FT-IR Spectroscopy

FTIR
 FT-IR stands for Fourier Transform Infra Red, the
preferred method of infrared spectroscopy
 A technique used to determine qualitative and
quantitative features of IR-active molecules in
organic or inorganic solid, liquid or gas samples
 It is a rapid and relatively inexpensive method for
the analysis of solids that are crystalline,
microcrystalline, amorphous, or films
 Another advantage of the IR technique is that it
also can provide information about the “light
elements” (e.g., H and C) in inorganic substances

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What is FT-IR?
◦ In infrared spectroscopy, IR radiation is passed
through a sample. Some of the infrared
radiation is absorbed by the sample and some
of it is passed through (transmitted)
◦ The resulting spectrum represents the
molecular absorption and transmission, creating
a molecular fingerprint of the sample
◦ Like a fingerprint no two unique molecular
structures produce the same infrared spectrum
◦ This makes infrared spectroscopy useful for
several types of analysis

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 FT-IR Spectroscopy

Fourier Transform Infrared Spectroscopy

Utilizes
IR light to determine the chemical
composition of a sample (qualitative)

Wavelength of absorbance related to the

inter-molecular bonding
◦ C-C, C-H, C-O, C=O, C-N, O-H bonds have
different absorbance wavelengths

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 What information can FT-IR provide?

It can identify unknown materials

It can determine the quality or consistency
of a sample
It can determine the amount of
components in a mixture

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FTIR
 It is a non-destructive technique
 It provides a precise measurement method which
requires no external calibration
 It can increase speed, collecting a scan every
second
 It can increase sensitivity – one second scans can
be co-added together to ratio out random noise
 It has greater optical throughput
 It is mechanically simple with only one moving part

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Components of FTIR

1. Source
2. Michelson Interferometer
3. Sample
4. Detector

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1. Sources
 Black body radiators
 Inert solids
◦ Resistively heated to 1500-2200 K
 Max radiation
◦ Between 5000-5900 cm-1 (2-1.7 mm), falls off to
about 1 % max at 670 cm-1 (15 mm)
 Nernst Glower
◦ Cylinder made of rear earth elements
 (composed of a mixture of certain oxides
such as zirconium oxide (ZrO2), yttrium oxide
(Y2O3) and erbium oxide (Er2O3) at a ratio of
90:7:3 by weight)
 Globar- SiC rod (silicon carbide)
 CO laser
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 Hg arc (Far IR)
◦ Tungsten filament (Near IR) 9
Sources
 The most common type of IR source used in
laboratories is a filament held at high temperature
 The type of filament used in the source depends on
the infrared range of interest
 Globar sources are versatile because they cover a wide
energy (wave number) range, producing radiation in the
far to near-IR (~9600 - 50 cm-1; ~1-200 m)
 Quartz halogen sources are used for near-visible IR
applications (~27 000-2000 cm-1; ~0.4-5 m)

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Sources
 In synchrotron-based IR, the electrons are
accelerated around a storage ring and may be
pulsed at tens of picoseconds to nanoseconds
 In free electron laser (FEL) sources, the electrons
are accelerated over short distances by a spatially
varied magnetic field and then several micro-
beams are added to create the radiation used for
analysis

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 2. Michaelson Interferometer

 1014 Hz is too fast for P to be directly measured as

a function of time
 Can not measure the FID signal directly
 Interferometer creates a replicate interference
pattern at a frequency that is a factor of 1010
times slower
 104-105 Hz can be measured electronically

f = (2vm/c)n = 10-10n, vm = 1.5 cm/s

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 2. Michaelson Interferometer…
 Parts

1) Beam splitter
2) Stationary mirror
3) Moving mirror at constant velocity
4) Motor driven Micrometer screw
5) He/Ne laser; sampling interval, control mirror
velocity

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 The beam splitter splits the source radiation with
wavelength  into two beams
 After which, one beam is reflected by a stationary
mirror with a fixed path length (represented by
wavelength ) and the other beam is reflected by a
moving mirror that moves over a distance A
 The moving mirror reflects the second beam with a
specific phase with respect to the first beam, and
the phase changes as a function of mirror position.
The difference in the path lengths is called the
optical path difference
 The mirror location at which both beams travel the
same path length is known as the zero path
difference(ZPD)
 The two beams are recombined at the beam
splitter and then interfere constructively and
destructively 14
 Different beam splitters are sensitive over certain
spectral ranges within the infrared region
 Common beam splitters are Mylar (far-IR), Ge-
coated KBr or CaF2 (mid-IR), and Si (near-IR)
 The interferogram is most intense at the ZPD
where the greatest amount of constructive
interference occurs and this area is known as the
centerburst
 The interferogram is typically converted to the
frequency domain using a Fourier Transform to
produce an infrared spectrum of intensity versus
energy in wavenumber or wavelength
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 Stationary mirror

HeNe laser
Beam Splitter

Source
Moving mirror

PMT

Sample

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 3. Sample
 Sample holder must be transparent to IR-
salts
 Liquids
◦ Salt Plates
◦ Neat, 1 drop
◦ Samples dissolved in volatile solvents- 0.1-
10%
 Solids
◦ KBr pellets
◦ Mulling (dispersions)
 Quantitative analysis-sealed cell with
NaCl/NaBr/KBr windows
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 4. Detector
I. Transducers
◦ The heating effect of radiation
II. Thermal transducer- black body, small,
very low heat capacity- DT=10-3 K,
housed in vacuum, signal is chopped
III. Thermocouples
◦ Two junctions of dissimilar metals, An and Bi
◦ One is IR detector, one is reference detector
◦ Potential difference that develops in
proportional to DT; detection of DTs of 10-6 K
is possible
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FT-IR Detectors
a. Pyroelectric tranducers
• Crystalline materials whose electric polarization
depends on temperature
• Changing temperature → change in charge
distribution → current
• Deuterated Triglycine Sulfate - DTGS
b. Photoconductive Detectors
• Semiconductor-based
• Thermal energy can promote e- from valence to
conduction band
• Fast response, susceptible to thermal noise
• Liquid Nitrogen Cooled
• Mercury Cadmium Telluride (MCT), Indium
Antinomide (InSb)
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The Sample Analysis Process
1. The Source: Infrared energy is emitted from a glowing
black-body source. This beam passes through an
aperture which controls the amount of energy presented
to the sample (and, ultimately, to the detector).
2. The Interferometer: The beam enters the
interferometer where the “spectral encoding” takes place.
The resulting interferogram signal then exits the
interferometer.
3. The Sample: The beam enters the sample compartment
where it is transmitted through or reflected off of the surface
of the sample, depending on the type of analysis being
accomplished. This is where specific frequencies of energy,
which are uniquely characteristic of the sample, are
absorbed.

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 The Sample Analysis Process…

4. The Detector: The beam finally passes to the

detector for final measurement. The detectors used are
specially designed to measure the special interferogram
signal.
5. The Computer: The measured signal is
digitized and sent to the computer where the Fourier
transformation takes place. The final infrared spectrum
is then presented to the user for interpretation and any
further manipulation.

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FT-IR

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Advantages of FT-IR
 Speed: Because all of the frequencies are
measured simultaneously, most measurements by
FT-IR are made in a matter of seconds rather than
several minutes. This is sometimes referred to as
the Felgett Advantage.
 Sensitivity: Sensitivity is dramatically improved
with FT-IR for many reasons. The detectors
employed are much more sensitive, the optical
throughput is much higher (referred to as the
Jacquinot Advantage) which results in much lower
noise levels, and the fast scans enable the
conddition of several scans in order to reduce the
random measurement noise to any desired level
(referred to as signal averaging) 23
Advantages of FT-IR

 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 HeNe laser as an internal wavelength
calibration standard (referred to as the Connes
Advantage). These instruments are self-
calibrating and never need to be calibrated by
the user.

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