THE UNIVERSITY OF DODOMA

CH 3107

MATERIAL SCIENCE
 BET

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INTRODUCTION
 BET is acronym representing names of three
Co-founders;-Stephen Brunauer, P.H. Emmet
and Edward Teller.
 This is the latest adsorption isotherm
developed in 1938 , the former ones being
Linear isotherm (…..resembling Henry’s law),
Freundlich isotherm, and Langmuir isotherm.
 Different from Langmuir isotherm which
advocate on monolayer adsorption, BET
isotherm advocates on multi-layer
adsorption.
 Thus, in BET isotherm adsorbate molecules
are considered to adsorb upon other
adsorbate molecules to form many layers.
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Cont…..

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cont…
 Generally, adsorption is experimentally
characterized by measuring the amount
of the substance being adsorbed against
the pressure of the substance
 And the dependence of the adsorption
degree Γ on gas pressure, [Γ = f(p) at
const T ]is known as the adsorption
isotherm.
NB:-BET is the first, accurate, precise and
proper method to measure the surface
area and porosity solids materials
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OPERATION PRINCIPLE
The BET method is based on
adsorption of gas on a surface.
Since adsorption is a surface
phenomena, and because the
surface area of a solid material
is equal to the total surface of
the sample that is in contact
with the external environment.
Then, specific surface area of
the sample can be determined
by physical adsorption of a gas
on the surface of the solid
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Cont……
 Usually, the amount of adsorbate gas
corresponding to a monomolecular
layer on the surface at a given pressure
is measured and used to determine the
surface area.
 Thus, by filling the first layer surface
area of the material can be determined.
EXPLANATION:- because the amount of
gas adsorbed when the mono-layer is
saturated is proportional to the entire
surface area of the sample

 This parameter(surface area) can

strongly be related to the pore size and
the pore volume 02/09/2025 Marwa Emmanuel 7
SURFACE&SAMPLE PREPARATION
 The major activity during surface preparation
is outgassing (….removal of gases)
 Thus, before the specific surface area of the
sample can be determined, it is necessary to
remove gases and vapours adsorbed onto the
surface during manufacture, treatment,
handling and storage.
EXPLANATION:-
 Because if outgassing is not achieved, the
specific surface area may be reduced or may
be varied since intermediate area of the
surface is covered with molecules of the
previously adsorbed gases or vapours.
 Therefore, outgassing conditions is critical for
obtaining the required precision and accuracy
of specific surface area measurements.
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Cont……
 Outgasing Conditions:. The outgassing process
should be carried out under defined conditions
of temperature, pressure and time .
 EXPLANATION:-So as to yield reproducible and
more perfect BET plots, to ensure constant
weight of test sample, and no detectable
physical or chemical changes in the test sample.
 Method of outgassing:- Outgassing of many
substances is oftenly achieved by;-
 Applying a vacuum.
 Purging the sample by flowing a stream of a
non-reactive, and dry gas.
 Applying a desorption-adsorption cycling
method.
NB:- In either case, elevated temperature is
sometimes applied to increase the rate at which
the contaminants leave the surface.
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Cont….
 The commonly used adsorbate
gas is nitrogen which is
admitted into the evacuated
space
 To give a defined equilibrium
pressure, P, of the gas.
 The nitrogen gas used is made
in and bought from industries
 Also noble gases, such as
helium , argon etc may be
employed for other purposes.
E.g.to measure02/09/2025
the Marwa
dead volume.10
Emmanuel
OPERATION PROCEDURES
(i).Admit a small amount of dry
nitrogen into the sample tube
 To prevent contamination of the
cleaned surface.
(ii).Remove the sample tube, insert
the stopper, and weigh it.
(iii).Calculate the weight of the
sample.
(iv).Attach the sample tube to the
volumetric apparatus
(v).Cautiously evacuate the sample
down to the specified pressure .
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Cont…
(iv). Raise a Dewar vessel containing liquid
nitrogen at a specified temperature.
 To determine the amount of adsorbed
nitrogen gas
(v).Admit a sufficient volume of adsorbate
gas
 To give the lowest desired relative
pressure
(vi).Then measure the volume adsorbed, Va.

NB:-For multi-point measurements, repeat

the measurement of Va at successively
higher P/Po values.

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Equipment
(FYI)

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BET-internal structure

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DETERMINATION OF SURFACE AREA
BY BET
The surface area of a solid material is
the total surface of the sample that is
in contact with the external
environment.
It is expressed in square meters per
gram of dry sample.
Depending on the number of data
point required, two(2) approaches can
be used in determining the surface
area namely;-
(a). Mult-point measurement
(b). Single point measurement
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 (a).MULTI-POINT
MEASUREMENTS
By this technique a minimum of
3 data points is required.
And the data obtained are
treated according to the BET
adsorption isotherm equation:

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Cont……
Where
P=partial vapor pressure of adsorbate gas in
equilibrium with the surface at 77.4 K (B.P. of
nitrogen), in paschal
Po=saturated pressure of adsorbate gas, in
pascals,
Va=volume of gas adsorbed at standard
temperature and pressure (STP) [273.15 K and
atmospheric pressure (1.013 × 105 Pa)], in
milliliters
Vm=volume of gas adsorbed at STP to produce an
apparent monolayer on the sample surface, in
milliliters,
C=dimensionless constant that is related to the
enthalpy of adsorption of the adsorbate gas on
the powder sample. 02/09/2025 Marwa Emmanuel 17
Cont……
 Then, the BET value:

from the eqn. above is plotted

against P/Po .
 This plot should yield a straight line with
 Slope = (C − 1)/VmC, and
 Intercept= 1/VmC,

Which are evaluated by linear regression

analysis.

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Cont…..
 From these values, Vm and C can be
computed.
 Vm is calculated by using the
formula;-

Vm= 1/(slope + intercept)

C is calculated by using the formula

C= [slope/intercept] + 1
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 Experimental Data:

EXAMPLE:-Multipoint BET
Data
No Relative pressure, Volume@STP, 1 / [ W((Po/P) - 1) ], g-1
P/P0 cc/g

1 1.10536e-01 7.5355 1.3195e+01

2 1.53021e-01 8.1192 1.7804e+01

3 1.99422e-01 8.7403 2.2803e+01

4 2.48028e-01 9.4102 2.8045e+01

5 2.97227e-01 10.1099 3.3472e+01

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Multipoint BET Plot

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Cont…..
From the plot BET summary is obtained:

Slope = 108.451

Intercept = 1.195e+00

Correlation coefficient, r = 0.99999

C = 91.759
Surface Area = 31.762 m²/g

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(B).SINGLE POINT
MEASUREMENT
 Under certain circumstances, it may be
acceptable to determine the specific
surface area of a sample from a single
value of Va measured at a single value of
P/Po.
 But normally, at least 3 measurements of
Va, each at different values of P/Po are
required for the determination of specific
surface area.
 Due to the errors associated with the
single-point method the multi-point
method can be used to evaluate and
hence reduce or eliminate those errors.
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 Cont…..
The single point measurements
starts by determination of Vm
from the single value of Va
measured at a single value of
P/Po by the equation:-

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Cont…..
Then, Vm calculated from by
equation above is used to
determine specific surface
area by the equation:-

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 DETERMINATION OF
 Many
POROSITY
solid and powder materials contain a
certain void volume of empty space.
 This is distributed within the solid mass in
the form of pores, of various shapes and
sizes.
 The total sum of the void volume is called
porosity.
 The surface area is strongly related to the
pore size and the pore volume
 Thus, "the larger the pore volume the
larger the surface area and the smaller the
pore size the higher the surface area and
vice versa”.
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Cont…..
 The characterization of solids
samples in terms of porosity by BET
involve determination the following
parameters.
i).Pore size-this cover a very wide
range.
 Depending on their size Pores can be
classified into three(3) main groups
namely:
 Micropores: less than 2 nm diameter
 Mesopores: between 2 and 50 nm
diameter
 Macropores: larger02/09/2025
than Marwa
50Emmanuel
nm 27
 Cont……
iii).Percentage porosity-represented
by ratio between the total pore
volume and the external (envelope)
sample volume multiplied by 100.
NB:- Alternatively, parameters
related to porosity can be
determined by sample porometer
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 SAMPLE POROMETER

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MERITS OF BET
 It is cheap
 Fast and reliable method
 It is a key instrument in nanotechnology
 It is very well understood and applicable
in many fields such as
 Pharmaceuticals
 Catalysts
 Projectile propellants
 Medical implants
 Filters
 Cements

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DEMERITS OF BET
 Not applicable to all types of
isotherms
 Need much expertise

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 FOURIER TRANSFORM INFRARED
SPECTROSCOPY (FTIR)

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 Fourier Transform Infrared (FTIR)
Spectroscopy
• FT-IR is the preferred method of infrared spectroscopy and is growing in
popularity for the multi component analysis of stack gases.
• It produces a infrared spectrum with a unique combination of bands
corresponding to an individual species, creating a distinct fingerprint for the
sample.

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 What is FTIR?
 The heart of the system is the
interferometer in which the light from
the source is divided into two
beams.

 Beams pass through the sample cell

and then recombine resulting in a
signal.

 All information required to identify

and quantify the gases in the sample
is present in the interferogram.

 Interferogram signal is converted to

a frequency spectrum by a
mathematical technique called
Fourier Transformation. A Typical Interferogram.

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 Introduction
• Absorption peaks in an infrared absorption
spectrum arise from molecular vibrations
• Absorbed energy causes molecular motions which
create a net change in the dipole moment.

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 What is FTIR
• Fourier-transform infrared spectroscopy is a
vibrational spectroscopic technique, meaning it takes
advantage of asymmetric molecular stretching,
vibration, and rotation of chemical bonds as they are
exposed to designated wavelengths of light.
• Fourier transform is to transform the signal from the
time domain to its representation in the frequency
domain

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 Theory and Instrumentation

• Light enters the spectrometer and is split by the beam splitter. The
figure above shows what is referred to as the Michelson interferometer

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 Theory and Instrumentation(contd.)
• Animation to demonstrate the process
• The light originates from the He-Ne laser
• Half of the light is reflected 90 degrees and hits a
fixed mirror, while the other half passes through
the beam splitter and hits the moving mirror
• The split beams are recombined, but having
traveled different distances, they exhibit an
interference pattern with each other
• As they pass through the sample, the detector
collects the interfering signals and returns a plot of
response v.(through) mirror displacement known
as an interferogram
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 Measurement Techniques
Though some emission spectroscopy is done most of the
work is in the absorption spectra area using FTIR.
1. If there is no sample present the spectrum is that of a
black body radiator modified by any transmission
characteristics of the interferometer components.
2. If the interferometer chamber is not evacuated or
purged with dry gas some absorption from the
atmospheric Co2 and H20 is observed. This is called the
background spectrum.
3. When the sample is introduced the spectrum now is a
superposition of the absorption bands of the sample on an
uneven background.
4. To obtain %T with wavenumber we ratio the single
beam sample spectrum with the background spectrum.

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 OPERATION PROCEDURES
Infrared radiation is largely thermal energy.
It induces stronger molecular vibrations in covalent bonds, which can
be viewed as springs holding together two masses, or atoms.

Specific bonds respond to (absorb) specific frequencies

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 VIBRATIONAL MODES
• Covalent bonds can vibrate in several modes, including stretching,
rocking, and scissoring.
• The most useful bands in an infrared spectrum correspond to
stretching frequencies, and those will be the ones we’ll focus on.

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 TRANSMISSION vs. ABSORPTION
When a chemical sample is exposed to the action of IR LIGHT, it can
absorb some frequencies and transmit the rest. Some of the light can
also be reflected back to the source.

Transmitted light
IR Chemical
Detector
source sample

From all the frequencies it receives, the chemical sample

can absorb (retain) specific frequencies and allow the
rest to pass through it (transmitted light).

The detector detects the transmitted frequencies, and by doing so also reveals the
values of the absorbed frequencies.

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 AN IR SPECTRUM IN ABSORPTION MODE
The IR spectrum is basically a plot of transmitted (or absorbed) frequencies
vs. intensity of the transmission (or absorption). Frequencies appear in the
x-axis in units of inverse centimeters (wavenumbers), and intensities are
plotted on the y-axis in percentage units.

The graph above shows a spectrum in absorption mode.

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 AN IR SPECTRUM IN TRANSMISSION MODE

The graph above shows a spectrum in transmission mode.

This is the most commonly used representation and the one found in most
chemistry and spectroscopy books. Therefore we will use this representation.
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 CLASSIFICATION OF IR BANDS
IR bands can be classified as strong (s), medium (m), or weak (w),
depending on their relative intensities in the infrared spectrum. A strong
band covers most of the y-axis. A medium band falls to about half of the
y-axis, and a weak band falls to about one third or less of the y-axis.

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 INFRARED ACTIVE BONDS
Not all covalent bonds display bands in the IR spectrum. Only polar
bonds do so. These are referred to as IR active.
The intensity of the bands depends on the magnitude of the dipole
moment associated with the bond in question:
• Strongly polar bonds such as carbonyl groups (C=O) produce strong
bands.
• Medium polarity bonds and asymmetric bonds produce medium
bands.
• Weakly polar bond and symmetric bonds produce weak or non
observable bands.

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 INFRARED BAND SHAPES
Infrared band shapes come in various forms. Two of the most common
are narrow and broad. Narrow bands are thin and pointed, like a
dagger. Broad bands are wide and smoother.

A typical example of a broad band is that displayed by O-H bonds,

such as those found in alcohols and carboxylic acids, as shown
below.

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 INFORMATION OBTAINED FROM IR SPECTRA

• IR is most useful in providing information about the presence or

absence of specific functional groups.

• IR can provide a molecular fingerprint that can be used when

comparing samples. If two pure samples display the same IR
spectrum it can be argued that they are the same compound.

• IR does not provide detailed information or proof of molecular

formula or structure. It provides information on molecular fragments,
specifically functional groups.

• Therefore it is very limited in scope, and must be used in conjunction

with other techniques to provide a more complete picture of the
molecular structure.

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 IR ABSORPTION RANGE
The typical IR absorption range for covalent bonds is 600 - 4000 cm-1. The graph
shows the regions of the spectrum where the following types of bonds normally
absorb. For example a sharp band around 2200-2400 cm-1 would indicate the
possible presence of a C-N or a C-C triple bond.

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 THE FINGERPRINT REGION
Although the entire IR spectrum can be used as a fingerprint for the purposes of
comparing molecules, the 600 - 1400 cm-1 range is called the fingerprint region.
This is normally a complex area showing many bands, frequently overlapping each
other. This complexity limits its use to that of a fingerprint, and should be ignored by
beginners when analyzing the spectrum. As a student, you should focus your
analysis on the rest of the spectrum, that is the region to the left of 1400 cm -1.

Focus your analysis on this region. This is where most stretching Fingerprint region: complex and difficult to
frequencies appear. interpret reliably.

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 FUNCTIONAL GROUPS AND IR TABLES

The remainder of this presentation will be focused on the IR

identification of various functional groups such as alkenes, alcohols,
ketones, carboxylic acids, etc. Basic knowledge of the structures and
polarities of these groups is assumed.

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 IR SPECTRUM OF ALKANES
Alkanes have no functional groups. Their IR spectrum displays only C-C and C-H
bond vibrations. Of these the most useful are the C-H bands, which appear
around 3000 cm-1. Since most organic molecules have such bonds, most organic
molecules will display those bands in their spectrum.

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 IR SPECTRUM OF ALKENES
Besides the presence of C-H bonds, alkenes also show sharp, medium bands
corresponding to the C=C bond stretching vibration at about 1600-1700 cm-1.
Some alkenes might also show a band for the =C-H bond stretch, appearing
around 3080 cm-1 as shown below. However, this band could be obscured by the
broader bands appearing around 3000 cm-1 (see next slide)

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 IR SPECTRUM OF ALKENES
This spectrum shows that the band appearing around 3080 cm-1 can be obscured
by the broader bands appearing around 3000 cm-1.

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 IR SPECTRUM OF ALKYNES
The most prominent band in alkynes corresponds to the carbon-carbon
triple bond. It shows as a sharp, weak band at about 2100 cm-1. The
reason it’s weak is because the triple bond is not very polar. In some
cases, such as in highly symmetrical alkynes, it may not show at all due to
the low polarity of the triple bond associated with those alkynes.

Terminal alkynes, that is to say those where the triple bond is at the end of
a carbon chain, have C-H bonds involving the sp carbon (the carbon that
forms part of the triple bond). Therefore they may also show a sharp, weak
band at about 3300 cm-1 corresponding to the C-H stretch.

Internal alkynes, that is those where the triple bond is in the middle of a
carbon chain, do not have C-H bonds to the sp carbon and therefore lack
the aforementioned band.

The following slide shows a comparison between an unsymmetrical

terminal alkyne (1-octyne) and a symmetrical internal alkyne (4-octyne).
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 IR SPECTRUM OF ALKYNES

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 IR SPECTRUM OF A NITRILE
In a manner very similar to alkynes, nitriles show a prominent band around 2250
cm-1 caused by the CN triple bond. This band has a sharp, pointed shape just
like the alkyne C-C triple bond, but because the CN triple bond is more polar, this
band is stronger than in alkynes.

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 IR SPECTRUM OF AN ALCOHOL
The most prominent band in alcohols is due to the O-H bond, and it appears as a
strong, broad band covering the range of about 3000 - 3700 cm-1. The sheer size
and broad shape of the band dominate the IR spectrum and make it hard to miss.

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IR SPECTRUM OF ALDEHYDES AND KETONES
Carbonyl compounds are those that contain the C=O functional group. In
aldehydes, this group is at the end of a carbon chain, whereas in ketones it’s in
the middle of the chain. As a result, the carbon in the C=O bond of aldehydes is
also bonded to another carbon and a hydrogen, whereas the same carbon in a
ketone is bonded to two other carbons.

Aldehydes and ketones show a strong, prominent, stake-shaped band around

1710 - 1720 cm-1 (right in the middle of the spectrum). This band is due to the
highly polar C=O bond. Because of its position, shape, and size, it is hard to
miss.

Because aldehydes also contain a C-H bond to the sp2 carbon of the C=O bond,
they also show a pair of medium strength bands positioned about 2700 and 2800
cm-1. These bands are missing in the spectrum of a ketone because the sp2
carbon of the ketone lacks the C-H bond.

The following slide shows a spectrum of an aldehyde and a ketone. Study the
similarities and the differences so that you can distinguish between the two.
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IR SPECTRUM OF ALDEHYDES AND KETONES

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 IR SPECTRUM OF A CARBOXYLIC ACID
A carboxylic acid functional group combines the features of alcohols and ketones
because it has both the O-H bond and the C=O bond. Therefore carboxylic acids
show a very strong and broad band covering a wide range between 2800 and
3500 cm-1 for the O-H stretch. At the same time they also show the stake-shaped
band in the middle of the spectrum around 1710 cm-1 corresponding to the C=O
stretch.

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 IR SPECTRA OF AMINES
The most characteristic band in amines is due to the N-H bond stretch, and it appears as a
weak to medium, somewhat broad band (but not as broad as the O-H band of alcohols). This
band is positioned at the left end of the spectrum, in the range of about 3200 - 3600 cm-1.

Primary amines have two N-H bonds, therefore they typically show two spikes that make this
band resemble a molar tooth. Secondary amines have only one N-H bond, which makes
them show only one spike, resembling a canine tooth. Finally, tertiary amines have no N-H
bonds, and therefore this band is absent from the IR spectrum altogether. The spectrum
below shows a secondary amine.

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 IR SPECTRUM OF AMIDES
The amide functional group combines the features of amines and ketones because
it has both the N-H bond and the C=O bond. Therefore amides show a very
strong, somewhat broad band at the left end of the spectrum, in the range between
3100 and 3500 cm-1 for the N-H stretch. At the same time they also show the
stake-shaped band in the middle of the spectrum around 1710 cm-1 for the C=O
stretch. As with amines, primary amides show two spikes, whereas secondary
amides show only one spike.

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 Advantages and Disadvantages of FTIR
 Advantages
 Analysers capable of measuring 50
determinants.
 Fewer interferences than IR
 Does not require frequent calibration.
 Typically have a range of 2.5 to 25 µm.

 Disadvantages
 Difficulty in obtaining a
representative background
 Generation of large amounts of
data from inferograms when Real time FTIR analyzer: supplied by
continuous emission monitoring Applitek, Venecoweg, 199810
Nazareth, Belguim.

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 Applications
Applications are vast and diverse.Some of them are

•Compositional analysis of organic, inorganic and polymers

•Biological and biomedical fields, like detection of water in
biological membranes
•Analysis of Aircraft exhausts
•Measurement of toxic gas in fuels
•Combustion
•Gas analysis
• and lots more

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THANK YOU

THE END

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