Lecture Notes

Chem 51A
S. King
Chapter 13
Infrared Spectroscopy
I. Background
Nearly every portion of the electromagnetic spectrum has been used to elucidate
the structures of atoms and molecules.
The Electromagnetic Spectrum:

10!2 100 102 104 106 108 1010 1012 $ (nm)

visible

"!ray X-ray UV infrared microwave radiowave

1020 1018 1016 1014 1012 1010 108 106 104 # (s!1)

400 nm 750 nm
!

visible spectrum

A variety of techniques are available, including Ultraviolet/Visible (UV/Vis)

Infrared (IR) and Nuclear Magnetic Resonance (NMR) Spectroscopy.

These techniques are based on the fact that molecules have different kinds of
energy levels, and therefore absorb radiation in several regions of the
electromagnetic spectrum. When a molecule absorbs light of a given frequency,
specific molecular effects occur, depending on the wavelength absorbed. Low
energy radiowaves, for example, cause nuclear spin flip transitions, whereas more
energetic UV radiation results in electrons being promoted to higher energy levels.
Energy is proportional to the frequency of light absorbed:

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Molecular effects associated with different regions of the EM spectrum:

Wavelength (!) Energy/mole Molecular effects

10"10 meter gamma rays 106 kcal

10"8 meter X-rays 104 kcal ionization

vaccum UV 102 kcal

near UV electronic transitions

10"6 meter visible 10 kcal

infrared 1 kcal molecular vibrations

10"4 meter (IR)
10"2 kcal
10"2 meter microwave rotational motion
10"4 kcal
100 meter radio 10"6 kcal nuclear spin transitions
102 meter

II. IR Spectroscopy
IR radiation causes groups of atoms to vibrate with respect to the bonds that
connect them.
rest of molecule

H H

 We will mostly be concerned with stretching vibrations because bending vibrations occur in a
region of the spectrum that is difficult to interpret.

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A. The frequency of the stretching vibration depends on two quantities:
m1 and m2: the masses of the atoms
f: the force constant, or spring constant (a measure of
the stiffness of the bond)

• Heavier atoms vibrate more slowly than lighter ones.

• The force constant is larger for stronger bonds (it takes more energy to
stretch a stronger bond) and smaller for weaker bonds, thus stronger
bonds usually vibrate at a higher frequency than weaker bonds between
similar atoms.

Examples:

1. O H

C H

2.

3. H Csp

H Csp2

H Csp3

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 B. The intensity of the absorption is proportional to the strength of the dipole
moment of the molecule.
R R R H R H
!+ !" !+ !"
C O C O vs. C C C C
H H H R H R
polar bond non-polar bond

∴ A symmetrical bond with no dipole moment will show only a weak

absorption or none at all.

H3C CH3

C. For a given type of bond, the frequency shows little change with the rest
of the molecule.

O H

H
C
H

∴ IR is especially useful in indicating the functional groups

present in a molecule.

How do you interpret an IR spectrum?

1) You will usually be given the molecular formula of the compound. Use
it to evaluate the units of unsaturation (see Chapter 10.)
2) Divide the spectra into 3 regions, and look for characteristic bands using
the IR chart given:
X-H region
sp region
double bond region
3) Practice, practice, practice!

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 Interpretation of Infrared Spectra

X-H Phenol & RO H 3700 - 3500 sharp

Region Alcohols or
3200 - 3600 broad (H-bonded)
O

Acids R O H 2800 - 3600 very broad

O
H
Amines & R N H 2 bands: N primary
Amides H
3300 - 3500
H
N H 1 band: N secondary
R

C-H Bonds C C H 3200 -3300

C C H 3000 - 3200

C C H 2900 - 3000
O

R H 2700 -2800

sp Acetylenes C C 2100 (weak or absent if highly symmetrical)

Region
Nitriles C N 2200

Carbon dioxide O C O 2350

Alkenes C C 1600 - 1670 weak unless conjugated

Double
Bond Imines C N 1600 - 1700
Region
Nitro NO2 1350 and 1550

Carbonyl Groups:
O O
1800 - 1840 Ketones: O O O
Anhydrides (2 bands) Acyclic and 1710 1680
O
O
O O
Acid Chlorides 1800 1740 1715
Cl
O O
Esters 1725 - 1750 1770
OR
O O O
Acids 1710
OH O 1770 O 1740
O
Amides 1650
NH2 Ring Contraction: Conjugation:
O add 30 for each subtract 30
contraction
Aldehydes 1725
H
O
Carboxylate 1550-1610 and 1400
O

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167
 OH

OH

168
O

O
OH

NH2

169
 O
NH2

CN
Br

170