CHAPTER 4

INFRARED SPECTROMETRY
IR region;

► wavenumber ~ 12,800 to 10 cm-1

► wavelength ~ 0.78 to 1000 μm

► near-0.78 - 3 μm, mid-3-30 μm and far- 30 -1000 μm

infrared

 The techniques and application of methods based upon the

three IR spectral regions are difference.

a. Near IR
- measurements are made with photometers and
spectrophotometers.

- is used in quantitative analysis of industrial and

agriculture materials.
b. Mid-IR

- Early 1980s, were largely of the dispersive type based on

diffraction gratings.

- was used largely for qualitative organic analysis and

structure determination based on absorption spectra.

- now, majority of new instrument are of the Fourier

Transform type.

- is beginning to be used in quantitative analysis of complex

samples by both absorption and emission spectrometry.
 c. Far-IR

- has at limited use because of experimental difficulties.

- is particularly useful for inorganic studies.

4.1. Theory of Infrared Absorption Spectrometry

 IR spectra – transitions of molecules from one vibrational or
rotational energy state to another state.

 In order to absorb infrared radiation, a molecule must undergo

a net charge in dipole moment as a consequence of its
vibrational or rotational motion.
 For example, the charge distribution around a molecule such
as HCl is not symmetric because the Cl has a higher electron
density than H. So, HCl has significant dipole moment and is
said to be polar.

 The dipole moment is determined by the magnitude of the

charge difference and the distance between the two center
of charge.

 No net charge in dipole moment occurs during the vibration or

rotation of homonuclear species such as O2, N2 or Cl2. So,
they cannot absorb the IR radiation.

 The absorption of IR radiation follows the Beer’s Law. So, the

absorption is directly related to the concentration of specific
bonds (or functional groups) within a sample and the
concentration of specific analytes.
 The molar absorptivity, ε of IR radiation are very much smaller
than those encountered for UV or visible light.

 The IR technique being used for the determination of trace

compounds.

4.2 Presentation of IR spectra

 IR spectra are normally displayed in a different manner to UV/

visible spectra. An IR spectrum of octane is shown in figure
below:
 IR absorption peaks are directed down the page:

IR Spectrum for octane

4.3 Types of Molecular Vibration

 The relative positions of atoms in a molecule are not exactly

fixed but instead fluctuate continuously as consequence
of a multitude of different types of vibrations and rotations
about the bonds in the molecule.

 Vibration fall into the basic categories;

a. Stretching
b. 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 four types;

a. Scissoring (gunting)
b. Rocking (goyang)
c. Wagging (kipas)
d. Twisting (pemiuhan)
Symmetrical Asymmetrical
stretching stretching

Scissoring Rocking

Wagging Twisting
 All of the vibration types shown in figure above maybe possible
in a molecule containing more than two atoms.

 Interaction or coupling of vibrations can occur if the vibrations

involve bonds to a single central atom.

4.4 Vibrational Modes

 Complex molecules may contain several types of atoms as well

as bonds. For these molecules, the many types of possible
vibrations gives rise to IR spectra that are much more difficult
to analyze.

 In defining the motion of molecule, we need to consider:

- the motion of the entire molecule through space (the

translational motion of its center of gravity).
 - the rotational motion of the entire molecule around its
center of gravity.

- the motion of each of its atoms relative to the other atom,

or in other words, its individual vibrations.

 The number of modes of vibration for a linear molecule is

given by 3N-5 whereas for non-linear is given by 3N-6. Each
of the 3N-5 or 3N-6 vibrations is called a normal mode.

 In practice, there are often fewer experimental peaks observed

than would be predicted from the theoretical number of normal
modes. Fewer peaks are found when:

a. The symmetry of the molecule is such that no change

in a dipole occurs via one or more possible molecular
vibrations.
 b. The energy of two or more vibrations are identical or
nearly identical.

c. The absorption intensity is slow.

d. The vibration energy is in a wavelength region beyond

the range of the instrument.

4.5 Vibrational Coupling

 The energy of a vibration and thus the wavelength of its

absorption peaks, may be influenced by (or coupled with) other
vibrators in the molecule. A number of factors influence the
extent of such coupling:

1. Strong coupling between stretching vibration occurs only

when there is an atom common to the two vibrations.
 2. Interaction between bending vibrations requires a
common bond between the vibration group.

3. Coupling between a stretching and a bending

vibrations can occur if a stretching bond forms one
side of the angle that varies in the bending vibration.

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.

https://www.youtube.com/watch?v=S8R30EdcIT4&t=5s
 In order to examine how absorption processes such as
coupling effects are expressed within IR molecular absorption
spectra, we shall consider two simple examples.

Example of absorption of a linear tri-atomic molecule – CO2

 CO2 is a linear molecule and thus has 3 x 3 – 5 = 4 normal

modes, therefore four absorption peaks. Experimentally, CO2
exhibits two absorption peaks at 667 and 2360 cm-1 as
depicted in figure below:

O=C=O
 IR spectrum for CO2
Why two absorption peaks not four?

 There are two stretching vibrations that can occur. One

couple vibrations is symmetric and the other is asymmetric.

Symmetric Asymmetric
 The symmetric vibration causes no change in dipole, since
the two oxygen atoms move away from or toward the central
carbon atom. Thus, the symmetric vibration is IR inactive.

 In the asymmetric vibration, one oxygen moves toward the

carbon atom as the carbon atom moves toward the other
oxygen. A net change in charge occurs, producing a change
in dipole moment, so absorption at 2360 cm-1 results.

 Two scissoring vibrational modes are also possible, as shown

below.

- + - Scissoring
Note: + indicates motion from page toward the reader;
- indicates motion away from the reader.
 The two vibrations are identical in energy and thus produce
a single peak at 667 cm-1.

Example of absorption of a non-linear tri-atomic molecule –H2O

 H2O is a non-linear molecule since the two hydrogen atoms

are linked to the oxygen via only one molecular bond each.

 The two hydrogens are not in line with each other, which gives
a permanent dipole within molecule.

 Theory predicts 3 x 3 – 6 = 3 normal modes, which take the

following forms:
Symmetric stretching Asymmetric stretching

Scissoring
Three absorption peaks indeed observed, corresponding as below:

- one symmetric stretching – 3650 cm-1

- one asymmetric stretching – 3760 cm-1
- one scissoring vibrational mode – 1595 cm-1

IR spectrum for H2O

4.6 Group Frequency Region

 Most of the absorptions are found within a wavenumber range

1250 – 3600 cm-1, which is known as group frequency region.

 The identification of absorption peaks can often be used to

help identify a class of molecule. The exact wavenumber at
which an absorption occurs is very often highly specific to an
individual molecule and this may help in the identification of
unknown compounds.

 Characteristic absorption regions are tabulated in correlation

charts to aid structural identification of spectra unknown
chemical species.

 A number of commonly encountered molecular vibrations,

together with the relevant molecular groupings and the group
 frequency regions for absorptions, are shown in table below:

Table of group frequencies for some molecular vibrations associate with commonly
encountered organic bonds and groups.
 Absorption peak within group frequency region often overlap
each other and this complicated structural and elucidation and
identification.

 Further variations in the spectrum can moreover also occur

depending on:

i- how a sample is prepared (e.g. within a mull, pellet,

powder).

ii- Whether the sample is in the gaseous, liquid or solid

form.
4.7 Fingerprint Region

 The wavenumber range 1200-700 cm-1 is known as the

fingerprint region.

 Small changes in molecular structure often gives rise to

significant changes in absorption peaks within fingerprint region,
so spectra of unknown samples can often be matched with
those of known compounds.

 A number of inorganic groups; e.g. nitrate, phosphate and

sulphate also rise to absorption peaks within the fingerprint
region, which complicate the spectra further.

 Matching a spectrum by eye with the spectra of unknown

compounds would be highly tedious. Many modern IR
spectrometers simplify the matching of spectra via computerized
data libraries.
 Figures below, a and b illustrate the unique character of IR
spectra, particularly in the fingerprint region. The two molecules
differ by just one methyl group, yet the two spectra differ
dramatically in appearance in the fingerprint.

Group frequency and fingerprint regions of mid-IR spectrum

2,3- dimethylbutane & 2-methylbutane
4.8 IR Sources

 IR sources comprise an inert solid that electrically heated to a

temperature in excess of 1500 oC. A maximum intensity of
the emitted radiation occurs at frequencies equivalent to
approximately 5000 – 6000 cm-1.

i. The Nernst Glower Source

- comprises a thin cylinder fabricated from rare earth

oxides of 20 mm length and 1-2 mm diameter.
- current is passed through the cylinder for heating via
electrical connections at either end.
- at operating temperatures, the cylinder glows dull red.
ii. The Globar Source

- is an electrically heated silicon carbide rod of around 5 cm

in length and 4 mm in diameter.
- typically provides a more intense source of IR radiation
than the Nernst glower below wavenumbers of 2000 cm-1.
iii. The Incandescent Wire Source

- is IR source formed from a tightly wound and electrically

heated spiral wire.
- it offers a greater longevity than many other sources although
it cannot provide the same intensity as the Nernst or globar
alternatives.
iv.The Mercury Arc Source

- high pressure mercury are is used for far-IR

applications.
- consists of a quartz-jacketed tube containing
mercury at pressure greater than 1 atm, through
which current is passed to form an internal plasma
that emits IR radiation in the far IR region.
v. The Tungsten Filament Source

- conventional tungsten filament lamps can be used as IR

sources for the near-IR region through a range of 4000 –
12500 cm-1.
vi.The Carbon Dioxide Laser Source

- tunable carbon dioxide lasers can be used as special

very high intensity IR sources for the determination of
analytes in aqueous solution and atmosphere airborne
pollutants.
- can facilitate the quantitative determination of
ammonia,benzene, ethanol and nitrogen dioxide.
- provides radiation only ranges from 900 – 1100 cm-1
4.9 IR Transducers (Detectors)

 There are three main classes of IR transducers:

1. thermal
2. pyroelectric (a very specialized thermal tranducer)
3. photoconducting

 Thermal and pyroelectric are commonly found in photometers

and dispersive spectrophotometers. Photoconducting
transducers are found in Fourier transform instruments.

1. Thermal Tranducers

- responses depend upon the heating effect of radiation.

- are employed for detection of all the shortest IR

wavelengths.
- the radiation is absorbed by a small blackbody and the
resultant temperature rise is measured.

- a blackbody in this context is one that absorbs all incident

radiation.

- Problem: measuring IR radiation is compounded by thermal

noise from the surroundings.

- Solution: thermal transducers are normally shielded from

ambient thermal radiation.

- Thermocouples are the most popular types of thermal

transducer.

- Bolometers is a type of resistance thermometer and are not

extensively used as other IR transducers for mid-IR region.
2. Pyroelectric Transducers

- typically comprise a layer of pyroelectric material

(such as deuterated triglycine sulphate) sandwhich
between two electrodes ( one of which is made of
an IR transparent material) to form a capacitor.

- IR radiation passing through the transparent

window causes a heating of the pyroelectric
material and gives a charge to the polarization and
capacitance of the transducer.

- the capacitance can be monitored electronically

and related to the intensity of the IR radiation.
Pyroelectric Transducers
3. Photoconducting Transducers

- consist of a thin film of semiconductor material, such as lead

sulfide, mercury/cadmium telluride that coats a non-
conducting glass surface housed within an evacuated glass
envelope.

- exposure of the semiconductor to IR radiation promotes

valence electrons from non-conducting states to conducting
states thereby increasing the conductivity of the device.

- can be monitored electronically and related to the intensity

of the IR radiation.
Photoconducting Transducers
4.10 General Purpose IR Spectrometers and Photometers

 There are four main types of IR spectrometers routinely used

for analytical applications:

1. Dispersive grating spectrometer

2. Fourier transform multiplex
3. Non-desipersive photometers
4. Reflectance photometers

Dispersive grating IR spectrometers

- are normally used in conjunction with a beam chopper to

discriminate between signal from source and extra IR
radiation from surrounding for IR.
- in many ways can be thought of as being similar to a UV/Vis
 instrument in the way it operates.

- has acted as the main analytical for IR applications within many

laboratories although instruments of this type are progressively
being replaced by Fourier transform multiplex instruments.

Schematic for a dispersive IR spectrometer.

Schematic for a dispersive IR spectrometer
Fourier transform multiplex spectrometers

- operate in entirely different approach to their dispersive

counterparts since all wavelength are depicted and measured
simultaneously.

- allow resolution, sensitivity and wavelength precision that

cannot be matched by dispersive instrumentation.

- modern FTIR instruments are typically smaller than dispersive

spectrometers and require less servicing than dispersive IR
spectrometers.
 interferometer

Schematic of a multiplex (Fourier transform) IR spectrometer

FTIR

https://www.youtube.com/watch?v=EmI2bCnbfHA

https://www.youtube.com/watch?v=CwmA6NZHj-4

Dispersive IR

https://www.youtube.com/watch?v=pYAyMeu4SHY