Physical Chemistry

1.Physisorption
Adsorption Absorption
Passes through
2.Chemisorption The concentration of a the surfaces
substances on the
surfaces
Desorption

Adsorbate Adsorbent
The substance on whose The substance adsorbed
surface adsorption occurs from the bulk phase

Example : water vapours are adsorbed by silica gel while water

vapours are absorbed by anhydrous CaCl2

2
3
The extent of surface coverage is normally expressed as
the fractional coverage
number of adsorption site occupied

number of adsorption site available

The rate adsorption, d/dt is the rate of change of surface

coverage and can be determined by observing the change
of fractional coverage with time
The principal techniques for measuring d/dt
a. Flows Methods
b. Flash desorption
c. Gravimetry 4
Molecules and atoms can attach to surfaces in
two ways :
a. Physisorption (physical adsorption)
There is a van der Waals interaction between
the adsorbate and the substrate
a. Chemisorption (chemical adsorption)
The particles stick to the surface by forming a
chemical bond (bond covalent) and tend to
find sites that maximize their coordination
number with the substrate
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characteristics Physisorption Chemisorption

1. Nature of It involves weak physical It involves very strong

forces. It is an exothermic chemical forces. It is also
forces process exothermic process
2. Heat of low and generally less than Very high and is of the
adsorption 20kJ/mole order of 20 200kJ/mole
It takes place at ordinary It takes place at high
3. Occurances
temperature temperature
4. Activation Need is insignificant Need is significant
energy
The rate of increase in Rate of increase
5. Effect of adsorption with pressure is adsorption with pressure
pressure much higher at higher progressively decreases,
pressure as pressure increases 6
 characteristics Physisorption Chemisorption

6. Structure of Multilayers (many molecule Monolayers (one

adsorbed layer thick) molecule thick)
7. The desorption
by heating is x/m x/m

graphically Temp
Temp
repersentated as
8. Effect of It is appreciable at low It occurs usually at high
temperature temperatures temperatures, even above
boiling temperatures
8. Types of In physical adsorption In chemical adsorption
adsorption
isotherm 7
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

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

The simplest isotherm is based on three assumptions :

1. Adsorption cannot proceed beyond 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.9
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

k a pN(1 ) p = the partial pressure

1-= the fraction of surface uncovered

The rate of change of surface coverage due to desorption

is
k d N
10
At equilibrium the net rate of adsorption is zero and solving for
gives the Langmuir Isotherm :

k x For adsorption without dissociation !!!

K a AM
kd xM Kp
Kp or
1 1 Kp
bila x AM
xM 1 For adsorption with dissociation
Kp
and K p K p
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 and Kp
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~ 11
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 pN 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 adsorptio to be zero leads to the isotherm

K
1
2

p

1 K
1
2
p
12
 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

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 P(atm)
4 6 8 10 0 2P(atm)4 6 8 10

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
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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 adH, the
standart enthalphy of adsorption at a fixed
surface coverage.

d ln K H
ad 2
dT RT

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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

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 p p 1
20

15
V V kV
p/torr/V/cm-3

10 Y = p/V
5
X=p
0
0 200 400 600 800 Y = 9 + 0.009x
p/torr

Y = A + Bx

The slope is 0.009, so V~= 110cm-3. the intercept at p= 0 is 9.0, so

1 1
K -3

110cm 3 x 9.0 Torr cm 3
1.0 x 10
Torr
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 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

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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
V 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 1z (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
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 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 19
 The data below relate to the adsortion of N2 on rutile
(TiO2) at 75 K. 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-3 601 720 822 935 1046 1146 1254

Answer :

p/Torr 1.20 14.0 45.8 87.5 127.7 164.4 204.7

10-3z 2.11 24.6 80.4 154 224 288 359

104z/(1-Z)(V/mm-3 0.035 0.35 1.06 1.95 2.76 3.53 4.47

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 4.5
z

1

C 1z
1 z V cVmon cVmon
3

3.5
10 z/(1-z)V/mm

2.5

1.5
4

0.5 Y = 0.034 10-4 + 1.23 10-3X

-0.5 0 100 200
1000z
300 400
The least-squared best line has an
intercept at 0.034, so
1
0.034 x 10 4 mm 3 3.4 x 10 6 mm 3
cVmon
the slope of the line is 1.23 x 10 2 , so
c 1
cVmon

1.23 x 10 2 x 10 -3 x 10 -4 mm 3 1.23 x 10 3 mm 3

solving these equation gives c 1 362 or c 363 and Vmon 810 mm -3

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

The Freundlich Isotherm

c1 p1 / c
2

V Plot ln V against ln p and

if so
Vmon slope 1/c2
Intersep ln (c1Vm)
lnV ln c1 Vm ln p
1
c2 22
 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 :
lnV ln c1 Vm
1 Plot ln V against ln p , slope 1/c2,
ln p
c2 Intersep ln (c1Vm)

p/Torr 100 200 300 400 500 600 700

Ln(p/Torr) 4.61 5.30 5.70 5.99 6.21 6.40 6.55
Ln(V/cm-3) 2.32 2.92 3.24 3.45 3.61 3.73 3.83

Y = A + Bx
Y = -1.22 + 0.770 x intersep = -1.22 Slope = 0.770
If B = 1/c2 so. c2 = 1/B = 1/ 0.770 = 1.298
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 non activated activated
Potential energy

Potential energy
D(A-A) D(A-A)

Ea

p Distance p Distance
from from
c Precursor state surface c Precursor state surface

The potential energy profile for the dissociative chemisorption of an A-A

molecule. In each case P is the enthalphy of (nondissociative) physosrption and
C that for chemisorption (at T=0). The raltive locations of the curves determines
whether the chemisorption is non activated or activated
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