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Types of Surface

Homogeneous surface
Heterogeneous surface

Considering from >>
Energy uniformity of the surface
Dependence of heat of adsorption
on the surface coverage
Techniques of Surface Study
Atomic Force Microscopy)
(AFM)
X-ray Photoelectron
Spectroscopy (XPS)
Scanning Tunnelling Microscope (STM)
SEM etc.
Glass surface NaCl Surface Au (100) surface
http://www.atom.rmutphysics.com/charud/scibook/nanotech/Page/Unit4-3.html

Adsorption
Absorption -
Adsorption a combination of physical
and chemical processes in which a
substance (adsorbate) accumulates on a
solid (adsorbent) surface
Attraction of a molecule to a
surface can be caused by physical and
chemical forces

Properties of Adsorbent
Surface area and porosity are two
important physical properties that
determine the quality and utility of many
materials. Differences in the surface area
and porosity of particles within a material
can greatly influence its performance
characteristics
INSTRUMENTS FOR PARTICLE SIZE,
SURFACE AREA, POROSITY, AND DENSITY
Specific Surface Areas
of Some Adsorbents
.




Alumina Chips 0.50 m
2
/g (N
2
)
0.46 m
2
/g (Kr)
Glass Powder. 5.3 m
2
/g
Carbon Black 24.1 m2/g
Carbon Powder 111 m2/g
Silica-Alumina Pellets
s.s.a. = 215 m
2
/g
p.v. = 0.60 cm
3
/g
a.p.d. = 115
s.s.a. = specific surface area, p.v. = pore volume, a.p.d. = average pore diameter
Adsorption of Gas on Solid Surface :
Adsorption Isotherm
The free gas and the adsorbed gas are in
equilibrium, The fraction coverage (u) of
the surface depends on pressure (P) of
the overlying gas.
Variation of u with P at a chosen
temperature is called adsorption isotherm


Thermodynamic viewpoint,
Molecules always prefer to be in a lower
energy state.
A moving gas molecule is normally at a
higher energy state.
When gas molecule is adsorbed on the solid
surface, its energy becomes lower.
The difference in the two energy states is
called the heat of adsorption (AH) and
this is the quantity of energy liberated
when the molecule is adsorbed
Adsorption Enthalpy
Adsorption is an exothermic process because
energy is liberated, therefore enthalpy is
always negative. Adsorption constants are
equilibrium constants, therefore they obey
van 't Hoff's equation:
K is a surface-coveraged constant
Physisorption
Basic physical forces :
(electrostatic forces)
- dipole-dipole interaction
- dispersion interactions or
- London-van der Waals force
- hydrogen bonding
involves relatively small heats of
adsorption about -25 kJ per mole
or less (exothermic)
multilayer adsorption
Chemisorption
involves the formation of strong
chemical bonds between
adsorbate molecules and specific
surface locations known as
chemically active site
forces and energies about -40 kJ
per mole (exothermic)
monolayer adsorption
Sorption Isotherms
A sorption isotherm (also adsorption isotherm) describes the
equilibrium of the sorption of a material at a surface (more
general at a surface boundary) at constant temperature.
It represents the amount of material bound at the surface
(the sorbate) as a function of the material present in the gas
phase and/or in the solution.
Sorption isotherms are often used as empirical models,[1]
which do not make statements about the underlying mechanisms
and measured variables. They are obtained from measured data
by means of regression analysis.
The most frequently used isotherms are the , Freundlich
isotherm, the Langmuir isotherm, and the BET model.
Sorption Isotherms
Langmuir isotherm
Freundlich isotherm
Brunauer-Emmett-Teller (BET)
Langmuir Isotherm
Three assumptions :
1. Adsorption cannot proceed beyond
monolayer coverage
2. All surface site are equivalent and
the surface is uniform
3. The ability of a molecule to adsorb
at the given site is independent of
the occupation of neighboring sites
Langmuir equation
Equilibrium between empty surface sites
S* and particles P and filled surface
sites S-P
Fraction coverage,
u = # active sites occupied
# active sites available
Fraction of non-occupied sites = (1- u)
Rate of adsorption :
du = k
ads
. P.N. (1-u) (1)
dt

Rate of desorption
du = - k
des
. N.u .(2)
dt

At equilibrium, (1) = (2)

K
ads

K
des

Langmuir equation :
K is a Langmuir adsorption constant
(Surface-coveraged constant)
u = K P
1 + K P
K = K
ads

K
des

Surface-coveraged constant
Adsorption constants are equilibrium
constants, therefore they obey van 't
Hoff's equation:
Or ln K
2
= - AH [ 1 - 1 ]
K
1
R T
2
T
1

Langmuir equation
Let u = the fraction of filled surface sites
= V = volume of sites occupied
V
m
volume of max. sites coverage
u = K P = V
1 + K P Vm
P = P + 1
V V
m
KV
m

P
P/V
Slope = 1/V


Intercept = 1/KV
m

Freundlich equation
The Frendlich Adsorption Isotherm is mathematically
expressed as
x/m = K p
1/n

or
x/m = K c
1/n
where
x = mass of adsorbate
m = mass of adsorbent
p = Equilibrium pressure of adsorbate
c = Equilibrium concentration of adsorbate in
solution.
K and 1/n are constants for a given adsorbate and
adsorbent at a particular temperature.
the plot of log(x/m) versus log P yields a straight line, it implies that the adsorption process
conforms with Freundlich isotherm. From the intercept, the parameter K is obtained,
while the slope is equal to (1/n).
The BET Isotherm
(Brunauer, Emmett, Teller)
1. Dealing with multilayer adsorption
(physical adsorption)
2. R
ads
on empty surface = R
des
on 1
st
layer
R
ads
on 1
st
layer = R
des
on 2
nd
layer
and so on
3. heat of adsorption of the upper layers are
equal to heat of liquefaction of adsorbate,
but not for the monolayer


The BET equation
u = V = cx
V
m
(1-x)[1+(c-1)x]
X = P/P
o
; V , x 1 (P=P
o
)
C = exp(AH
des
-AH
vap
)/RT = const.
The BET Isotherm
( )
( )
0 0
1 1
P
P
C V
C
C V P P V
P
m m

+ =

P
o
= vapor pressure of adsorbate (liquid)
P = vapor pressure of gas on surface
V = volume of surface sites occupied
V
m
= max. volume forming monolayer
C = constant = exp(AH
des
- AH
vap
)/RT
Langmuir isotherm (red) and BET isotherm (green)
Surface Area Determination
V
m
= max. volume of sites coverage


L
Surface area = V
m
/L >>>> per molecule
L = length of a molecule
Specific surface area (m
2
/g)
Alumina Chips
0.50 m
2
/g (N
2
)
0.46 m
2
/g (Kr)
Surface Area Determination
V
m
= (n mole) (22,414 cm
3
/mole)
w(g)

T R
V P
n
m
=
A
sp
= specific surface area
N
A
= Avogadro #
o
o
= area occupied per molecule

A
sp
= V
m
N
A
o
o

(22,414)
Exercise :

From the BET isotherm of N2 on 1.00 g
Fe/Al2O3 surface at 77K, the maximum volume
of N2 to form a monolayer on the surface was
found to be 2.86 cm
3
at STP. Determine the
surface area of Fe/Al2O
3

(Given N-N bond = 110 pm)
The End