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Instrumental Analysis II (Chem.2052)

Chapter 6
Infrared spectroscopy
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3.1 Introduction
 Absorption of electromagnetic radiation in the
infrared region of the spectrum resulting in
changes in the vibrational energy of
molecules.
 This region covers approximately between 750
and 3000 nm. Thus, there are three sub regions in
the IR region.

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Usually the IR region is expressed in terms of wavenumber
instead of λ b/c wavenumber is directly related with frequency,
wavenumber is read as frequency in IR region (It is not exactly
frequency υ = ῡ).

IR radiation is not energetic enough to bring about the kind of

electronic transition that we have encountered in UV-Vis. Thus, the
transitions responsible for IR bands are due to molecular vibrations
and rotations, i.e. to periodic motions involving stretching or
bending of bonds.
EMR of IR is absorbed by a molecule with a non-zero change in
dipole moment during vibration. It is absorption of IR radiation due
to the interaction of oscillating dipole moment of vibrating
molecules and oscillating field of the IR radiation (i.e. molecule
electric field (dipole moment) interacts with IR photon electric
field).
 Thus, homodiatomic molecules (homonuclear molecules)
don’t interact with the IR for net dipole change
vibration. Examples: H2, N2, O2, F2, Cl2, Br2 and I2

Polar bonds are associated with strong IR absorptions

while symmetrical bonds may not absorb at all. The
magnitude of a dipole moment is determined by charge and
separation of charge. Vibration or rotation causes varying
separation of atoms in a molecule.
Molecule must have change in dipole moment due to
vibration or rotation to absorb IR radiation. Molecules with
permanent dipole moments (μ) are IR active.

 IR spectrum is Absorption versus frequency.

 Vibrational Modes: Examples
 IR-activity Inactive
requires dipole Active
changes Active
during
vibrations! Active

 For example, this is

Problem 16-3 from
Skoog (6th edition): Inactive

Active

Inactive
3.2. Energy levels in vibrating and rotating molecules

Types of Molecular Vibrations

There are two major vibration types. These are:

1.Stretching: involves change in bond length (bond angle
is constant)
Symmetric
Asymmetric
2.Bending: involves change in bond angle (bond length
is constant)
Rocking ( in - plane)
Scissoring ( in - plane)
Wagging (out – of - plane)
Twisting/
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Which needs more energy for stretching? The asymmetric
because it increase the net dipole moment.

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 Molecular vibration
• Molecules are not rigid assemblage of atoms
• The common molecular vibrations that are excited by IR
radiation are stretching vibrations and bending vibrations. These
are called modes of vibration.
• Stretching involves a change in bond lengths
• Bending involves a change in bond angle

• The CO2 molecule on the left is undergoing a symmetric stretch,

the one in the middle an asymmetric stretch and the one on the
right an in-plane bend. The symmetric
• For polyatomic molecules, the spectra are usually recorded as
liquids, solids or in solution, the complexity of the spectrum
increases rapidly with the number of atoms N in the molecule.
• The number of fundamentals or normal modes of vibration is
given by 3N – 6 and 3N – 5 for non linear and linear
molecules respectively. A normal mode of vibration is defined
as the movement of all the atoms of the molecule in phase. In
the case of polyatomics, the number of fundamentals includes
both stretching and bending vibrations.
 Harmonic oscillator and Hook’s low
• The stretching frequency of a bond can be approximated
by Hooke’s Law.
• 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, k , by the
following formula:

where k is the force constant; m is the mass; υ is the frequency of the vibration 14
Bond Properties and Absorption trends
i. Force constant of the bond
As for any harmonic oscillator, when a bond vibrates its energy of
vibration is continuously periodically changing from kinetic
energy to Potential energy and back again.
 The classical analogy of a vibrating diatomic molecule is that
of two weights connected by a spring.

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• The following formula has been derived from Hooke’s
law. For the case of a diatomic molecule

f= force constant of the bond (dyne/cm)

 How does the mass influence the
vibration? H I2
2

MM =2 g/mole MM
=254 g/mole

 The greater the mass - the lower the wavenumber

• the vibrational frequency of a bond would increase with the decrease
in reduced mass of the system. It implies that C-H and O-H
stretching absorptions should appear at higher frequencies than C-C
and C-O stretching frequencies
• As the force constant increases, the vibrational frequency
(wavenumber) also increases.
Examples of stretching frequencies and correlations with bond
strengths (bond order)

Bond strength* Bond order 

350 1 1000 cm-1

C-C

C=C 600 2 1600 cm-1

3 2200 cm-1
C C 840

*In kJ/mol For same reduced mass!

 The requirements for the absorption of IR radiation by
molecules can be summarized as follows:
1. The natural frequency of vibration of the molecule must
equal the frequency of the incident radiation.
2. The frequency of the radiation must satisfy ΔE = hv , where
ΔE
is the energy difference between the vibrational states
involved.
3. The vibration must cause a change in the dipole moment of
the molecule.
• Some molecular vibrations may not give rise to
absorption bands b/c
A. their frequency may fall out side the normal IR region
( if
heavy atom is present
B. some of vibration may have the same frequency and
overlap
• In addition to fundamental vibrations, other frequencies can
be generated. Like overtones
• Over tone bands results in weak absorption
• Overtone bands appear at integral multiples of fundamental
vibrations. Therefore, the strong absorptions at say 800 cm-1
and 1750 cm-1 will also give rise to weaker absorptions at
1600 cm-1 and 3500 cm-1, respectively.
• In the IR spectra of benzaldehyde and acetophenone , due
to C=O stretching vibration a weak overtone can be seen at
3400 and 3365 cm-1, respectively.

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• One interesting phenomenon which is occasionally occur
when a fundamental frequency is near an overtone from some
other frequency . The result is an increase in the intensity of
the overtone and and decrease in the fundamental ( fermi
resonance)

• Vibrational coupling which complicates the spectra

• ** stretching absorption of a bond appears at higher frequency

in the IR spectrum than bending absorption frequency of the
same bond.
• ** assymetric stretching appears at higher enegry
• The vibrational frequency of a bond, being part of a molecule, is
significantly affected by the electronic and steric factors of the
surroundings, in addition to the bond strength and atomic masses
discussed above.

• Example: The carbonyl stretching frequency in RCOCH3 (~1720

cm-1) is lower than acid chloride RCOCl (1750-1820 cm-1). This
change in frequency of the C=O stretching may be arising due to
(i)difference in mass between CH3 and Cl (ii) the inductive or
mesomeric influence of Cl on the C=O bond (iii) coupling
interactions between C=O and C-Cl bonds (iv) change in bond
angles arising due to steric factors etc.
 Example of IR spectra
Cyclohexanol

OH bending
O-H
stretch C-O
stretch
sp3 C-H stretch
 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 700 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. But it is unique and
thus is “fingerprint” of a compound that is unlikely to be found
even in other quite similar cpds. The use of this region to
confirm the identity of a compound with the authentic sample is
considerably more reliable
 Application of IR spectroscopy
1. Establishing conclusively the identity of two samples that have
identical spectra when determined in the same media
• Using the finger print region
2. Peaks in the functional group region ( 4000-1300 cm-1) are
characteristics of a particular functional group such as –OH, -
CH, -NH, -SH, C=O, C=C-H, and CΞC-H
3. Existence of strong peak in the region of 910-650 cm-1
indicates that the compound may aromatic . No compound is
aromatic if there is no strong peak in this region
Quantification
Characteristic Vibrational Frequencies for Common Functional
Groups
Frequency (cm-1) Functional Group Comments
3200-3500 alcohols (O-H) Broad
amine, amide (N-H) Variabl
alkynes (CC-H) e Sharp
3000 alkane (C-C-H)
alkene (C=C-H)
2100-2300 alkyne (CC-H)
nitrile (CN-H)
1690-1760 carbonyl (C=O) ketones, aldehydes, acids
1660 alkene (C=C) Conjugation lowers amide
imine (C=N) frequency
amide
(C=O)
1500-1570 nitro (NO2)
1300-1370
1050-1300 alcohols, ethers, esters, acids
(C-O)
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Instrumentation of IR

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• Dispersive instruments: with a monochromator to
be used in the mid-IR region for spectral scanning and
quantitative analysis.
• Fourier transform IR (FTIR) systems: widely applied
and quite popular in the far-IR and mid-IR spectrometry.
• Nondispersive instruments: use filters for wavelength
selection or an infrared-absorbing gas in the detection
system for the analysis of gas at specific wavelength.
 Instrumentation for Vibrational Spectroscopy
 Two IR Absorption methods:
– Dispersive methods: Scanning of wavelengths using a grating
(common examples are double-beam, like a spectrometer discussed
in the optical electronic spectroscopy lecture).

Radiation Wavelength Detector

Sample
Source Selector (transducer)

– Fourier-transform methods: based on interferometry, a method of

interfering and modulating IR radiation to encode it as a function of
its frequency.

Radiation Detector
Interferometer Sample
Source (transducer)
 IR Emission Spectroscopy

 Emission is seldom used for chemical analysis

 The sample must be heated to a temperature

much greater than its surroundings (destroying
molecules)

 IR emission is widely used in astronomy and in remote

sensing applications on heated materials.
 Fourier Transform IR Spectroscopy: Rationale
• Advantages of FT methods:
– The Jacqinot (throughput) advantage: FT instruments have few slits,
or other sources of beam attenuation
– Resolution/wavelength accuracy (Connes advantage): achieved by a
colinear laser of known frequency
– Fellgett (multiplex) advantage: all frequencies detected at once,
signal averaging occurs and thermal noise grows more slowly than
signal (good with IR detectors)
• These advantages are critical for IR spectroscopy
• The need for FT instruments is rooted in the detector
– There are no transducers that can acquire time-varying signals in the
1012 to 1015 Hz range – they are not fast enough!
• Why are FT instruments not used in UV-Vis?
– The multiplex disadvantage (shot noise) adversely affects signal
averaging – it is better to multiplex with array detectors (such as the
CCD in ICP-OES)
– In some cases, there are technical challenges to building
interferometers with tiny mirror movements
 Inteferometers for FT-IR and FT-Raman
• The Michelson
interferometer, the
product of a famous
physics
experiment:

Figures from Wikipedia.org

 Produces interference
patterns from
monochromatic and
white light
 Inteferometers
 For monochromatic
radiation, the
interferogram looks like a
cosine curve
 For polychromatic
radiation, each frequency
is encoded with a much
slower amplitude
modulation
 The relationship between
frequencies:

2v
f  cM 
Where:
 is the frequency of the radiation
c is the speed of light in cm/s
vm is the mirror velocity in cm/s

 Example: mirror rate = 0.3 cm/s modulates 1000 cm-1 light at 600 Hz
 Example: mirror rate = 0.2 cm/s modulates 700 nm light at 5700 Hz36
 FTIR Spectrometer Design
• It is possible to build a detector that detects multiple frequencies for
some EM radiation (ex. ICP-OES with CCD, UV-Vis DAD)
• FTIR spectrometers are designed around the Michelson
interferometer, which modulates each IR individual frequency with an
additional unique frequency well suited to the time response of IR
detectors:
Fourier Transform - IR Spectrum

IR Source

Beamsplitter
Michelson
Interferometer

Detector

Sample

Interferogram

Fixed Mirror Moving Mirror

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 The Basics of the Fourier Transform
• The conversion from time- to frequency domain:
b

Continuous: g ( )   K 1 (, t) f (t)d K ( , t) 

a
N 1 exp(iωt)
Discrete: fn

1
 dke 2ikn / N
N k 0

Time domain 2
Frequency domain
0.5

1.5

50 100 150 200 250 FT 1

-0.5
0.5

-1
50 100 150 200 250

2.5
2

1.5
2

1.5
0.5

50 100 150 200 250

FT 1

-0.5

0.5
-1

-1.5
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50 100 150 200 250
 IR source

A rod or cylinder made from 1-50 µm

Nernst Glower several grams of rare earth oxides,
heated to 1200-2200K by an (mid- to far-IR)
electric current.
Similar to the Nernst glower
but made from silicon carbide 1-50 µm
Globar SiC, electrically heated. Better
performance at lower (mid- to far-IR)
frequencies.heated
Tungsten (W) 0.78-2.5 µm
Heated to 1100 K
filament (Near-IR)
lamp
High-pressure mercury vapor tube, 50 - 300 µm
Hg arc lamp
electric arc forms a plasma. (far-IR)
High-intensity, tunable radiation
CO2 laser used for quantitation of 9-11 µm
specific analytes
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 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.
• For recording an IR spectrum, the sample may be gas, a
liquid, a solid or a solution of any of these. The samples
should be perfectly free of moisture, since cell materials
(NaCl, KBr, CsBr etc.) are usually spoiled by the
moisture.
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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
Common IR Solvents

 The horizontal lines indicate regions where solvent transmits at least 25%
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of
 Gas samples analysis
• A gas sample cell consists of a cylinder of
glass or sometimes a metal. The cell is closed
at both ends with an appropriate window
materials (NaCl/KBr) and equipped with
valves or stopcocks for introduction of the
sample.

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 Liquid samples
• Liquids are studied neat or in solution. In case of neat liquid, a
thin film of < 0.01 mm thickness is obtained by pressing the
liquid between two sodium chloride plates and plates are
subjected to IR beam.

• Spectra of solutions are obtained by taking 1-10 % solution of

the sample in an appropriate solvent in cells of 0.1-1 mm
thickness. A compensating cell, containing pure solvent is
placed in the reference beam of the instrument. The choice of
solvent depends on the solubility of the sample and its own
minimal absorption in IR region. Carbon tetrachloride,
chloroform and carbon disulfide are preferred solvents.
 Solid samples
•Spectra of solids are obtained as alkali halide discs (KBr), mulls (e.g. Nujol, a
highly refined mixture of saturated hydrocarbons) and films (solvent or melt
casting)

Alkali halide discs:

1. A milligram or less of the fine ground sample mixed with about 100
mg
of dry KBr powder in a mortar or ball mill.
2. The mixture compressed in a die to form transparent disc.
Mulls
1. Grinding a few milligrams of the powdered sample with a mortar or with
pulverizing equipment. A few drops of the mineral oil added (grinding
continued to form a smooth paste).
2. The IR of the paste can be obtained as the liquid sample.
 IR Detectors
 Thermal transducers
– Response depends upon heating effects of IR radiation (temperature
change is measured)
 Slow response times, typically used for dispersive instruments or
special applications
 Pyroelectric transducers
– Pyroelectric: insulators (dielectrics) which retain a strong electric
polarization after removal of an electric field, while they stay below
their Curie temperature.
– DTGS (deuterated triglycine sulfate): Curie point ~47°C
 Fast response time, useful for interferometry (FTIR)
 Photoconducting transducers
– Photoconductor: absorption of radiation decreases electrical
resistance. Cooled to LN2 temperatures (77K) to reduce thermal
noise.
– Mid-IR: Mercury cadmium telluride
(MCT) 45
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 Interpretation of IR Sprctra
• Step 1
– Look first for the carbonyl C=O band.
– Look for a strong band at 1820-1660 cm-1.
This band is usually the most intense absorption band in a
spectrum. It will have a medium width. If you see the
carbonyl band, look for other bands associated with
functional groups that contain the carbonyl by going to step
2.
– If no C=O band is present, check for alcohols and go to step
3.
• Step 2
– If a C=O is present you want to determine if it is part of an
acid, an ester, or an aldehyde or ketone. At this time you may
not be able to distinguish aldehyde from ketone.
• ACID
– Look for indications that an O-H is also present.
– It has a broad absorption near 3300-2500 cm-1.
– This actually will overlap the C-H stretch. There will
also be a C-O single bond band near 1100-1300 cm-1.
– Look for the carbonyl band near 1725-1700 cm-1.
• ESTER
– Look for C-O absorption of medium intensity near 1300-1000
cm-1.
– There will be no O-H band.
• ALDEHYDE
– Look for aldehyde type C-H absorption bands. These are
two weak absorptions to the right of the C-H stretch near
2850 cm-1 and 2750 cm-1 and are caused by the C-H bond
that is part of the CHO aldehyde functional group.
– Look for the carbonyl band around 1740-1720 cm-1.
• KETONE
– The weak aldehyde CH absorption bands will be
absent. Look for the carbonyl CO band around 1725-
1705 cm-1.
• Step 3
– If no carbonyl band appears in the spectrum, look for
an alcohol O-H band.
• ALCOHOL
– Look for the broad OH band near 3600-3300 cm-1 and a C-
O absorption band near 1300-1000 cm-1.
• Step 4
– If no carbonyl bands and no O-H bands are in the spectrum,
check for double bonds, C=C, from an aromatic or an
alkene.
• ALKENE
– Look for weak absorption near 1650 cm-1 for a double bond.
There will be a CH stretch band near 3000 cm-1.
• AROMATIC
– Look for the benzene, C=C, double bonds which appear as
medium to strong absorptions in the region 1650-1450 cm-1.
The CH stretch band is much weaker than in alkenes.

– Also check the region of 950-650 cm-1 and around 3030

cm-1 ( the –CH stretching)
C-H stretching region
• Alkanes C-H sp3 stretch < 3000 cm-1
• Alkenes C-H sp2 stretch > 3000 cm-
• Alkynes C-H sp stretch
1 ~ 3300 cm-1
• C-H Bending region
• CH2 bending ~ 1460 cm-1
• CH3 bending (asym) appears near the same value
• CH3 bending (sym) ~ 1380 cm-1
• Step 5
– If none of the previous groups can be identified, you may
have an alkane.
• ALKANE
– The main absorption will be the C-H stretch near 3000 cm-1.
The spectrum will be simple with another band near 1450
cm-1.
• Step 6
– If the spectrum still cannot be assigned you may have an
alkyl halide.
• ALKYL BROMIDE
– Look for the C-H stretch and a relatively simple spectrum
with an absorption to the right of 667 cm-1.
 Examples

C6H12O

CH3 O

CH3 CH CH2 C CH3

C-H stretch C=O stretch
 C8H8O

C-H stretch

C CH3 aromatic C=C

conj C=O
 C6H12O

OH bending
O-H
stretch C-O
stretch
sp3 C-H stretch
Thank You !

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