Physical Chemistry

6th week

Adsorption Isotherm
 Gas/liquid (adsorbate)
accumulates on the
surface of a solid
(adsorbent)
Solid Adsorbent
ADSORPTI
ON VS
ABSORPTIO
N
 Affinity of one or more components to collect on the
surface of a solid
WHY
ADSORPTIO The affinity depends on:
• Molecular size
N CAN • Shape
HAPPEN? • Polarity
• System temperature or pressure
 Properties Physical Chemical
PHYSICAL VS
Bonding Weak, long range Van der Short, short range
CHEMICAL Waals interaction ionic or covalent
ADSORPTIO bond
Heat of Low (20-40 kJ/mol) High (>40 kJ/mol)
N adsorption

Saturation Monolayer or multilayer Monolayer only

Nature Reversible (by changing T Mostly irreversible

or P)
 Adsorption on Solid Surface
Illustration of fractional coverage . The surface (orange parallelogram)
contains a series of adsorption sites (white circles). The reactant (blue
spheres) exists in an equilibrium between free reactants and
adsorbates. The fractional coverage is the number of occupied
adsorption sites divided by the total number of sites on the surface.
A critical parameter in evaluating surface adsorption
is the fractional coverage defined as
The fractional coverage is often expressed in terms
of the volume of adsorbate adsorbed by θ = V/V∞,
where V∞ is the volume of adsorbate
corresponding to complete monolayer
coverage. In each case, the volumes in the
definition of θ are those of the free gas measured
under the same conditions of temperature and
pressure, not the volume the adsorbed gas occupies
when attached to the surface.

Adsorptio
n
Isotherms
Langmuir
Adsorbent consists of
individual adsorption sites
which capable of adsorbing
one molecule each and have
equal adsorption potential
Chemi/Physisorption
(single component)
• Equilibrium relationship between the mass of volume
adsorbed to the partial pressure or concentration of
adsorbate in the solution at constant temperature.
• To determine the adsorbent capacity
• Different system → different isotherm
• Which isotherm model to be used is determined by
matching experimental data
Brunauer-Emmet-Teller (BET) Freundlich
Adsorbent consists of individual Adsorbent consists of individual
adsorption sites which capable of adsorption sites with different
adsorbing more than one layer of adsorption potential
molecules
Chemi/Physisorption Multilayer Physisorption
Types of Isotherm Adsorption

Temperature : at the boiling point of gas used

Types 1

❑ An inherent property of Type I isotherms is that

adsorption is limited to the completion of a single
monolayer of adsorbate at the adsorbent surface.

❑ Type I isotherms are observed for the adsorption of gases

on microporous soilds whose pore sizes are not much
larger than the molecular diameter of the adsorbate.

❑ Complete filling of these narrow pores corresponds to the

completion of a molecular monolayer. An example is the
adsorption of oxygen on carbon black at -183 C. o

Adsorption in all other types do not reach a limit

corresponding to the completion of a monolayer.

❑ Can be either chemisorption or physisorption

❑ No desorption
Types 2
❑ Type II isotherms do not exhibit a saturation limit as did
Type I. This type of isotherm indicates an indefinite multi-
layer formation after completion of the monolayer and is
found in adsorbents with a wide distribution of pore
sizes. Near to the first point of inflexion (point A) a monolayer
is completed, following which adsorption occurs in successive
layers. An example is the adsorption of water vapour on carbon
black at 30 C.
o

❑ Has high energy of adsorption

❑ No desorption
Types 3

❑ Type III isotherm is obtained when the amount of gas

adsorbed increases without limit as its relative
saturation approaches unity. This type of isotherm is
obtained when bromine is adsorbed on silica gel at
20 C.
o

❑ Characteristic of material which is not porous, or

possibly macroporous, and has a low energy of
adsorption

❑ Adsorption = desorption
Types 4

❑ This is characteristic of a material,

which contains mesoporosity and
has a high energy of
adsorption.

❑ These often contain hysteresis

attributed to the mesoporosity
Types 5

This is characteristic of a material,which

contains mesoporosity and has a low
energy of adsorption. These often contain
hysteresis attributed to the mesoporosity
Types 6

Probably has multiple pore sizes.

Interpretasi kurva isotherm adsorpsi

Historically, the monolayer was selected as being

approximately at the position of the “knee” of the
isotherm

To fix this problem, an non-bias analytical method was

pursued. Several equations were constructed to
describe these isotherms, some of which will be
reviewed here.
BET Analysis to Calculate the surface area
BET Analysis to Calculate the surface area
BET Analysis to Calculate the surface area
BET Analysis to Calculate the surface area
BET Analysis to Calculate the surface area
 Langmuir  Gas system:
Isotherms

Linearized
form

• Liquid system:

Other form

To check if Langmuir model is valid for a certain
system: [p/q vs p] or [c/q vs. c] is plotted
Where:
qA : amount of species A adsorbed (kg/kg adsorbent or
mol/kg adsorbent)
PA : partial pressure of species A (mmHg, kPa, etc.)
cA: liquid concentration (mol/m3 or kg/m3)
KA : adsorption equilibrium constant
There are three classifications of porosity. Officially the IUPAC has classified these according to pore diameter as
follows:

• Below 2 nm – “micropores”
• Between 2 and 50 nm – “mesopores”
• Large than 50 nm – “macropores”

Analysis of surface area can be obtained either from BET or from  (chi) plot
Determining Porosity by Physical Adsorption

❑ The first step is to determine if the porosity consists of micropores or mesopores

❑ Type I isotherm is usually interpreted as an indication of micropores

❑ Type IV,V, and possibly VI are characteristic of mesopores

 plot
A  plot is a plot of amount of adsorbed versus the quantity –ln(-ln(P/Ps)

The basic equation for the  theory is

 plot
 plot
Micropore Analysis
The data used for CS2 adsorption on The plot in figure 37 is transformed to  plot in figure 37
activated charcoal

Fig. 36. A typical type I adsorption isotherm

Fig. 37. The Transformed plot using a standard curve to
indicating microporosity
change the x axis.
Micropore Analysis
1. Leave the y-axis as amount adsorbed, preferably in units of moles.
Transform the P/Ps using a standard plot. Here the
analytical  plot equation is being used for the standard plot.

2. Fit the high and low values to a straight line. These are
labeled in the figure as Slo and Shi.

3. Extract the slopes from the high and low lines and the
intercept from the high line.

4. The slopes, Slo and Shi,can be related to the surface areas of the
pores and the external surface. This is an approximation for
which one can find a minimum and a maximum surface area for
Fig. 37. The Transformed plot using a
pores. For the conversion, e.g. surface area, one must use either
standard curve to change the x axis.
that listed for the standard isotherm, based on the BET, or use
the  theory conversion. Here, for illustration, the  is being used.
Micropore Analysis
The areas As corresponding to the lower slope and Aex corresponding to the higher slope.

As = Ap + Aw

Aex = Aw + Ao

As = total surface area

Ap = area inside the pores
Ao = total area of the pore opening (luas penampang)
Aw = the area of the edge-on walls or the non-porous area of the outer surface

For micropore Ao << Aw, thus making Aex = Aw and Ap = As – Aex

Other assumption → if the wall thickness of the zeolite were about the same size as the pore radius, then Aw  Ao,
therefore Aw  0,5 Aex
Micropore Analysis
Example. The slopes and the high intercept, Ihi, in Fig. 37 are

Using the conversion factor from Eq. (39) and the standard
curve calibration (or for , Eqs. (4) and (5)) with the molar
volume Vm = 6.02 x 10-5 m3 mol-1 and therefore Am = 1.30 x 105
m2 g-1 the following areas and volumes are obtained: Fig. 37. The Transformed plot using a
standard curve to change the x axis.

Calculate : As, Ap,Vp????

Micropore Analysis
Cylindrical pores
Mesoporosity Analysis
Fig. 38 illustrates the parameters to be extracted from
the  plot (a plot of n adsorbed versus  value). The
following symbols are used in this analysis:

(45) Fig. 38. Preliminary parameters obtained from the isotherm to

analyze surface area and porosity. Data values were extracted
from an article by Krug and Jaroniec [10].
Mesoporosity Analysis
Mesoporosity Analysis
If Aw << Ap then Ap can be obtained from Eq. (45) directly; otherwise it is true that

Ap = fAmSlo

These considerations may be used to make one of the estimates of the pore diameter, dp. From the determined
values,

=
Temperature Programmed Desorption
Temperature Programmed Desorption
➢ Temperature programmed desorption is an important technique for studies on gas desorption from a solid by
programmed heating.

➢ In a typical temperature programmed desorption experiment, a small amount of the catalyst is contained in
a reactor that can be heated by a furnace. An inert carrier gas, usually argon, nitrogen or helium flows over the
catalyst.

➢ Downstream from the reactor a suitable gas chromatographic detector is used to analyse the changes in the
carrier gas stream.

➢ A gas/vapour is adsorbed on the catalyst surface, usually by injection of the adsorbate into the carrier
gas, upstream from the reactor.

➢ After sufficient time is allowed for the gas that was not adsorbed to flush out of the system, the catalyst
is heated to create a linear rise in temperature with time.

➢ As the catalyst is heated, the adsorbate is desorbed into the carrier gas stream and is detected by
the detector.
Temperature Programmed Desorption

❑ As the catalyst is heated to higher temperature the rate of desorption increases/ initially at an exponential rate
and the surface gradually becomes depleted of adsorbed gas.

❑ The rate of desorption goes through a maximum as a function of temperature and drops back to zero as all the
absorbed gas is desorbed.

❑ The temperature programmed desorption spectrum thus obtained depends on several parameters such as the
nature of the catalyst/ heating rate and surface coverage. If desorption involves more than one mechanism or if
there are different binding sites for a given species, the desorption spectrum may contain several peaks.
Information from TPD
Determination of surface coverage
Surface coverage of reactants and the surface composition of adsorbed species at the time of product formation can
be determined directly.

Determination of nature of surface of the catalyst

The availability of different binding sites for the same adsorbate (intrinsic heterogeneity) and the availability of
different desorption mechanisms for an initially homogeneous adlayer or adsorbate-adsorbate interactions (induced
heterogeneity) can be determined from a study of the desorption spectrum.

Determination of kinetic parameters

Kinetic parameters most often determined are the order of desorption, activation energy for desorption and pre-
exponential factor.