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
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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

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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)

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 Surface Chemistry in Important
5
Technologies
 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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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

 Adsorption is a surface phenomenon.

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

solid or liquid surface

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

between a surface and the species being adsorbed

 The term adsorption  solid surfaces in contact with liquids and gases

 The substance, which accumulates on the surface is called

adsorbate

 the adsorbing phase is called adsorbent. 06/06/2013

 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

 adsorption in solid adsorbents is enhanced

when finely divided solid particles are used.

 This is because the surface area increases

tremendously with the use of finely divided
particles.

 Very good adsorbents such as charcoal, silica

gel, alumina gel and clay have large surface
areas due to their porous structures.
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 Characteristic Good Adsorbent
16

 High surface area with proper sturcture and size

distribution.
 Good mechanical strenght.
 Posessess thermal stability.

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 Surface area , m2/g
17

Charcoal – 500-3000 m2/g

 Alumina – 80- 250 m2/g

Zeolite – 50-60 m2/g

SiO2 – 100 m2/g
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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
19

Adsorption

Physical Chemical
adsorption adsorption
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 Types of Adsorption
20

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 Adsorption
21

 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 (G<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. 06/06/2013
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
26

(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).

(iii) Reversible nature:

Physical adsorption of a gas by a solid is generally reversible. Thus,

Solid + Gas l Gas/Solid + Heat

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). 06/06/2013
 Characteristics of physisorption
27

(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.
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 Adsorption isoterm of Physisorption
28

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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CHEMISORPTION
 Characteristics of chemisorption
30

(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.

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 Characteristics of chemisorption
31

(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.

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 Adsorption isotherm of chemisorption
32

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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 Physisorption vs Chemisorption

• General phenomenon with a • Dependent on reactivity of

relatively low degree of specificity adsorbent and adsorptive
• Molecular interaction forces • Involves chemical bonds
• Multilayers (used BET model) • Only monolayer (used Langmuir
• Retains identity; desorbs to fluid Model)
phase in its original form Reversible • Chemisorbed molecule may react or
and fast dissociate May be nonreversible
• Exothermic adsorption similar to the and slow
energy of condensation Hads = • Energy is similar to energy change
10-40kJ/mol for chemical reaction Hads
• Rapid equilibration; transport = 100-400kJ/mol
limited Occur close to the boiling • Activated process at elevated
point temperature temperature Occurs at high
• Involved Van der waals temperatures (>200oC)
interaction • Involved Chemical bonding
 Adsorption of Gases on Solids
34

 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

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 Adsorption Isotherms

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.

BET
(multilayer)

Langmuir Adsorption Isotherm Freundlich Adsorption Isotherm

(monolayer) (multilayer)

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 Langmuir Adsorption Isotherm
37

b.P

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
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 Derivation of the Langmuir isotherm
38

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.

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 Derivation of the Langmuir isotherm
39

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) 06/06/2013

 Derivation of the Langmuir isotherm
40

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

Rearranging gives the expression for surface coverage:

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= Langmuir isoterm plot
41

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
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 Langmuir isoterm plot
42

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
43

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
 Vml = 221 STPcc/g  b = 0.0744 kPa–1
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 ASSIGMENT 1
44

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

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 Langmuir Isotherm Assumption
45

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.
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 Langmuir Model of Adsorption
46

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.
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 Brunauer, Emmett, Teller (BET)

Named after Stephen Brunauer, P.H. Emmet

and Edward Teller

Modification of Langmuir isotherm

Both monolayer and multilayer adsorption

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 BET MODELS

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

n layers of adsorbed molecules

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 BET Isoterm Assumptions
49

Assumptions:
(1) multilayer adsorption;
(2) adsorption of first layer has a heat of adsorption,
ΔHa;
(3) the subsequent layers are controlled by heat of
condensation, ΔHc.

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 BET equation
50

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]
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 BET graph
51

BET graph
Dividing 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)

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

Value Vm and C can be calculated using this graph

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 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

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 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 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

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 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
 Pass year exam – Jun 2012
55

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 Kand refer to 1.00 g of
substrate.
(answer : V max = 814 mm3 ; C =303)
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 Answer Pass year exam – Jun 2012
56

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

 Exercise
57

Repeat the calculation for the following data:

P/Torr 1.20 14.0 45.8 87.5 127.7 164.4 204.7

V/cm3 235 559 649 719 790 860 950

Answer : 370, 615 cm3

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 MICROMERITICS ASAP 2020
58

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 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