12 12- -1 1

William H. Brown Beloit College

William H. Brown
Christopher S. Foote
Brent L. Iverson
Eric Anslyn
http://academic.cengage.com/chemistry/brown
Chapter 12
Infrared Spectroscopy
12 12- -2 2
ChemActivity
ChemActivity
16: Spectroscopy
16: Spectroscopy
Split quickly in groups of 4
Assign one role to each person: 1) Manager, 2)
Recorder, 3) Time-keeper, 4) Spokesperson
Go to the purple book to page 137 (Chem Activity
16, Part A)
Work on the critical thinking questions (1-9)
You have 15-20 min
We will discuss the questions in 5 min
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Electromagnetic Radiation
Electromagnetic Radiation

Electromagnetic radiation:
Electromagnetic radiation: Light and other forms
of radiant energy.

Wavelength (
Wavelength (

):
): The distance between
consecutive peaks on a wave.

Frequency (
Frequency (

):
): The number of full cycles of a
wave that pass a given point in a second and is
reported in hertz, which has the units s
-1
.

Hertz (Hz):
Hertz (Hz): The unit in which radiation frequency
is reported: s
-1
(read per second ).
12 12- -4 4
Electromagnetic Radiation
Electromagnetic Radiation
Common units used to express wavelength()

Angstrom () 1 = 10
-10
m
Relation
to Meter
Unit
1 mm = 10
-3
m
1 nm = 10
-9
m
1 m = 10
-6
m
Nanometer (nm)
Micrometer (m)
Millimeter (mm)
Meter (m) ----
12 12- -5 5
Molecular Spectroscopy
Molecular Spectroscopy

Molecular spectroscopy
Molecular spectroscopy The study of which
frequencies of electromagnetic radiation are
absorbed or emitted by a particular substance
and the correlation of these frequencies with
details of molecular structure.
we study three types of molecular spectroscopy
Nuclear spin states
Electronic energy levels
Infrared
Radio frequency
Ultraviolet-
visible
Absorption of
Electromagnetic
Radiation Results
in Transition Between
Region of the
Electromagnetic
Spectrum
Nuclear magnetic
resonance
Infrared
Ultraviolet-
visible
Type of
Spectroscopy
Frequency
(hetz)
2.5 x10
14
-1.5x10
15
3 x10
7
-9x10
8
1 x10
13
-1x10
14
Vibrational energy levels
12 12- -6 6
Infrared Spectroscopy
Infrared Spectroscopy
The vibrational IR extends from 2.5 x 10
-6
m (2.5
m) to 2.5 x 10
-5
m (25 m).
The frequency of IR radiation is commonly expressed in
wavenumbers.
Wavenumber Wavenumber: : 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
.
()
-
=
= 400 cm
-1
= 4000 cm
-1
=
10
-2
mcm
-1
2.5 x 10
-6
m
10
-2
mcm
-1
2.5 x 10
-5
m
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Infrared Spectroscopy
Infrared Spectroscopy
Infrared spectrum of 3-methyl-2-butanone.
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Molecular Vibrations
Molecular Vibrations
Atoms joined by covalent bonds undergo continual
vibrations relative to each other.
The frequencies of rather than 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
.
12 12- -9 9
Molecular Vibrations
Molecular Vibrations
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 polar bonds.
H
3
C
C C
CH
3
H
3
C CH
3
H
3
C-C C-CH
3
2,3-Dimethyl-2-butene 2-Butyne
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Molecular Vibrations
Molecular Vibrations
For a nonlinear molecule containing
n
n atoms,
there are
3
3
n
n
-
-
6
6 allowed fundamental vibrations.
For even a relatively small molecule, a large
number of vibrational energy levels exist and
patterns of IR absorption can be very complex.
The simplest vibrational motions are bending
and stretching.
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Molecular vibrations
Molecular vibrations
Fundamental stretching and bending vibrations
for a methylene group.
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Molecular Vibrations
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; E = h where h is Plancks constant.
The frequency of a stretching vibration is given by an
equation derived from Hookes law for a vibrating
spring.
K = a force constant, which is a measure of bond
strength; force constants for single, double, and triple
bonds are approximately 5, 10, and 15 x 10
5
dynes/cm.
= reduced mass of the two atoms, (m
1
m
2
)/(m
1
+ m
2
),
where m is the mass of the atoms in amu.
K

= 4.12

12 12- -13 13
Molecular Vibrations
Molecular Vibrations
From this equation, we see that the peak
position
position
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 intensity of absorption depends primarily on the
polarity of the vibrating bond.
K

= 4.12

12 12- -14 14
Correlation Tables
Correlation Tables
Infrared stretching frequencies of selected
functional groups.
C-H
N-H
O-H
C=O
C=C
C-O 1000-1250 strong
weak to medium 1600-1680
1630-1820 strong
2700-3300
weak to medium
weak to strong 3200-3650
medium
3100-3550
Intensity
Stretching
Frequency (cm
-1
)
Bond
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Hydrocarbons
Hydrocarbons
-
-
Table 12.5
Table 12.5
Stretching
3300
Medium to strong
Stretching 2100-2250 Weak
Weak to medium 1600 - 1680
Stretching
Weak to medium
3000 - 3100
Stretching
Alkyne
Alkene
Alkane
Vibration
Stretching
Hydro-
carbon
Frequency
(cm
-1
)
Intensity
2850 - 3000
Medium
Bending
1450-1475 Medium
Bending
1375 and 1450 Weak to medium
C C
C-H
CH
3
C=C
C-H
C-H
C-C (Not useful for interpretation - too many bands
Arene
Stretching 3030
Weak to medium
C-H
Medium 1450-1600
Stretching C=C
Bending 690-900
Strong
C-H
CH
2
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Alkanes
Alkanes
Infrared spectrum of decane.
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Alkenes
Alkenes
Infrared spectrum of cyclohexene.
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Alkynes
Alkynes
Infrared spectrum of 1-octyne.
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Aromatics
Aromatics
Infrared spectrum of toluene.
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Alcohols
Alcohols
The free O-H is not intrinsically weak. Its intensity depends on
concentration and the hydrogen bonding character of the solvent
Infrared spectrum of 1-hexanol
O- H (free)
O- H (H bonded)
C-O
Bond
Intensity Frequency , cm
-1
Medium 1000 - 1250
Medium, broad 3200 - 3500
3600-3650 Weak
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Ethers
Ethers
Infrared spectrum of dibutyl ether.
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Ethers
Ethers
Infrared spectrum of anisole.
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Amines
Amines
Infrared spectrum of 1-butanamine, a 1 amine.
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IR of Molecules with C=O Groups
IR of Molecules with C=O Groups
C=O
C=O
C-H
O H
RCOH
O
RCH
O
RCR'
O
C=O
Strong 1700-1725 Stretching
Carboxylic acids
Aldehydes
Vibration
Carbonyl Group
Frequency
(cm
-1
)
Intensity
Stretching 1630-1820 Strong
Stretching 2720 Weak
Stretching 2500-3300 Strong (broad)
Ketones
Stretching 1630-1820 Strong
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IR of Molecules with C=O Groups
IR of Molecules with C=O Groups
C=O
sp
3
C O
sp
2
C O
C=O
C=O
N H
CN
RC N
RCOCR
O O
RCOR'
O
RCNH
2
O
C O Stretching
900-1300 Strong
Strong 1735-1800 Stretching
Carboxylic esters
Stretching 1000-1100 Strong
Stretching 1200-1250 Strong
Acid anhydrides
Stretching 1740-1760 and
1800-1850
Strong
Strong 1630-1680 Stretching
Amides
Stretching 3200, 3400 Medium
(1 amides have two N-H stretches)
(2 amides have one N-H stretch)
Nitriles
Stretching 2200-2250 Medium
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Aldehydes and Ketones
Aldehydes and Ketones
Infrared spectrum of menthone.
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Carbonyl groups
Carbonyl groups
The position of C=O stretching vibration is
sensitive to its molecular environment.
as ring size decreases and angle strain increases,
absorption shifts to a higher frequency.
conjugation shifts the C=O absorption to lower
frequency.
1850 cm
-1
1780 cm
-1
1745 cm
-1
1715 cm
-1
O
O
O
O
1690 cm
-1
1700 cm
-1
1717 cm
-1
O O
H
O
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Carboxylic acids
Carboxylic acids
Infrared spectrum of pentanoic acid.
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Esters
Esters
Infrared spectrum of ethyl butanoate.
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Infrared
Infrared
Spectroscopy
Spectroscopy
End Chapter 12
End Chapter 12