Lecture22A IR 112805

Infrared Spectroscopy
Provides information about the vibrations of

functional groups in a molecule
Therefore, the functional groups present in a

molecule can be deduced from an IR spectrum
Two important parameters in all IR spectra:
The frequency of the signal, 
The intensity of the signal, I
What structural features of a molecule do 

and I depend on?
The functional group concept of organic chemistry
IR spectroscopy can identify functional groups!
Some Important and Charac teristic Infrare d Absorption Frequencies and
Wave lengths for Some Common Stretching Motions
Atom Group Typi cal of Frequency (c m-1) Wavelength ()
O-H (free) Alcoho ls (dilute) 3550-3650 c m-1 2.8 

O-H (H bonded) Alcoho ls 3200-3400 c m-1 3.0 
(concen trated)
Carboxy li c acids
C C H Acetylene (CH) 3300 cm-1 3.0 
C C H Benzene ( CH), 3010-3100 c m-1 3.3 
Ethy le ne (CH)
C_____C_____H Ethane (CH) 2950-3000 c m-1 3.5 
C C Acetylene 2100-2260 c m-1 4.5 
C N Nitr ile s 2000-2300 c m-1 4.5 
C O Carbony l 1650-1750 c m-1 5.5- 6.0 
C C Alkene 1620-1680 c m-1 6.0 
C C Alkane 600-1500 c m-1 6.7-17 
C O Alcoho ls , 1000-1300 c m-1 10-7.7 
Ethers
In gen eral we w ill only be using the d ata in an IR spectrum for stretching v ibration s
which have ene rgies higher than 1620 cm-1. Although the b ands a t lower ene rgy a re
known and assigned , the region b elow 1620 c m-1 is very conge sted wit h single bond
stretche s of two heavy atoms (see C-C and C-O in table) and C-H bend s and a re beyond
the scope of wha t we wan t to do.
n-Hexane: CH3CH2CH2CH2CH2CH3
1650 cm-1
3100 cm-1
1-Hexene: CH2=CHCH2CH2CH2CH3
3-heptanone:
CH2 CH2 CH2 CH
H3C CH2 3
O
1-Hexanol: CH3CH2CH2CH2CH2CH2OH
Where are
What in
the saturated
the
C-H stretches?
world is
this
peak CH3CH2CH2CH2CH2CH3
due to?
n-hexane
Where are
the saturated
C-H stretches?
CH3CH3
H3C C C CH3
H H
2,3-dimethyl butane
What’s this?
Where are
the C-H stretches?
CH2 CHCH2CH2CH2CH3
1-hexene
Where are
the =C-H stretches?
Why are the =C-H
stretches of lower
Where is intensity than the
the C=C stretch? saturated C-H stretches?
Where is the
the C N stretch?
CH3CH2CH2CH2CH2CH2CH2C N
1-heptyl cyanide
Where is the
C C stretch?
Where is the C-H

stretch of C C H ?
HC CCH2CH2CH2CH2CH3
1 - he p tyne
Where is the
O
C
stretch?
O
CH3CH2C CH2CH2CH2CH3
3 - he p tan o n e
Why is
the C-H
stretch so
small
compared
to the
other
Where is the
spectra?
O
C
stretch?
O
H3C C OCH2CH3
EthylAce tate
What in
the world
is this
peak due
to?
Where is the
O
stretch?
C O
CH3CH2CH2CH2CH2CH2C H
1 - h e p tan al
Where is the
OH stretch?
Where is the
C=O stretch?
CH3CH2CH2CH2CH2CH2OH
1 - h e p tan o l
Where is the
OH stretch?
Where is the
O
O
C
stretch? CH3CH2CH2CH2CH2CH2COH
1 - He p tano licAcid
IR: Masses, Atoms and Springs
A Model: Picture the atoms of a diatomic molecule
as point masses connected by springs (bonds).
As a first approximation use Hooke’s Law

F = -kx
F = force, restoring back to equilibrium
position
k = characteristic stretching constant
x = displacement from the equilibrium

position
IR Stretching Frequencies of two
bonded atoms:
What Does the Frequency, ,
Depend On?
1 k m1 m2
 mr 
m1  m 2
2 mr
 = frequency
k = spring strength (bond stiffness)
mr = reduced mass (~ mass of largest atom)
Vibrations, potential energy and motion
X Y X Y F = d PE/ dr
a b
X Y X Y
PE
c d
r re re
Internuclear Internuclear
separation separation
X Y X Y
Light atoms Heavy atoms

and / or and /or
strong bonds weak bonds
IR Stretching Frequencies: What Do
they Depend On?
Directly on the strength of the bonding
between the two atoms ( ~ k)
Inversely on the reduced mass of the two

atoms (v ~ 1/m)
Expect:  will increase with increasing bond

strength (bond order) and decreasing mass
Examples of stretching frequencies and
correlations with bond strengths (bond
order)
Bond strength* Bond order 
C-C 350 1 1000 cm-1
C=C 600 2 1600 cm-1
840 3 2200 cm-1

C C
*In kJ/mol For same reduced mass!

Quantum mechanics: The frequency () depends
on the energy gap between vibrational levels
E = h= hc/(cm-1)
Only the natural frequency will be absorbed
The natural frequency (8.67 x 1013 s-1) is

absorbed selectively
What does the absorption intensity depend on?
The absorption intensity depends on how efficiently the
energy of an electromagnetic wave of frequency  can be
transferred to the atoms involved in the vibration
The greater the change in dipole moment during a vibration,

the higher the intensity of absorption of a photon
Dipole Moment Must Change during
for a vibration to be “IR active”!
• In order to interact
strongly with the EM
radiation, the motion
of the molecule must
be such that the dipole
moment changes.
Which of the vibrations are “IR” active”?

What is the intensity of an IR signal of:
O2 or N2 or H2?
Ans: In order to absorb infrared radiation, a

molecular vibration must cause a change in the
dipole moment of the molecule
O2, N2 and H2 DO NOT ABSORB IR LIGHT!
The are not “Greenhouse” gases

Does O=C=O absorb IR light?
Ans: vibrations of O=C=O which cause a

change in the dipole moment of the molecular
absorb IR light
vibrations of O=C=O which do not cause a
change in the dipole moment of the
molecular DO NOT absorb IR light
No dipole Dipole
generated generated
Which should have a higher stretching
frequency, CO, CO+, or CO-? Why?
Ans: The higher the bond order, the stronger the

bond and the higher the frequency for the IR
stretch.
CO = ()2()4 CO+ = ()2()3 CO- = ()2()4()1
Bond order: CO = 3, CO+ = 5/2, CO- = 5/2
CO will have the higher stretching frequency

CO+ and CO- will have similar, lower frequencies
IR Stretching Frequencies of two
bonded atoms:
What Does the Frequency, ,
Depend On?
1 k m1 m2
 mr 
m1  m 2
2 mr
 = frequency
k = spring strength (bond stiffness)
mr = reduced mass (mass of largest atom)
The influence of reduced mass on the stretching
frequency 
For any X-H bond the reduced mass is

approximately equal to the mass of the very
light hydrogen atom = 1
For a C-C bond the reduced mass is

approximately equal to the mass of a carbon
atom = 12
From the formula for , compute the differences

in  for a X-H and C-C bond of equal strengths.
Infrared Spectroscopy: further review
region of infrared that is most useful lies between

2.5-16 m (4000-625 cm-1)
depends on transitions between vibrational

energy states
stretching
bending
Stretching Vibrations of a CH2 Group
Symmetric Antisymmetric
Bending Vibrations of a CH2 Group
In plane In plane
Bending Vibrations of a CH2 Group
Out of plane Out of plane

Infrared Spectrum of Hexane
bending
C—H stretching
bending bending
CH3CH2CH2CH2CH2CH3
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw-Hill Companies, Inc. All rights reserved.
Infrared Spectrum of 1-Hexene
C=C
C=C—H H—C
H2C=C
H2C=CHCH2CH2CH2CH3
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Infrared Absorption Frequencies
Structural unit Frequency, cm-1

Stretching vibrations (single bonds)
sp C—H 3310-3320
sp2 C—H 3000-3100
sp3 C—H 2850-2950
sp2 C—O 1200
sp3 C—O 1025-1200

Stretching vibrations (multiple bonds)
C C 1620-1680
—C C— 2100-2200
—C N 2240-2280
Structural unit Frequency, cm-1 C O

Stretching vibrations (carbonyl groups)
Aldehydes and ketones 1710-1750
Carboxylic acids 1700-1725
Acid anhydrides 1800-1850 and 1740-1790
Esters 1730-1750
Amides 1680-1700

Bending vibrations of alkenes
RCH CH2 910-990
R2C CH2 890
cis-RCH CHR' 665-730
trans-RCH CHR' 960-980
R2C CHR' 790-840


Bending vibrations of derivatives of benzene
Monosubstituted 730-770 and 690-710
Ortho-disubstituted 735-770
Meta-disubstituted 750-810 and 680-730
Para-disubstituted 790-840
Infrared Spectrum of tert-butylbenzene
Ar—H
C6H5C(CH3)3
H—C Monsubstituted
benzene
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Infrared Absorption Frequencies: functional groups

Stretching vibrations (single bonds)
O—H (alcohols) 3200-3600
O—H (carboxylic acids) 3000-3100
N—H 3350-3500
Infrared Spectrum of 2-Hexanol
H—C
O—H
CH3CH2CH2CH2CHCH3
OH
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Infrared Spectrum of 2-Hexanone
CH3CH2CH2CH2CCH3
O
H—C
C=O
3500 3000 2500 2000 1500 1000 500

Wave number, cm-1

Lecture22A IR 112805

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Infrared Spectroscopy

Provides information about the vibrations of

Therefore, the functional groups present in a

The frequency of the signal, 

The intensity of the signal, I

What structural features of a molecule do 

Atom Group Typi cal of Frequency (c m-1) Wavelength ()

O-H (free) Alcoho ls (dilute) 3550-3650 c m-1 2.8 

Where is the C-H

As a first approximation use Hooke’s Law

k = characteristic stretching constant

x = displacement from the equilibrium

Light atoms Heavy atoms

Inversely on the reduced mass of the two

Expect:  will increase with increasing bond

Bond strength* Bond order 

C-C 350 1 1000 cm-1

C=C 600 2 1600 cm-1

840 3 2200 cm-1

*In kJ/mol For same reduced mass!

The natural frequency (8.67 x 1013 s-1) is

The greater the change in dipole moment during a vibration,

Which of the vibrations are “IR” active”?

Ans: In order to absorb infrared radiation, a

O2, N2 and H2 DO NOT ABSORB IR LIGHT!

The are not “Greenhouse” gases

Ans: vibrations of O=C=O which cause a

Ans: The higher the bond order, the stronger the

CO = ()2()4 CO+ = ()2()3 CO- = ()2()4()1

Bond order: CO = 3, CO+ = 5/2, CO- = 5/2

CO will have the higher stretching frequency

For any X-H bond the reduced mass is

For a C-C bond the reduced mass is

From the formula for , compute the differences

region of infrared that is most useful lies between

depends on transitions between vibrational

Out of plane Out of plane

3500 3000 2500 2000 1500 1000 500

3500 3000 2500 2000 1500 1000 500

Structural unit Frequency, cm-1

Structural unit Frequency, cm-1

Structural unit Frequency, cm-1 C O

Structural unit Frequency, cm-1

RCH CH2 910-990

R2C CH2 890

cis-RCH CHR' 665-730

trans-RCH CHR' 960-980

R2C CHR' 790-840

Structural unit Frequency, cm-1

3500 3000 2500 2000 1500 1000 500

Structural unit Frequency, cm-1

3500 3000 2500 2000 1500 1000 500

3500 3000 2500 2000 1500 1000 500

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