Surface chemistry

Trieu Tuan Anh

 Objectives
After studying this chapter, students should be able to
 Define important principles
 Describe the two types of adsorption, physisorption
and chemisorption
 Explain how a unimolecular layer is formed
 Develop the equations necessary to derive the
Langmuir isotherm and plot the fraction of surface
covered against concentration for adsorption with and
without dissociation
 Explain the conditions under which the BET isotherm
occurs
 Calculate surface area of a solid sample using
Langmuir and/or BET equations
 Contents

 Introduction

 Basic principles

 Adsorption

 Adsorption Isotherm

 Surface tension and capillarity

Introduction
Introduction
Introduction
 Introduction
Many industrial processes
using heterogeneous catalyst
such as sulfuric acid,
ammonia, and nitric acid,
petroleum industrial,
synthesis methanol from
carbon monoxide and
hydrogen(*)

Sinfelt JH (2002) Role of surface science in catalysis. Surf Sci 500:923–946.

 Introduction
Not just in industrial processes, heterogeneous catalyst
also be used in pollution control and prevention, reduces
the pollutant emission from automobiles.

Annual average of
toxic mobile
emissions in Los
Angeles County

http://www.arb.ca.gov/app/emsinv/emssumcat.php,
 Introduction
To synthesis clean energy sources: biodiesel from waste
cooking - oil, animal fat, jatropha oils, microalgae,…
scientists also use heterogeneous catalyst

http://www.arb.ca.gov/app/emsinv/emssumcat.php,
 Introduction
Conversion chemical energy to electric energy,
heterogeneous catalysts were used in both cathode and
anode site.

http://americanhistory.si.edu/fuelcells/basics.htm
 Introduction
Another approach to produce green energy source is
using photocatalyst to convert water and CO2 into fuel

http://spie.org/newsroom/5838-solar-fuel-production-for-sustainable-energy-supply
 Introduction
Semiconductor based technology is very important in
modern world. Advances in epitaxial growth of silicon
thin films, chemical vapor deposition, and surface
etching techniques

http://www.arb.ca.gov/app/emsinv/emssumcat.php,
 Introduction
Surface chemistry processes for implant biomaterials

http://rsif.royalsocietypublishing.org/content/11/95/20140169
 Introduction
Surface chemistry processes for chromatography
separations,

http://rsif.royalsocietypublishing.org/content/11/95/20140169
 Introduction
Surface chemistry processes for biosensors

SPR-based
biosensor for lung
cancer detection
using dendrimers
as surface
enhancement
polymers

https://www.researchgate.net/figure/263016557_fig1_Fig-3-SPR-based-biosensor-for-lung-cancer-detection-using-
dendrimers-as-surface
 Surface & interface

A boundary that separates two phases is known as a

surface or an interface.

Laidler, 4ed, 931

 Surface free energy
(a) the net force acting on will essentially be zero,
(b)The net forces acting on a unit at the surface will be
unbalanced in the direction of the bulk phase.

Laidler, 4ed, 931

 Absorption & Adsorption

Laidler, 4ed, 931-933

 Absorption & Adsorption
Absorption Adsorption
Definition Assimilation of molecular Accumulation of the molecular
species throughout the bulk species at the surface rather
of the solid or liquid is termed than in the bulk of the solid or
as absorption. liquid is termed as adsorption.
Phenomenon It is a bulk phenomenon It is a surface phenomenon.

Heat exchange Endothermic process Exothermic process

Temperature It is not affected by It is favoured by low

temperature temperature
Rate of It occurs at a uniform rate. It steadily increases and reach
reaction to equilibrium
Concentration It is same throughout the Concentration on the surface of
material. adsorbent is different from
that in the bulk
Laidler, 4ed, 931-933
 Adsorption - physisorption

 Physisorption: the forces are of a physical nature

and the adsorption is relatively weak ( van der
Waals forces)

 Heat ~ 20kJ/mol

Laidler, 4ed, 931-933

 Adsorption - physisorption
In “Physisorption of Hydrogen on
Microporous Carbon and Carbon
Nanotubes” papers on J. Phys. Chem. B
1998, 102, 10894-10898, M. Rzepka*,
P. Lamp and M. A. de la Casa-Lillo
investigated the storage capability of
microporous carbon materials for
gaseous hydrogen both theoretically
and experimentally and for a storage
pressure of 10 MPa a maximum
adsorbed hydrogen density of 14kg/m3
can be reached
http://pubs.acs.org/doi/abs/10.1021/jp9829602
 Adsorption - physisorption

Question! What is the volume of

14kg of hydrogen
1. At STP?
2. At 0oC, 10 MPa

http://pubs.acs.org/doi/abs/10.1021/jp9829602
 Adsorption - physisorption
In “An overview of technologies for immobilization of enzymes and
surface analysis techniques for immobilized enzymes” Mohamad
and colleagues confirm:
1. The enzymes being physically adsorbed or attached onto the
support material. Adsorption can occur through weak non-specific
forces such as van der Waals, hydrophobic interactions and
hydrogen bonds.
2. The reversibly immobilized enzymes can be removed from the
support under gentle conditions, a method highly attractive as
when the enzymatic activity has decayed, the support can be
regenerated and reloaded with fresh enzyme. The cost of the
support is often a primary factor in the overall cost of
immobilized catalysts.

http://pubs.acs.org/doi/abs/10.1021/jp9829602
 Adsorption - chemisorption

 Chemisorption: the adsorbed molecules are held

to the surface by covalent forces of the same
general type as those occurring between atoms in
molecules.

 Heat ~ 100 – 500 kJ/mol

 Called activation adsorption

Laidler, 4ed, 931-933

 Adsorption - chemisorption

The extent of adsorption A

increases with increasing pressure p,
but eventually approaches a
saturation limit when the pressure
becomes sufficiently high. This
means that the chemisorption
process is complete when the
surface is covered by a single layer
of molecules
Laidler, 4ed, 931-933
 Adsorption
Physisorption Chemisorption
Weak van der Waals force Chemical bonds
It occurs at low temperature It occurs at high temperature
Heat of adsorption ~ 20 kJ/mol Heat of adsorption 100 – 500
kj/mol
Reversible process Irreversible process

Multilayer adsorption, several Monolayer adsorption

molecules thick (unimolecular thickness

Laidler, 4ed, 931-933

 The Langmuir Isotherm
 The rate of the adsorption ?
 The rate of the desorption?

Laidler, 4ed, 933-935

 The Langmuir Isotherm

The rate of the adsorption will then be proportional

to the concentration [A] of the molecules in the gas
or liquid phase and also the proportional to the
fraction of the surface.

va  ka [A](1   )

Laidler, 4ed, 933-935

 The Langmuir Isotherm

The rate of the desorption vd is proportional only

to the number of molecules attached to the
surface, which in turn is proportional to the
fraction of the surface covered.

vd  kd

Laidler, 4ed, 933-935

 The Langmuir Isotherm

 At equilibrium

ka [A](1   )  kd
kd 
  [A]
1   ka

  K [A] {K  kd / Ka }
1 
K [A]
 
1  K [A]

Laidler, 4ed, 933-935

 The Langmuir Isotherm – example

Benzene adsorbed on graphite is found to obey the

Langmuir isotherm to a good approximation. At the
pressure of 1.00 Torr the volume of benzene
absorbed on a sample of graphite was found to be
4.2mm3 at STP (0oC and 1 atm pressure) anf 3.00
torr it was 8.5 mm3. Assume a benzene molecule to
occupy 30Å2 and estimate the surface of the
graphite.

Laidler, 4ed, 933-935

 The Langmuir Isotherm – example

 Using the Langmuir equation K [A]


 Apply it for each case 1  K [A]

 Can replace [A] by pressure P

 Suppose that the amount of adsorbed when the

surface is saturated is x mm3

 Calculating x value ( two equations, two variables)

 Calculation the area of graphite

Laidler, 4ed, 933-935

 Adsorption with Dissociation

Laidler, 4ed, 935-936

 Adsorption with dissociation

The process of adsorption is now a reaction

between the gas molecule and two adjacent surface
sites, and the rate of adsorption is therefore.

va  ka [A](1   )
2

Laidler, 4ed, 935-936

 Adsorption with dissociation

The desorption process involves reaction between

two adsorbed atoms, and the rate is therefore
proportional to the square of the fraction of
surface covered

vd  kd 2

Laidler, 4ed, 935-936

 Adsorption with dissociation

At the equilibrium the rates are equal, and

therefore,

1/2
  ka  1 1
  [A]   K [A]
2 2
1    kd 

Laidler, 4ed, 935-936

 Adsorption with dissociation

Above equation can be written as

1 1
K 2 [A] 2
 1 1
1  K 2 [A] 2

Laidler, 4ed, 935-936

 Competitive adsorption

 The isotherm for two substances adsorbed on the

same surface is of importance in connection with
inhibition and with kinetics of surface reactions
involving two reactants A and B

Laidler, 4ed, 936-937

 Competitive adsorption

 Suppose that the fraction of surface covered by

molecules type A is θa, type B is θb. The fraction
bare is 1- θa- θb

 v
The rates of adsorption A a
A
 ka [A](1   a  b )
A

 The rates of adsorption B vaB  kaB [B](1  a  b )

 The rates of desorption v k 
A A
d d A

v k 
B
d
B
d B

Laidler, 4ed, 936-937

 Competitive adsorption

 At equilibrium vd = va for both of subtances A

and B

KA [A]
A 
1  KA [A]  KB [B]
KB [B]
B 
1  KA [A]  KB [B]

Laidler, 4ed, 936-937

 BET isotherm
This is an extension of the Langmuir treatment to allow
for the physisorption of additional layers of adsorbed
molecules. It was delivered by balancing the rates of
adsorption and condensation for the various layers ( only
one enthalpy adsorption for the first layer, and the
enthalpy of liquefaction applies to the second and
subsequent layer)

PPo 1 P
 
V (Po  P ) V0K Vo
Laidler, 4ed, 937-938
 Surface tension and capillarity

The floating needle

Laidler, 4ed, 948-951

 Surface tension and capillarity

The floating needle

Laidler, 4ed, 948-951

 Surface tension and capillarity

Awesomely Perfect and Refreshing Example of

Surface Tension

Laidler, 4ed, 948-951

 Surface tension and capillarity
 A molecule in the interior of a liquid: no resultant
force tending to move it in any direction.
 A molecule at the surface: a net inward attraction on
the surface molecules.

Laidler, 4ed, 948-951

 Surface tension and capillarity
 F (N) = γ(N/m)[2l (m)]
 ɣ: is known as the surface
tension.

Laidler, 4ed, 948-951

 Surface tension and capillarity
 F = ɣ2π(r+R)

Laidler, 4ed, 948-951

 Surface tension and capillarity
 Liquid wets the glass, the level of liquid
will rise in the tube
 Force by surface tension F1=2πrɣ
 Force due to the weight of liquid
F2=πr2hρg
 If the liquid does not completely wet the
glass. There is an angle θ between the
meniscus and the surface

rhρh
γ
2cosθ

Laidler, 4ed, 948-951

 Surface tension and capillarity
 Langmuir’s film balance

Laidler, 4ed, 948-951

 Surface tension and capillarity
Pendant Drop Method

mg = 3a cos()

 is the surface tension of liquid

 is the contact angle at which a liquid/vapor
interface meets the solid surface.

Contact Angle Goniometer.

Laidler, 4ed, 948-951

 Surface tension and capillarity

 Directly depends on intermolecular forces in

the solution

 Inversely depends on temperature

  of metallic liquid > ionic liquid > covalent

liquid
 Surface tension and capillarity

Liquid in a Vertical Tube

 ls   la cos
ls = liquid-solid surface tension
Concave la = liquid-air surface tension
= contact angle

Concave Adhesive>>Cohesive
Convex Adhesive<<Cohesive

Convex
 Surface tension and capillarity

Interface Tension and Spreading

 Surface tension and capillarity
Spreading Coefficient, S in Water at 20oC

S =

S  WA   OA   OW 
liquid B
n-hexadecane 72.8-(30.0+52.1) = - 9.3 Drop on water surface
n-octane 72.8-(21.8+50.8) = + 0.2 Spreading
n-octanol 72.8-(27.5+8.5) = +36.8 Spreading against
inpurity
Exercise 2
The following data relate to the adsorption of nitrogen at
77K on a 1.00 g sample of silica gel.
At 77K the saturation vapor pressure Po of nitrogen I
101.3 kPa. Estimate the surface area of the gel, taking
the molecular area of nitrogen to be 1.62*10-19m2

P/kPa 15.2 54.8

V/cm3(STP) 135 247

Laidler, 4ed, 948-951

Exercise 2
Using BET equation

There are two variations need to be pointed out

Vo:

K:

PPo 1 P
 
V (Po  P ) V0K Vo

Laidler, 4ed, 948-951

Exercise 3
A surface I half-covered by a gas when the
pressure is 1 bar. If the simple Langmuir
isotherm applies:
a.What is K/bar-1?
b.What pressure give 75%, 90%, 99% and
99.9% coverage?
c.What coverage is given by pressure of 0.1
bar, 0.5 bar, 1000 bar?
Laidler, 4ed, 948-951
Exercise 3
1. Finding K by applying Langmuir Isotherm!

2. Replace K value to calculate pressure

3. Using K value to determine coverage

K [A]

1  K [A]

Laidler, 4ed, 948-951

Exercise 4
Show that, if V is the volume of gas adsorbed at
pressure P. the Langmuir isotherm is obeyed, a plot of
P/V against is linear. Explain how, from such a plot, the
volume Vo corresponding to complete coverage and the
isotherm constant can be determined

KPA

1  KPA

Laidler, 4ed, 948-951

Exercise 5
The following results were reported by Langmuir for the
adsorption of nitrogen on mica at 20oC
a. Make a linear plot of these values in order to test the
Langmuir isotherm, If it applies, evaluate the constant
K.
b. Suppose that 1015 molecules cover 1cm2 of the surface.
Make an estimate of the effective surface area in
Langmuir’s experiment

Pressure/atm 2.8 4.0 6.0 9.4 17.1 33.5

V gas adsorbed at
12.0 15.1 19.0 23.9 28.2 33.0
20oC, 1atm/mm3
Laidler, 4ed, 948-951
Exercise 5
1. Using Langmuir isotherm equation

KPA

1  KPA

2. Replace θ = V/Vo

Laidler, 4ed, 948-951

Exercise 6
1. Suggest a method of making a linear plot to test the
applicability of the Brunauer, Emmett, and Teller
(BET) isotherm when volumes adsorbed, V, are known
at various pressures.

2. Show that the BET equation reduces to the Lanmuir

isotherm when Po>> P

PPo 1 P KPA
  
V (Po  P ) V0K Vo 1  KPA

Laidler, 4ed, 948-951

Exercise 6
The following data were obtained for the adsorption of
krypton on a 1.21 g sample of a porous solid. If the
saturation vapor pressure is 19.0 Torr, estimate a
surface area for the solid, assuming that a molecule of
krypton occupies an area of 2.1*10-21m2.

Pressure/Torr 1.11 3.08

Volume adsorbed/cm3 (STP) 1.48 1.88

PPo 1 P
 
V (Po  P ) V0K Vo
Laidler, 4ed, 948-951
Exercise 7
The decomposition of ammonia on platinum
2NH3 ↔ N2 + 3H2
Is the first order in NH3 and the rate is inversely
proportional to the hydrogen concentration (eq.18.39).
Write the differential rate equation for the rate of
formation of hydrogen, dx/dt, interms of the initial
concentration of ammonia, ao, and the concentration x
of hydrogen at time t.

Laidler, 4ed, 948-951

Exercise 8
The surface tension of water at 20oC is
7.27*10-2Nm-1 and its density is 0.998 gcm-3.
Assuming a contact angle θ of zero, calculate
the rise of water at 20oC in a capillar tube of
radius (a) 1 mm and (b) 10-3 cm. take g=9.81 ms-2.

Laidler, 4ed, 948-951

Exercise 9
The density of liquid mecury at 273K is
13,6gcm-3 and the surface tension is 0.47Nm-1.
If the contact angle is 140oC, calculate the
capillary depression in a tube of 1 mm diameter

Laidler, 4ed, 948-951