Infrared (IR)Spectroscopy

g-rays X-rays UV IR Microwave Radio

Visible
 Applications
• Qualitative determination of substances
• Structural elucidation by determining the
functional groups.
• Detection of impurities
• Identification of geometrical isomers for
both organic & inorganic samples
• Detection of presence of water in sample
 Electromagnetic Spectrum

• Radiant energy is proportional to its frequency

• Freq.(cycles/s =Hz) as a wave (Amplitude is its height)
• Classified by frequency or wavelength ranges
 Absorption spectra
• Organic compound exposed to electromagnetic
radiation, can absorb energy of only certain
wavelengths (unit of energy)
-Transmits, energy of other wavelengths.

• Changing wavelengths to determine which wavelengths

are absorbed and which are transmitted produces an
absorption spectrum

• Energy absorbed is distributed internally in a distinct and

reproducible way
 Planck’s Equation

ΔE = hv =hc/λ

E = energy of 1 photon
h =Planck’s constant, 6.62 x 10-34 J-s
ν =frequency, s-1
λ =wavelength, cm
c = speed of light, 3.00 x 1010 cm/s
 IR of Organic Molecules
• IR region has lower energy than visible light (below red –
produces heating as with a heat lamp)

• 2.5 × 10−6 m to 2.5 × 10−5 m region used by organic

chemists for structural analysis

• IR energy in a spectrum is usually measured as wave

number cm-1), the inverse of wavelength and
proportional to frequency

Wave number= υ (cm-1) =1/λ(cm)

• Absorption of IR radiation in this region causes bonds to

change from a lower to higher vibrational energy.
 FTIR Instrumentation

FTIR collects all wavelengths simultaneously and scans at once.

 Radiation sources
Produces intense & steady radiation
 Monochromators

An optical device that transmits a mechanically

selectable narrow band of wavelenghth of light or
other radiation.

Monochromators are 2 types

1. Prismatic Monochromators:
Composed of glass or quartz and coated by alkyl
halides (NaCl)
 Monochromators
2. Grating Monochromators:
• High dispersion and resolution than prismatic
monochromators

• Reflection Grating Monochromator are common than

Transmittance Gratings
Detectors/Transducers
 Advantages
• Fast & sensitive

• All frequencies can be modulated at once

• Simple mechanical design with only one moving

part

• No stray light is involved

• Availability of easy sampling accessories

• Air pollutants like CO, ethylene oxide etc. can be

analysed
 Sample Preparation
Solids- MULL

• Small amount of sample is ground in agate or mullite mortar with mulling

material (colourless paraffin oil) in a thin paste.

• Sample is then transferred to a window of NaCl or KBr and covered with

another window.

• A thin film is produced by gentle pressure with a slight rotation.

• 2 plates with mull is placed in cell holder and the spectrum recorded.

• Strong bands at 2900cm-1, 1470cm-1and 1370 cm-1 and weak band at 720 cm-
1
is due to paraffin.
 Sample Preparation
• Solids- PRESSED PELLET

• A few milligrams of sample is ground with 100x the quantity of matrix

material (transparent material: KBr used for this)

• Ground powder is transferred to stainless steel dice (~13mm in diameter).

• Air removed using vacuum pump.

• Power is pressed into a disc between stainless steel dice.

• Well made pellet will have 80-90% transmittance in regions below 3000cm -
1
.
 Sample Preparation

• Liquid and solutions

• Place one drop of the liquid onto a disc of NaCl or KBr.

• Cover the drop with another disc.

• Mount the discs on the holder and run the spectra.

• Teflon spacers may be used to give various path lengths.

 Infrared Energy Modes
• IR energy absorption corresponds to specific modes or combinations of
atomic movements, such as bending and stretching of bonds
between groups of atoms called “normal modes”

• Energy is characteristic of the atoms in the group and their bonding

• Corresponds to vibrations and rotations

 Vibrational Modes
• Energy is absorbed when the energy of the radiation is
the same as the energy difference between two
vibrational frequencies.
Infrared Spectra
 Interpreting IR Spectra

• Most functional groups absorb at about the same

energy and intensity independent of the molecule they
are in

• Characteristic higher energy IR absorptions can be used

to confirm the existence of the presence of a functional
group in a molecule

• IR spectrum has lower energy region characteristic of

molecule as a whole (“fingerprint” region)
 Regions of IR Spectra
• 4000-2500 cm-1 N-H, C-H, O-H • 2000-1500 cm-1 double bonds
(stretching) (stretching)
• 3300-3600 cm-1 N-H, O-H •C=O 1680-1750 cm-1
• 3000 cm-1 C-H •C=C 1640-1680 cm-1
• 2500-2000 cm-1 C≡C and C≡N • Below 1500 cm-1 “fingerprint”
(stretching) region
 Differences in Infrared Absorptions
• Molecules vibrate and rotate in normal modes, which are
combinations of motions (relates to force constants)

• Bond stretching dominates higher energy modes

• Light atoms connected to heavy atom vibrate fastest:

C-H, N-H, O-H

• For two heavy atoms, stronger bond requires more

energy: C≡C, C≡N > C=C, C=O, C=N > C-C, C-O, C-N,
C-halogen
 Factors affecting Infrared Absorptions
• Symmetry- has no dipole moment, therefore does not generate oscillating dipole.
(vibrations give rise to absorption if it is associated with oscillating electric dipole)

• Coupling of vibrations
– in-phase and out-of phase
– Stretching and bending

• Fermi resonance
– Coupling of vibration with an overtone

• Hydrogen bonding
– Broadening of peaks

• Ring strain
– Frequency increases with increase in angle strains

• Electronic Effects
– Resonance and inductive effects (higher freq with inductive effect eg acid chloride= 1800 while
aldehyde=1730cm-1)

• Isomerism
– Constitutional, stereoisomers, conformational and tautomerism
 Infrared Spectra of Some Common
Functional Groups

• Alkanes, Alkenes, Alkynes

• C-H, C-C, C=C, C ≡ C have characteristic peaks
• absence helps rule out C=C or C ≡ C
Hexane
1-Hexene
Hexyne
 IR: Aromatics

• Weak C–H stretch at 3030 cm−1

• Weak absorptions 1660 - 2000 cm −1 range
• Medium-intensity absorptions 1450 -1600 cm −1
Benzene
Ethylbenzene
IR: Alcohols and Amines
IR: 1-Hexanol
Acetic acid
Primary amine
Secondary amines
Tertiary amine
 IR: Aldehydes

• Strong, sharp C=O peak 1670 to 1780 cm−1

• Exact absorption characteristic of type of carbonyl
compound
• 1730 cm−1 in saturated aldehydes
• 1705 cm−1 in aldehydes next to double bond or aromatic ring
 IR: Ketones
• 1715 cm−1 in six-membered ring and acyclic ketones
• 1750 cm−1 in 5-membered ring ketones
• 1690 cm−1 in carbonyl groups next to a double bond or an aromatic ring
 IR: Esters

• 1735 cm−1 in saturated esters

• 1715 cm−1 in esters next to aromatic ring or a double bond

Which is cyclohexane and which is
cyclohexene?
Identify the structure
 YouTube Videos
http://www.youtube.com/watch?v=DDTIJgIh86E

http://www.youtube.com/watch?v=7d3KUcbq58U&feature=related

http://www.youtube.com/watch?v=0nxrFd7i_fM

http://www.youtube.com/watch?v=XIWc9eT476c