IR Spectroscopy

Structural Prediction of Organic Compounds

 IR Spectra
% Trasmittance

2-Pentanone
2-Pentanone

Wavenumbers (cm-1)
 IR Spectroscopy-Basics and principle
• Molecules are flexible, atoms and groups of atoms can rotate about single
covalent bonds.
• Bonds can stretch and bend just if their atoms were joined by flexible springs.
• Infrared spectroscopy, also called IR spectroscopy, probes stretching and
bending vibrations of molecules.
• Atoms joined by bonds are not fixed in one position but rather undergo
continual vibrations relative to each other. The energies associated with
these vibrations are quantized, which means that, within a molecule, only
specific vibrational energy levels are allowed.
• The energies associated with these transitions between vibrational energy
levels in organic molecules correspond to frequencies in the infrared region
which stretches from 4000 to ~600 cm-1.
3
 IR Spectroscopy-Basics and principle
• IR Spectroscopy is not used for complete structural characterization of
compounds. It is used to determine the various functional groups present in
the molecule.

• It is very difficult to assign all the peaks obtained in the IR spectra of a

compound.

• Two compounds will never show similar IR spectra (except enantiomers).

• In order to be IR active, a vibration must cause a change in the dipole

moment of the molecule.

4
 Presentation of the IR Spectra
Designation Abbreviation Wavelength
Near-Infrared NIR 0.78–3 μm
Mid-Infrared MIR 3–50 μm
Far-Infrared FIR 50–1000 μm

• Wavelength of IR Radiation used in IR spectroscopy is from 2.5 μm to 17 μm

approximately.
• The position of an infrared absorption band is specified in frequencies units
by its wavenumber (n) measured in reciprocal centimetres (cm-1).
• Therefore, in terms of wavenumber in cm-1 , IR spectra range is from 4000 to
600 cm-1.
• An infrared spectrum is the graph of % transmittance versus frequency
expressed as wavenumbers.
• Each dip in a spectrum called a band or peak, represents absorption of
infrared radiations at that frequency by the sample. A 100 % transmittance
means no absorption and if all the radiation is absorbed the transmittance is
0 percent.

5
(a) High Frequency Region: (4000 to 1650 cm-1)
• This region is especially useful for identification of various functional groups.
• This region shows absorption arising from stretching modes and often contains only a
few bands.
(b) Fingerprint Region: (1650 to 600 cm-1)
• It is called fingerprint region because the pattern of absorption in this region are unique
to any particular compound, just as a person’s fingerprint are unique.
• Many of the vibrational modes in the fingerprint region depend on complex vibrations
involving the entire molecule, it is impossible for any two different compounds (except
enantiomers) to have precisely the same IR spectrum.
• Both stretching and bending modes give rise to absorptions here. One therefore, cannot
correlate an individual band with a specific functional group with accuracy in this
region. 6
 Molecular Vibrations
HCl molecule as an anharmonic
oscillator vibrating at energy level E3

• Bonds behave as if they are tiny springs

connecting the atoms.
• The vibrational motion is quantized as shown
for a diatomic molecule (HCl).
• At room temp, most of the molecules in a given
sample are in the lowest vibrational state.
• However, on absorption of light of appropriate
energy the molecule becomes excited to the
second vibrational level. In this level, the
amplitude of the molecular vibration is greater.

• For the excitation of a molecule from one vibrational energy level to another, the
molecule has to absorb IR radiation of a particular energy (i.e, radiation of particular
wavelength or frequency).
7
 Molecular Vibrations

• There are two types of molecular vibrations, stretching and bending.

• A molecule consisting of n atoms has a total of 3n degrees of freedom,
corresponding to the Cartesian coordinates of each atom in the molecule.
• In a nonlinear 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:

8
 Symmetric and Asymmetric Vibration

Calculation reveals that a simple molecule such as propane, C3H8, has 27

fundamental vibrations, and therefore, you might predict 27 bands in an IR
spectrum!

The fundamental vibrations for water, H2O (n= 3; non linear; fundamental
vibrations = 9 – 6 = 3), are shown in picture. Water, which is nonlinear, has
three fundamental vibrations (two stretching + one bending).

Stretching vibrations require higher energy than bending vibrations and occur
at higher frequency!!
9
 Stretching and Bending
Carbon dioxide, CO2, is linear and hence has four (9-5) fundamental
vibrations.

The asymmetrical stretch of CO2 gives a strong band in the IR at 2350 cm–1.
You may notice this band in samples which you run on the instruments in the
labs, since CO2 is present in the atmosphere.

The two scissoring or bending vibrations are equivalent and therefore, have
the same frequency and are said to be degenerate, appearing in an IR
spectrum at 666 cm–1.

The symmetrical stretch of CO2 is inactive in the IR because this vibration

produces no change in the dipole moment of the molecule.
10
 Stretching and Bending
Symmetric stretching Antisymmetric stretching

Stretching Vibrations

Rocking Wagging Twisting

Scissoring

Bending Vibrations 11
 Different stretching modes in acetic acid

• Apart from these characteristic absorptions (stretching vibrations) which throw light
on the general nature and the presence of functional groups in the compound there
are other absorption bands (bending vibrations) as well.

• Vibrational bending modes are Scissoring, Wagging, Twisting, and Rocking.

• Order of energy; asymmetric stretching>symmetric stretching> bending

• Neither there is necessity nor time for a skilled chemist to interpret these absorptions
because of the complexity of vibrational modes!
12
 Role of Dipole Moment in IR

• In order to be IR active, a vibration must cause a change in the dipole

moment of the molecule.

• The reason for this involves the mechanism by which the photon transfers
its energy to the molecule, which is beyond the scope of this discussion.

• Carbon monoxide (CO) and iodine chloride (I-Cl) absorb IR radiation, but
hydrogen (H2), nitrogen (N2), Chlorine (Cl2) and other symmetrical
diatomics do not.

• In general, the larger the dipole change, the stronger the intensity of the
band in an IR spectrum.

• Bands of hydrocarbons which are only composed of carbon and hydrogen

atoms are weak, whereas bands associated with bonds connecting atoms
differing considerably in electronegativity, e.g., C=O are usually quite
strong.

13
Trans dichloroethylene shows no C=C stretching around 1640 cm-1, whereas, the cis
isomer shows this band. It may be noted that both isomers show bands for C-H and
C-Cl stretchings.

14
 Calculation of Vibrational Frequencies

The frequency of vibration is dependant on two quantities, the

masses of the atoms and the stiffness of the bond. Vibrational
frequencies can be calculated by applying Hooke’s Law.

15
• The actual range for C–H absorptions is 2850–3100 cm–1.

• The region of an IR spectrum where bond stretching vibrations are seen

depends primarily on whether the bonds are single, double, or triple or
bonds to hydrogen.

16
From the knowledge of bond dissociation energies, one knows that a C-H bond (104
kcal/mole, i.e., 435 kJ/mol) is only slightly stronger than a C-C bond ( 88 kca/mol, i.e.,
368.2 kJ/mol, ethane). Even then, the difference is nicely reflecting in the stretching
frequencies of these two bonds (2950 and 1200 cm-1, respectively).

17