SPECTROSCOPY

AGENDA:

A. IR SPECTROSCOPY
B. FTIR SPECTROSCOPY
C. ATTENUATED TOTAL REFLECTANCE
Define spectroscopy
• Spectroscopy is the science of studying the interaction between matter and
radiated energy.

• It's the study of absorption characteristics of matter, or absorption behavior

of matter, when subjected to electromagnetic radiation.
IR(INFRARED) SPECTROSCOPY
Infrared (IR) spectroscopy is a technique that measures the interaction between infrared
radiation and matter. It can be used to study and identify chemical substances or
functional groups in solid, liquid, or gaseous forms
What is Infrared?
 Infrared radiation lies between the visible and microwave portions of the
electromagnetic spectrum.
 Infrared waves have wavelengths longer than visible and shorter than
microwaves, and have frequencies which are lower than visible and higher
than microwaves.
 The Infrared region is divided into: near, mid and far-infrared.
 Near-infrared refers to the part of the infrared spectrum that is closest to
visible light and far-infrared refers to the part that is closer to the
microwave region.
 Mid-infrared is the region between these two.
1. The primary source of infrared radiation is thermal radiation. (heat)
2. is the radiation produced by the motion of atoms and molecules in an
object. The higher the temperature, the more the atoms and molecules
move and the more infrared radiation they produce.
Any object radiates in the infrared. Even an ice cube, emits infrared.
IR SPECTROSCOPY
Range = 0.7-1000 µm = 14000-10 cm^-1
(IR Spectroscopy also known as Vibrational Spectroscopy)
The Near IR
• Higher energy
• 14000-4000 cm^-1 (0.7-2.5 µm)
• Can excite overtone or combination modes of molecular vibration

The mid IR
• 4000-400 cm^-1(2.5-25 µm)
• Used to study the fundamental vibrations are associated Rotational-
Vibrational Structure
The Far IR
• 400-10 cm^-1(25-1000 µm)
• It has low energy and it is Rotational

Wavenumber = 1/Wavelength(in cm)

Classification of Vibrational modes

• Stretching Vibrations - (4000-1250 cm^-1)

• Bending Vibrations – (1400-666 cm^-1)
IR Active And Inactive

What is Dipole Moment?

A dipole moment is a measurement of
the separation of two opposite
electrical charges.
IR spectrum of propan-1-ol
From this Two figures we may
conclude that , Above 1500 cm^-1
The stretches of vibrations were
similar, For the Functional
Groups. Below 1500cm^-1,That
mean
IR Spectrum of Propan-2-ol
In the Fingerprint region The
Vibrations Were Unique
What is Fingerprint Region?
This is a typical infra-red spectrum:
• Each trough is caused because energy is being absorbed from that particular
frequency of infra-red radiation to excite bonds in the molecule to a higher state of
vibration - either stretching or bending. Some of the troughs are easily used to
identify particular bonds in a molecule. For example, the big trough at the left-hand
side of the spectrum is used to identify the presence of an oxygen-hydrogen bond
in an -OH group.
• The region to the right-hand side of the diagram (from about 1500 to 500 cm-1)
usually contains a very complicated series of absorptions. These are mainly due to
all manner of bending vibrations within the molecule. This is called the fingerprint
region.
• It is much more difficult to pick out individual bonds in this region than it is in the
"cleaner" region at higher wavenumbers. The importance of the fingerprint region is
that each different compound produces a different pattern of troughs in this part of
the spectrum.
From The above Figure ,It is clear to understand that

• Frequency of Vibration α Bond Strength

• Frequency of Vibration α 1/atomic mass
• Frequency of Vibration α Energy
Basic IR absorption values
Construction of IR spectrometer
• IR radiation sources like incandescent lamp or Nernst glower or mercury lamp or glower
source to produce intense and steady radiation containing wide range of wavelengths

• A grating monochromator separates the incident beam of infrared radiation of different

frequencies by dispersion

• The detector , identifies the frequencies that are absorbed and the frequencies that are
transmitted

• The signal coming out from the detector is amplified and then recorded as infrared
spectrum
INSTRUMENTATION OF IR
SOURCE – Electrical heating of the source to temperatures in the range 200-1200°C generates IR radiation.
a. Nichrome heating coil wound on ceramic support
b. Nernst glower – a filament made of oxides of zirconium,yttrium,cerium and thorium
c. Globar silicon carbide (carborundum rod)

DOUBLE BEAM – Two equivalent beam of light is generated from the source, one passes through the test sample
and other through the blank/reference

MONOCHROMATOR – The polychromatic light from the sample/reference is dispersed by the monochromator
and reaches the detector
The Transmitted light after being absorbed by the sample dispersed into its component frequencies
e.g. Prism made of NaCl , KCl , Diffraction grating etc.

OPTICAL CHOPPER – The Reference and sample beams are alternatively focused on the detector for optical
comparison of transmitted light of reference and sample. It Reflects or transmits the sample beam alternately
into the monochromator

Detector/transducer
d. Selective detector – e.g Photocell,photoconductive cells or semiconductor devices (mercury-cadmium telluride
detector)
e. Converts the radiation falling on the detector to electric current
• DETECTOR/TRANSDUCER-
• Non-selective detector – thermal detectors that convert thermal radiant energy into temperature sensitive
response.
a. Thermocouple (EMF/voltage changes)
b. Thermistor and bolometer(changes in resistance)
c. Pyroelectric (change in electric polarisation)
d. Pneumatic cell(change in pressure of enclosed gas)
AMPLIFIER (optional) – It is used if the Signal produced by the detector is Weak

RECORDER- Each frequency that passes through the sample is measured individually by the detector which
slows the process of scanning the entire IR range

Applications
I. Identification of unknown compound
II. Determination of the Molecular structure from the absorption peaks
III. Detection of Functional group
IV. Study of the Progress of a reaction
V. Determination of Impurities(it will give extra peaks)
FTIR SPECTROSCOPY
 Difference between FTIR and IR?

Data Acquisition:
IR (Infrared Spectroscopy):
• In traditional IR spectroscopy, a dispersive grating or prism is used to separate infrared
light into its different wavelengths. A detector then measures the intensity of each
wavelength individually as it passes through the sample. This process is time-consuming
because it requires scanning through a range of wavelengths sequentially.

FTIR (Fourier-Transform Infrared Spectroscopy):

• FTIR is a more advanced and modern technique. It employs an interferometer to
simultaneously collect data over a wide range of infrared wavelengths. This interferogram
data is then mathematically transformed using a Fourier algorithm to obtain an IR
spectrum. FTIR is much faster and more sensitive than traditional IR spectroscopy

 The main difference between FTIR and IR spectroscopy lies in the method
of data acquisition and analysis. FTIR is a more advanced and versatile
technique that offers advantages in terms of speed and sensitivity
compared to traditional IR spectroscopy.
• ATTENUATED TOTAL REFLECTANCE

• ATR is based on total internal reflection where infrared (IR) light and sample
interact only at the point where IR light is reflected
• Minimal or no sample preparation
• USES
• For some materials normal sampling techniques are not applicable, For
example,
• Polymer films or foams,
• Fabrics
• Thick pastes
• Coatings such as paint films or paper glazes,
• Printing inks on metal
PRINCIPLE
• Sample is in contact with the ATR Crystal . The IR radiation travels through the crystal and
interacts with the sample on the surface in contact with the ATR Crystal.
• When IR hits the surface between two optical media of two different refractive indices at a
certain angle of incidence, total internal reflection occurs.
• This reflection forms the so called “Evanescent Wave”
Which extends into the sample
• A small part of the IR is absorbed when the evanescent wave interacts with the sample,
resulting in a slightly attenuated(weakened) total reflection
• To obtain total internal reflection , ATR crystal materials must have a higher refractive index
than the tested sample material.
ATR CRYSTAL MATERIALS
ATTENUATED TOTAL REFLECTANCE IN FTIR SPECTROMETERS
• Different ATR accessories are available for FTIR spectrometers
• They can be divided into ATR cells with
1. A single reflection (one bounce) and
2. Cells with multiple reflections (multiple bounce).
SINGLE-BOUNCE ATR CELL
• In this setup the IR beam and the sample interact only once at a single point of
reflection
• Modern FTIR spectrometers with sufficiently large signal-to-noise ratios allow
for reasonable spectra even with only one bounce
• The clear advantage of single-bounce ATR minimal amount of sample needed
for a measurement
• Commonly used for solid samples or powders or whenever only small sample
volumes of liquids are available
MULTIPLE-BOUNCE ATR CELL
• In multiple-bounce ATR cells the IR beam is reflected multiple times
• Each reflection on the ATR crystal’s surface exhibits an evanescent wave which interacts with
the sample
• Since the interactions are independent of one another the absorptions are additive and
• The sensitivity of the recorded spectrum can be increased due to significantly higher signal-
to-noise ratio
• A background spectrum is first recorded, with the empty ATR cell in place, and then the
spectrum with the sample is recorded; subtraction of background from sample is then carried
out as usual

Difference between FTIR and ATR spectroscopy?

• FTIR Spectroscopy: In traditional FTIR spectroscopy, the sample is typically prepared as a thin
film between two transparent plates, pressed into a pellet, or dissolved in a suitable solvent. The
sample is often required to be in a relatively thin and uniform form to obtain high-quality
spectra.

• ATR Spectroscopy: ATR spectroscopy, on the other hand, requires minimal sample preparation.
The sample is placed in direct contact with an ATR crystal, which may be made of materials like
diamond, zinc selenide, or germanium. This eliminates the need for complex sample preparation,
making ATR spectroscopy more convenient for many applications.
Depth of Analysis:
• FTIR Spectroscopy: FTIR provides information about the bulk properties of a sample. It
penetrates deeper into the sample, typically in the order of micrometers to millimeters,
depending on factors like sample thickness and composition.
• ATR Spectroscopy: ATR spectroscopy is a surface-sensitive technique. It probes only a
few micrometers into the sample, making it suitable for analyzing thin films, coatings,
and surface layers.

Sensitivity:
• FTIR Spectroscopy: Traditional FTIR can be less sensitive for some samples, especially
those with weak absorptions. However, this limitation can be mitigated with more
advanced FTIR setups and techniques, such as FTIR microscopy or using specialized
sampling accessories.
• ATR Spectroscopy: ATR spectroscopy is generally more sensitive than traditional FTIR for
samples that have weak IR absorptions because it enhances the interaction of light with
the sample at the ATR crystal interface.
Sample Compatibility:
• FTIR Spectroscopy: FTIR can analyze a wide range of sample types, including liquids,
gases, and solids. It is particularly well-suited for the analysis of liquid and gas
samples.
• ATR Spectroscopy: ATR is most commonly used for solid or semi-solid samples, but it
can also be applied to liquids. It is not as well-suited for analyzing gases.
Instrumentation:
• FTIR Spectroscopy: FTIR instruments can vary in complexity from simple benchtop
devices to high-end research-grade spectrometers. They use interferometers to
measure the interference patterns produced by the sample and reference beams.
• ATR Spectroscopy: ATR attachments can be added to existing FTIR instruments to
enable ATR spectroscopy. The ATR crystal is an essential component of the setup.
CONCLUSION
I. FTIR and ATR spectroscopy are both valuable techniques for analyzing the IR spectra
of materials, but they are suited to different types of samples and provide different
information.
II. FTIR is more versatile and penetrates deeper into samples, while ATR is simpler in
sample preparation and provides surface-specific information. Researchers choose
between them based on their specific analytical needs and the nature of the samples
they are studying.