CHAPTER 8

SURFACE CHEMISTRY

What is a surface?
Definition: A surface is the interface between
two phases of matter
Sometimes the word interphase is used.
Generally, the word surface is used to refer to an
interface of which one phase is gaseous and
the other is condensed .. i.e, solid/gas and
liquid/gas interfaces
The physicochemical nature of a surface is
different from that either of the two
associated bulk phases.

Surface Chemistry
Is a study of physical and chemical phenomena
that occur at the interface of two phase:
i) gas/solid
ii) liquid/solid
The boundary that separate the two phases is
called surface or interface.
The adhesion of gas or liquid molecules to
surface is known as adsorption.

Common Features of Adsorption

1. Highly selective (amount depends):
i) nature of adsorbent surface
ii) previous treatment of adsorbent surface
iii) nature of adsorbed substance (adsorbate)
2. A rapid process
rate increases with increase in temperature
rate decreases with increase in amount
adsorbed
3. A spontaneous process
It is a exothermic reaction.

Adsorbent
Adsorbents are used usually in the form of spherical
pellets, rods, moldings, or monoliths
Hydrodynamic radius between 0.25 and 5 mm.
Have high abrasion resistance, high thermal
stability and small pore diameters
- higher exposed surface area and hence high
capacity for adsorption.
The adsorbents must also have a distinct pore
structure that enables fast transport of the gaseous
vapors.

Adsorbent
Characteristics of good absorbent:
High surface area with proper pore structure
and size distribution
Good mechanical strength
Possess thermal stability

Adsorbent
Most industrial adsorbents fall into one of 3 classes:
Oxygen-containing compounds
Hydrophilic and polar, including materials such
as silica gel and zeolites.
Carbon-based compounds
Hydrophobic and non-polar, including materials such
as activated carbon and graphite.
Polymer-based compounds
Polar or non-polar functional groups in a porous
polymer matrix.
http://en.wikipedia.org/wiki/Adsorption

Adsorption of Gas and Vapours on

Solids
When gas/vapour (adsorbate) is in contact with
clean solid surface (adsorbent) it get
attached to the surface.
Gas (adsorbate)
Adsorbed layer

Surface (adsorbent)

Types of Adsorption
1.

Physical adsorption (Physisorption)

- adsorbate and surface of adsorbent interact
by van der Waals forces
- adsorbed molecules weakly bound to the
surface
- heat of adsorption are low.

Types of Adsorption
2. Chemical adsorption (Chemisorption)
- adsorbate react chemically with surface
(adsorbent)
- bonds are broken and formed usually
covalent or dative bonds
- heat of adsorption has same range of values
as chemical reaction.

Characteristics of physisorption
and chemisorption
Physisorption

Chemisorption

The adsorbed layer vary in

thickness from monolayer to
multilayer. Van der waal forces
can extend from one layer of
molecules to another
Amount of adsorption on
surface is a function more of
adsorbate that adsorbent
The attainment of equilibrium
is rapid. There is no activation
involved
Occur more readily at lower
temperatures

The surface become saturated

after is been covered with a
single layer of adsorbed
molecules. Only a monolayer
can be formed
Amoung of adsorption
characteristic of both
adsorbate and adsorbent
Very slow. It is a specific
process which requires
activation energy
Occurs at high temperatures

Characteristics of physisorption
and chemisorption (cont)
Physisorption

Chemisorption

Van der Waals interactions are weak.

Hp is the same magnitude as
enthalpy of
condensation/vaporisation. (~ 40kJmol-1 )
The amount adsorbed increases with
increase in pressure of adsorbate.
The process can be reversed

Hc > Hp (~ -200kJmol-1)

More common

Found only when the adsorbent and

adsorbate tend to form a compound

Amount adsorbed decreases with

increase in pressure of adsorbate.
Not readily reversible

Potential Energy Diagram

1. As adsorbate approaches adsorbent,
physisorption takes place.

Dispersion
forces
Surface

Held loosely
Physisorption

When temperature high enough and Ea is

overcome, adsorbate approaches closely,
stronger bond formed, chemisorption takes
place.

Chemisorption

2.

Chemisorption Curve
- characterize by deep minimum
Hc > Hp
- chemisorption is not easily reversed due to
stronger bonding near surface.

3.

Physisorption Curve
- first physically adsorbed
- involves approaching solid surface along a
low energy path.
- shallow Hp - weak bond (dispersion forces)
- transition from physisorption takes place at
point where curve for C and P intersect.

POTENTIAL ENERGY DIAGRAM:

Potential Energy

PHYSISORPTION AND CHEMISORPTION CURVE

Enthalpy of
physisorption
Activation
energy
Enthalpy of
chemisorption
Distance between adsorbate and adsorbent

Enthalpy of Adsorption
G = H - TS
G = Gibbs free energy
H= enthalpy of adsorption
S = entropy

For adsorption to occur at an appreciable extent,

G = - x
At adsorption, molecules moving from chaotic to
orderly state, S = -y
For G = - x, H has to be negative
(exothermic reaction)
Heat is released when adsorption takes place.

Adsorption Isotherms
Graphical presentations of relationship
between the amount of gas adsorped on
surface or the fractional coverage of surface
() and the pressure of gas at constant T.

Types of Isotherms
Volume adsorbed/cm3(STP)g-1

1. Chemisorption eg. H2 on Cu powder at 25oC.

Saturation of adsorbing surface

Strong tendency of surface to bind to

gas molecules

Pressure, bar

Types of Isotherms
Volume adsorbed/cm3(STP)g-1

2. Physisorption eg. N2 on silica

Pressure=vapour pressure
Condensation occurs

Increase in gas pressure,

Large increase in amount of gas
adsorbed
0

Relative Pressure, P/Po

Fractional coverage ()
Is the extent of adsorption or extent of surface
coverage

= number of adsorption sites occupied

number of adsorption sites available

Rate of adsorption
Rate of change of surface coverage is
determined by change of fractional coverage
with time.
Extent of adsorption depends:
1.Temperature
2.Pressure of adsorbate
3.Effective surface area of adsorbent

Before a reaction can take place on the

surface of adsorbent in a heterogenous
system (g/s, l/s)
1. Adsorbate molecules must be adsorbed
2. Dynamic equilibrium exists
Molecules in
molecules
bulk medium
adsorbed on surface of
adsorbent

Examples of Well Established

Isotherms
1. Langmuir Isotherm
2. Freundlich Isotherm
3. BET Isotherm

Langmuir Model of Adsorption

Assumptions:
1. Homogeneous surface every site has same
energy
2. Only adsorbate-adsorbent interactions
considered
3. Adsorption limited to a single monolayer.

Langmuir Model of Adsorption

Elastic collision

Desorption
Adsorption

Langmuir Isotherm
Kinetic Derivation of Langmuir Adsorption Eq.
Derivation 1:
= fraction of surface covered with molecules
(1- ) = remaining fraction still available for further
adsorption
= given pressure of gas

Rate of molecules adsorbed on surface= kads (1- )

kads = proportionality constant

Derivation 2:
Rate molecule leaving the surface increase the
larger the no. of molecules on the surface
proportional to (proportion of surface
covered with molecules)
Rate of desorption= kdes
kdesis a second proportionality constant

Derivation 3:
At dynamic equilibrium:
Rate of adsorption = Rate of desorption
kads (1- ) = kdes
Divide above by kdes and let kads/kdes = K
K(1- ) =
Rearrange:
K - K =
K = +K
= (1 + K )
= K
1 + K

Derivation 4:
i) Low pressure, k is very small
(1 + K) ~ 1
= K ( , corresponds initial steep
rise of the isotherm curve)
i) High pressure, K >> 1
(1 + K) = K
= K = 1 ( is independent of change in
K
pressure, and approaching unity)
Chemisorption type surface becomes saturated
with molecules at high pressure.

At adsorption equilibrium
Where = V/Vm is the coverage ( 1)
Rate ads = Rate des
Note limits:
High = 1
Low
=k

1.0

Pressure

Langmuir Isotherm without

dissociation
1. As increases with increasing , approaches =1 at
very high pressure, gas molecules squashed to all
available site of surface.
2. Different curves with different k values at different
temperature (k is temp dependent)
Fractional
Coverage

k = 10 atm-1
k = 1 atm-1
k = 0.1 atm-1

Pressure

Practice Exercise
The adsorption of nitrogen on Alumina is
described by the Langmuir Isotherm at 25oC
with a constant k = 0.68 kPa-1. Calculate the
pressure at which the fractional surface
coverage is 0.17.

Solution
= k
1 + k
0.17 = 0.68
1 + 0.68
0.17(1 + 0.68) = 0.68
0.17 + 0.12 = 0.68
= 0.17/0.56 = 0.30 kPa

Derivation 5:
Experimental Isotherm data.(Just for Monolayer adsorption)
= V
V=amount of gas adsorbed at pressure
Vm

Vm = amount of gas to form monolayer

(complete coverage)

V = 1 + k

V = Vm (1 + k)

Vm
Rearrange: (linearised Langmuir Equation)
= 1 +
1
since y = mx + c
V
Vm
kVm
plot graph, y = /V, x =
m = 1/Vm intercept = 1/kVm
y
m x
c

Plot of /V Vs
If data fit Langmuir theory, a straight line is obtained.

/V

x
1
kVm

y =

Vm

Deviation of Langmuir Plots

Plots may deviate from linearity at high
concentration or high pressure due to:
1. Isotherm derived for adsorption of only
monolayer coverage of adsorbate by
chemisorption
2. High conc. or high pressure implies that
layers of physisorbed adsorbates have
formed on top of chemisorbed monolayer,
forming multilayer adsorption pattern.

Practice Exercise
Refer to Pg 10, example 7.1
1. To confirm the data fit Langmuir isotherm
2. To determine the constants k, Vm
3. To determine the number of molecules
involved for complete coverage

Solution
Since x = , y = /V
Treat the data first.

100

200

300

400

500

600

700

10.2

18.6

25.5

31.5

36.9

41.6

46.1

/V
yaxis

9.8

10.8

11.8

12.7

13.6

14.4

15.2

(xaxis)

A straigth line confirms data fits

Langmuir Isotherm
m (slope)= 0.009
1/Vm = 0.009
Vm = 111cm3

p/V

Langmuir Isotherm
16
14
12
10
8
6
4
2
0

p/V

100 200 300 400 500 600 700

p

c(y-intercept) = 7.8
c = 1/kVm
k= 1/cVm
k = 1/7.8 x 111
= 1.16 x 10-3 Torr-1

To determine number of molecules

for complete coverage
Molar Volume (at 273K) = 22.4 dm3/mol
= 22.4 x 103 cm3/mol
Since Vm = 111 cm3
111 cm3 gas required for complete coverage
nCO = 111 cm3 /22.4 x 103 cm3/mol
= 4.96 x 103 mol
No of CO molecule = nCO x NA
= 4.96 x 103 mol x 6.02 x 1023 molecules/mol

= 2.98 x 1021 molecules

Freundlich model of Adsorption

- Is a non ideal adsorption and deviate from Langmuir
Isotherm:
1. Surface is not uniform
2. Interaction between adsorbed molecules
3. When a molecule is attached to a surface it is
difficult for another molecules to be attached to
neighboring site
4. Energetically most favorable sites occupied first
5. Isotherm fails if concentration or pressure of
adsorbate is too high.

Freundlich Equation
X=
m

=kp1/n

X = mass of gas adsorbed by solid

m = mass of adsorbent
k,n = constant for given gas & solid
1/n unity

Since = V/Vm
V = kp1/n
Rearrange equation: V
m
Log the equation
ln V = lnk + 1 lnp
lnV = lnVmk + 1 lnp
Vm
n
n
y
c
m x

X =kp1/n
m

ln V

Graph for Freundlich Isotherm

Slope = 1/n

lnVmK

ln p

BET Model of Adsorption

Assumptions:
1. Homogeneous surface every site has same
energy
2. Only adsorbate-adsorbent interactions
considered
3. Multilayers are possible
4. Adsorbates adsorb/desorb one at a time
5. First layer different from the (liquid-like)
others.

BET Model of Adsorption

Elastic collision

Desorption
Adsorption

BET Isotherm
Deals with multilayer adsorption on non-porous
solid surfaces. The entire adsorption process
include:
1. Attachment of molecules to sites on the solid
surfaces mostly by chemisorption
2. Attachment of molecules to site already
occupied by adsorbed molecules by
physisorption

BET Isotherm

V ads

At high presures the isotherm rise indefinitely:

Vm

BET equation
P Po
=
V(Po- P)

1
+ P
VmK
Vm

V = vol. of gas adsorped at pressure P

Vm = monolayer capacity
(vol. of gas required to cover unit mass of
adsorbent with a complete monolayer)
Po = saturation vapour pressure of adsorbate
K = equilibrium constant of adsorption
P = pressure of adsorbate

Application of BET equation

Rearrange BET equation:
P
=
1
+ 1 P
V(Po- P)
VmKPo
Vm Po

P
V(Po- P)

y
b
m x
A linear graph is obtain.
P/Po
Vm calculate from the slope, and enable specific area
for solid to be calculate.
K calculated from the intercept.

Exercise
1. The following data were obtained for the adsorption of N2 on
1 g of TiO2 at 75 K.
P/kPa

0.160

1.87 6.11

11.67

17.02

21.92

27.29

V/mm3

601

720

935

1046

1146

1254

822

At 75K, Po= 76 kPa and the volume V, in the table has been corrected
to 1 atm and 273 K (at STP). Confirm that the data given in the table fit
a BET isotherm in the range of pressures reported and evaluate Vm
which is the volume of gas required to cover unit mass of the adsorbent
with a complete monolayer.

Solution
Using the BET isotherm equation:
P
=
V(Po- P)

1
+ 1 P
VmKPo
Vm Po

P/kPa

0.160

1.87

6.11

11.67

17.02

21.92

27.29

V/mm3

601

720

822

935

1046

1146

1254

P/V(Po-P)
x 10-5
(y-axis)
P/Po x 10-3
(x-axis)

0.35

3.50

10.6

19.4

27.6

35.4

44.7

2,10

24.6

80.4

153.6

223.9

288.4

359

Graph: plot {P/V(Po-P)} vs (P/Po) and obtain a straight line, confirm the data fit BET
isotherm.
Slope = 1/Vm = 1.23 x 10-3 mm-3
Vm = 1/1.23 x 10-3 = 813 mm3

2. The data obtained for the adsorption of nitrogen, N2 on 1 g

sample of silica gel at 77 K are found to fit a BET isotherm in
the range of pressures reported. At this temperature, the
saturation vapour pressure, Po of Nitrogen is 0.99 atm. The
slope and the Y-intercept of the linear plot of P/V(Po-P)
versus P/Po are recorded as:
slope = 1.25 x 10-3 cm-3
y-intercept = 3.3 x 10-6 cm-3

a) Determine the value of the constants, K and Vm

(volume of Nitrogen to form monomolecular layer)
b) Estimate the surface area of 1 g of silica gel if 1 molecule
occupies an area of 1.62 x 10-19 m2. (Given the molar
volume at 25 oC and 1 atm = 24.0 dm3mol-1, Avogadros No
= 6.02 x 1023 mol-1)

a) The equation for BET isotherm:

P
=
V(Po- P)

1
VmKPo

+ 1
Vm

P
Po

Slope = 1/Vm
Vm = 1/slope
= 1/1.25 x 10-3 cm-3
= 800 cm3
Intercept = 1/ VmKPO
K = 1/800cm3 x 0.99atm x 3.3 x 10-6 cm-3
= 382.6 atm-1

b) Estimate the surface area of 1 g of silica gel if 1

molecule occupies an area of 1.62 x 10-19 m2. (Given the
molar volume at 25 oC and 1 atm = 24.0 dm3mol-1,
Avogadros No = 6.02 x 1023 mol-1)
At 25 oC, molar volume = 24 dm3mol-1 = 24 x 103 cm3
no of mole of N2 = Vm/molar volume
= 800/24 x 103
= 0.033 mol
No of molecules on surface = 0.033 mol x 6.02 x 1023
molecules mol-1
= 1.987 x 1022 molecules
Surface area of 1 molecule = 1.62 x 10-19 m2
Surface area of adsorbent = 1.987 x 1022 molecules x
1.62 x 10-19 m2 molecule-1
= 3.22 x 103 m2

Figure 16.24

The metal-catalyzed hydrogenation of ethylene

H2C CH2 (g) + H2 (g)

H3C CH3 (g)

Figure 16.24