FTIR- Fourier Transform Infrared Spectroscopy

M.Sc. Chemistry Practical Inorganic

Chemistry (Paper- 4106)
Semester- IV

Dr. Neeraj Kumar and Dr. Sanjay Kumar Saroj

Inorganic Group- II

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 Introduction

Spectroscopy is the study of the interaction

between matter and electromagnetic spectrum.

 Electromagnetic radiation displays the properties of both

particles and waves.

 The particle component is called a photon.

 The energy (E) component of a photon is proportional to the

frequency. Where h is Planck’s constant and n is the frequency
in Hertz (cycles per second)
E = hn
also E=hc/λ
Infrared spectroscopy (IR spectroscopy) is the spectroscopy that
deals with the infrared region of the electromagnetic spectrum.

Frequency, n in Hz
~1019 ~1017 ~1015 ~1013 ~1010 ~105

Wavelength, l
~.0001 nm ~0.01 nm 10 nm 1000 nm 0.01 cm 100 m

g-rays X-rays UV IR Microwave Radio

nuclear core electronic molecular molecular Nuclear Magnetic
excitation electron excitation vibration rotation Resonance NMR
(PET) excitation (p to p*) (MRI)
(X-ray
cryst.)

Visible
IR spectroscopy is an absorption technique.
Absorption of infrared radiation brings about changes in molecular
vibrations within molecules. So, it is a kind of vibrational spectroscopy.

The frequency at which a particular bond absorbs infrared radiation

will be different over a range of bonds and modes of vibration depending
on atom size, bond length and bond strength.

Hookes' Law
 When can absorption occur?

1. Infrared absorption only occurs when infrared radiation interacts with

a molecule undergoing a permanent change in dipole.

2. Infrared absorption only occurs when the incoming infrared photon

has sufficient energy for the transition to the next allowed vibration
energy state.

If these two rules are not met ,no absorption can occur.

 N2 or O2 has no infrared spectrum (no dipole change).

 CO does have.
 Vibration Types

• There are two different types of vibrational modes.

Vibrations can either involve a change in bond length

(stretching) or bond angle (bending).

Stretching Vibrations Bending vibrations

 Vibrational Modes

1.Stretching – Vibration or oscillation along the line of the bond.

H H
C C
H H

symmetric asymmetric

2.Bending – Vibration or oscillation not along the line of the bond.

H H H H
C C C C
H H H
H
twist wag
scissor in plane rock out of plane

n Asym  n Sym  n Bending

 What is FTIR

 Fourier-transform infrared spectroscopy is a less intuitive

way to obtain the information.
 Rather than shining a monochromatic beam of light at the
sample, this technique shines a beam containing many
frequencies of light at once and measures how much of
that beam is absorbed by the sample.
 Fourier transform is to transform the signal from the time
domain to its representation in the frequency domain.
 All FTIR spectrometers are based on the Michelson
Interferometer.
Instrumentation
 Components of FTIR

IR Source Sample
compartment Detector
 IR source
Nernst Glower heated rare earth oxide rod 1-50 µm
(~1500 K) (mid- to far-IR)

Globar heated SiC rod (~1500 K) 1-50 µm

(mid- to far-IR)

Tungsten filament 1100 K 0.78-2.5 µm

lamp (Near-IR)

Hg arc lamp plasma 50 - 300 µm

(far-IR)

CO2 laser stimulated emission lines 9-11 µm

 The Sample Analysis Process

Interferogram : intensity vs time

after the Fourier transformation: intensity vs frequency:-an IR
spectrum
 Theory and Instrumentation
 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 known as an
interferogram.
 Stationary mirror

HeNe laser
Beam Splitter

Source
Moving mirror

PMT

Sample

Detector
 Optical Diagram of
Michelson Interferometer

Light He-Ne gas laser

source

Beam splitter Interferogram

Movable mirror

Sample chamber

DLATGS (deuterated L-
alanine doped triglycene
Fixed mirror sulphate)
Detector
Interferometer
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 Interference Of Two Frequencies
Movable mirror

Fixed mirror
Movable mirror l
Same-phase -2l -l 0 2l

Continuous phase shift

Fixed mirror
Movable mirror Opposite-phase

Signal strength
Fixed mirror
Movable mirror
Same-phase -2l -l 0 l 2l
0 l
Interference pattern of light manifested by the optical-path difference
Detectors
The beam finally passes to the detector

 Thermal detectors
•Thermocouples
•Bolometer

Photoconducting detectors
• most sensitive detectors.

Pyroelectric detectors
• much faster response time
• insulator material
• Triglycine sulphate
Absorption Regions
 Advantages of FT-IR
Speed Because all of the frequencies are measured simultaneously.

• Sensitivity is dramatically improved with FT-IR ; detectors are much

more sensitive,higher signal to noise ratio.

• Mechanical Simplicity The moving mirror in the interferometer is the

only continuously moving part in the instrument. Thus, there is very
little possibility of mechanical breakdown.

• Internally Calibrated These instruments employ a He-Ne laser as an

internal wavelength calibration standard .These instruments are self-
calibrating and never need to be calibrated by the user.

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 Disadvantages of FTIR
 Cannot detect atoms or monoatomic ions - single atomic
entities contain no chemical bonds.

 Cannot detect molecules comprised of two identical

atoms -such as N2 or O2.

 Aqueous solutions are very difficult to analyze- water is a

strong IR absorber.

 Complex mixtures - samples give rise to complex spectra.

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 Applications of FT-IR
Pharmaceutical research
Forensic investigations
Polymer analysis
Foods research
Quality assurance and control
Environmental and water quality analysis
methods
Biochemical and biomedical research
coatings and surfactants
 References
• Instrumental Methods of Analysis, Willard et al, 4th edition, CBS
Publishers and Co.

• Fourier Transform Infrared Spectroscopy, Peter R. Griffiths, 2nd

edition, John Wiley & Sons.

• http://www.photonics.com/Category.aspx?CatID=38300

• http://mtweb.mtsu.edu/nchong/Spectroscopy-CHEM6230.pdf

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