INFRA-RED

OBJECTIVES:
 1. Discuss absorption of energy on the
basis of vibrations and rotations of the
absorbing molecule in the IR region
 2. Understand IR spectroscopy as one of
the tools in identifying unknown
compounds like medicinal agents
 3. Describe the techniques for IR
analysis
 4. Identify the different functional groups
of a compound from a given spectra
OUTLINE:
 Discussion on IR spectroscopy
 Functional Groups and their
characteristic IR absorption frequencies
 Interpretation of IR spectra
 Techniques in IR analysis
KEYPOINTS
Principles:
 emr ranging bet. 400 cm-1 and 4000 cm-1
(2500 and 20000 nm) is passed thru a sx
and is absorbed by the bonds of the
molecules causing them to stretch or
bend
 An important tool of the organic chemist
is Infrared Spectroscopy, or IR spectra
 are acquired on a special instrument,
called an IR spectrometer. IR is used
both to
 gather information about the structure of
a compound and as an analytical tool to
 assess the purity of a compound.
Applications:
 Qualitative fingerprint check for the
identity of raw material
 Preliminary check for compound identity
 Fingerprint test for films, coating and
packaging plastics
 Use to detect polymorphs of drugs
 Use also for identification tests for
pharmaceutical substances
Strength:
 Computer control of instrument means
matching of the spectrum of a compound
to its standard fingerprint

Limitations:
 Rarely used as a quantitative technique
because of difficulty in sample
preparation and complexity of spectra
 Sample prep requires skill since sx
handling can have effect on spectrum
 Same laws are also applied in the IR
region
 Infra (latin) – below
 Red – color of the longest wavelength of
VIS region (620 -780 nm)
 Some drugs assayed by IR region:
acetazolamide
propoxyphene
thiotepa
diethyltoluamide
 Of the 3 IR regions – the MEDIUM IR
region (3 – 15 µm) is most often applied for
ID purposes
 Chemists prefer to work with numbers
which are easy to write; therefore IR
spectra are sometimes
 reported in µm, although another unit, ν
(nu bar or wavenumber), is currently
preferred
 In wavenumbers, the mid IR range is
4000–400 cm–1. An increase in
 wavenumber corresponds to an increase
in energy
 Infrared radiation is absorbed by organic
molecules and converted into energy of
molecular vibration. In IR spectroscopy, an
organic molecule is exposed to infrared
radiation.
 Humans at normal temperature radiate
chiefly at λ around 12 µm
 Bright sunlight provides irradiance of over
1kw/m2: at this energy 527 w is IR radiation
445 w is vis
32 w is UV
 To meet the required set in the
compendium, the spectrum of medicinal
agent under investigation and the
corresponding USP/NF ref. std. are
prepared and compared w/ one another.
 The spectrum of the medicinal agent must
exhibit absorption maxima and minima
only at the same λ as that of ref. std.
 In IR-EMS, water cannot be used as
solvent because:
1. it absorbs most of ir radiation thereby
obscuring absorption by the solute
2. water could destroy NaCl cells which
hold the sample
3 METHODS AS SAMPLE
PREPARATION:
A. Dispersing finely ground solid in liquid
petrolatum (MULL TECHNIQUE)
 100 mg spl
 Place in agate mortar and pestle
 Grind
 Add drops of liq. petrolatum and ground
 mull is formed
 Transfer to NaCl plates
 Absorption/transmittance spectrum is
then run
 Repeat w/ ref. std.
B. Dissolving solid in organic solvent

organic solvents used:

CHCl3
CS2
C. Incorporating solid in KBr pellet
1. 1.5 mg spl
2. add 500 mg ir quality KBr in mortar and
pestle
3. mix
4. transfer about 200 mg mixture to
compression chamber
5. compress mixture
6. remove the pellet
7. transfer to holder
8. obtain absorption spectrum
9. same procedure using ref. std.
 For liquid spls, a thin layer of subst. is
placed directly between NaCl plates
(neat or straight spls)
OTHER APPLICATIONS OF IR:
IR filters – for night vision googles
Thermography – for thermographic cameras
Tracking or IR homing
Heating :
IR saunas
de icing (remove ice from wings of
aircraft), IR thermometric therapy
garments (warmth to heal pain, injury,
arthritis)
cooking
Communication – IR data transmission
 Far IR waves are thermal – ex. heat from
sunlight
 Near IR are not hot at all – ex. TVs
remote control
 The warmer the object, the more IR rad it
emits:
ex. hot charcoal may not give off light but it
emits IR rad w/c use fuel as heat,

rattlesnakes have sensory used to image

IR light thus detecting warm blooded
animals even in dark
IR spectrometry
– identify pure organic and inorganic
compounds (exemptions: O2, N2, Cl2)
- considered less precise for quantitative
analyses (few applications)
IR spectra – greater complexity of spectra
compared to UV VIS
IR Instruments:
Types:
For Qualitative Identification:
1. Dispersive spectrometers
2. Fourier-transform (FTIR)

For Quantitative:
1. Filter photometer
 Some Characteristic
Infrared Absorption Peaks:
Fxnl. Grp. Absorption Peaks
Wavenumber, Wavelength, µm
cm-
Ether-aliphatic 1160-1060 8.6 - 9.4
Aldehyde-ketone 1740-1660 5.7 - 6
Carboxylic acid 1740 - 1660 5.7 - 6
ester 1750 - 1700 5.7 - 5.9
IR Spectrum
 Usually represented w/ %T (ordinate)
and wavenumber (abscissa) –
Theory:
In order for IR radiation to be absorbed by
a molecule:
1. Molecule should possess a vibrational or
rotational frequency identical to that of
impinging EM radiation
Types of Molecular vibrations:
1. Stretching
2. Bending :
Scissoring
Rocking
Wagging
Twisting
 The stretching frequency of a bond can
be approximated by Hooke’s Law. In this
approximation, two atoms and the
connecting bond are treated as a simple
harmonic oscillator composed of 2 masses
(atoms) joined by a spring:
 According to Hooke’s law, the frequency
of the vibration of the spring is related to
the mass and the force constant of the
spring
 Hooke’s law, law of elasticity discovered by the
English scientist Robert Hooke in 1660, which
states that, for relatively small deformations of
an object, the displacement or size of the
deformation is directly proportional to the
deforming force or load. Under these
conditions the object returns to its original
shape and size upon removal of the load.
Elastic behaviour of solids according to
Hooke’s law can be explained by the fact that
small displacements of their constituent
molecules, atoms, or ions from normal
positions is also proportional to the force that
causes the displacement.
 All molecules in nature contain a specific
quantity of energy at a given
temperature. This energy is referred to as
internal energy (E) and is equal to the
sum of electronic (Ee), vibrational (Ev),
rotational (Er), and translational (Et).
 A molecule consisting of n atoms has a
total of 3 n degrees of freedom, In non-
linear molecule, 3 of these degrees are
rotational and 3 are translational and the
remaining correspond to fundamental
vibrations; in a linear molecule, 2
degrees are rotational and 3 are
translational.
 The net number of fundamental
vibrations for nonlinear and linear
molecules is therefore:
molecule degrees of freedom:
 nonlinear 3n – 6
 linear 3n – 5
 Of the linear molecules,
carbon monoxide and iodine chloride
absorb IR radiation, while hydrogen,
nitrogen, and chlorine do not
C≡O I—Cl H2 N2 Cl2
absorb in IR do not absorb in IR