Physical Adsorption Theory

Basic Concepts
and Models

Michael L. Strickland
Micromeritics Instrument Corp.
Norcross, GA U.S.A.

Isotherm

P/Po

Measuring the Isotherm

An isotherm is a graphical representation of
the gas uptake quantity as a function of
pressure at a constant temperature.
q

General Types of Isotherms

The Isotherm Data Set

Accurate measurement of the isotherm is
fundamental to any information obtained about the
sample surface

data reduction methods interpret shape

of isotherm based on adsorption theories

and models of surface coverage and pore
filling

any inflections or deviations caused by

erroneous measurement data result in
error being incorporated into final analysis
information

The Isotherm Data Set

Accurate measurement of the isotherm
alone is not sufficient
Surface coverage and pore filling models
must apply to the material under test
Data reduction methods must be used within
the applicable analysis range

Techniques for Determining Quantity of

Gas Adsorbed as a Function of Pressure
Flowing Gas (Dynamic)
Static Volumetric
Mass detection

Flowing Gas (Dynamic) Technique

TCD

Equilibration pressure equals partial pressure of adsorptive

TCD

Static Volumetric Technique

Adsorptive
Port
Valve, closed

Vacuum
Port

Pressure
transducer

Valves, open
Coolant bath

Sample
holder

Equilibration pressure is measured directly; quantity adsorbed is

determined from pressure, volume & temperature using gas law.

The Physical Adsorption Process

Molecular chaos
at Pressure P1

1. Adsorption
3. Spontaneous
desorption

2. Temporary
retention

The Physical Adsorption Process

Molecular chaos
at Pressure P2
where P2>P1

More molecules on surface at any given time

compared to number on surface at lower P

Observation
At equilibrium, adsorption rate equals
desorption rate
The quantity of gas adsorbed (q) is
proportional to the pressure (P)
Q=kP
This relationship holds only when the
number of molecules on the surface is very
small and the surface is homogeneous.

The Langmuir Model

Assumptions

The surface is homogeneous in respect to

adsorption sites
Adsorbed molecules do not effect adsorption on the
remaining free surface
Molecules will not adsorb on molecules
Fractional coverage of the surface is
proportional to pressure

Formation of a monolayer
Ultimately, a mono-molecular layer is
formed on the solid surface

The Langmuir equation

Relates fractional coverage to pressure P

P = k[/(1- )]
where = Vadsorbed / Vmonolayer
Linear form with substitution for
P/Va = 1/(bVm) + P/Vm
If the adsorption process conforms to the
Langmuir model, a plot of experimental values of
P/Va versus P will yield a straight line.

Brunauer, Emmett and Teller model of

adsorption in multi-molecular layers
The Motivation
Evidence of multilayer adsorption existed
Layer polarization theory inadequate

The Model

B.E.T. theory would be generalization

of Langmuirs theory
Main difference would be allowing condensation
on previously adsorbed molecules

The BET model

Si layer

At equilibrium, layer distribution is

Unoccupied adsorption sites
constant
on free surface

S3 layer

S2 layer
S1 layer
S0 layer
S0
S1
S2
S3

Solid surface of sample, Area = 14 units

Free surface:
4 units
Surface occupied by single layer:
4 units
Surface occupied by double layer:
3 units
Surface occupied by triple layer:
3 units
TOTAL SURFACE
14 units

Derivation of the BET equation

Equilibrium and the state
of the bare surface

The rate of adsorption onto the bare surface must

equal the rate of evaporation from the first layer for
S0 to remain constant, therefore
a1PS0 = b1S1e-E1/RT
(Langmuirs equation)
where P is pressure, E1 the heat of adsorption of the first
layer, and a1 and b1 are constants. RT has its usual meaning.

Derivation of the BET equation

Equilibrium and the state of the first layer

The rate of adsorption onto the bare surface must

equal the rate of evaporation from the first layer,
and ...

The rate of adsorption onto the first layer must

equal the rate of evaporation from the second layer,
therefore
a1PS0 + b2S2e-E2/RT= b1S1e-E1/RT+ a2PS1
.

and so through the ith layer.

Derivation of the BET equation

Simplification
Substitution of the S0 expression into the S1
expression yields

b2S2e-E2/RT= a2PS1
with similar substitutions for all layers

biSie-E2/RT= aiPSi-1

Derivation of the BET equation

The total surface area is

A = Si

The total volume adsorbed is

V = V0 iSi

where V0 is the quantity of gas molecules required

to cover a unit area of the surface

From these relations it follows

iSi
V = V
=
Si
AV0 Vm

The assumption which makes the

equation tractable
In order to solve the summation, it must be
assumed that E1.Ei are equal.
This implies that the evaporation-condensation
properties of the molecules in higher layers are
the same as those of the first layer.

The BET equation

V/Vm =

cP
(P0-P){1+(c-1)(P/P0)}

In linear form1
P
=
+
V(P0-P)
Vmc

c-1 P

Vmc P0

Where c is related to the energy of adsorption

BET c-value and the isotherm

Quantity
adsorbed
(V)
c= 1000

c= 100

c= 10

0.1

0.2

P/P0

BET transform
P/V(P0-P)

c-1
slope =
Vmc

1
Vmc
0.05

0.3 P/P0

Single point approximation

Assume that the value of c is sufficiently

large that 1/Vmc 0 (intercept = 0)

A large value of c also implies that c-1 c
With these assumptions, the BET equation
c-1 P
1
P
+
=
Vmc P0
Vmc
V(P0-P)
reduces to
1 P
P
=
Vm P0
V(P0-P)

Application of Langmuir and

BET models
Plotting the linear form of BET or Langmuir
equation allows determination of the
monolayer volume Vm
Knowing Vm allows the number of molecules
to be calculated
Multiplying the number of molecules by the
surface area occupied by each molecule
yields the total surface area of the sample

Instrumentation
FlowSorb 2305
FlowSorb 2310

Single point BET, multi-point

BET/Langmuir with effort

Gemini

Single and multi-point BET, and

Langmuir

ASAP 2020

Single and multi-point BET, and

Langmuir

ASAP 2420

Single and multi-point BET, and

Langmuir

Thickness of adsorbed multimolecular films

BET and Langmuir equations are

employed when the volume of the

monolayer is of primary interest
Neither model adequately reproduces the
isotherm at higher degrees of coverage

Thickness of adsorbed multimolecular films

Various thickness equations were
developed to relate thickness of
adsorbed film to pressure
Harkins and Jura
Halsey (Frenkel-Halsey-Hill)
These equations lead to standard isotherms for
adsorption of specific classes of non-porous solids

Pore filling
Two distinct pore-filling mechanisms
Micropore (<20 diameter) filling
Filling of larger pores
Theories of micropore filling are covered
elsewhere
But, some information about micropores can be
determined without reference to filling mechanism

Using the thickness models to

investigate porosity
Thickness equations apply to non-porous

solids
A direct relation exists between thickness
and specific volume of gas adsorbed (Va/m)
Therefore, thickness equations predict Va
at various pressure for non-porous materials
Plotting experimental data against thickness
equation data yields a straight line for nonporous solids and a deviated line for porous
solids.

Using the thickness models to

investigate porosity- the t-plot
Preparing data for a t-plot

Experimental data
P/P0
Vol. Ads.
0.xxx
xxxxx
0.xxx
xxxxx
0.xxx
xxxxx

Predicted thickness
P/P0
Thickness (t)
0.xxx
xxxxx
0.xxx
xxxxx
0.xxx
xxxxx

Interpolate to produce common values

t-Plot data
Vol. Ads.
t
xxxxx
xxxxx
xxxxx
xxxxx
xxxxx
xxxxx

Using the thickness models to

investigate porosity
t-Plot
Vads

Meso-/macroporous

microporous
Micorpore
volume

Non-porous
Linear region extrapolating to
zero indicates no micropores

Using the thickness models to

investigate porosity
Information derived from t-plot
Y-Intercept equals pore volume
Slope yields external surface area (surface
area not including micropores)

Additional information now available

BET or Langmuir total surface area minus
t-plot external surface area gives micropore
surface area

Determination of
total pore volume
Calculate from total volume adsorbed
Collect isotherm data to pressure near
saturation to assure all pores are filled
Assume that gas volume adsorbed on free
surface is insignificant compared to volume
adsorbed in pores
Convert gas volume adsorbed to liquid
volume in pores

Instrumentation
FlowSorb 2305

Total pore volume, t-Plot with effort, but

not recommended

FlowSorb 2310

Gemini 2365,
2380

Total pore volume, editable Halsey and

Harkins-Jura thickness equations.

ASAP 2020

Total pore volume, editable Halsey and

Harkins-Jura thickness equations

ASAP 2420

Total pore volume, editable Halsey and

Harkins-Jura thickness equations

More information about porosity

Additional information about the pore
geometry is desired.

Pore volume distribution by size

Surface are of pore walls
Pore area distribution
Mean pore diameter
Additional theories and methods are required

Lord Kelvins observations

A capillary pore fills spontaneously with
condensed liquid when a certain relationship
existed between vapor pressures and capillary
diameter

Ln(P*/P0) = -(2 cos )/RTrm

where P* is the critical pressure, rm the radius of
curvature of meniscus, the liquid surface tension,
molar volume of condensed vapor, the contact angle
between solid and condensed phase, and P0, R and T
have their usual meaning.

Film thickness combined with the

Kelvin equation
Condensed film builds on free surface and on pore
t
walls as a function of pressure
r

Effective radius rof pore is less than

r
actual pore radius r by thickness t of adsorbed film
At P* when effective radius of pore equals rm,
center of pore will fill

Film thickness combined with the

Kelvin equation
Filling of the core of the pore
Condensed liquid

Pressure step immediately

prior to reaching critical
pressure

Pressure step at which

pressure equals or
exceeds critical pressure

The BJH calculation method

Begin at high P/P0 value to include large
pores

Data from either the adsorption or

desorption branch of the isotherm may be
used
With each step down isotherm, attribute
volume difference to evaporation of cores
and to evaporation from pore walls

The BJH calculation method

Assumption: pore geometry (typically
cylindrical but other geometries can be used)
Assumed pore geometry will determine how wall
surface area is calculated from pore volume
Define per cent of pores open at both ends since
evaporation mechanism is different in each case

Instrumentation
FlowSorb
2305/2310
Gemini 2380
ASAP 2020
ASAP 2420

BJH possible, but not recommended

Adsorption and desorption isotherms;
BJH computation with editable
Halsey and Harkins-Jura thickness
equations.
Adsorption and desorption isotherms;
BJH computation with editable
Halsey and Harkins-Jura thickness
equations.

Adsorption and desorption isotherms;

BJH computation with editable
Halsey and Harkins-Jura thickness
equations.

Conclusions
Know what the model implies

Assumptions built into theory

Assumptions about pore geometry

Know when the model applies

Over what range of isotherm

To what pore types
To what solid/gas system
Does the transformed experimental data
produce a straight line when plotted

Thank you from Micromeritics USA

The End