The theoretical no.
of fundamental vibrations will seldom
be observed because overtones (multiples of a given
frequencies) and combination tones (sum of two other
vibrations) increase the no. of bands.
Other phenomena reduce the no. of bands including:
1. Fundamental frequencies that fall outside the 4000-400
cm-1 region.
2. Fundamental bands that are too weak to be observed.
3. Fundamental bands that are so close that they coalesce.
4. The occurrence of a degenerate band from several
absorptions of the same frequency in highly symmetrical
molecules.
5. The failure of certain fundamental vibrations to appear
in the IR because of the lack of change in molecular
dipole.
IR-Active and Inactive
A polar bond is usually IR-active.
A nonpolar bond in a symmetrical molecule
will absorb weakly or not at all.
Transmission
100%
50%
0%
Vibrational Spectroscopy
4500 4000 3500 3000 2500 2000 1500
Wavenumber (cm )
-1
Instrumentation
1. Radiation source 2. Monochromator
3. Solvents, sample cells, samples 4. Readout / Recorder
schematic diagram of a double beam double-grating infrared spectrophotometer
SOLVENTS, CELLS, SAMPLES
Solvents
1. Must be transparent in the region studied: no single solvent is
transparent throughout the entire IR region
2. Water and alcohols are seldom employed to avoid O-H band of water .
3. Must be chemically inert (does not react with substance or cell holder).
CCl4, CS2, or CHCl3; may be used but we should consider its IR spectrum
Cells
- NaCl or KCl cells may be used (moisture from air and sample should
be avoided: even with care, their surfaces eventually become fogged
due to absorption of moisture)
- Very thin (path length = 0.1 to 1.0 mm)
- Sample concentration = about 0.1 – 10%
Samples
1. Solid KBr disk (1 mg solid sample + 100 mg KBr pressed into a disk)
Mull: 1 mg solid sample suspended in Nujol (heavy liquid hydrocarbon)
2. Liquid Neat (thin film of liquid between two NaCl plates solution in
CCl4 and put in special NaCl cells.
3. Gas IR spectrum is obtained directly by permitting the sample to
expand into an evacuated special cells.
Use of IR spectra
• Identification of functional groups on a
molecule – this is a very important tool in
organic chemistry
• Spectral matching can be done by computer
software and library spectra
• Since absorbance follows Beer’s Law, can do
quantitative analysis
FEATURES OF AN IR SPECTRUM
An IR spectrum is a plot of per cent
transmittance (or absorbance) against
wavenumber (frequency or wavelength).
• A 100 per cent transmittance in the spectrum implies no
absorption of IR radiation. When a compound absorbs IR
radiation, the intensity of transmitted radiation
decreases. This results in a decrease of per cent
transmittance and hence a dip in the spectrum. The dip is
often called an absorption peak or absorption band.
• Different types of groups of atoms (C-H, O-H, N-H,
etc…) absorb infrared radiation at different
characteristic wavenumbers.
IR Correlation Diagram
Region I Region II
3600-2700 cm-1 1800-1600 cm-1
100
O-H N-H C-H C=O
Transmittance (%)
80 bond stretching Fingerprint
alcohols
acid chlorides Region
60 phenols
anhydrides (below 1500 cm-1)
esters
carboxylic acids
ketones
40 amines aldehydes
amides carboxylic acids
amides
20 alkynes C-H
alkenes =C-H
alkanes -C-H
0
4000 3500 3000 2500 2000 1500 1000
2.5 3.0 4.0 5.0 6.0 10.0
Frequency (cm-1) / Wavelength (microns, mm)
IR Spectrum
Baseline
Absorbance/
Peak
• No two molecules will give exactly the same
IR spectrum (except enantiomers)
• Simple stretching: 1600-3500 cm-1
• Complex vibrations: 400-1400 cm-1, called the
“fingerprint region”
• In general, the IR spectrum can be split into
four regions for interpretation:
• 4000 2500 cm-1: Absorption of single bonds
formed by hydrogen and other elements e.g.
OH, NH, CH
• 2500 2000 cm-1: Absorption of triple bonds
e.g. C≡C, C≡N
• 2000 1500 cm-1: Absorption of double bonds
e.g. C=C, C=O
• 1500 400 cm-1:This region often consists of
many different, complicated bands. This part
of the spectrum is unique to each compound
and is often called the fingerprint region. It is
rarely used for identification of particular
functional groups.
The O-H stretching region
• O-H 3600 cm-1 (alcohol, free)
• O-H 3300 cm-1 (alcohols & acids, H-bonding)
broadens
shifts
FREE H-BONDED
3600 3300
HYDROGEN-BONDED HYDROXYL
Many kinds of OH
R R bonds of different
lengths and strengths
O H O This leads to a broad
H H
absorption.
R O R O O
H R
“Neat” solution.
H
O
R H Longer bonds are
weaker and lead to
lower frequency.
Hydrogen bonding occurs in concentrated solutions
( for instance, undiluted alcohol ).
“FREE” HYDROXYL
The “free” hydroxyl vibrates without interference from any other molecule.
Distinct bond has a well-defined
CCl4 length and strength.
CCl4
R O CCl4
H
CCl4
CCl4
Solvent molecules surround
but do not
hydrogen bond.
Occurs in dilute solutions of alcohol in an “inert” solvent like CCl4.
ALCOHOL
Cyclohexanol
neat solution
OH
O-H CH2
H-bond
C-O
C-H
CARBOXYLIC ACID
Butanoic
neat solution
Acid
O-H
H-bond
C-O
CH2 O
C-H C=O CH3 CH2 CH2 C OH
CARBOXYLIC ACID DIMER
O H O
R C C R
O H O
Strong hydrogen bonding in the dimer weakens the OH
bond and leads to a broad peak at lower frequency.
Typical Infrared Absorption Regions
N-H WAVELENGTH (mm)
2.5 4 5 5.5 6.1 6.5 15.4
O-H C-H C N C=O C=N C-Cl
Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *
4000 2500 2000 1800 1650 1550 650
FREQUENCY (cm-1)
The N-H stretching region
N-H 3300 - 3400 cm-1
• Primary amines give two peaks
H H
N N
H H
symmetric asymmetric
• Secondary amines give one peak
• Tertiary amines give no peak
PRIMARY AMINE
aliphatic
1-Butanamine
NH2
scissor CH3
CH2
NH2
CH3 CH2 CH2 CH2 NH2
PRIMARY AMINE
aromatic
3-Methylbenzenamine
-CH3
Ar-H NH2
NH2
benzene
CH3 Ar-H
SECONDARY AMINE
N -Ethylbenzenamine
NH
NH CH2 CH3
CH3
Ar-H
benzene
TERTIARY AMINE
N,N -Dimethylaniline
Ar-H
-CH3
CH3
no N-H
N
CH3
CH3
benzene Ar-H
C-H STRETCH
STRONGER BONDS HAVE LARGER FORCE CONSTANTS
AND ABSORB AT HIGHER FREQUENCIES
increasing frequency (cm-1)
3300 3100 3000 2900 2850 2750
=
=C-H =C-H -C-H -CH=O
(weak)
sp-1s sp2-1s sp3-1s aldehyde
increasing s character in bond
increasing CH Bond Strength
increasing force constant K
CH BASE VALUE = 3000 cm-1
ALKANE
Hexane
CH bending vibrations
discussed shortly
CH includes
stretching CH3 sym and asym
vibrations CH2 sym and asym
CH3 CH2 CH2 CH2 CH2 CH3
C N AND C C STRETCH
Typical Infrared Absorption
Regions
C=N
=
WAVELENGTH (mm)
2.5 4
C=C
= 5 5.5 6.1 6.5 15.4
O-H C-H C N C=O C=N C-Cl
Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *
4000 2500 2000 1800 1650 1550 650
FREQUENCY (cm-1)
The triple bond stretching region
• C =N 2250 cm-1
• C =C 2150 cm-1
The cyano group often gives a strong, sharp peak
due to its large dipole moment.
The carbon-carbon triple bond gives a sharp peak,
but it is often weak due to a lack of a dipole. This is
especially true if it is at the center of a symmetric
molecule.
R C C R
NITRILE
Propanenitrile BASE = 2250
=
C=N
CH3 CH2 C N
ALKYNE
BASE = 2150
1-Hexyne
=
=C-H =
C=C
HC C CH2 CH2 CH2 CH3
C=O STRETCHING
Typical Infrared Absorption
Regions
WAVELENGTH (mm)
C=O
2.5 4 5 5.5 6.1 6.5 15.4
O-H C-H C N C=O C=N C-Cl
Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *
4000 2500 2000 1800 1650 1550 650
FREQUENCY (cm-1)
THE CARBONYL STRETCHING REGION
This region stretches from about 1800 to 1650
cm-1 - RIGHT IN THE MIDDLE OF THE SPECTRUM
The base value is 1715 cm-1 (ketone)
The bands are very strong !!! due to the large
C=O dipole moment.
C=O is often one of the strongest peaks in
the spectrum
KETONE
BASE = 1715
2-Butanone
1715
overtone
2x C=O
C-H CH bend
O
C=O
C=O
CH3 C CH2 CH3
C=O IS SENSITIVE TO ITS ENVIRONMENT
EACH DIFFERENT KIND OF C=O COMES AT A DIFFERENT FREQUENCY
acid carboxylic
chloride ester aldehyde ketone acid amide
O O O O O O
R C R C R C R C R C R C
Cl OR' H R OH NH2
1800 1735 1725 1715 1710 1690
anhydride
O O
BASE
R C O C R VALUE
1810 and 1760 THESE VALUES ARE
( two peaks ) WORTH LEARNING
all are +/- 10 cm-1
SUMMARY
Ketones are at lower frequency than Aldehydes because of
the second electron-donating alkyl group.
Acid chlorides are at higher frequency than ketones because
of the electron-withdrawing halide.
Esters are at higher frequencies than ketones due to the
electron-withdrawing oxygen atom. This is more important than
resonance with the electron pair on the oxygen.
Amides are at lower frequencies than ketones due to
resonance involving the unshared pair on nitrogen. The electron-
withdrawing effect of nitrogen is less important than the
resonance.
Note the electronegativity difference, O versus N, weights the
two factors (resonance/ e-withdrawal) differently in esters
than in amides.
Acids are at lower frequency than ketones due to H-bonding.
