SURFACE CHEMISTRY

Chapter 5 (Part B)
1
 SUBTOPIC

1. Adsorption Isotherm
a) Freundlich Adsorption Isotherm
b) Langmuir isotherm
c) BET isotherm

2
 1. FREUNDLICH ADSORPTION
ISOTHERM
◻ 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).

x = mass of adsorbate
m = mass of adsorbent
x/m = mass of adsorbate per gram adsorbent
 1. Freundlich Adsorption Isotherm

1909 or

◻ 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
1/n and the intercept equal to log k.
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
log x = 1/n log C + log k log x = 1/n log P + log k
m m
m m
x c x c
y
y

n usually less than 1

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

Slope= 1/n
Slope= 1/n
Intercept = log k
Intercept=log k

Log C Log p

6
 EXAMPLE
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:
Use these figures to show the validity of the Freundlich
isotherm, and to find the values of the constant n.
Acid adsorbed (mol) 0.29 0.60 0.75 0.90 1.05

Equil. conc. of acid (mol 0.03 0.08 0.115 0.175 0.260

dm-3)

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 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 = kC1/n
m

log x/m = log k + 1/n log C

Find the value x (mass adsorbate) by using mol
acid given:

Example: 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 (g) 26.1 54 67.5 81 94.5
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 C

1/n = Y2 – Y1 0
0 0.3 0.6 0.9 1.2 1.5
X2 – X1 -0.2

-0.4

1/n = -1.52 – (-0.59) -0.6

0.72 – 1.28 1/n

Log x/m
-0.8 y = 1.6148x - 2.7163
R² = 0.9819
-1
= -0.93 -1.2
` -0.56
-1.4

-1.6
= 1.66
-1.8

Slope = 1.66

1/n = 1.66
n = 0.602 n usually less than 1
 2. LANGMUIR ADSORPTION
12 ISOTHERM

1916 θ = bP
1 + bP

 Relationship between the number of active sites of the

surface undergoing adsorption and pressure.
 Relates 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 θ - number of sites of the

surface which are covered
P = gas pressure or concentration with gaseous molecules.
b = constant
 DERIVATION OF THE LANGMUIR
13
ISOTHERM

• 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.
S + A SA
14 Derivation of the Langmuir isotherm
• An equilibrium constant, K, can be written:
S+A SA

K = [SA]
[S] [A]

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

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

15
Derivation of the Langmuir isotherm

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

k= θ
(1-θ)P

• Rearranging gives the expression for surface coverage:

θ = kP
1 + kP
=

Langmuir isotherm plot

16

θ = kP • θ – ratio of the volume of gas adsorbed V(ads)

divided by the volume of gas adsorbed evenly to
1 + kP form a complete monolayer (Vm)

• Substitute θ = V/Vm
Vads = kP • Vm = The volume corresponding to complete
Vm 1 + kP coverage
• Rearranged into; • Plot P/V as ‘y’ against P as ‘x’
P = P + 1 P = 1 (P) + 1
V(ads) Vm kVm V(ads) Vm kVm

Slope, m = 1/Vm and

y = mx + C intercept , c = 1/kVm
17
18 Langmuir isotherm plot
• A plot of P/V against P should give a straight line of
slope 1/Vm and intercept 1/KVm

P/V

06/06/2013
 Langmuir isotherm plot
19

Ammonia on activated charcoal (O°C)

P (kPa) V s (STPcc/g) P/Vs
6.8 74 0.092
13.5 111 0.122
26.7 147 0.182
53.1 177 0.300 P/V = 0.00452 P + 0.0608
79.4 189 0.420
Shaw (1992)

Slope = 1/Vm Intercept = 1/bVm = 0.0608

= 0.00452 ⇒b = 0.0744 kPa–1
⇒ Vm = 221 STPcc/g
20
Langmuir Isotherm Assumption
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 adsorbate molecules on
adjacent sites.

iv) A dynamic equilibrium exists between the adsorbed

molecules and the free gas molecules.
21 Langmuir Model of Adsorption

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.
LEARNING CHECK

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 3. 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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 Adsorbate
molecules, N2
BET MODELS

⮚ θ0, θ1, ..., θ n = Surface area (cm-2) covered by 0, 1, ...,

n layers of adsorbed molecules
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Give two assumptions of BET isotherm
(Dec 2016)

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BET Isotherm Assumption

Assumptions:

(1) Multilayer adsorption;

(2) Adsorption of first layer has a heat of
adsorption, ΔHa;
(3) Subsequent layers are controlled by heat of
condensation, ΔHc.

Condensation - The conversion of a vapour or gas to a liquid

26 BET EQUATION
This BET theory for multi-layer adsorption is the
expansion of Langmuir equation, which is for the single
layer adsorption.
P = 1 + C-1.P
V(PO–P) CVm CVm.PO

Vm – Monolayer adsorption amount

V – Adsorption amount at the equilibrium pressure P
 BET graph
z/V(1-z)
BET graph
✔Where z = P/P0 and (BET equation valid for
0.05<P/P0 < 0.3)

Slope= C-1/VmC Z = 1 + C-1 Z

Intercept=1/VmC
V(1-z) VmC VmC

y c m x
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.
28
 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 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
 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.

LEARNING CHECK

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DIFFERENCES BETWEEN LANGMUIR
AND BET ADSORPTION ISOTHERM

Langmuir
• Monolayer
• More surface area

BET
• Monolayer + Multilayer
• Less surface area
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 TYPE I ADSORPTION
ISOTHERM
Described by Langmuir
equation

Microporous materials

Organic vapors on zeolites

and molecular sieves

No multilayer adsorption

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 TYPE II ADSORPTION
ISOTHERM
Sigmoid type
graph

Vapors of non-
polar organic
substances on Multilayer
mesoporous adsorption
activated carbons.

Described by
the BET
equation Nonporous or
macroporous solids.
(pore diameter > 50
nm).

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 PASS YEAR EXAM – JUN 2012
36

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 PAST YEAR EXAM –
37
JUNE 2012

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
38

The data given below are for the adsorption of CO on

charcoal at 273 K. 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 1.00 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