Dr.

Bencan Tang
Bencan.tang@nottingham.edu.cn

H82INC: Interfacial Chemistry

Lecture 3 – Adsorption Fundamentals:
The Langmuir and BET Models

Physical Chemistry
Atkins & dePaula
p. 916-925
What is adsorption?
Adsorption refers to the condensation of gases on free surfaces as opposed
to absorption where molecules penetrate into the mass of absorbent in a
process similar to dissolution.

High surface areas are very crucial, such as highly porous solids (charcoal,
activated carbons, silica gel……).

Activated carbon Silica gel

Gas phase surface adsorption
A solid surface (adsorbent) in contact with a
gas usually attracts an adsorbed layer of gas
molecules (adsorbate).

Adsorption is spontaneous,

ΔG = ΔH − T ΔS

ΔG < 0 (spontaneous process)

ΔS < 0 (reduction in degrees of freedom)

Therefore, ΔH must be negative and large!

That is , the process is exothermic
Adsorption
Over the next 3 lectures we will look at

•how adsorption plays important role in many processes- catalysis,

electronic devices, corrosion…

•characterization- Adsorption can also be used to characterise porous

materials - provide information about the surface areas and nature of the
material.

•catalysis- The weakening or breaking of chemical bonds that occurs

during adsorption makes some solid surfaces effective as heterogeneous
catalysts.
Specific Surface Areas (SSA)
SSA = Area / Mass (m2 g−1)
High surface areas can occur in solids when they have some form of porous
structure or when the solid is in very small particle sizes.
In the case of non-porous solids, as a sample of known mass is split into
smaller and cubes the SSA can increases dramatically:

Cube size 1 cm 1 mm 1 nm
Surface Area/ cm2 6 60 60000000
Total Mass / g (ρ = 1) 1 1 1
SSA / cm2 g−1 6 60 60000000
Measurement of Adsorption
Gas adsorption is generally measured by one of two methods:
1) Measuring the amount of gaseous adsorbate present after
exposure of the gas to a solid. (Volumetric or Flow)
2) Using a very sensitive quartz crystal microbalance(QCM) to
investigate the increase in weight as the sample is exposed to
the adsorbate (Gravimetric)

QCM Microbalance
Volumetric Methods

1) Load ‘blank’ sample bulb

2) Evacuate the system
3) Isolated sample from the apparatus
4) Fill the apparatus with gas (N2, H2)
5) Difference in pressure is measured on
the right arm of the manometer, when
the sample tap is opened.
6) Repeat experiment with sample in the
tube and measure the difference
between blank and sample.
Gravimetric Methods
Adsorbate -
Adsorbent – porous material in gas
solid adsorbs the phase capable of
material in gas being adsorbed but
phase not yet adsorbed

Spring balance

• Uses a quartz crystal

microbalance (QCB)
• Extremely sensitive
• Can detect a single
monolayer

Porous solid on spring balance

Types of Adsorption
Two classifications distinguished by the magnitude of their
enthalpies of adsorption

Physisorption: long-range but weak van der Waals-type

interactions with negligible exchange of electrons.
−ΔHAD < 20 kJmol−1

Chemisorption: formation of a chemical bond (covalent, ionic,

metallic) with exchange of electrons
−ΔHAD > 80 kJmol−1
Enthalpy of chemisorption depends strongly on surface coverage (interactions).
Spectroscopic techniques are used to confirm chemisorption.
Potential Energy Profile
• The potential energy curve for the adsorption process is a
representation of the variation of the energy (PE or E) of the system
as a function of the distance (d) of an adsorbate from a surface.

• This is a very simplistic model which neglects many other

parameters, including for example

o The angular orientation of the molecule

o Changes in bond angles and bond lengths of the molecule

o The position of the molecule parallel to the surface plane

Physisorption
Physisorption: Lennard-Jones Potential

−ΔHads < 20 kJ mol−1

Repulsive coulombic interactions
Pauli repulsion

0
DHPhys z

Attractive van der Waals

interactions
Chemisorption
Chemisorption: Lennard-Jones Potential

−ΔHads > 80 kJ mol−1

Repulsive coulombic interactions
Pauli repulsion

0
z
DHChem
Attractive chemical
bond interactions
Phys or Chemisorption
Chemisorption and Physisorption

0
DHPhys z
DHChem
Activated or Not Activated

Non activated Activated

Progression to the Chemisorbed state can be described as activated or non activated
depending on the activation energy barrier (Ea)
Phys or Chemisorption
PHYSISORPTION CHEMISORPTION

WEAK, LONG RANGE BONDING STRONG, SHORT RANGE BONDING

Van der Waals interactions (e.g. London dispersion, dipole- Chemical bonding involving orbital overlap and charge
dipole).. transfer.

NOT SURFACE SPECIFIC SURFACE SPECIFIC

Physisorption takes place between all molecules on E.g. Chemisorption of hydrogen takes place on
any surface providing the temperature is low enough. transition metals but not on gold or mercury.

−ΔHads = 5 ….. 35 kJ mol−1 −ΔHads = 35 ….. 500 kJ mol−1

Non activated with equilibrium achieved relatively Can be activated, in which case equilibrium can be
quickly. Increasing temperature always reduces slow and increasing temperature can favour
surface coverage. adsorption.

No surface reactions. Surface reactions may take place:- Dissociation,

reconstruction, catalysis.

MULTILAYER ADSORPTION MONOLAYER ADSORPTION

BET Isotherm used to model adsorption equilibrium. Langmuir Isotherm used to model adsorption
equilibrium..
 Adsorption- The Key Step
Extent of adsorption usually given by fractional coverage, θ

Ns Ns = number of surface sites occupied

= N = number of adsorption sites available
N
Vs Vs = volume of adsorbate adsorbed
= V∞ = volume of adsorbate for complete monolayer coverage
V
m ms = mass of adsorbate adsorbed
= s m∞ = mass of adsorbate for complete monolayer coverage
m

When θ = 1 we have monolayer coverage.

Associative (or non-dissociative) adsorption is when a molecule adsorbs without fragmentation

Dissociative adsorption is when fragmentation occurs during the adsorption process.

Adsorption Isotherms
p = pressure
θ = ƒ(p, T, gas, solid) T = temperature

For a given gas adsorbed on a particular solid at a fixed temperature

θ = ƒ(p)T, gas, solid

If the temperature is below the critical temperature of the gas then it can be
expressed as
po = saturated vapour pressure of the adsorptive
θ = ƒ(p/po)T, gas, solid The saturation pressure is the pressure at which condensation would commence; i.e. the
equilibrium vapour pressure of the liquefied gas at the chosen experimental temperature.
p/po = relative vapour pressure

This equation is an expression of the adsorption isotherm which is the relationship between gas
adsorbed and the pressure at constant temperature, an equilibrium relationship. Similar relationships
can be determined between gases and solids where the amount of gas adsorbed is measured at
constant pressure, changing temperature, these are called isobars instead of isotherms.
Adsorption Isotherms
Isotherms can have very different shapes

0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8

p/po p/po

More on this in the next lecture…

The Langmuir isotherm
Models describing equilibrium between the gaseous and the
adsorbed phases at a given fixed temperature

The simplest physically plausible isotherm is based on three assumptions:

1. Adsorption cannot procees beyond monolayer

coverage.
2. All sites are equivalent and the surface is uniform
(that is, the surface is perfectly flat on a microscopic
scale).
3. The ability of a molecule to adsorb at a given site is
indelendent of the occupation of neighbouring sites
Irving Langmuir (that is, there are no interactions between adsorbed
1881-1957 molecules)
Nobel prize 1932
Adsorption Isotherms
The free gas and the adsorbed gas are in dynamic equilibrium, and the fractional
coverage of the surface depends on the pressure of the overlying gas. The
variation of θ with pressure at a chosen temperature is called the adsorption
isotherm.
The results of adsorption studies / measurements are usually plotted in the form
of an adsorption Isotherm, i.e. the amount of gas adsorbed at different gas
pressures, p (at constant temperature).
Langmuir Isotherm
(Space for taking notes)
Langmuir Isotherm
(Space for taking notes)
Langmuir Isotherm
(Space for taking notes)
Langmuir Isotherm
The dynamic equilibrium is

with rate constants Ka for adsorption and Kd for desorption. The rate of change of surface
coverage due to adsorption is proportional to the partial pressure p of A and the number
of vacant sites N(1− θ ), where N is the total number of sites:
Langmuir Isotherm
Langmuir Isotherm
Associative Adsorption Molecules in the gas phase are in
equilibrium with those on the surface

adsorption rate = k a p (1 −  )
desorption rate = k d
At equilibrium:
Ns
= Ns = number of surface sites occupied
N = total number of surface sites
rate of desorption = rate of adsorption
N k a p (1 −  ) = k d
Simplifying assumptions
• Adsorption proceeds to monolayer Rearrange
formation only
• All sites are equivalent and the surface is
uniform Kp ka
• Molecule adsorption is independent of = K=
occupation of neighbouring sites 1 + Kp kd
Langmuir Isotherm
Ns m V Kp
= = = =
N m V 1 + Kp

Using the volume of adsorbate as an example we can rearrange the equation

into the form y = mx + c

A plot of P/V against P will yield a straight line with..

P P 1
= + 1 1
V V KV slope = intercept =
V KV
(Space for taking notes)
Using the Langmuir Isotherm
P P 1
= +
V V KV
1 A plot of P/V against P will yield a straight line
slope =
V and so V∞ and K can be calculated.

From V∞ (or m∞) we can calculate N and the

specific surface area (SSA)

pV
1 n =
intercept = RT
KV

N = n N A
We can easily calculate the total surface area
Atkins & dePaula p. 918 (SA) if we know the area of 1 molecule (Am). The
Attard & Barnes p. 4 SSA is the total surface area per unit mass.
See the practice questions to have a go!
Langmuir Isotherm
Dissociative Adsorption Molecules in the gas phase are in
equilibrium with those on the surface

adsorption rate = k a p (1 −  ) 2
desorption rate = k d 2
At equilibrium:
Ns
= Ns = number of surface sites occupied
N = total number of surface sites
rate of desorption = rate of adsorption
N
k a p(1 −  ) = k d 2
2

Simplifying assumptions Rearrange

• Adsorption proceeds to monolayer
formation only
• All sites are equivalent and the ka
Kp
surface is uniform = K=
• Molecule adsorption is independent 1 + Kp kd
of occupation of neighbouring sites
Dissociative Adsorption
K
K

Associative adsorption isotherms Dissociative adsorption isotherms

Heats of Adsorption
Gas adsorption to a solid is nearly allways exothermic.
The magnitude and variation of K as a function of temperature at constant
coverage can reveal information about bonding on the surface.
(Space for taking notes)
 Heats of Adsorption
Gas adsorption to a solid is nearly allways exothermic.
The magnitude and variation of K as a function of temperature at constant
coverage can reveal information about bonding on the surface.


KP = or ln K = -ln P + constant Constant θ
1−
Recognizing that K is essentially an equilibrium constant we can use the
van’t Hoff equation (see CPE lecture 4)
  ln P    ln K  D ad H  d (1 T ) 1
  = −  =− We know that =− 2
 T   T 
2
RT dT T

A plot of lnP against 1/T will yield a straight line with..

  ln P  D H
  = ad D ad H 
  (1 T )  R slope =
R
Heats of Adsorption
Atkins & de Paula, p. 991

  ln P  D ad H 
  =
  (1 T )  R
BET Isotherm
When adsorption of a gas can occur over a previously adsorbed monolayer of
the gas. Brunauer, Emmett & Teller extends the Langmuir isotherm model to
multilayer adsorption

Assumptions:
1. Adsorption of 1st layer takes place on a surface of uniform energy
2. 2nd layer only adsorbs on 1st, 3rd on 2nd, etc. When p = p*, infinite layers
form.
3. At equilibrium, rates of condensation & evaporation (these are terms often
used when talking about adsorption) are same for each individual layer
4. For layers ≥ 2, ΔH0des = −Δ H0vap
BET Isotherm

V cz p
= z=
V (1 − z )1 − (1 − c )z  p*

V∞ = Volume of monolayer coverage (Vmon)

c = A constant which is related to the difference between the enthalpy of
desorption from a monolayer (ΔH0des) with the enthalpy of vaporization of the
liquid adsorbate (ΔH0vap):

c=e (DH  
des − DH vap )/ RT
You do NOT need to learn or be able to derive this equation
BET Isotherm
V cz p
= z=
V (1 − z )1 − (1 − c )z  p*
“knee” in some isotherms
represents monolayer coverage.
This become more pronounced as
Values of ‘c’ c gets larger

BET underestimates adsorption at

low p and overestimates
adsorption at high p
 Dissociative Adsorption
K

BET Isotherm
Langmuir Isotherm
Associative adsorption isotherms
BET Isotherm
V cz p
= z=
V (1 − z )1 − (1 − c )z  p*
Using the volume of adsorbate (V and V∞) as an example we can rearrange
the equation into the form y = mx + c
BET Isotherm
V cz p
= z=
V (1 − z )1 − (1 − c )z  p*
Using the volume of adsorbate (V and V∞) as an example we can rearrange
the equation into the form y = mx + c

z
A plot of against z will yield a straight
( − )
(c − 1)z line with.. 1 z V
z 1
= +
(1 − z )V cV cV slope =
(c − 1) 1
intercept =
cV cV
Using the BET Isotherm
V cz
=
V (1 − z )1 − (1 − c )z 
z
A plot of (1 − z )V against z will yield a straight
line and so V∞ and c can be calculated.

From V∞ (or m∞) we can calculate N and the

specific surface area (SSA) uing the same
method as we used for the Langmuir isotherm

This is the principle behind most surface area

and pore size analyzers. Nitrogen at 77K is
used as an adsorbate. Knowing size of the
molecule, the surface area and/or pore size
can be determined from the isotherm.
Atkins & dePaula p. 921 See the practice questions to have a go!
Other Isotherms
The Langmuir isotherm assumes that all adsorption sites are
independent and equivalent. However, experimentally it is often found
that the first sites to be occupied are energetically more favourable
Various attempts have been made to take this into account, e.g.

Temkin: Assumes
enthalpy changes
linearly with pressure
 = c1 ln(c2 p )

Freundlich: Assumes
enthalpy changes 1
logarithmically with  = c1 p c2

pressure
Where c1 and c2 are constants
Summary
• What is adsorption
• Measurement of adsorption
• Types of adsorption:physorption and chemsorption
• Adsortion isotherms
▪ Langmuir isotherm
▪ BET isotherm