Infrared Spectroscopy

Introduction
Spectroscopy is an analytical technique
which helps determine structure.

It destroys little or no sample (non-

destructive method).

The amount of light absorbed by the

sample is measured as wavelength is
varied.
Chapter 12 2
 Types of Spectroscopy
Infrared (IR) spectroscopy measures the bond
vibration frequencies in a molecule and is used
to determine the functional group.
Mass spectrometry (MS) fragments the molecule
and measures the masses.
Nuclear magnetic resonance (NMR)
spectroscopy detects signals from hydrogen
atoms and can be used to distinguish isomers.
Ultraviolet (UV) spectroscopy uses electron
transitions to determine bonding patterns. =>
Chapter 12 3
Electromagnetic Spectrum
Examples: X rays, microwaves, radio waves, visible light, IR, and UV.

Electromagnetic radiation has the characteristics of both

waves and particles
The wave nature of electromagnetic radiation is described by
wavelength (l) or frequency (n)
The relationship between wavelength (or frequency) and
energy (E) is well defined

Wavelength and frequency are inversely proportional (n= c/l)

The higher the frequency, the greater the energy of the wave
The shorter the wavelength, the greater the energy of the
wave
Chapter 12 4
The Spectrum and
Molecular Effects

=>
Chapter 12 5
=>
 The IR Region
Just below red in the visible region.

Wavelengths usually 2.5-25 mm.

More common units are wavenumbers, or

cm-1, the reciprocal of the wavelength in
centimeters.

Wavenumbers are proportional to frequency

and energy. Chapter 12 => 6
 Molecular Vibrations
Covalent bonds vibrate at only certain
allowable frequencies.

=>
Chapter 12 7
Stretching Frequencies

Frequency decreases with increasing

atomic weight.
Frequency increases with increasing
bond energy. =>

8
Chapter 12
Chapter 12 9
 Vibrational Modes

Nonlinear molecule with n atoms usually has

3n - 6 fundamental vibrational modes.

Chapter 12 10
Chapter 12 11
 Fingerprint of Molecule
No two molecules will give exactly the
same IR spectrum (except enantiomers).

Simple stretching: 1600-3500 cm-1has the

most common vibrations, and we can use
it to get information about specific
functional groups in the molecule.

Complex vibrations (bending): 600-

1400 cm-1, called the fingerprint region
and has the most complex
Chapter 12 vibrations. 12
 IR-Active and Inactive
A polar bond is usually IR-active.
A nonpolar bond in a symmetrical
molecule will absorb weakly or not at all.

Chapter 12 13
Chapter 12 14
An Infrared Spectrometer

Chapter 12 15 =>
 FTIR Spectrometer
Has better sensitivity.
Less energy is
needed from source.
Completes a scan in
1 to 2 seconds.
Takes several scans
and averages them.
Has a laser beam that
keeps the instrument
accurately calibrated.
 Carbon-Carbon (C-C)
Bond Stretching
Stronger bonds absorb at higher
frequencies:
C-C 1200 cm-1
C=C 1660 cm-1
CC 2200 cm-1 (weak or absent if internal)
Conjugation lowers the frequency:
isolated C=C 1640-1680 cm-1
conjugated C=C 1620-1640 cm-1
aromatic C=C approx. 1600 cm-1 =>
Chapter 12 17
Chapter 12 18
Carbon-Hydrogen (C-H)
Stretching
Bonds with more s character absorb at a
higher frequency.

sp3 C-H, just below 3000 cm-1 (to the right)

sp2 C-H, just above 3000 cm-1 (to the left)
sp C-H, at 3300 cm-1

=>
Chapter 12 19
Examples

Chapter 12 20
An Alkane IR Spectrum
n >3000; d 1465, 1375

=>
Chapter 12 21
An Alkene IR Spectrum

=>
Chapter 12 22
An Alkyne IR Spectrum

=>
Chapter 12 23
 O-H and N-H Stretching
Both of these occur around 3300 cm-1,
but they look different.
Alcohol O-H, broad with rounded tip.
Secondary amine (R2NH), broad with one
sharp spike.
Primary amine (RNH2), broad with two
sharp spikes.
No signal for a tertiary amine (R3N) =>

Chapter 12 24
Chapter 12 25
Chapter 12 26
 The O-H stretching absorption is very characteristic
In very dilute solutions, hydrogen bonding is absent and there is a
very sharp peak at 3590-3650 cm-1
In more concentrated solutions, the hydroxyl groups hydrogen bond
to each other and a very broad and large peak occurs at 3200-
3550 cm-1

Chapter 12 27
An Alcohol IR Spectrum

=>
Chapter 12 28
 An Amine
IR Spectrum

=>
Chapter 12 29
Carbonyl(n C=O) Stretching
The C=O bond of simple ketones,
aldehydes, and carboxylic acids absorb
around n 1710 cm-1.
=>

Chapter 12 30
 Usually, its the strongest IR signal.

Carboxylic acids will have O-H also.

Aldehydes have two C-H signals around

2700 and 2800 cm-1.

Chapter 12 31
 A Ketone
IR Spectrum

=>
Chapter 12 32
An Aldehyde (n HC=O)
IR Spectrum

=>
Chapter 12 33
 O-H Stretch of a
Carboxylic Acid
This O-H absorbs broadly, 2500-3500 cm-1,
due to strong hydrogen bonding.

=>
Chapter 12 34
 Variations in
C=O Absorption
Conjugation of C=O with C=C lowers the
stretching frequency to ~1680 cm-1.
The C=O group of an amide absorbs at an
even lower frequency, 1640-1680 cm-1.
The C=O of an ester absorbs at a higher
frequency, ~1730-1740 cm-1.
Carbonyl groups in small rings (5 Cs or
less) absorb at an even higher frequency.
=>
Chapter 12 35
Chapter 12 36

Portions of the infrared spectra of three cyclic ketones and
three exocyclic alkenes show the influence of ring strain on
the C=O and C=C stretching frequency. Please indicate
your combination and explain your reasons.

CH2 O
H2C O
CH2 O

Chapter 12 37

The C=O vibration frequencies are varied to different
molecules which reveals the influence of conjugation
and other factors. Show the order of the carbonyl
absorption of the following molecules and explain
your reasons for full credits.
(I) (II) (III)
O
O O

O
O O
OH CH3
(IV)
(V)
O
O
CH3
O CH3
O Chapter 12 38
 An Amide
IR Spectrum

=>
Chapter 12 39

The absorption of carbonyl group in amide is usually in
the range from 1680 to 1630 cm-1. However, the
following compound has the C=O band appearing about
1700cm-1. Please explain this observation.

N
C=O:1700cm-1

Chapter 12 40
 Carbon - Nitrogen
Stretching (C~N)
C - N absorbs around 1200 cm-1.
C = N absorbs around 1660 cm-1 and is
much stronger than the C = C
absorption in the same region.
C N absorbs strongly just above 2200
cm-1. The alkyne C C signal is much
weaker and is just below 2200 cm-1 .
=>
Chapter 12 41
 A Nitrile
IR Spectrum

=>
Chapter 12 42
Chapter 12 43
Summary of IR Absorptions

=>
=>
Chapter 12 44
TODAYS CHEMIST AT WORK

Chapter 12 45
 In addition to the physical symptoms, diseases cause
changes in the chemical composition of the organs,tissues,
or fluids they affect; these differences are the basis of
everyday clinical chemical tests, tissue staining, and medical
imaging techniques.

IR spectroscopy not only probes the chemical composition

of a sample but also determines the precise position and
amplitude of IR absorption bands that reflect interactions
among the matrix constituents. Because of its sensitivity to
both molecular structure and molecular interactions, the
spectrum is often referred to as a molecular fingerprint of the
sample;

the specificity of that fingerprint is the basis for biomedical

applications.
Chapter 12 46
 Strengths and Limitations
IR alone cannot determine a structure.
Some signals may be ambiguous.
The functional group is usually indicated.
The absence of a signal is definite proof
that the functional group is absent.
Correspondence with a known samples
IR spectrum confirms the identity of the
compound. =>
Chapter 12 47