IR

Infrared Spectroscopy
Spectroscopic tool used for identification of the functional groups (with

covalent bonds) in organic compounds
Absorption of vibrational motions Chart infers

infrared energy of the bonds functional groups
Only those bonds, which have a dipole moment, are capable of absorbing infrared
radiation. Symmetric bonds like H-H or Cl-Cl will not absorb infrared radiation.
The bond must be unsymmetric.
R C C R C C R H H
R H H
Symmetric Alkynes Symmetric Alkenes Cl Cl
The Chart (Spectrum) of the IR is a relation between % of Transmittance (% T)
and the Wavenumber  (reciprocal of wavelength) The range of spectrum

extends from 4000 to 650 cm-1
1 -1
 = (cm )

Finger Print Region

The region, which is specific for each compound (650-1430 cm -1)
The Modes of Vibration
1- Stretching Vibrations: Change in the bond length
H H
C C
H H
Symmetric Asymmetric Stretching

Stretching
2- Bending Vibrations: Change in the bond angle
H H H
C C
H
Scissoring Wagging
H H H
C C
H
Rocking Twisting
In Plane Out of Plane
For the groups of three or more atoms (at least two atoms are identical)
they have two modes of stretching (symmetric and asymmetric) as shown in the
given Table.
Symmetric Stretching Asymmetric Stretching
H H
Methyl C H C H
H H
-1
~2872 cm -1 ~2962 cm
O O O O
C C C C
Anhydride O O
~1760 cm -1
~1800 cm-1
H H
Amino N N
H H
~3300 cm-1 ~3400 cm-1
O O
Nitro
N N
O O
~1550 cm-1
~1350 cm-1
Overtone bands: resulted from excitation of the molecule from ground state
to higher energy states (multiple integer of fundamental frequencies 2 , 3, …
etc).
Combination band: coupling of two vibrational frequencies (comb. = 1+2).
Difference band: difference of two vibrational frequencies (diff. = 1-2).
Fermi Resonance: Coupling of fundamental frequency with an overtone
or combination band
Calculation of Vibrational Frequencies

Hook`s
Law
1
 = K/ 
c
K: Force constant = 5X105 dyne/cm of single bond
= 10X105 dyne/cm of double bond
= 15X105 dyne/cm of triple bond
; reduced mass
m1m2
=
m1+m2
C C C C C C
-1 -1 -1
2150 cm 1650 cm 1200 cm
As the atom bonded to carbon increase in mass,  will increase and  will
decrease
C H C C C C Br C I
C O
Cl
- - - - - -1
2960 cm 1200 cm 1100 cm 800 cm 550 cm 500 cm
1 1 1 1 1
The bond is stronger in the order SP > SP2 > SP3
C H C H C H
SP3 SP2 SP
~ 2960 cm-1 ~ 3100 cm-1 ~ 3300 cm-1
Wavenumber (  ) of Functional Groups

Hexane (C6H14)
1-Hexene (C6H12)
1-Hexyene (C6H10)
Toluene (C7H8)
Cyclohexanol
Dibutyl ether
Types of Hydrogen Bonds

1- Intermolecular H-bond: Between one molecule and other molecule.
Many kinds of OH bonds of different lengths and strengths leads to a broad
absorption.
This type of bands are largely decreases by dilution and the peak of (OH)
group changes from broad into sharp.
2- Intramolecular H-bond: Within the same molecule and the shape of the
peak not affected by dilution
Wave numbers of carbonyl compounds (C=O)
Acid Chloride
Ester
Carboxylic Acid
Ketone
Aldehyde
Amide
Wave numbers of other functional groups
Primary Amnies
Secondary Amines
Tertiary Amines
Nitro Compound
Factors Affecting on Vibrational Frequency (  ) on (C=O)
1. Inductive (I) and Resonance (R ) Effect
The groups with (-I) will shift the electrons and increase the double bond
character (the force constant will increase) and thus (  ) will increases. On the
other hand, the groups with (+I) or (+R) will enhance the polarization and
decrease the double bond
character (the force constant will decrease) and thus (  ) will

decreases.
O O
O
R R` R H
R Cl
Ketones - Alhehydes
Acid ~ ~ 1725 cm
-1
1 1715 cm
Chloride
-1
~ 1800 cm
-
O O
R NH2 R
NH2
Acid Amide
-
~ 1690-1640 cm
1
2. Effect of Conjugation
Conjugation of (C=O) or (C=C) with ,-unsaturation or aryl group leads
to polarization of the double bond, thus decrease double bond character
and decrease (  )
In case of ester, conjugation of oxygen atom with ,-unsaturation or aryl
group leads to increase (  ) of (C=O) group.
3. Effect of Hydrogen Bond

H-bond increase the length of (C=O) group and decrease the force
constant, thus decrease the (  )
(  ) = 1680 cm-1
4. Effect of Ring Strain

In case of cyclic ketones, cyclic esters (Lactones) and cyclic amides (Lactams)
as the ring size decrease the (  ) increase due to the increasing of S-

character of (C=O) group.
O O O
Cyclohexanone Cyclopentanone Cyclobutanone

1715 cm-1 1750 cm-1 1775 cm-1
O O O
O O O
d-Valerolactone g-Butyrolactone b-Propionolactone

1735 cm-1 1770 cm-1 1785 cm-1
O O O
NH
NH NH
d-Valerolactame g-Butyrolactame b-Propionolactame

1660 cm-1 1705 cm-1 1745 cm-1

IR

Uploaded by

Copyright:

Available Formats

IR

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

IR

Uploaded by

Copyright:

Available Formats

Infrared Spectroscopy

Spectroscopic tool used for identification of the functional groups (with

Absorption of vibrational motions Chart infers

The Chart (Spectrum) of the IR is a relation between % of Transmittance (% T)

and the Wavenumber  (reciprocal of wavelength) The range of spectrum

Finger Print Region

Symmetric Asymmetric Stretching

2- Bending Vibrations: Change in the bond angle

In Plane Out of Plane

Calculation of Vibrational Frequencies

The bond is stronger in the order SP > SP2 > SP3

Wavenumber (  ) of Functional Groups

Types of Hydrogen Bonds

Wave numbers of other functional groups

character (the force constant will decrease) and thus (  ) will

group leads to increase (  ) of (C=O) group.

3. Effect of Hydrogen Bond

constant, thus decrease the (  )

4. Effect of Ring Strain

as the ring size decrease the (  ) increase due to the increasing of S-

Cyclohexanone Cyclopentanone Cyclobutanone

d-Valerolactone g-Butyrolactone b-Propionolactone

d-Valerolactame g-Butyrolactame b-Propionolactame

You might also like