IR Seminar on the Principles and Applications of Infrared

Spectroscopy

By Miediegha Oyeintonbara

Department of Pharmaceutical and Medicinal Chemistry,

Faculty of Pharmacy, Niger Delta University
 Introduction
 Infrared spectroscopy is a photospectroscopic technique

 A very useful analytical method widely employed in the elucidation of

chemical structures.

Almost any compound having covalent bonds, whether organic or inorganic,

absorbs various frequencies of electromagnetic radiation in the infrared
region of the electromagnetic spectrum.
 Not all bonds in a molecule are capable of absorbing infrared energy, even
if the frequency of the radiation exactly matches that of the bond motion.
 Only those bonds that have a dipole moment that changes as a function
of time are capable of absorbing infrared radiation. Symmetric bonds, such
as those of H2 or Cl2, do not absorb infrared radiation.
 A bond must present an electrical dipole that is changing at the same
frequency as the incoming radiation for energy to be transferred. The
changing electrical dipole of the bond can then couple with the sinusoidally
changing electromagnetic field of the incoming radiation. Thus, a
symmetric bond that has identical or nearly identical groups on each end
will not absorb in the infrared.
 For the purposes of an organic chemist, the bonds most likely to be
affected by this restraint are those of symmetric or pseudosymmetric
alkenes (C=C) and alkynes (C≡C).

Only those bonds that have a dipole moment that changes as a function of time are capable
every type of bond has a different natural frequency of vibration, and because
two of the same type of bond in two different compounds are in two slightly
different environments, no two molecules of different structure have exactly
the same infrared absorption pattern, or infrared spectrum.
The Electromagnetic Spectrum
 The electromagnetic spectrum is the range of all possible frequencies, from zero to
infinity. The electromagnetic spectrum can be divided into 7 regions composed of
radio waves, microwaves, infrared (IR), visible light, UV light, X-rays and gamma-
rays.

 The spectrum is however, continuous, and the exact positions of the dividing lines
between the different regions are more or less arbitrary.
 The EM radiations all travel at the speed of light 3 x 1010 cm/s, but differ in their
wavelengths and frequencies.
The wavelength is inversely related to frequency, as shown in the equation below:

λ∝ Or λ∝

= speed of light (3 * 1010 cm/sec)

= frequency in hertz
λ = wavelength in centimeters

𝐸=h𝑣 =h 𝑐 / 𝜆
where h is Planck’s constant, 6.62 * 10-37 kJ.sec
 Type of Radiation Frequncy Range Wavelength Range
(Hz) (cm)
Gamma rays 1020 – 1024 ˂ 10-12m

X-rays 1017 – 1020 1 nm – 1 pm

Ultra violet light 1015 – 1017 400 nm – 1 nm

Visible 4 – 7.5*1014 750 nm – 400 nm

Near infrared 1*1014 – 4*1014 2.5 µm – 750 nm

Infrared 1013 – 1014 25 µm – 2.5 µm

Microwaves 3*1011 – 1013 1 mm – 25 µm

Radio waves < 3*1011 > 1 mm

The mid- (fundamental) infrared region (IR or MIR) extends from 4000 cm1 (2.5 m) to 400 cm1 (25 m). It is
surrounded by the far-IR region (FIR) from 400 cm1 (25 m) to 10 cm1 (1 mm) and the very important near-IR region
(NIR) from 12500 cm1 (800 nm) to 4000 cm1 (2.5 m).
The sensitivity limits of the human eye extend from violet light (λ = 400 nm, 4 x 10-7 m) through the rainbow colours to red light
(A = 800 nm, 8 x 10-7 m) . Wavelengths shorter than 400 nm and longer than 800 nm exist, but they cannot be detected by the
human eye. Ultraviolet light (λ < 400 nm) can be detected on photographic film or in a photoelectric cell , and infrared light (λ
>800 nm) can be detected either photographically or using a heat detector such as a thermopile .
Stretching and Bending Vibrations
A bond vibrates with both stretching and bending motions.
■ A stretch is a vibration occurring along the line of the bond; a stretching vibration
changes the bond length.
■ A bend is a vibration that does not occur along the line of the bond; a bending vibration
changes the bond angle.

Diatomic molecules, e.g. H-Cl, can undergo only a stretching vibration because it has no
bond angles.

Molecules with three or more atoms undergo stretches and bends.

 Stretching and bending vibrations can be symmetric or asymmetric.
 Bending vibrations can be either in-plane or out-of-plane, and are often referred to by
the terms rock, scissor, wag, and twist.
Infrared radiation
 The range of frequencies of infrared radiation (4000 to 600 cm-1) correspond to the

frequencies of the stretching and bending vibrations of the bonds in organic molecules .

 Each stretching and bending vibration of a given bond occurs with a characteristic frequency.
When a molecule is bombarded with radiation of a frequency that exactly matches the
frequency of the vibration of one of its bonds, the molecule absorbs energy.

 This allows the bond to stretch and bend a bit more. By experimentally determining the
wavenumbers of the energy absorbed by a particular compound, we can ascertain what kinds of
bonds it has.
Infrared spectrum

 A plot of the percent transmission of radiation versus the wavenumber (or

wavelength) of the radiation transmitted.

 At 100% transmission all the energy of the radiation (of a particular

wavenumber) passes through the molecule. Lower values of percent
transmission mean that some of the energy is being absorbed by the
compound.

 Each downward spike in an IR spectrum represents absorption of energy.

The spikes are called absorption bands.

 Locations of absorption bands are preferably reported in wavenumbers.

The Functional Group and Fingerprint Regions

 An infrared spectrum could be divided into the Left and Right parts. The area on the left (4000-
1400 cm-1) is where most of the functional groups show absorption bands. This is called the
functional group region.

 The area on the right (1400-600 cm-1) is called the fingerprint region because it is
characteristic of the compound as a whole, just as a fingerprint is characteristic of an
individual.

 No two molecules have identical IR spectra because the functional groups are not in exactly
the same environment in both compounds.

 For example, 2-pentanol and 3-pentanol have the same functional groups, so they show similar
absorption bands in the functional group region. But their fingerprint regions are different
because the compounds are different.
 IR spectra can be quite complex as the stretching and bending vibrations of each
bond in a molecule can produce an absorption band.

 It is easier to focus on the functional groups.

 In order to identify an unknown compound, analysts often use IR spectroscopy

in conjunction with information obtained from other spectroscopic techniques.
CHARACTERISTIC INFRARED ABSORPTION BANDS
 Stretching vibrations require more energy than bending vibrations, so absorption
bands for stretching vibrations are found in the functional group region (4000-
1400 cm-1), whereas those for bending vibrations are typically found in the
fingerprint region (1400-600 cm-1).

 As a result, stretching vibrations are the ones most often used to determine what
kinds of bonds a molecule has.
Frequencies of some stretching vibrations associated with different types of bonds
ABSORPTION BAND INTENSITY

 When a bond stretches, the increasing distance between the atoms increases its
dipole moment. The intensity of the absorption band depends on the size of this
change in dipole moment.

 The greater the change in dipole moment, the more intense the absorption.

 For example, absorption bands for the stretching vibrations of C=O and C=C
bonds appear at similar frequencies, but they are easily distinguished: the one for
C=O is much more intense because it is associated with a much greater change
in dipole moment since the bond is more polar.
2-Pentanone: Intense absorption band at ~1720 cm-1 indicates a C=O bond
2-Cyclohexenone intense absorption band at ~1720 cm-1 indicates a C=O bond
 A compound could be positively identified by comparing its fingerprint
region with the fingerprint region of the spectrum of a known sample of the
compound.

 The stretching and bending vibrations of each bond in a molecule can

produce an absorption band.
  The stretching vibration of an O–H bond would experience a greater change
in dipole moment than that of an N–H bond, because the O–H bond is more
polar.
Expected intensity of absorption: O–H > N–H > C–H

 Absorption band intensity also depends on the number of bonds

responsible for the absorption.

 For example, the absorption band for C–H stretch is more intense for 1-
iodohexane (13 C–H bonds) than for methyl iodide (3 C–H bonds).

 Sample concentration also affects the intensity of the absorption bands.

THE POSITION OF ABSORPTION BANDS
The frequency of a stretching vibration (the amount of energy required to
stretch a bond) depends on the strength of the bond and the masses of the
bonded atoms.

The stronger the bond, the greater the energy required to stretch it. Also,
heavier atoms vibrate at lower frequencies.

Lighter atoms show absorption bands at larger wavenumbers.

C¬H ~3000 cm-1; C¬D ~2200 cm-1; C¬O ~1100 cm-1; C¬Cl
~ 700 cm-1
Bond Order (Stronger bonds show absorption bands at larger wavenumbers)
Whether a bond is a single bond, a double bond, or a triple bond, affects bond
strength. Therefore, bond order affects the position of absorption bands

Bond Strength (frequency)

A C≡C (~2100 cm-1) > C═C (~1650 cm-1) > C–C (1300 to 800 cm-1)

Because C–C bonds are weak and very common, these vibrations are of little
value in identifying organic compounds.

Also, C=O (~1700 cm-1) > C–O (~1100 cm-1),

and C≡N (~2200 cm-1) > C=N (~1600 cm-1) C–N (~1100 cm-1).
 Electron delocalization, hybridization and hydrogen bonding affect the
position and shape of an absorption band

 The exact position and shape of a group’s absorption band depends on

other structural features of the molecule, such as electron delocalization,
the electronic effect of neighboring substituents, and hydrogen bonding.
Electron delocalization gives the carbonyl group less double-bond character,
so it absorbs at a lower frequency (~1680 cm-1)
Hydrogen Bonding
 O–H bonds show intense absorption bands.
Both the position and the shape of an O–H absorption band depend on
hydrogen bonding.

 Intermolecular O–H bond is easier to stretch.

 Hydrogen-bonded OH groups have broad absorption bands because

hydrogen bonds vary in strength, and bonds with different strengths absorb
at different frequencies.
Hybridization

 The strength of a C–H bond depends on the hybridization of the carbon.

The greater the s character of the carbon, the stronger is the bond that it
forms
S/ Wavenumber (cm-1)
N
1 C≡C–H ⁓3300

2 C=C−H 3100−3020
3 C−C−H 2960−2850
Bending Vibrations

 If a compound has sp3 carbons, a look at 1400 cm-1 will indicate whether
the compound has a methyl group. All hydrogens bonded to sp3 carbons
show a C−H bending vibration slightly to the left of 1400 cm-1. Methyl
groups show an additional C−H bending vibration slightly to the right of
1400 cm-1.

 If a compound has a methyl group, absorption bands will appear both to

the left and to the right of 1400 cm-1; otherwise, only the band to the left
of 1400 cm-1 will be present.
APPLICATIONS

• Identification of substances through comparism of spectrums

• Determination of molecular structure

• For evaluation and progress monitoring of reactions

• Detection of impurities in compounds

• Resolution or confirmation of isomers: trans isomers give a simpler

spectrum

• Identification of functional groups