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 Infra red spectroscopy (IR)

Tools for establishing molecular structure

 Lecture 18 - Learning Objectives

• Comprehend the basis for absorption of IR

radiation
• Define frequency ranges for absorptions of major
functional groups
• Distinguish between different functional groups which
absorb in similar regions of the IR spectrum
– NH (NH2) vs. OH
• Distinguish between molecules which have different
functional groups containing the same chromophore
– Ketone vs. aldehyde
– Ester vs. amide
– Amide vs. carboxylic acid
 IR Spectroscopy
Energy is absorbed in the form of electromagnetic (EM)
radiation resulting in a change in the vibrational energy
state of the molecule

Energy is absorbed from the infrared region of the EM

spectrum

Identical IR spectra is strong evidence for chemical

identity

Similar functional groups give rise to bands at or near the

same frequency regardless of the structure of the rest of
the molecule
 Vibrational energy levels and IR

• Each bond can be considered as a harmonic

oscillator
• Frequency needed to induce vibration depends on
the mass of atoms and the strength of bonds
 IR spectrum

Fingerprint region

No need to analyse peaks in the

fingerprint region for the
purpose of this course

4000 3000 2000 1500 1000 500

wavenumber cm-1
 Chromophores

A chromophore is an easily identified part of the

molecule that characteristically absorbs EM
radiation

Useful chromophores in IR spectroscopy

• absorb strongly
• absorb above 1500 cm-1 (outside the fingerprint region)
• provide structural information about the molecule
 Selection rule #1
Only vibrations that result in a change in dipole moment
can be excited by EM radiation

FORBIDDEN e.g. N2 ALLOWED e.g. HCl

✖ ✔

Oscillating dipole moment interacts with electric component

of an EM wave

Energy levels are described by quantum numbers

n=0, n=1, n=2 …..
 Vibrational energy levels for diatomics
En = (n + 1/2)h
n = vibrational quantum For n = 0
number (0, 1, 2, …) E0 = (0 + ½)h = ½ h
h = Planck’s constant For n = 1
 =  E1 = (1 + ½)h = 1½ h
where  is the For n = 2
fundamental vibrational E2 = (2 + ½)h = 2½ h
frequency

At room temperature most molecules are in the vibrational

ground state
 Selection rule #2
n = ± 1
The most common transition
n=0  n=1
E = En=1 - En=0
=3 ½h - ½h
= h

Energy change is determined by fundamental

vibration frequency
TPQ
 IR spectra of polyatomics
• More complex than diatomics
– Diatomics have a single mode of vibration (stretching)
• A molecule of N atoms has 3N degrees of freedom
• For a non-linear molecule
Translation Rotation Vibration

3N-6

• A linear molecule has 3N-5 vibrational degrees of

freedom
 Fundamental modes of vibration in
polyatomics

• Stretching (change of interatomic distance)

• Bending (change in bond angles)

Modes of stretching

Symmetric stretch Asymmetric stretch

 Modes of bending

Rocking Scissoring

Wagging Twisting
 IR spectrum

Fingerprint region

No need to analyse peaks in the

fingerprint region for the
purpose of this course

4000 3000 2000 1500 1000 500

wavenumber cm-1
 Important vibrational bands
Single bond Triple Double Fingerprint
stretching bond bond region

OH, NH CC, CN BEND ROCK

stretch stretch
C-O
CH C=C, C=N C-N
stretch C=O C-C

4000 3500 3000 2500 2000 1500 1000 400

There are four general regions of the spectrum
• > 3000 cm-1 - single bond stretching
• 2000-2500 cm-1 - triple bond stretching
• 1500-2000 - double bond stretching
• Fingerprint region - various coupled stretching/bending bands
 Distinguishing between absorptions at
similar frequency
OH-stretch NH-stretch

NH bend

CH stretch

4000 3000 2000 1500 4000 3000 2000 1500

 Summary
• IR excites vibrational energy levels
– selection rules
• Fundamental vibration frequencies
– effects of mass, bond strength
– different modes of vibration
• stretching, bending
• Useful chromophores
• Interpretation of spectra
Distinguishing between C=O containing
compounds
Which of the following can be distinguished
by their IR spectra?
 Which of the following compounds is most
likely to give the infra-red spectrum below?

A. 1

B. 2

C. 3

D. 4
4000 3000 2000 1500 1000 500
Wavenumber cm-1

0% 0% 0% 0%

4
 Which of the following compounds is most
likely to give the infra-red spectrum below?

A. 1

B. 2

C. 3

D. 4
4000 3000 2000 1500 1000 500
Wavenumber cm-1

0% 0% 0% 0%

4
 Appendix

Distinguishing between C=O containing

compounds
 Carbonyl containing compounds
give strong bands 1850-1550 cm-1
Electronic interactions • Hydrogen bonding
– Inductive effects – Decreases double bond
strengthen bond character (solvent effects)
H Br Cl F  lower wavenumbers
> > >
C=O C=O C=O C=O
 higher wavenumbers • Ring strain
– e.g. cyclic ketones; smaller
– Resonance effects decrease ring  stronger bond
double bond character
 higher wavenumbers
O O
>

 lower wavenumbers
 Ketones
aliphatic ketones 1715 cm-1 cyclohexanone 1715 cm-1
conjugated ketones 1685-1666 cm-1 cyclopentanone 1745 cm-1
cyclobutanone 1780 cm-1

C=O stretch
 Aldehydes
aliphatic aldehydes 1740-1720 cm-1
conjugated aldehydes 1710-1685 cm-1

(aldehyde CH doublet 2720, 2780 cm-1)

C=O stretch
 Carboxylic acids

In solid state or non H-

bonding solvents carboxylic
acids form dimers
– broad band 3300-2500 cm-1
(For monomers
– OH stretch 3650-3585 cm-1 )
– carbonyl stretch
• aliphatic 1760 cm-1
• conjugated 1710-1685 cm-1
• COH bend 940-920 cm-1
 Carboxylic esters Amides
aliphatic ester 1750-1735 cm-1 Symmetric stretch 3350 cm-1
conjugated ester 1730-1715 cm-1 Asymmetric stretch 3150 cm-1
C=O stretch 1680 cm-1
N-H bend 1630 cm-1
 Aliphatic vs. aromatic compounds

aliphatic C-H 3000-2850 cm-1 aromatic C-H 3150-3000 cm-1

C-H bending 1460-1370 cm-1

overtone region ~2000-1800 cm-1

ring breathing 1600, 1500 cm-1
aliphatic stretch below 3000 cm-1 in plane deformation ~1000 cm-1
out of plane deformation ~750 cm-1
 Important vibrational bands
Single bond Triple Double Fingerprint
stretching bond bond region

OH, NH CC, CN BEND ROCK

stretch stretch
C-O
CH C=C, C=N C-N
stretch C=O C-C

4000 3500 3000 2500 2000 1500 1000 400

There are four general regions of the spectrum
• > 3000 cm-1 - single bond stretching
• 2000-2500 cm-1 - triple bond stretching
• 1500-2000 - double bond stretching
• Fingerprint region - various coupled stretching/bending bands
IR spectrum of aspirin (KBr Disc)
aromatic bands

ester
Carboxylic acid dimer

2 x C=O stretch
aliphatics