Surface chemistry

¨ the study of physical and chemical

phenomena that occur at the interface
of two phases, including solid-liquid
interfaces, solid-gas interfaces, solid-
vacuum interfaces, and liquid-gas
interfaces
- Physical :
Surface area, SA , pore volume , Vm and
pore diameter.
- Chemical : monolayer or multilayer
adsorption
2

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 Example Physical Properties
3

Absorbent catalyst SABET Vp Dp

(m2g-1) (cm3g-1) (nm)
Al2O3 154 0.241 6.2
3 wt.%Ru/Al2O3 141 0.246 6.9

SiO2 130 0.607 18.6

3 wt.%Ru/SiO2 132 0.735 21.8

Bentonit 27 0.096 14.2

3 wt.%Ru/Bentonit 18 0.083 17.9

TiO2 8 0.020 9.5

3 wt.%Ru/TiO2 8 0.041 16.9
4 (d) Penjerapan
Penyahjerapan
Isipadu N2 terjerap (a.u.)

3 wt.% Ru/bentonit

bentonit

0.0 0.2 0.4 0.6 0.8 1.0

Tekanan Relatif (P/P0)

 Surface Chemistry in Important
Technologies
5

§ Surface chemistry in Catalyst

§ Surface Chemistry in Pharmacy
§ Surface Chemistry in Food and Feed
§ Surface Chemistry in Detergency
§ Surface Chemistry in Agriculture
§ Surface and Colloid Chemistry in Photographic Technology
§ Surface Chemistry in Paints
§ Surface Chemistry of Paper
§ Surface Chemistry in the Polymerization of Emulsion
§ Colloidal Processing of Ceramics
§ Surface Chemistry in Dispersion, Flocculation and Flotation
§ Surface Chemistry in the Petroleum Industry
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7
8

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9
Adsorption
Definitions
Adsorption ® Enrichment in an interfacial layer
Adsorbate ® Substance in the adsorbed state
Adsorptive ® Adsorbable substance in the
liquid phase
Adsorbent ® Solid material on which
adsorption occurs
Adsorption

Physical Adsorption
(Physisorption)
Adsorption without chemical
bonding

Chemical Adsorption
(Chemisorption)
Adsorption with chemical
bonding
Phenomena of Physisorption/Chemisorption

Lennard-Jones Diagram
 Adsorption
13

Ø Adsorption is a surface phenomenon.

Ø Process in which atoms or molecules move from a bulk phase onto a

solid or liquid surface

Ø At a molecular level, adsorption is due to attractive interactions

between a surface and the species being adsorbed

Ø The term adsorption à solid surfaces in contact with liquids and gases

Ø The substance, which accumulates on the surface is called

adsorbate

Ø the adsorbing phase is called adsorbent.

 Adsorption Process
Adsorptive - adsorbate before being adsorbed on the surface

Adsorbate - the gas adsorbed on the

surface of solids

Adsorbent - the solid where adsorption takes place

Adsorption is brought by the forces acting between the solid and the
molecules of the gas. These forces are of two kinds: physical
14 (physiosorption) and chemical (chemisorption) 06/06/2013
 Phenomenon of adsorption
15

v adsorption in solid adsorbents is enhanced

when finely divided solid particles are used.

v This is because the surface area increases

tremendously with the use of finely divided
particles.

v Very good adsorbents such as charcoal, silica

gel, alumina gel and clay have large surface
areas due to their porous structures.
 Adsorbent Materials
• Activated Carbon

• Activated Alumina Activated carbon

• Silica Gel

• Molecular Sieves (Zeolites)

• Polar and Non-polar adsorbents

Activated alumina
Silica gel
 Characteristic Good Adsorbent
17

v High surface area with proper structure and size

distribution.
v Good mechanical strenght.
v Posessess thermal stability.
 Surface area , m2/g
18

Charcoal – 500-3000 m2/g

¨ Alumina – 80- 250 m2/g

Zeolite – 50-60 m2/g

SiO2 – 100 m2/g
Effect of crushing a
solid.

When a single solid is

subdivided into much
smaller pieces, the total
surface area on all of the
pieces becomes very
large.
 Types of Adsorption
20

Adsorption

Physical Chemical
adsorption adsorption
 Types of Adsorption
21
 Adsorption
22

¨ Adsorption is generally accompanied by release of

energy, that is, most adsorption processes are
exothermic in nature.

¨ Adsorption is a spontaneous process; therefore its

free energy change is negative (DG<0).

¨ However, the entropy change associated with

adsorption is generally negative because the
adsorbate molecules lose their translation freedom
when they get attached to the surface of the
adsorbent.
PHYSISORPTION
Physisorption
Monolayer Adsorption
Molecules from the gas phase strike the surface.
At equilibrium the molecule adsorbs, lose the heat of
adsorption (q), and subsequently desorb from surface
At equilibrium,
the rate of condensation = the rate of desorption
Constant surface coverage at equilibrium
Physisorption
Multilayer Adsorption
As the system pressure is increased (gas concentration also
increases) multiple layers sorb to the surface
The monolayer coverage, a densely packed single adsorbed
layer is used for determining surface area
As pressure is further increased and adsorption proceeds
gas condenses in the pores and this volume of condensed
adsorptive is used for characterizing porosity.
 Characteristics of physisorption
27

(i) Lack of specificity:

A given surface of an adsorbent does not show any
preference for a particular gas as the van der Waals’
forces are universal.

(ii) Nature of adsorbate:

The amount of gas adsorbed by a solid depends on the
nature of gas. In general, easily liquefiable gases (i.e., with
higher critical temperatures) are readily adsorbed as van
der Waals’ forces are stronger near the critical
temperatures.
Thus, 1g of activated charcoal adsorbs more sulphur
dioxide (critical temperature 630K), than methane (critical
temperature 190K) which is still more than 4.5 mL of
dihydrogen (critical temperature 33K).
 ......characteristics of physisorption
28

(iii) Reversible nature:

Physical adsorption of a gas by a solid is generally

reversible. More of gas is adsorbed when pressure
is increased as the volume of the gas decreases
(Le–Chateliers’s principle) and the gas can be
removed by decreasing pressure.

Since the adsorption process is exothermic, the physical

adsorption occurs readily at low temperature and
decreases with increasing temperature
(Le-Chatelier’s principle).
 .....characteristics of physisorption
29

(iv) Surface area of adsorbent:

The extent of adsorption increases with the increase of
surface area of the adsorbent. Thus, finely divided
metals and porous substances having large surface
areas are good adsorbents.

(v) Enthalpy of adsorption:

physical adsorption is an exothermic process but its
enthalpy of adsorption is quite low (20–40 kJ mol-1).
This is because the attraction between gas molecules
and solid surface is only due to weak van der Waals’
forces.
CHEMISORPTION
 Characteristics of chemisorption
31

(i) High specificity:

Chemisorption is highly specific and it will only occur if there is some
possibility of chemical bonding between adsorbent and adsorbate.
For example, oxygen is adsorbed on metals by virtue of oxide formation
and hydrogen is adsorbed by transition metals due to hydride formation.

(ii) Irreversibility:
As chemisorption involves compound formation, it is usually irreversible in
nature. Chemisorption is also an exothermic process but the process is
very slow at low temperatures on account of high energy of activation.
Like most chemical changes, adsorption often increases with rise of
temperature. Physisorption of a gas adsorbed at low temperature may
change into chemisorption at a high temperature. Usually high pressure is
also favourable for chemisorption.
 ...characteristics of chemisorption
32

(iii) Surface area:

Like physical adsorption, chemisorption also
increases with increase of surface area of the
adsorbent.

(iv) Enthalpy of adsorption:

Enthalpy of chemisorption is high (80-240 kJ mol-1)
as it involves chemical bond formation.
 Adsorption isotherm of Chemisorption
33

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

Volume adsorbed/cm3(STP)g-1

Saturation of adsorbing surface

Strong tendency of surface to bind to

gas molecules

Pressure, bar
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 Adsorption isoterm of Physisorption
34

2. Physisorption eg. N2 on silica

Volume adsorbed/cm3(STP)g-1

Pressure=vapour pressure
Condensation occurs

Increase in gas pressure,

Large increase in amount of gas
adsorbed

0 Relative Pressure, P/Po 1

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 Physisorption vs Chemisorption
• General phenomenon with a
relatively low degree of specificity
• Molecular interaction forces
• Multilayers (used BET model)
• Retains identity; desorbs to fluid
phase in its original form Reversible
and fast
• Exothermic adsorption similar to the
energy of condensation DHads =
10-40kJ/mol
• Rapid equilibration; transport
limited Occur close to the boiling
point temperature
• Involved Van der waals
interaction
• Dependent on reactivity of
adsorbent and adsorptive
• Involves chemical bonds
• Only monolayer (used Langmuir
Model)
• Chemisorbed molecule may react or
dissociate May be nonreversible
and slow
• Energy is similar to energy change
for chemical reaction DHads
= 100-400kJ/mol
• Activated process at elevated
temperature Occurs at high
temperatures (>200oC)
• Involved Chemical bonding
 The differences between physical adsorption and
chemical adsorption
36

Chemisorption
Type of bonding/ Strong covalent bonds. Bonds
forces are broken and formed
Temperature range Virtually unlimited (but a
(over which given molecules may
adsorption occurs) effectively adsorbed only
over a small range)
Adsorption Wide range (related to the
enthalpy chemical bond strength) –
typically 40- 800 kJ mol-1
Nature of Often dissociative
adsorption May be irreversible
Saturation uptake Limited to one monolayer
Kinetic of Very variable – often an
adsorption activated process
Physisorption
Weak molecular forces – van der
waals forces. No bonds broken or
formed
Near or below condensation point
of the gas
(e.g. Xe < 100K, CO2 < 200K,
N2 < 77K.
Related to factors like molecular
mass and polarity but typically 5-
40 kJ mol-1.
Non-dissociative
Reversible
Multilayer uptake possible
Fast- since it is a non-activated
process
 Adsorption of Gases on Solids
37

¨ Adsorption of gases on solids depends

on the following factors:

i) Nature of the gas (adsorbate)

ii) Nature of the solid (adsorbent)
iii) Specific area of the solid
iv) Pressure of the gas
v) Temperature
 Adsorption Isotherms
38

The variation in the amount of gas adsorbed by the adsorbent with

pressure at constant temperature can be expressed by means of a curve
termed as adsorption isotherm.

1. The Freundlich adsorption isotherm

2. The Langmuir adsorption isotherm
3. The BET (Brunauer, Emmett and Teller)
isotherm
 Adsorption Isotherms

BET
(multilayer)

Langmuir Adsorption Isotherm Freundlich Adsorption Isotherm

(monolayer) (multilayer)

39
40
 1. Langmuir Adsorption Isotherm
41

b.P
q=
1916

1 + b.P

relates to the adsorption of molecules on a solid surface

to gas pressure or concentration of a medium above the
solid surface at a fixed temperature

θ = fractional coverage of the surface

P = gas pressure or concentration
b = constant
 Derivation of the Langmuir isotherm
42

The adsorption process between gas phase molecules, A, vacant surface

sites, S, and occupied surface sites, SA, can be represented by the
equation,

assuming that there are a fixed number of surface sites present on

the surface.
 Derivation of the Langmuir isotherm
43

An equilibrium constant, K, can be written:

Note that
[SA] is proportional to the surface coverage of adsorbed molecules, or
proportional to θ
[S] is proportional to the number of vacant sites, (1 - θ)
[A] is proportional to the pressure of gas, P

θ = Fraction of surface sites occupied (0 <θ< 1)

 Derivation of the Langmuir isotherm
44

Thus it is possible to define the equilibrium constant, b:

Rearranging gives the expression for surface coverage:

= Langmuir isoterm plot
45

with θ = V/Vm

Vm = is the volume corresponding to complete coverage

By dividing above equation with bV; this expression can be rearranged into

Y = mx + C
 Langmuir isoterm plot
46

A plot of P/V against P should give a straight line of slope 1/Vm and
intercept 1/KVm

P/V

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 Example of Langmuirian adsorption
47

Ammonia on activated charcoal (O°C) 0.45

0.4
s s
P (kPa) V (STPcc/g) P/V 0.35
0.3
6.8 74 0.092 0.25

P/V
13.5 111 0.122 0.2
0.15
26.7 147 0.182 0.1
P/V = 0.00452 P + 0.0608
53.1 177 0.300 0.05
0
79.4 189 0.420 0 20 40 60 80 100
Shaw (1992)
P

Slope = 1/Vml Intercept = 1/bVml

= 0.00452 = 0.0608
Þ Vml = 221 STPcc/g Þ b = 0.0744 kPa–1
 ASSIGMENT 1
48

The data given below are for the adsorption of CO on charcoal at 273 K.
Confirm that they fit the Langmuir isoterm, and find the constant K and the volume
coressponding to complete coverage. In each case V has been corrected to 1.00
atm

P/Torr 100 200 300 400 500 600 700

V/cm3 10.2 18.6 25.5 31.5 36.9 41.6 46.1

Answer : Vm = 111 cm3 ; K = 1.00 x 10-3 Torr-1

 Langmuir Isotherm Assumption
49

i) Adsorption does not proceed beyond monolayer coverage.

ii) All the sites available on the adsorbent surface are equivalent
and the surface is perfectly uniform, that is flat.

iii) The ability of a gas molecule to get adsorbed at a particular

site is independent of the occupation of neighboring sites. This
implies that there is no interaction between adjacent adsorbed
molecules.

iv) A dynamic equilibrium exists between the adsorbed molecules

and the free gas molecules.
 Langmuir Model of Adsorption
50

Elastic
collision
Adsorption
Desorption

Assumptions:
1. Homogeneous surface – every site has same energy.
2. Only adsorbate–adsorbent interactions considered.
3. Adsorption limited to a single monolayer.
 2. Brunauer, Emmett, Teller (BET)

ØNamed after Stephen Brunauer, P.H. Emmet

and Edward Teller

ØModification of Langmuir isotherm

ØBoth monolayer and multilayer adsorption

51
 BET MODELS

Ø θ 0, θ1, ..., θ n = Surface area (cm-2) covered by 0, 1, ...,

n layers of adsorbed molecules

52
 BET Isoterm Assumptions
53

Assumptions:
(1) multilayer adsorption (on non porous
surfaces)
(2) adsorption of first layer has a heat of adsorption,
ΔHa;
(3) the subsequent layers are controlled by heat of
condensation, ΔHc.
 BET Isoterm : Adsorption process
54

¨ Firstly, the process involves the attachment of

molecules to the sites on the solid surface. The
strength of binding to the solid surface is much
higher than that of physisorption.

¨ Then the attachment of molecules to the sites

already accupied by adsorbed molecules is takes
place. This mainly done by physisorption.
 BET equation
55

V : volume of adsorbed vapor at STP

Vm: monolayer capacity at STP
P : partial pressure of the adsorbate
Po : saturation vapor pressure of the adsorbate
C≈exp[(ΔHA -ΔHL)/RT]
 BET graph
56

BET graph
üDividing equation with 1/P0 ; the equation became

Z 1 C -1
= + ×Z
(1 - z )V VmC VmC
Where z = P/P0 and (BET equation valid for 0.05<P/P0 < 0.3)

üBy plotting z/(1-z)V against z give staright line with c-1/cVm is the intercept and
slope 1/cVm .

üValue Vm and C can be calculated using this graph

 B.E.T equation

Z 1 æ C -1 ö
= + çç ÷÷ Z
V(1 - z) Vm C è Vm C ø
where
Z = P/Po
V = volume of the gas adsorbed at pressure P and temperature, T
P ! = the saturated vapour pressure of the adsorbate at a given temperature
V0 = volume of gas adsorbed in making a unimolecular layer
C = constant

57
z/ V(1-z)

z 1 æ C -1 ö
Slope= C-1/VmC = +ç ÷Z
Intercept=1/VmC
V(1 - z) Vm C è VmC ø

y c x
m
Z

¨ A plot of z/ V(1 -z) against Z will give a straight line with slope equals to
C-1/ VmC and the intercept equals to 1/VmC from which the values of Vm
and C can be calculated
¨ The Vm can be used for determining the surface area of the adsorbent

58
 To determine surface area, Sm
From graph Langmuir and BET ;
get Vm = volume to form monolayer
From equation PV = nRT ;
calculate nm = mole to form monolayer
Sm = nm x NA x δ ; NA = 6.023 X 1023 molecule
per moles
δ = cross section of molecule
Sm = surface area to form monolayer

59
To calculate area occupied by one
molecule
Charcoal – 500-3000 m2/g

Let say for 1 gram charcoal = area occupied = 500 m2

Molar mass of gas at STP = 22.4 dm3/mol

\1 mol = 22.4 dm3

1 dm3 = 1000 cm3 ; Vm = 814 cm3 ; = 814 cm3 / 1000 cm3 = 0.814 dm3

no of mole = 0.814 dm3 / 22.4 dm3 = 0.0363 mole

No of molecule for complete coverage = mole x NA

= 0.0363 x 6.023 x 1023 = 2.19 x 10 22 molecules

Area occupied by one molecule = 500 m2 / 2.19 x 1022

= 2.28 x 10-20 m2 per molecule

60
 SUMMARY ON BET
• The BET method is based on adsorption of gas on a
surface
• The amount of gas adsorbed at a given pressure allows to
determine the surface area
• It is a cheap, fast and reliable method
• It is very well understood and applicable in many fields
• Not applicable to all types of isotherms
 3. Freundlich Adsorption Isotherm
62

¨ A relationship between x/m and the equilibrium concentration, C (of

solution) or pressure, P (of gas) of the adsorbate at fixed
temperature is called ‘adsorption isotherm’

¨ This may be obtained experimentally by determining x/m as a

function of C (or P)
let x = mass of adsorbate
m = mass of adsorbent
x
= mass of adsorbate per gram adsorbent
m
 Freundlich Adsorption Isotherm

1909

x 1 x 1
= Kc n or = Kp n
m m

x = mass of adsorbate
m = mass of adsorbent
p = equilibrium pressure of adsorbate
c = equilibrium concentration of adsorbate in solution
K & 1/n = constants for a given adsorbate and adsorbent at a
particular temperature
….Freundlich Adsorption Isotherm

¨ The Freundlich adsorption isotherm is represented by the equation;

x
= kC n ( for solutions )
m
x
= kP n ( for gases)
m

¨ The parameters k and n depend upon the nature of the adsorbent

and the adsorbate and can be determined by plotting log (x/m)
against log C (or log p).
¨ The straight line graph gives a slope which is equal to n
and the intercept equal to log k.
64
 x x
= kC n ( for solutions ) = kP n ( for gases)
m m

log x = n log C + log k log x = n log P + log k

m m
m m
x
c x c
y
y

n usually less than 1

let x = mass of adsorbate

m = mass of adsorbent
x
= mass of adsorbate per gram adsorbent
m 65
Log x/m Log x/m

Slope= n
Slope= n

Intercept=log k Intercept=log k

Log C Log p

66
Eg:
The amount of oxalic acid, in moles, adsorbed by 5 g of activated charcoal
varies with equilibrium concentration of acid according to the following
figures:

Acid adsorbed (mol) 0.29 0.60 0.75 0.90 1.05

Equil. conc. of acid (mol dm-3) 0.03 0.08 0.115 0.175 0.260

Use these figures to show the validity of the Freundlich isotherm, and
to find the values of the constant n.

67
- Adsorbent – activated carbon (substance on whose
surface adsorption takes place)
- Adsorbate – oxalic acid, H2C2O4 (substance get
adsorbed)

x – mass adsorbate (oxalic acid)????

m – mass adsorbent (activated carbon) 5 g

x = kCn
m
log x/m = log k + n log C
Find the value x by using mol acid given:
Eg : 0.29 mol
mol = mass/RMM
\ mass = mol X RMM
= 0.29 x RMM H2C2O4
= 0.29 x 90
= 26.1 g
 Mass adsorbent, m = 5 g
Acid (mol) 0.29 0.60 0.75 0.90 1.05
Acid (mass), x 26.1 54 67.5 81 94.5
(g)
x/m 5.22 10.8 13.5 16.2 18.9
Log x/m 0.72 1.03 1.13 1.21 1.28
C acid 0.03 0.08 0.115 0.175 0.260
Log C -1.52 -1.10 -0.94 -0.76 -0.59

Plot graph log (x/m) against log C

 log x/m

log k
n = 1.28 – 0.72
1.52 – 0.59

= 0.56
0.93
n
= 0.602

log C
n usually less than 1
 Pass year exam – Jun 2012
72

The data below relate to the adsorption of N2 on rutile

(Ti02) at 75 K. Confirm that they fit a BET isotherm in the
range of pressures reported, and determine Vmax and C.

p/Torr 1.2 14.0 45.8 87.5 127.7 164.4 204.7

V/cm3 601 720 822 935 1046 1146 1254

Given at 75 K, p* = 570 Torr. The volumes have been

corrected to 1.00 atm and 273 K and refer to 1.00 g of
substrate.
(answer : V max = 814 mm3 ; C =303)
 Answer Pass year exam – Jun 2012
73

p/Torr 1.2 14.0 45.8 87.8 127.7 164.4 204.7

V/mm3 601 720 822 935 1046 1146 1254
Z, 10 -3 2.11 24.6 80.4 154 224 288 359
(1-Z)V 599.73 702.29 755.91 791.01 811.69 815.95 803.81
z/(1-z)V, 0.035 0.350 1.06 1.95 2.76 3.53 4.47
10 -4

Intercept = 1/cVm = 4.06 x 10-6 so; cVm = 246 x 103

Slope = c-1/cVm = 1.23 x 10-3 ; c-1 = 302.58 ; c = 303

Vm = 303 x 4.06 x 10-6 = 814 mm3 06/06/2013