IR Spectroscopy:

Spectral Analysis

Dr. Hasina Yasmin

Professor
Department of Pharmacy
 IR Spectroscopy: Quick Review
• If a substance is irradiated by IR radiation, the wavelength of which is constantly
changing, different bond will absorb energy at different frequencies.
• As a result, an Infrared absorption spectrum is obtained in which percentage of
intensity of the transmitted IR light is plotted against the wavelength (or wave
number) of that light.
 IR Spectroscopy: Quick Review
• Frequency of vibration of a bond in a molecule depends on the nature of the atoms joined by
the bond, arrangement of atoms within the molecule (i.e. environment), mass of the atom
and strength of the bonds, no two molecule of different structure have exactly the same
infrared spectrum.
• For this reason, the Infrared spectrum can be used for molecules such as a fingerprint can be
used for humans.

• For example,
-OH group of alcohols absorbs strongly at 3200-3600 cm-1
-CO- group of ketone absorbs at 1710 cm-1
-CN group at 2250 cm-1
-CH3 group at 1375-1450 cm-1, etc.
 IR Spectroscopy: Quick Review

• An IR spectrum is used to identify functional groups that are present (or absent).
• Cannot conclusively identify a structure by IR alone unless an IR spectrum of an authentic
(known) sample of the compound is available.
• Absorptions from specific functional groups are found in certain regions of the IR spectrum.
 IR Spectroscopy: Quick Review
• Increasing bond order leads to higher frequencies:
• C-C 1200 cm-1 (fingerprint region)
• C=C 1600 - 1680 cm-1
• CC 2200 cm-1 (weak or absent if internal)

• Conjugation lowers the frequency:

• isolated C=C 1640-1680 cm-1
• conjugated C=C 1620-1640 cm-1
• aromatic C=C approx. 1600 cm-1

• C=C peaks are generally weak to moderate in intensity.

 How to look for when examining IR spectra
• wavenumbers
• Shape of the peaks: broad or sharp
• Intensity of the peaks: strong (s), medium (m), weak (w)

For instance, to some extent C=O and C=C bonds

absorb in the same region of the infrared spectrum:
C=O 1850–1630 cm−1
C=C 1680–1620 cm−1
However, the C=O bond is a strong absorber,
whereas the C=C bond generally absorbs only weakly
A comparison of the intensities of the
C=O and C=C absorption bands
How to look for when examining IR spectra…………..

The shape and fine structure of a peak often give clues to its identity as well. Thus, although
the N-H and O-H regions overlap,
O-H 3650–3200 cm−1
N-H 3500–3300 cm−1
the N-H absorption usually has one or two sharp absorption bands of lower intensity,
whereas O-H, when it is in the N-H region, usually gives a broad absorption peak.

A comparison of the shapes of the O-H and N-H groups

IR spectrum of 3-methyl-2-butanone
Carbon-Hydrogen Bonds

• Bonds with more s character absorb at a higher frequency.

• sp3 (alkane) C-H
• just below 3000 cm-1 (to the right)

• sp2 (alkene or aromatic hydrocarbon) C-H

• just above 3000 cm-1 (to the left)

• sp (alkyne) C-H
• at 3300 cm-1
* Alkane
• The spectrum is usually simple, with few peaks.
• sp3 C-H absorption always occurs at frequencies < 3000 cm−1 (3000–2840 cm−1).
• CH2 Methylene groups have a characteristic bending absorption at 1465 cm−1.
• CH3 Methyl groups have a characteristic bending absorption at 1375 cm−1.
• CH2 The bending (rocking) motion associated with four or more CH2 groups in an open
chain occurs at about 720 cm−1 (called a long-chain band).
• C-C Stretch not interpretatively useful; many weak peaks.
Alkane
 * Alkene
• =C-H Stretch for sp2 C-H occurs at values >3000 cm−1 (3095–3010 cm−1).
• =C-H Out-of-plane (oop) bending occurs in the range 1000– 650
cm−1.
• C=C Stretch occurs at 1660–1600 cm−1; conjugation moves C=C stretch to
lower frequencies and increases the intensity.
• Symmetrically substituted bonds (e.g., 2,3-dimethyl-2-butene) do not absorb in the
infrared (no dipole change).
• Symmetrically di-substituted (trans) double bonds are often vanishingly weak in
absorption; cis are stronger.
Alkene
Alkynes
 * Alcohol
• O-H The hydrogen-bonded O-H band is a broad peak at 3400–3300 cm−1 (alcohols not
dissolved in a solvent).
The free O-H stretch is a sharp peak at 3650–3600 cm−1.

This band appears in combination with the hydrogen-bonded

O-H peak when the alcohol is dissolved in a solvent. free O-H gives relatively weak bands on
the left.

•C-O Stretching vibration usually occurs in the range 1260–1000 cm−1. This band
can be used to assign a primary, secondary, or tertiary structure to an alcohol.

• 3° Alcohols (saturated) C-O: 1150 cm-1

• 2° Alcohols (saturated) C-O: 1100 cm-1
• 1° Alcohols (saturated) C-O: 1050 cm-1
Alcohol

Long chain bend

CH3 bend

CH2 bend
Alcohols not dissolved Alcohol dissolved Alcohol is diluted
in a solvent in a solvent free O-H gives weak
hydrogen-bonded O-H band band appears in
is a broad peak
bands when there is
combination with the no hydrogen bond
hydrogen-bonded
O-H peak. Free O-H
gives relatively weak
bands on the left.
O-H of alcohols and N-H Bonds of amines

• Both O-H and N-H stretches appear around 3300 cm-1, but they look
different.
• Alcohol O-H
• broad with rounded tip when hydrogen bonding
is present (sharp in the absence of hydrogen bonding)
• Primary amine (RNH2)
• Broad (usually) with two sharp spikes.
• Secondary amine (R2NH)
• Broad (usually) with one sharp spike
• No signal for a tertiary amine (R3N)
 N–H Bend: primary amines
• A broad, round peak may be observed around 1600 cm-1 for the N – H bend,
especially with primary amines.

NH2
stretch
N-H
bend
N-H bend has
a different
shape than an
aromatic ring
or C=C
N–H: secondary amines
Carbonyl compounds
• Carbonyl stretches (-C=O) are generally strong:
• Aldehyde ~1725 cm-1
• Ketone ~1715 cm-1
• Carboxylic acid ~1710 cm-1
• Ester ~1730 - 1740 cm-1
• Amide ~1640-1680 cm-1
• Conjugation shifts all carbonyl absorptions to lower frequencies.
• Ring strain shifts carbonyl absorptions to higher frequencies. -1
1745 cm

O
H3C
 1725 cm-1
Aldehydes
 1715 cm-1
Ketones
Carboxylic acid

• O-H Stretch, usually very broad (strongly H-bonded), occurs at 3400–

2400 cm−1 and often overlaps the C-H absorptions.

• C=O Stretch, broad, occurs at 1730 –1700 cm−1. Conjugation moves the
absorption to a lower frequency.

• C-O Stretch occurs in the range 1320 –1210 cm−1, medium intensity
Carboxylic Acids
 Esters O

O
• C=O stretch at ~ 1735-1750 cm-1
• C-O stretch at 1000-1300 cm-1 (broad) strong
(Note: other functional groups may have peaks in the 1000-1300 cm-1 region too!)

1743 1245
Amides
• C=O stretch at 1640-1700 cm-1 (sometimes a double peak)
• N-H stretch (if 1o or 2o) around 3300 cm-1
Aromatic compounds
• C-H bonds of the ring show up similar to vinyl C-H at 3000-3100 cm-1 (m)
• Due to the delocalization of electrons in the ring, where the bond order between carbons is 1 ½, the
stretching frequency for these bonds is slightly lower in energy than normal C=C
• These bonds show up as a pair of sharp bands, 1500 (s) & 1600 cm-1 (m), where the lower frequency
band is stronger
Aromatic compounds
• If the region between 1667-2000 cm-1 (w) is free of interference (C=O stretching frequency is in this region)
a weak grouping of peaks is observed for aromatic systems
• Analysis of this region, can lead to a determination of the substitution pattern on the aromatic ring

Monosubstituted
G
G
1,2 disubstituted (ortho or o-)

G
1,3 disubstituted (meta or m-)
G
G

1,4 disubstituted (para or p-)

G
Aromatic compounds
The out-of-plane bending peaks that appear in the range 900–690 cm-1 can also be used to assign
substitution on the benzene ring.
Nitriles
• C  N absorbs just above 2200 cm-1 (med – strong)

• The alkyne C  C signal is much weaker and is just below

2200 cm-1
IR Spectroscopy
Example: Interpret the following IR spectrum by assigning each of the major
peaks. Identify what functional group(s) are present.

3403
cm-1

1604
cm-1
IR Spectroscopy
Example: Interpret the following IR spectrum by
assigning each of the major peaks. Identify what
functional group(s) are present.

2733
cm-1
2814
cm-1

1691 1642
cm-1 cm-1
 Infrared Spectroscopy

Example: Which one of the following compounds is the most reasonable

structure for the IR spectrum shown below?
O
O
OCH3 OH
O O

1721
 Infrared Spectroscopy
Example: Which of the following compounds is the most
reasonable structure for the IR spectrum shown below?

O O
OH OH
NH2 OH OH
O O

1603

1689