Organic Lecture Series

Infrared
Spectroscopy
(Chapter 12)

Organic Lecture Series

This reaction from Ochem 1

How do we know if it worked? The reactant is

cyclohexene; the product is cyclohexanol. How can we
tell the difference?

Infrared Spectroscopy (IR) is

an easy way to do it.

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Electromagnetic Radiation
• Electromagnetic radiation: light and other
forms of radiant energy
• Wavelength (λ): the distance between
consecutive peaks on a wave
• Frequency (ν): the number of full cycles of
a wave that pass a given point in a second
• Hertz (Hz): the unit in which radiation
frequency is reported; s-1 (read “per
second”)
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Electromagnetic Radiation

• Common units used to express

wavelength λ

Relation
Un it to Meter
Meter (m) ---- c = λν
Millimeter (mm) 1 mm = 10-3 m
Micrometer (μm) 1 μm = 10-6 m E = hν
N anometer (nm) 1 nm = 10-9 m E is kJ/mol
An gs trom (Å ) 1 Å = 10-10 m h= 3.99 X 10-13 kJzszmol-1
ν = frequency in Hz

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E=hν

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Infrared Spectroscopy
• The vibrational IR extends from 2.5 x 10-6 m (2.5
μm) to 2.5 x 10-5 m (25 μm)
– the frequency of IR radiation is commonly expressed in
wavenumbers
– Wavenumber ν: the number of waves per centimeter, with
units cm-1 (read reciprocal centimeters)
– expressed in wavenumbers, the vibrational IR extends
from 4000 cm-1 to 400 cm -1
-2 -1 -1 10-2 m•cm -1 -1
ν = 10 m•cm = 4000 cm ν = = 400 cm
2.5 x 10-6 m 2.5 x 10-5 m

25 μm to 2.5 μm
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Sections of an IR Spectrum

This is the most common scale.

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• IR spectrum of 3-methyl-2-butanone

Strong
absorption

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• IR spectrum of 3-methyl-2-butanone

C-H
Stretch C=O
Stretch

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Molecular Vibrations
–atoms joined by covalent bonds undergo continual
vibrations relative to each other
–the energies associated with these vibrations are
quantized; within a molecule, only specific
vibrational energy levels are allowed
–the energies associated with transitions between
vibrational energy levels correspond to
frequencies in the infrared region:

4000 to 400 cm-1 11

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• For a molecule to absorb IR radiation

– the bond undergoing vibration must be polar and
– its vibration must cause a periodic change in the
bond dipole moment
• Covalent bonds which do not meet these
criteria are said to be IR inactive
– the C-C double and triple bonds of symmetrically
substituted alkenes and alkynes, for example, are
IR inactive because they are not polarized bonds
H3 C CH3
C C H3 C- C C- CH3
H3 C CH3
2,3-Dimethyl-2-butene 2-Butyne 12
 Organic Lecture Series

Molecular Vibrations
• Consider two covalently bonded atoms as two
vibrating masses connected by a spring
– the total energy is proportional to the frequency of vibration
– the frequency of a stretching vibration is given by an
equation derived from Hooke’s law for a vibrating spring

ν K
= 4.12 μ

K = a force constant, which is a measure of the bonds’

strength; force constants for single, double, and triple
bonds are approximately 5, 10, and 15 x 105 dynes/cm
μ = reduced mass of the two atoms, (m1m2)/(m1 + m2),
where m is the mass of the atoms in grams
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The simplest vibrational motions are bending

and stretching.
Here are the fundamental stretching and
bending vibrations for a methylene group:

http://en.wikipedia.org/wiki/Infrared_spectroscopy 14
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Symmetric Asymmetric Scissoring

Rotation Wagging Twisting

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Molecular Vibrations

ν K
= 4.12 μ

• From this equation, we see that the position

(i.e. wavenumber) of a stretching vibration:
– is proportional to the strength of the vibrating bond
– is inversely proportional the masses of the atoms
connected by the bond
• The intensity (i.e. weak, s, m) of absorption
depends primarily on the polarity of the
vibrating bond
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Correlation Tables
Table 12.4 Characteristic IR absorptions for the
types of bonds and functional groups
encountered most often:

Stretching
Bon d Frequ ency (cm -1) Intens ity
O-H 3200-3650 w eak to s trong
N-H 3100-3550 mediu m
C-H 2700-3300 w eak to medium
C=C 1600-1680 w eak to medium
C=O 1630-1820 strong
C-O 1000-1250 strong
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Organic Lecture Series

Hydrocarbons-Table 12.5

Hydro- Frequen cy
-1
carbon Vib ration (cm ) Intens ity
Alk ane
C-H Stretchin g 2850 - 3000 Mediu m
Bend ing 1450-1475 Mediu m
CH3 Bend ing 1375 and 1450 Weak to medium
C-C (N ot useful for interpretation - too man y b ands
Alk ene
C-H Stretchin g 3000 - 3100 Weak to medium
C=C Stretchin g 1600 - 1680 Weak to medium
Alk yn e
C-H Stretchin g 3300 Mediu m to stron g
C C Stretchin g 2100-2250 Weak
Arene
C-H Stretchin g 3030 Weak to medium
C=C Stretchin g 1450-1600 Mediu m
C-H Bend ing 690-900 Strong
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Alkanes

• IR spectrum of decane (Fig 12.4)

3000

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Alkenes
• IR spectrum of cyclohexene (Fig 12.5)

3000

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Alkynes

• IR spectrum of 1-octyne (Fig 12.6)

3000

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Aromatics
• IR spectrum of toluene (Fig 12.7)

3000

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Alcohols
Bond Frequency, cm-1 Inten sity
O-H (free) 3600-3650 Weak
O-H (H b ond ed) 3200 - 3500 Medium, broad
C-O 1000 - 1250 Medium

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Effect of Concentration Upon Hydrogen Bonding

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Effect of Concentration Upon Hydrogen Bonding

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Ethers
• IR spectrum of dibutyl ether (Fig 12.9)

3000

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Ethers
• IR spectrum of anisole (Fig 12.10)

3000

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Amines
• IR spectrum of 1-butanamine (Fig 12.11)

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IR of Molecules with C=O Groups

Frequency
Carbonyl Group Vibration (cm-1 ) Intensity
O Ketones
RCR' C=O Stretching 1630-1820 Strong
O Aldehydes
RCH C=O Stretching 1630-1820 Strong
C-H Stretching 2720 Weak

O Carboxylic acids
RCOH C=O Stretching 1700-1725 Strong
O H Stretching 2500-3300 Strong (broad)

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Organic Lecture Series

IR of Molecules with C=O Groups

O Amides
RCNH2 C=O Stretchin g 1630-1680 Strong
N H Stretchin g 3200, 3400 Mediu m
(1° amides h ave tw o N -H stretches )
(2° amides h ave one N -H stretch )

O Carboxylic esters
RCOR' C=O Stretchin g 1735-1800 Strong
2
sp C O Stretchin g 1200-1250 Strong
3
sp C O Stretchin g 1000-1100 Strong

O O Acid anhydrides
RCOCR C=O Stretchin g 1740-1760 and Strong
1800-1850
C O Stretchin g 900-1300 Strong
RC N Nitriles
C≡N Stretchin g 2200-2250 Mediu m
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Aldehydes and Ketones

• IR spectrum of menthone (Fig 12.12)

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Carboxylic acids

• IR spectrum of pentanoic acid (Fig 12.13)

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Amide

• IR of N-methylpropanamide (Fig 12.14)

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Esters

• IR of Ethyl butanoate (Fig 12.15)

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Strategies for IR Interpretation

Inspect the spectrum from left to right.
9If there is a strong, but broad band 3500 cm-1
then, OH is present. One or two weak peaks in this
area are indicative of amines (N—H stretch).
9Examine the 3000 cm-1 C—H aliphatic stretches
are to the right and C—H from alkenes & aromatics
are to the left.
9Aldehyde C—H stretch will be ~ 2720 cm-1
9Check the area from 1820 to 1630 cm-1. Strong
peaks in this area indicate C=O and this is often the
strongest peak in the spectrum.
9The area from 1250 to 1000 cm-1 are the C—O
stretches of ethers, esters, acids.
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