers are all k
a
and k
d
& #he number of sites corresponding to
Kero, monolayer, bilayer, J coverage at any stage are $
%
, $
&
, $
2
, etc& and $
"
in general&
#he condition for equilibrium of the initial layer is the equality of the rates of its formation
and desorption,

4 3
$ k p$ k
d a
=
/9:&*&*+0
#he condition for equilibrium of the ne%t layer is
& 9 * , general in and
4 * 4
,... , " $ k p$ k $ k p$ k
" d " a d a
= = =

#his condition may be e%pressed in terms of $
%
as follows8

4

=
"
d
a
"
p$
k
k
$

3
4
4
4
4 *
*
*
*
& $ p
k
k
k
k
$ p
k
k
$ p
k
k
"
d
a
"
d
a "
d
a
"
d
a

3
4
$ p
k
k
k
k
$
"
d
a
"
d
a
"

/9:&*&*:0
writing
x
k
k
d
a
=

and
cx
k
k
d
a
=
, then
B
3
4
$ cxp x $
" "
"

=
( )
3
$ xp c $
"
"
= /9:&*&*>0
(ow, we calculate the total volume, I, of adsorbed material& I is proportional to the total
number of particles adsorbed, and so

=
= + + + =
4
9 * 4
&&&& 9 *
"
"
"$ $ $ $ V
/9:&*&*)0
!ecause each layer contributes number of particles according to its thic$ness, i&e&, a
monolayer one particle, a bilayer site two particles etc&
'f there were complete monolayer coverage the volume adsorbed would be I
mono
, with

=
= + + + =
4
* 4 3
&&&
"
" mono
$ $ $ $ V
/9:&*&*B0
!ecause each site contributes only one particle to the total it follows then
( )


=

=
= =
4
3
3 "
"
"
"
$ xp "c "$ V
( )

=
=
4
3
"
"
xp " c$
( )

=
L 4
4
3
"
"
xp " xp c$
( )
*
3
4
4
xp
xp c$

=
( )
*
3
4

= xp xp c$ V
/9:&*&930
From equation /9:;*;*B0,

&&&
3
* 4 3
+ + + = =

= "
" mono
$ $ $ $ V

=
+ =
4
3
"
"
$ $

=
+ =
4
3 3
0 /
"
"
$ xp c $


xp
xp c$
$

+ =
4
3
3
( ) ( ) &&& 4
*
3
+ + + + = xp xp xp c$ $
o
/9:&*&940
( ) ( ) &&& 4 4
* 4
+ + + =

xp xp xp
43
From equation /9:;*;930 and 9:;*;940, we have

( )
( )
4
3 3
*
3
4
4

=
xp xp c$ $
xp xp c$
V
V
mono
/9:;*;
9*0
( ) ( )( )
*
4 * 4 xp c xp c
cxp
+ +
=

( )
( ) ( )
* *
M - 4 M - * 4
M -
p p c p p c
p p c
+ +
=
( ) ( )
*
4 * 4 ' c ' c
c'
+ +
=
/9:&*&990


4
,
M
a
d
K
x
k p

= =

pM ? equilibrium pressure, /ads0

vapour
putting M - p p ' =
( ) ( ) { } ' c '
c'
c' ' ' c'
c'
V
V
mono

=
+ +
=
4 4 4 * 4
* *
/9:&*&9=0

( ) ( ) { } M - 4 4 M - 4
M - &
p p c p p
p p c
+
=
44

( ) ( ) [ ]
o
p
p p c p p
p p c
- 4 4 M - 4
- &
+
=


( ) ( ) ( ) ' c
c V
' '
V
mono

=
4 4 4 -
( ) ( ) ( ) ' c
c V
' '
V
mono

=
4 4 4 -
( )
( )
mono mono
cV
' c
cV V '
' 4 4 4
&
4

+ =

/9:&*&9+0
( )
mono
cV
c 4
can therefore be obtained from the slope of a plot of
( )V '
'
4
against K, and
cI
mono
can be found from the intercept at K?3, the result being combined to give c and I
mono
from the corresponding value of I
mono
at *>9 E and 4 atm, number of molecules present in
I
mono
could be calculated& !y $nowing the contact area of a molecule, surface area of the
adsorbent per unit mass could be determined&
36.3 +etermination o& ,eat o& adsorption
#he temperature dependence of E can be used to determine the isoseric enthalpy of
adsorption /
(

, the enthalpy of adsorption at a fi%ed surface coverage0&

From Langmuir adsorption isotherm fraction of covered surface,
Kp
Kp
+
=
4

/9:&9&40
or
constant is where ,
4

= Kp
the from so, constant ln ln = + p K
equation
*
ln d K (
dT RT

=


*
ln ln P d K (
T dT RT

= =

/9:&9&*0
using
*
4
4
T dT
T
d
=

, this rearranges to,

4*
4
ln
d
P ( T
T R dT

= +

ln

4
P dT (
T R
d
T

ln

4
d P (
R
d
T

=



/9:&9&90
#hus, a plot of lnP against 4-# should be a straight line with slope
(
R

&#herefore

(
could be determined from the slope&

36.% -ea"tion on sur&a"es
'n case a solid immersed in a solution, the reactants in the solution must diffuse to the
interface, get adsorbed there and participate in a given reaction mechanism on the solid
surface, the product on the surface must then desorb and diffuse into the solution&
36.%.1 .nimole"ular rea"tions on sur&a"es
onsider the surface catalysis of isomerisation or dissociation of a substance A on surface
G as follows, substance G gets adsorbed on the surface forming AG and then dissociates to
product,
A F G AG /9:&=&40
AG
*
K
2roduct /9:&=&*0
Aeaction velocity,
* AS
! k C =
/9:&=&90
.here,
*
moles
concentration of A on the surface
cm
AS
C

=


'f,
*
sites-cm surface of total =
S
C and represents the surface sites covered by A,
then
C
AG
? C
s

or, reaction velocity,
49
k
1
k
-1
v ? $
*

Again, if let Ca ? concentration of A either in gas or solution

Gince C
s
is constant, it can be incorporated into rate constant
*
! k =

Applying steady state appro%imation to AG,
( )
* 4 4
4 3 k k C k
dt
dC
a
AS
= =

where a represents the concentration of A either in gas or solution,

* 4 4
4
k k C k
C k
a
a
+ +
=

4 *
4 4 *
,
a
a
k k C
!
k C k k

=
+ +
/9:&=&=0

4 *
* 4 *
4 4
a
k k
! k k k C

+
= +
/9:&=&+0
A plot of
4 4
v
a
s
! C
yields
*
4
k
as the intercept and
* 4
* 4
k k
k k +

as the slope&
Nsually it is more convenient to use limiting cases as follows8
/ase I
$
*
, the rate of decomposition is very large compared with the rate of adsorption and
desorption& 'n this case, k
2
OO /k
&
C
a
F k
)&
0 and hence equation /9:&=&=0 reduces to,
! * k
&
C
a
2hysically, the assumption that k
2
is large implies that an adsorbed molecule decomposes
immediately after coming in contact with the surface& #his situation is found for the
decomposition of @l on 2t and (
*
O on gold&
/ase II
$
*
is very small /negligible0 in comparison to /k
&
C
a
+ k
)&
0 and hence equation /9:&=&=0
reduces to 8
4 *
4 4
a
a
k k C
!
k C k

=
+
4=
4
4 *
,
4

) a
a
k
k
K
KC
KC k
=
+
=
at low concentration of the species A, E
a
PP 4
* a
! k KC =
.here as at high concentration KC
a
OO 4 or Q 4
*
! k =
ub(/ase o& I
A diatomic molecule A
*
dissociates upon adsorption to the surface&
#his reaction can be written as
( ) ( ) *
*
g S
A S +
( )
*
S
AS
/9:&=&:0
[ ]
[ ] [ ]
*
*
*
S A
AS
k
k
K
d
a
C
= =
!ecause two surface sites are involved in the adsorption and desorption process, the rates
of adsorption,

a
, and desorption
d
, are
( )
*
*
*
4
a a s A
! k p C =
/9:&=&>0
* *
a d s
! k C = /9:&=&)0
.here, s ? total surface sites- cm
*
, ? fraction of the surface covered and p represents the
pressure of the molecules A
*
&
At equilibrium, these rates are equal, and so
( )
*
*
*
4
a A d
k p k =
( )
* *
4 =
A
Kp
4- * 4- *
4- * 4- *
*
*
4
A
A
K p
K p
=
+
/9:&=&&B0
4- * 4- *
*
4 4
4
A
K p
= +
/9:&=&430
A plot of

4
vs 4- *
*
4
A
p
will yield a straight line with slope
* - 4
4
K
and intercept 4&
36.%.2 Bimole"ular rea"tions on sur&a"es:
4+
k
d
k
a
A bimolecular reaction between two molecules A and ! on a surface may occur
through different alternative steps out of which following two are important
0i1 #an$muir 2 ,inshel3ood me"hanism :
#he two reacting molecules A and ! react after being adsorbed on neighbouring
sites on the surface of the catalyst& #his mechanism is called as Langmuir ; @inshelwood
mechanism& Aeaction rate v, for such reaction may be written as follows8
A
! k =
/9:;=;440
2utting the values of
A
and from equations /9:&*&4+0 and /9:&*&4:0, we get
*
/4 0
A A
A A
kK K p p
!
K p K p
=
+ +
/9:&=&4*0
Above equation could be subjected to two special cases as follows8
4& 'f the pressures of A and ! species, p
A
and p

are both sufficiently low so that K

A
p
A
and K

p

may be neglected in comparison with unity, the rate equation becomes,
[ ] [ ]
A
! kK K A =
/9:&=&490
#his would mean reaction to be second order& #his a frequently observed behaviour in
Langmuir H@inshelwood mechanism&
*& 'f a reactant A is very wea$ly adsorbed, k
A
p
A
in the denominator of equation /9:&=&440
may be neglected, and the rate equation become,
*
/ 0
A A

kK K p p
!
l K p
=
+
/9:&=&4=0
Aeaction of hydrogen with ethylene on copper follows a nearly similar rate law as follows8
4:
[ ] [ ]
[ ]
* * =
*
* =
/4 0
K ( C (
!
K C (
=
+
'f reactant ! is adsorbed very strongly such that K

p

4, equation /9:&=&490 becomes

A A
p K
p kK
! =
/9:&=&4+0
#he rate is now inversely proportional to 2
!
& Guch behaviour is observed in reaction
between carbon mono%ide and o%ygen on quartK and on platinum& 'n these cases rate in
inversely proportional to the pressure of carbon mono%ide, which must be strongly
adsored&
0ii1 #an$muir ( -ideal me"hanism:
'f reaction is due to collision of a gaseous molecules A with an adsorbed ! molecules, the
mechanism is $nown as Langmuir H Aideal mechanism and the rate law in this case will
be,
A
! k p =
/9:&=&4:0
or,
4
A A
A A
kK p p
!
K p K p
=
+ +
/9:&=&4>0

#he reaction of ethylene and @
*
on copper surface presents nearly similar situation of
Langmuir H rideal mechanism&
*
@
=
gets adsorbed much strongly on the surface& Aate
equation for the reaction of *@= and @* on copper surface follows as below8

[ ] [ ]
[ ] ( )
* * =
*
* =
4
k ( C (
!
c C (
=
+
/9:&9&4)0

36.) ur&a"e /atalysis
6any industrial chemical reactions are carried out in the presence of solid catalyst e&g&, Fe;
catalyKed synthesis of (@
9
from (
*
and @
*
, GiO
*
-Al
*
O
9
catalyKed crac$ing of high
molecular weight hydrocarbons to gasoline& Aeactions involving catalysts of a phase
different from reactants are $nown as heterogeneous catalyst& !esides other usual
4>
applications, heterogeneous catalysis is e%tremely important and will be discussed in
details&
@eterogeneous catalysis, li$e its homogeneous counterpart, changes the rate of a reaction
by providing an alternate reaction mechanism& Golid catalysts lower activation energies by
much greater e%tend than homogeneous catalysts& For the reaction *@' '
*
F @
*
without
catalyst, the activation energy is == $cals-mol, *+ $cals-mol when catalyKed by Au, and is
only 4= $cals- mol when catalyKed by 2t& NncatalyKed reaction *@
*
O
/aq0
*@
*
F O
*
has
activation energy 4> $cal-mol, 4* $cal-mol when catalyKed by colloidal 2t and only *
$cal-mol when catalyKed by enKyme catalase&
Gimilarly, decomposition of (
*
O in gas phase without a catalyst has activation energy *+3
$,-mol, and with catalyst with Au and 2t is about 4*+ $,-mol&
#he substances most often studied and used as heterogeneous catalyst are transition metals,
alloys and semiconducting o%ides and sulfides& #he effectiveness of a catalyst can be
measured by the amount of product formed per unit time per unit surface area of the
catalyst& Activity of a catalyst depends on the nature of active sites present on the surface
e&g&, point defects, lattice distortion of C d;character of the metallic bond within the solid
metal& atalysts with different surface property may lead to the formation of different
product from the same starting reactant& For e%ample, isopropanol undergoes
dehydrogenation on a surface of RnO while dehydration occurs on Al
*
O
9/s0
& RnO is n;type
semiconductor whereas Al
*
O
9
is an ionic insulator and acts as a Lewis acid& #he probable
mechanism may be given as follows8
II.
O Al O
OH
H
H
3
C C CH
3

Al
2
O
3(S)
(CH
3
)
2
CHOH CH
3
CH CH
2
+ H
2
O

I.
ZnO
(s)
Net reaction is (CH
3
)
2
CHOH CH
3
C CH
3
+ H
2
(9)
Zn O Zn O Zn
H
3
C C O
CH
3
-H
-H
ZnO
(S)
CH
3
H
3
C C OH
(CH
3
)
2
CHOH Zn O Zn O Zn
O
'n a surface catalyKed reactions activation energy is normally lowered due to adsorption of
reacting molecules on the surface of the catalysts& After adsorption surface molecules are
not allowed to perform translational motion but are able to perform vibrational motion&
4)
36.6 Appli"ations o& Adsorption
#he process of adsorption is very important as it has many applications in domestic as well
as in industrial processes, to name some of them are follows8
1 In hetero$eneous "atalysis: Gurface active material are widely used as catalyst
mostly due to adsorption processes& 'f the surface active materials /adsorbents0 have
different phase with that of substrates, then the catalysis is called heterogeneous
catalysis& A system where both the catalyst and substrate are in same phase is called
homogeneous catalysis&
2. In remo'al o& "olourin$ material: 6any coloured materials or impurities are
removed through adsorption by suitable surface active materials li$e charcoal&
Activated charcoal has been e%tensively used for this purpose&
3. In ion ex"han$e resins: Geveral polymeric materials are used for the separation of
ionic substances in chromatography through ion;e%change&
%. In adsorption indi"ators: Geveral dyes li$e eosin and fluoresein are used as
indicators in the titrations of l
;
, !r
;
etc& against Ag
F
/Fajan7s method0&
). In $as mas4s8 Activated charcoal is used to remove to%ic gases in gas mas$s&
6. In dyein$ o& "loth: 6any substances wor$ as mordants for dyeing of cloths& Geveral
metal cyanogen comple%es, alums wor$ as efficient mordants in dyeing cloths&
5. In de humidi6ers: 6any substances when they adsorb water change their colour&
Gilica and alumina gels are used as adsorbents for removing moisture& Gilica is
colourless but after adsorbing water becomes blue&Gilica is colourless but after
adsorbing water becomes blue&
36.5 ummary
'n the present lecture on surface chemistry, we began by distinguishing between
physisorption and chemisorption and also between monolayer adsorption and multiplayer
adsorption& #he binding energies in physisorption are much smaller and in the range of )
to *+ $,-mole& A relation between the amount of adsorbate adsorbed on a given surface at
constant temperature and the equilibrium concentration of the substrate in contact with the
adsorbent is $nown as Adsorption 'sotherm& .e have outlined the main ingredients of
some important isotherms such as the adsorption isotherms of Gibbs, Freundlich and
Langmuir
Amultiplayer adsorption was characteriKed through the !"# isotherm&
#he heat of a reaction was obtained using an adsorption& .e also outlined the mechanisms
of unimolecular and bimolecular reactions at surfaces& #he Langmuir H @inshelwood
mechanism and the Langmuir H Aideal mechanism of bimolecular surface reactions were
described in detail& #owards the end, the role of adsorption in surface catalysis was
highlighted and the other applications of adsorption were listed&
4B