INFRARED

SPECTROMETRY
Introduction

 The infrared region of the spectrum

encompasses radiation with wavenumbers
ranging from about 12,800 to 10 cm-1 or
wavelengths from 0.78 to 1000 m.
 The infrared spectrum is divided into near-,
mid-, and far-infrared radiation.
Electromagnetic radiation
IR spectral regions
IR spectral regions
 Near IR:
 Photometers and spectrophotometers are used.
 This region is mainly used for quantitative analysis of
industrial and agricultural materials and for process
control.
 Mid IR:
 Until1980’s dispersive type instruments were used and
they used diffraction grating.
 Now – majority of instruments are Fourier Transform
type.
IR spectral regions
 Uses of mid IR
 Composition of gases and atmospheric contaminants
 Qualitative organic analysis

 Structure determination based on absorption spectra

 Quantitative analysis of complex samples by both

absorption and emission spectrometry
 For microscopic studies of surfaces

 Analysis of solids by attenuated total reflectance and

diffuse reflectance
 Photoacoustic measurement
IR spectral regions
 Far IR:
 In the past this region had limited use
 The few sources of this type of radiation are
notoriously weak
 Useful for inorganic studies

 Far IR studies of inorganic solids provide useful

information about lattice energies of crystal and
transition energies of semiconducting materials
 THEORY OF INFRARED
ABSORPTION SPECTROMETRY
Theory of infrared absorption spectrometry

 Frequency and wavelength are inversely proportional

( = c/). Thus, energy and wavelength are inversely
proportional.
E = h = hc/
 When electromagnetic radiation strikes a molecule,
some wavelengths, but not all, are absorbed.
 For absorption to occur, the energy of the photon must
match the difference between two energy states in
the molecule
Theory of infrared absorption spectrometry

 The larger the energy difference between two states,

the higher the energy of radiation needed for
absorption, the higher the frequency, and the shorter
the wavelength.
 UV VIS IR RADIO waves

Increasing wavelength- Decreasing frequency Decreasing Energy

Absorption of UV Result of promotion of electron to a

higher energy level i.e Electronic transition

Absorption of IR  Result in increase of vibration of

bonds i.e. Vibrational transition
Theory of infrared absorption spectrometry

IR absorption, emission, and reflection spectra for

molecular species

arise from various changes in energy brought about

by transition of molecules from one vibrational or
rotational energy state to another
 Theory of infrared absorption spectrometry

 Infrared (IR) spectroscopy is used to identify the functional

groups in a compound.
 IR radiation is the energy source used in IR spectroscopy.

 Frequencies in IR spectroscopy are reported using a unit

called wavenumber.
 Wavenumber is inversely proportional to wavelength and

is reported in reciprocal centimeters (cm–1).

 Frequency (and therefore, energy) increases as the
wavenumber increases.
 IR spectrum
 An IR spectrum is a plot of the amount of transmitted
light versus its wavenumber.
 The ordinate is linear in transmittance.
 The abscissa is linear in wavenumber with units of
reciprocal centimeters.
 Modern instruments utilize a microcomputer capable of
producing a variety of other output formats, such as
transmittance versus wavelength and absorbance versus
wavenumber or wavelength.
IR spectrum
 In an IR spectrometer, light passes through a sample.
Frequencies that match the vibrational frequencies
are absorbed, and the remaining light is transmitted
to a detector
 The IR spectrum is divided into two regions: the
functional group region (at  1500 cm-1), and the
fingerprint region (at < 1500 cm-1).
 IR absorption spectrum of a thin polystyrene film.

(Scale change on the x-axis at 2000 cm-1 .

The expanded scale in the region from 2000 to 650 cm -1 permits
easier identification of spectral features. Numerous IR bands
usually appear in this region)
Two Conditions Necessary for
Infrared Spectroscopy

1. For absorption, vibration frequency equals incident

radiation frequency
2. Oscillating dipole moment
Dipole Moment Changes During
Vibrations and Rotations
 Infrared radiation is not energetic enough to bring
about electronic transitions.
 Absorption of infrared radiation is thus confined
largely to molecular species that have small energy
differences between various vibrational and
rotational states.
 In order to absorb infrared radiation, a molecule
must undergo a net change in dipole moment as a
consequence of its vibrational or rotational motion.
 The dipole moments is determined by the magnitude
of the charge difference and the distance between
the two centers of charge.
Dipole Moment Changes During
Vibrations and Rotations
 Eg-The charge distribution around HCl is not
symmetric because chlorine has higher electron
density than the hydrogen. Thus HCl has significant
dipole moment and is said to be polar. Absorption of
radiation takes place.
 If the frequency of the radiation exactly matches a
natural vibrational frequency of the molecule,
absorption of radiation takes place that produces a
change in the amplitude of the molecular vibration.
Dipole Moment Changes During
Vibrations and Rotations
 No net change in dipole moment occurs during the
vibration or rotation of homonuclear species such as
O2, N2, or Cl2;
 consequently, such compounds cannot absorb in the
infrared.
Dipole Moment Changes During
Vibrations and Rotations
 The rotation of asymmetric molecules around their
centers of mass results in periodic dipole moment
fluctuations that allow interaction with the radiation
field.
Rotational transitions
 Energy required to cause a change in rotational
level is quite small and corresponds to radiation of
ύ≤ 100cm-1 (>100µm).
 Rotational levels are quantized
 Absorption in far IR region
 Characterized by discrete , well defined lines.
 In liquids and solids, intramolecular collisions and
interactions cause broadening of lines into a
continuum.
Vibrational-Rotational Transitions
 Vibrational energy levels are quantized, and for
most molecules the energy differences between
quantum states correspond to the mid-infrared
region.
 The IR spectrum of gas usually consists of a series of
closely spaced lines because there are several
rotational levels for each vibrational levels.
 Rotation is restricted in liquids and solids; in such
samples discrete vibrational–rotational lines
disappear, leaving only somewhat broadened
vibrational bands.
• When the frequency of IR light matches the frequency of a
particular vibrational mode, the IR light is absorbed, causing
the amplitude of the particular bond stretch or bond bend to
increase.
Types of Molecular Vibrations

 The relative position of atoms in a molecule are not

fixed but instead fluctuate continuously as a
consequence of different types of vibrations and
rotations about the bonds in the molecule.
 For simple diatomic and triatomic molecules , it is easy
to define number and nature of such vibrations and
relate these to energies of absorptions.
 Large molecule large number of vibrating centre
Types of Molecular Vibrations
 Vibrations fall into the basic categories of stretching
and bending.
 A stretching vibration involves a continuous change in
the interatomic distance along the axis of the bond
between two atoms.
 Bending vibrations are characterized by a change in
the angle between two bonds and are of four types:
scissoring, rocking, wagging, and twisting.
Stretching modes

Symmetric Asymmetric
Different bending modes

Rocking Scissoring

Wagging Twisting
 The IR Spectroscopic Process
5. There are two types of bond vibration:
• Stretch – Vibration or oscillation along the line of the bond

H H
C C
H H

symmetric asymmetric

• Bend – Vibration or oscillation not along the line of the bond

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

33
Mechanical model of a stretching vibration
in a diatomic molecule

Vibrational Frequency:

The natural frequency of the

oscillation is

1 k
m 
2 m

m = natural frequency
m = mass of the attached body
k = force constant of the spring
Fig: Potential energy diagram : Harmonic oscillator
Quantum Treatment of Vibrations
h k
 E  h m 
2 
h k
Eradiation  h   E  h m 
2 
The radiation in wavenumbers,

1 k 12 k
  5.3  10
2 c  
Where,
  is the wavenumber of an absorption peak in cm-1,
 k is the force constant for the bond in newtons per meter
(N/m),
 c is the velocity of light in cm/s, and
 the reduced mass  has units of kg.
 k has been found to lie in the range between 3 x 102 and 8 x
102 N/m for most single bonds, with 5 x 102 serving as a
reasonable average value.
 Double and triple bonds are found by this same means to have
force constants of about two and three times this value (1 x
103 and 1.5 x 103 , respectively).
Selection rule
 Vibrational levels are equally spaced for harmonic
oscillator.
 Only transitions that can take place are those in
which the vibrational quantum number changes by
unity i.e. ∆ν = ±1.
only a single absorption peak should be observed
for a given molecular vibration.
 There must be change in dipole moment during the
vibration.
Vibrational Modes

A molecule can vibrate in many ways, and each

way is called a vibrational mode.
 In defining the motion of a molecule, we need to
consider
(1) the motion of entire molecule through space
( translational motion of its centre of gravity)
(2) the rotational motion of the entire molecule
around its centre of gravity
(3) the motion of each atoms relative to the other
atoms ( its individual vibration)
  Number of possible modes
 Nonlinear molecule: 3N – 6
 Linear molecule: 3N – 5
 3 degrees of freedom – i.e., 3 coordinates in space
 3 translations and 3 rotations account for 6 motions
of molecule
 Rotation about center bond in linear molecule is
indistinguishable
 Remaining degrees of motion represent vibrational
motion (i.e., number of vibrations within the molecule)
 Each of the 3N – 6 or 3N – 5 vibrations is called a
normal mode.
Factors Influencing the Normal Modes

Four factors tend to produce fewer experimental peaks

than would be expected from the theoretical number of
normal modes. Fewer absorption bands are found when:
(1)the symmetry of the molecules is such that no change in
dipole results from a particular vibration;
(2) the energies of two or more vibrations are identical or
nearly identical;
(3) the absorption intensity is so low as to be undetectable
by ordinary means; or
(4) the vibrational energy is in a wavelength region beyond
the range of the instrument.
Factors Influencing the Normal Modes

Occasionally, more peaks are found than are expected

based upon the number of normal modes.
 The occurrence of overtone peaks that occur at two or three
times the frequency of a fundamental peak.
 In addition combination bands are sometimes encountered
when a photon excites two vibrational modes simultaneously.
 The frequency of the combination band is approximately
the sum or difference of the two fundamental frequencies.
 This process occurs when a quantum of energy is absorbed
by two bonds rather than one.
Vibrational Coupling
The energy of a vibration, and thus the wavelength of
its absorption peak, may be influenced by other
vibrators in the molecule. A number of factors
influence the extent of such coupling.
1. Strong coupling between stretching vibrations
occurs only when there is an atom common to the two
vibrations.
2. Interaction between bending vibrations requires a
common bond between the vibrating groups.
3. Coupling between a stretching and a bending
vibration can occur if the stretching bond forms one
side of the angle that varies in the bending vibration
Vibrational Coupling
4. Interaction is greatest when the coupled groups
have individual energies that are approximately
equal.
5. Little or no interaction is observed between
groups separated by two or more bonds.
6. Coupling requires that the vibrations be of the
same symmetry species.
CO2 Molecule
 Let us consider the infrared spectrum of carbon
dioxide.
 If no coupling occurred between the two C=O bonds,
an absorption peak would be expected at the same
wavenumber as the peak for the C=O stretching
vibration in an aliphatic ketone (about 1700 cm-1).
 Experimentally, carbon dioxide exhibits two
absorption peaks, the one at 2350 cm-1 and the other
at 667 cm-1.
 Carbon dioxide is a linear molecule and thus has 3 x
3 – 5 = 4 normal modes.
CO2 Molecule
 Two stretching vibrations are possible. The symmetric
vibration causes no change in dipole. Thus, the
symmetric vibration is infrared inactive.
 The asymmetric vibration produce a change in dipole
moments, so absorption at 2350 cm-1 results.
CO2 Molecule
 The remaining two vibrational modes of carbon dioxide
involve scissoring.

 These two bending vibrations are the resolved

components at 90 deg to one another of the bending
motion in all possible planes around the bond axis.
 The two vibrations are identical in energy and thus
produce a single peak at 667 cm-1.
For CO2 Molecule

Stretching

Bending
H2O molecule
 Triatomic molecule such as water, sulfur dioxide, or
nitrogen dioxide have 3 x 3 – 6 = 3 vibrational
modes.
 The central atom is not in line with the other two, a
symmetric stretching vibration will produce a change
in dipole and will thus be responsible for infrared
absorption.
 Stretching peaks at 3657 and 3766 cm-1 appear in
the infrared spectrum for the symmetric and
asymmetric vibrations of the water molecule.
H2O molecule
 There is only one component to the scissoring vibration
for this nonlinear molecule.
 For water, the bending vibration cause absorption at
1595 cm-1.
The difference in behavior of:
 Linear Triatomic molecules: Two absorption peaks.

 Non linear triatomic molecules: Three absorption

peaks.
 illustrates how infrared absorption spectroscopy can

sometimes used to deduce molecular shapes.

 Coupling of vibration is a common phenomena.
 As a result, the position of an absorption band
corresponding to a given organic functional group
cannot be specified exactly.
 The C-O stretching freq in methanol is 1034cm-1, in
ethanol it is 1053cm-1 and in 2-butanol it is 1105cm-1.
 These variations result from a coupling of the C-O
stretching with adjacent C-C stretching or C-H
vibrations.
INFRARED SOURCES AND
TRANSDUCERS
INFRARED SOURCES
 Instruments for measuring IR absorption all require a
source of continuous IR radiation.
 Infrared sources consist of an inert solid that is heated
electrically to a temperature between 1500 and
2200 K.
 Continuum radiation approximating that of a
blackbody results.
 The maximum radiant intensity at these temperatures
occurs between 5000 to 5900 cm-1.(2 and 1.7µm)
INFRARED SOURCES
 At longer wavelength , the intensity falls off smoothly
until it is about 1% of the maximum at 670cm-1 (15µm)
 On the short wavelength side, the decrease is much
more rapid, and a similar reduction in intensity is
observed at about 10,000cm-1 (1µm).
 The Nernst Glower
 The Globar

 Incandescent wire source

 The Mercury Arc

 The Tungsten Filament lamp

 The carbon dioxide laser source

The Nernst Glower

 The Nernst glower is composed of rare earth oxides formed into

a cylinder having a diameter of 1 to 3 mm and a length of
perhaps 2 to 5 cm.
 Platinum leads are sealed to the ends of the cylinder to permit
electrical connection to what amounts to a resistive heating
element.
 As current is passed through the device, temperature between
1200 K and 2200 K result.
 It has a large –ve temp coefficient of electrical resistance, and it
must be heated externally to a dull red heat before the current is
large enough to maintain the desired temp.
 Because the resistance decreases with increasing temperature ,
the source circuit must be designed to limit the current or the
glower rapidly becomes so hot that it is destroyed.

Fig: Spectral distribution of energy from a Nernst glower

operated at approx 2200K.
Overall shape is similar to blackbody. The small peaks and depressions
are a function of the chemical composition of the device.
The Globar Source

 A Globar is a silicon carbide rod, usually about 5cm

in length and 5 mm in diameter.
 It also is electrically heated (1300 to 1500 K) and
has the advantage of a positive coefficient of
resistance.
 Spectral energies of the Globar and the Nernst
glower are comparable except in the region below
5m, where the Globar provides a significantly
greater output.
Incandescent Wire Source

 A source of somewhat lower intensity but longer life

than the Globar or Nernst glower is a tightly wound
spiral of nichrome wire heated to about 1100 K by an
electrical current.
 A rhodium wire heater sealed in ceramic cylinder-
similar property but more expensive.
 Nichrome wire sources are less intense than many IR
sources.
 Requires no cooling and is nearly maintenance free.
Often used where reliability is paramount such as in
process analyzer
The Mercury Arc

 For the far-infrared region of the spectrum (> 50 m),

none of the thermal sources just described provides
sufficient radiant power for convenient detection.
 Here, a high-pressure mercury arc is used.
 This device consists of a quartz-jacketed tube containing
mercury vapor at a pressure greater than one
atmosphere.
 Passage of electricity through the vapor forms an internal
plasma source that provides continuum radiation in the
far-infrared region.
 The Tungsten Filament Lamp

 An ordinary tungsten filament lamp is a convenient

source for the near-infrared region of 4000 to 12,800
cm-1 (2.5 to 0.78µm)
The Carbon Dioxide Laser Source

 A tunable carbon dioxide laser is used as an

infrared source for monitoring the concentrations of
certain atmospheric pollutants and for determining
absorbing species in aqueous solutions.
 A carbon dioxide laser produces a band of radiation
in the 900 to 1100 cm-1 range which consists of about
100 closely spaced discrete lines.
 Any one of these lines can be chosen by tuning the
laser.
 This source is useful for quantitative determination of
a number of compounds.
 An important property of laser source is the radiant
power available in each line, which is several orders
of magnitude greater than that of blackbody sources.
 Carbon dioxide lasers are widely used in remote
sensing applications such as light detection and
ranging(lidar).
Infrared Transducers
Infrared transducers are of three general types:
(1) Thermal transducers (found in older dispersive
instruments)
(2) Pyroelectric transducers (found in
photometers,FTIR spectrophotometers and dispersive
spectrophotometers)
(3) Photoconducting transducer (found in many FTIR
instruments
Thermal Transducers

 Thermal transducers, whose responses depend upon

the heating effect of radiation, are employed for
detection of all but the shortest infrared wavelengths.
 With these devices, the radiation is absorbed by a
small blackbody and the resultant temperature rise is
measured.
 To prevent thermal noise from surrounding it is housed
in a vacuum and are carefully shielded from thermal
radiation emitted by other nearby objects.
 Beam chopped.
Thermocouples

 In its simplest form, a thermocouple consists of a pair of

junctions formed when two pieces of a metal such as bismuth are
fused to either end of a dissimilar metal such as antimony.
 A potential develops between the two junctions that varies with
their difference in temperature.
 The transducer junction for IR radiation is formed from very fine
wires or alternatively by evaporating the metals onto
nonconducting support. Response time 30ms.
 The reference junction has relatively larger heat capacity and
shielded from incident radiation.
 What is a thermopile????
Bolometers

 A bolometer is a type of resistance thermometer constructed of

strips of metals such as platinum or nickel, or from a
semiconductor.
 Thermistor
 These materials exhibit a relatively large change in resistance as
a function of temperature.
 The responsive element is kept small and blackened to absorb
the radiant heat.
 Bolometers are not so extensively used for mid IR region.
However, Germanium bolometer, operated at 15K , is excellent
for 5 to 400cm-1 range.
 Response time few milliseconds.
Pyroelectric Transducers
 Pyroelectric transducers are constructed from single
crystalline wafers of pyroelectric materials, which are
insulators (dielectric materials) with very special
thermal and electrical properties.
 Triglycine sulfate, (NH2CH2COOH)3. H2SO4 is the
most important pyroelectric material used in the
construction of infrared detection systems.
Pyroelectric Transducers
 The degree of polarization of this dielectric material
is temperature dependent.
 A temperature dependent capacitor is made by
sandwiching it between two electrodes.
 It has short response time/ sensitive in mid IR.
Photo conducting Transducers

 Infrared photoconducting transducers consist of a thin film of a

semiconductor material, such as lead sulfide, mercury/cadmium
telluride, or indium antimonide, deposited on a nonconducting
glass surface and sealed into an evacuated envelope to protect
the semiconductor from the atmosphere.
 Absorption of radiation by these materials promotes
nonconducting valence electrons to a higher energy conducting
state, thus decreasing the electrical resistance of the
semiconductor.
 Typically, a photoconductor is placed in series with a voltage
source and load resistor, and the voltage drop across the load
resistor serves as a measure of the power of the beam of
radiation.
IR Instrumentation
IR Instrumentation
 Three types of instruments for IR absorption are commonly
available:
1. Dispersive spectrophotometers with a grating
monochromator that are used primarily for qualitative
work
2. Fourier transform spectrometers employing an
interferometer that are suited to both qualitative and
quantitative infrared measurements,
3. Nondispersive photometers using filter or an absorbing
gas that have been developed for quantitative
determination of a variety of organic species in the
atmosphere by absorption, emission , and reflectance
spectroscopy.
Diagram of a basic
FTIR spectrometer
Single - beam FTIR spectrometer
Double - beam FTIR spectrometer
Schematic diagram of a double – beam, dispersive
IR spectrometer
Applications of Infrared
Spectrometry
 Applications of Infrared Spectrometry

 Infrared spectrometry is applied to the qualitative and

quantitative determination of molecular species of all
types.
 The most widely used region is the mid-infrared that
extends from about 670 to 4000 cm-1 (2.5 to 14.9 m).
 The near-infrared region from 4000 to 14,000 cm-1
(0.75 to 2.5 m) also finds considerable use for the
routine quantitative determination.
 The far-infrared region ( 15 to 1000 µm) has been for
the determination of the structures of inorganic and
metal-organic species based on absorption
measurement.
MID-INFRARED ABSORPTION
SPECTROMETRY
•Sample handling
•Qualitative Analysis

•Quantitative Application
 Sample Handling

 No good solvents exist that are transparent

throughout the region of interest.
 As a consequence, sample handling is frequently the
most difficult and time-consuming part of an infrared
spectrometric analysis.
 Some of the common techniques for the sample
preparation are as follows:
 Gases, Solutions, Liquids ,Solids
Gases

 The spectrum of a low-boiling liquid or gas can be

obtained by permitting the sample to expand into
an evacuated cylindrical cell equipped with suitable
windows.
 For this purpose variety of sample cells are
available with path lengths that range from a few
centimeters to 10 m or more.
Solutions
 A convenient way of obtaining infrared spectra is on
solutions prepared to contain a known concentration of
sample.
 This technique is somewhat limited in its applications,
however, by the availability of solvents that are
transparent over significant regions in the infrared.
Solvents

 No single solvents is transparent throughout the

entire mid-infrared region.
 Water and alcohols are seldom employed, not only
because they absorb strongly, but also because they
attack alkali-metal halides, the most common
materials used for cell windows.
 Care must be taken to dry the solvent before use
with typical cells.
Solvents for IR spectroscopy.
Horizontal lines indicate useful regions.
 Cells
 Because of the tendency for solvents to absorb IR radiation, liq cells
are much narrower ( 0.01 to 1 mm).
 Relatively high sample concentration ( 0.1% to 10%) are required.
Liq cells are frequently designed for easy disassembly and use
Teflon spacers to allow variation in path length.
 Fixed path length cells can be filled or emptied with a hypodermic
syringe.

Expanded view of demountable IR cell for liq

samples. Teflon spacers ranging from 0.015 to
1mm thick are available
Cells
 Variety of window materials are available.
 Sodium chloride and KBr windows are most
commonly employed; even with care, however,
their surfaces eventually become fogged due
to absorption of moisture.
 Polishing with a buffing powder returns them
to their original condition.
 For aqueous samples calcium and barium
fluoride are suitable.
Liquids
 When the amount of liquid sample is small or when a
suitable solvent is unavailable, it is common practice to
obtain spectra on the pure (neat) liquid.
 A drop of the neat liquid is squeezed between two
rock-salt plates to give a layer that has a thickness of
0.015 mm or less.
 The two plates, held together by capillary action ,are
then placed in the beam path.
 Such a technique does not give reproducible
transmittance data, but the resulting spectra are usually
satisfactory for qualitative investigations.
 Solids

 Most organic compounds exhibit numerous absorption

peaks throughout the mid-infrared region, and finding a
solvent that does not have overlapping peaks is often
impossible.
 As a consequence, spectra are often obtained on
dispersions of the solid in a liquid or solid matrix.
 Solid sample must be ground until its particle size is less
than the wavelength of the radiation to avoid the effects
of scattered radiation.
 Different techniques for handling solid samples are: as
solution, solid powder, pelleting, mulls etc.
Pelleting

 One of the most popular techniques for handling solid

samples has been KBr pelleting.
 A milligram or less of the finely ground sample is
intimately mixed with about 100 mg of dried
potassium bromide powder.
 The mixture is then pressed in a die at 10,000 to
15,000 pounds per square inch to yield a
transparent disk.
 The disk is then held in the instrument beam for
spectroscopic examination.
 Mulls
 Infrared spectra of solids that are not soluble in an
infrared-transparent solvent or are not conveniently
pelleted in KBr are often obtained by dispersing the
analyte in a mineral oil or fluorinated hydrocarbon mull.
 Mulls are formed by grinding 2 to 5 mg of the finely
powdered sample in the presence of one or two drops
of a heavy hydrocarbon oil (Nujol).
 If hydrocarbon bands interfere, Fluorolube, a
halogenated polymer, can be used.
 The resulting mull is then examined as a film between
flat salt plates.
Qualitative Analysis
 The appearance of I.R. instrument revolutionized the
way chemists went about identifying organic, inorganic,
and biological species.
 The time required to perform a structural determination
was reduced by a factor of ten, one hundred, or even
one thousand.
 Identification of an organic compound is a two-step
process.
 The first step involves determining what functional
groups are most likely present by examining the group
frequency region. (3600 to approx 1250 cm-1 )
Qualitative Analysis
 The second step then involves a detailed comparison of
the spectrum of the unknown with the spectra of pure
compounds that contain all of the functional groups
found in the first step.
 The fingerprint region, from 1200 to 600 cm -1 is
particularly useful because small differences in the
structure and constitution of a molecule result in
significant changes in the appearance and distribution
of absorption peaks in this region.
Group Frequencies
 The approximate frequency (or wavenumber) at which an
organic functional group, such as C=O, C=C, C—H, CC,
or O—H absorbs infrared radiation can be calculated
from the masses of the atoms and the force constant of
the bond between them.
 These frequencies, called group frequencies, are seldom
totally invariant because of interactions with other
vibrations associated with one or both of the atoms
composing the group.
 A range of frequencies can be assigned within which it is
highly probable that the absorption peak for a given
functional group will be found.
The “Fingerprint” Region

 Small differences in the structure and constitution of

a molecule result in significant changes in the
distribution of absorption peaks in this region of the
spectrum that extends from about 1200 to 600 cm-1.
 As a consequence, a close match between two
spectra in this fingerprint region constitutes strong
evidence for the identity of compounds yielding the
spectra.
 Exact interpretation of spectra in this region is seldom
possible because of the complexity of the spectra.
IR Absorptions
• Bonds absorb in four predictable regions of an IR spectrum.
IR Absorptions
The group frequency region of mid IR (~3600-1250 cm-1 ) is used to
identify common functional groups. The finger print region (~1200 –
600 cm-1) is used to identify compounds.
 Computer Search Systems
 Virtually all infrared instrument manufactures now offer computer
search systems to assist chemist in identifying compounds from
stored infrared spectral data.
 The position and relative magnitudes of peaks in the spectrum of
the analyte are determined and stored in memory to give a
peak profile, which can then be compared with profiles of pure
compounds stored.
 The computer then matches profiles and prints a list of compounds
having spectra similar to that of the analyte.
 Usually the spectrum of the analyte and that of each potential
match can then be shown simultaneously on the computer display
for comparison.
Quantitative Applications
 Quantitative infrared absorption methods differ
somewhat from ultraviolet/visible molecular
spectroscopic methods because of the greater
complexity of the spectra, the narrowness of the
absorption bands, and the instrumental limitations of
infrared instruments.
 Quantitative data obtained with infrared instruments
are generally significantly inferior in quality to data
obtained with ultraviolet/visible spectrophotometers.
Quantitative Analysis
 IR more difficult than UV-Vis because
 narrow bands (variation in e)
 complex spectra
 weak incident beam
 low transducer sensitivity
 solvent absorption
 IR mostly used for rapid qualitative but not quantitative
analysis
 Beer’s law failure
 Long optical path-length required
 Regular FT-IR is worse than UV-VIS
 Exception - Tunable IR laser, quantum cascade laser, OPO