Physical Chemistry

1. Used to be the entalphy of adsorption

(values less negative than -25 kJ/mol were
taken to signify physisorption and values
more negative than about -40 kJ/mol were
taken to signify chemisorption)
2. Spectroscopic techniques (to identify the
adsorbed species are now available)
3. LEED

2
The variation of Ө with pressure at a chosen
temperature is called the adsorption isotherm

The simplest isotherm is based on three assumptions :

1. Adsorption can proceed monolayer coverage
2. All sites are equivalent and the surface is uniform (that
is, the surfaces is perfectly flat on a microscopic
scale)
3. The ability of a molecule to adsorb at a given site is
independent of the occupation of neighbouring sites.

3
The dynamic equilibrium is
ka
A(g) + M(surface) AM(surface)
kd
ka = rate constants for adsorption
kd = rate constants for desorption

The rate of change of surface coverage due to

adsorption is N = the total number of sites

θ = k a pN(1 − θ) p = the partial pressure

1-Ө= the fraction of surface uncovered

The rate of change of surface coverage due to desorption

is
θ = k d Nθ
4
At equilibrium the net rate of adsorption is zero and solving for Ө
gives the Langmuir Isotherm :

k x For adsorption without dissociation !!!

K = a = AM
kd xM  K.p
K.p = or θ =
1− 1 + K.p
bila x AM = 
xM = 1 −  For adsorption with dissociation
K. p
θ = and K.p = K.p.θ + θ
V = volume of gas adsorbed at given pressure 1+ K. p
V~ =volume required to form a complete a
V p
complete monomolecular layer to saturate the θ= and K.p =
surface of the adsorbent V V
k= constanta p p 1
so = +
V V kV
Langmuir Isotherm
equation Plot p/V against p should give a straight line of
slope 1/v~ and intercept 1/kV~ 5
The rate of adsorption is proportional to the pressure and to the probability
that both atoms will find sites, which is proportional to the square of the
number of vacant sites
d
= k a pN (1 −  )2
dt
The rate of desorption is proportional to the frequency of encounters of
atoms on the surface and is therefore second-order in the number of
atoms present
d
= − k d ( N )
2

dt
The condition for the net rate of adsorption to be zero leads to the
isotherm
1

=
( K. p) 2
1
1 + (K . p )2
6
 The Langmuir isotherm for a. non dissociation
b. dissociation for different values of K

a. 1.0 b. 1.0
10atm-1 10atm-1
0.9 0.9
1atm-1
0.8 0.8 1atm-1
0.7 0.7
Ө
Ө 0.6 0.6
0.1atm-1
0.5 0.5
0.1atm-1
0.4 0.4
0.3 0.3
0.2 0.2
0.1 0.1
0 2 4 6 8 10 0 2 4 6 8 10
P(atm) P(atm)
The fractional coverage increases with increasing pressure and
approaches 1 only at very high pressure when the gas is forced on
to every available site of the surface
7
Different curves (values of K) are obtained at
different temperatures and the temperature
dependences of K can be used to determined
the isosteric enthalphy of adsorption ΔadHӨ, the
standart enthalphy of adsorption at a fixed
surface coverage.

 d ln K   H
  = ad 2
 dT  RT

8
The data given below are for the adsorption of CO on charcoal at
273K. Confirm that they fit the Langmuir Isotherm and find the
constant K and the volume corresponding to complete coverage. In
each case V has been corrected to 1 atm

p/Torr 100 200 300 400 500 600 700

V/cm-3 10.2 18.6 25.5 28.4 36.9 41.6 46.1

Answer:

p/Torr 100 200 300 400 500 600 700

(p/Torr)/(V/cm-3) 9.8 10.8 11.8 12.7 13.6 14.4 15.2

9
 Exercises
Repeat the calculation for the following data

p/Torr 100 200 300 400 500 600 700

V/cm-3 10.3 19.3 27.3 34.1 40.0 45.5 48.0

10
Used isotherm dealing with multilayer adsorption was
derived by Stephen Brunauer, Paul Emmett, and
Edward Teller and is called the BET Isotherm
V cz p
= where z =
Vmon (1 − z )1 − (1 − c )z p*

P* = is the vapour pressure above a layer of adsorbate that is more

than one molecule thick and which resembles a pure bulk liquid
Vmon= is the volume corresponding to monolayer coverage
c = is a constant which is large when the enthalphy of desorption
from a monolayer is large compared with the enthalphy of
vaporization of the liquid adsorbat
z
=
1
+
(C − 1)z (c-1)/cVmon can be obtained from the slope
(1 − z )V cVmon cVmon of a plot of the expression on the left against
z and cVmon can be found from the intercept
at z=0
11
 5.0
When the coefficient c is large
4.5 (c>>>1) the BET isotherm takes the
4.0 simpler form
3.5
V 1
=
V/Vmon

3.0
2.5
Vmon 1 − z
2.0
1000
1.5
1.0 100 10 1
0.5
0 0.2 0.4 0.6 0.8 1.0
z
Plots of the BET isotherm for different values of c.The value of V/Vmon rises
indefinitely because the adsorbate may condense on the covered substrate
surface 12
 The data below relate to the adsortion of N2 on rutile
(TiO2) at 75 K and p* = 570 torr. Confirm that they fit a
BET isotherm in the range of pressure reported and
determine Vmon and c
p/Torr 1.20 14.0 45.8 87.5 127.7 164.4 204.7

V/mm-3 601 720 822 835 1046 1146 1254

Answer :

13
The Temkin Isotherm
Ө= c1ln(c2p)
where c1 and c2 are constants, corresponds to
supposing that the adsorption enthalpy changes
linearly with pressure Freundlich Isotherm

The Freundlich Isotherm

 = c1 p 1 / c
2

V Plot ln V against ln p and

if  = so
Vmon slope 1/c2
1 Intersep ln (c1Vm)
lnV = ln (c1 Vm ) + ln p
c2 14
• Decide whether the Freundlinch isotherm is a better representation
than the Langmuir isotherm for the data
p/Torr 100 200 300 400 500 600 700
V/cm-3 10.2 18.6 25.5 28.4 36.9 41.6 46.1
Answer : 1
lnV = ln (c1 Vm ) + ln p Plot ln V against ln p , slope 1/c2,
c2 Intersep ln (c1Vm)