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CHAPTER TWO
INFRARED(IR)
SPECTROPHOTOMETRY
Aklilu Samuel
[email protected]
 Infrared(IR) Spectrophotometry
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Content
◻ Introduction
◻ Functional group analysis
◻ Instrumentation
◻ Types of IR instrument
◻ Application
 Introduction to IR
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• IR region; 0.8 µm to 1000 µm wavelength

• Subdivided
• Near infrared (overtone region): 0.8-2.5 µm (12,500-4000 cm -1)
• Middle infrared (vibration-rotation region): 2.5-50 µm (4000-200 cm-1)
• Far infrared (rotation region): 50-1000 µm (200-10 cm-1)
 Introduction cont…
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Middle infrared (2.5 to 50 µm)

• Is the fundamental region

• The main region of interest for analytical purposes is from 2.5 to 25 µm,
i.e. 4000 to 400 cm-1
• Provides greatest information for the elucidation and identification of molecular
structure

• Most IR spectrophotometers are limited to measurements in this region

 Introduction cont…
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• Absorption of IR radiation causes change in

vibrational energy of molecules
• Molecular vibrations are classified as
i.) Stretching: A stretch is a vibration occurring along the line
of the bond that changes the bond length.
ii.) Bending vibrations: A bend is a vibration that does not
occur along the line of the bond, but changes the bond angle.
 Intro. ..
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1. Stretching
• Involves change in bond length
• More energetic than the bending vibrations

H H
C
C
H
H

• Symmetrical
• Asymmetrical
 Introduction- IR …
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1. Stretching
❑ A diatomic molecule such as HCl can undergo only a
stretching vibration since it has no bond angles
 Introduction cont…
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2. Bending vibrations In plane

bending

• Involves change in bond angle H H

C C
H H
scisso roc
r k

Out of plane
bending
H H
C
C
H
H
twis
t wa
g
 Introduction cont…
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2. Bending vibrations In plane

bending
❑Three bonded atoms can H H
undergo a Stretches and C
H
C
H
Bending vibrations scisso roc
r k

Out of plane
bending
H H
C
C
H
H
twis
t wa
g
 Introduction- IR …
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Fundamental vibrations
◻ In order for the electrical component in electromagnetic
radiation to interact with a bond, the bond must have a
dipole.
◻ Thus symmetrical bonds, such as those in O2 or N2,
Ethene, do not absorb infrared radiation. However, the
majority of organic molecules have plenty of
asymmetry.
🞑 C=C stretching vibration of ethene is described as infrared
inactive
 Introduction cont…
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The IR Spectroscopic Process

• As a covalent bond oscillates an electromagnetic field is produced due to the
oscillation of the dipole of the molecule

• The greater the dipole moment change through the vibration, the more intense
the EM field that is generated
 Introduction cont…
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• When a wave of infrared light encounters this oscillating EM field generated by

the oscillating dipole of the same frequency, the two waves couple, and IR
light is absorbed
• The coupled wave now vibrates with twice the amplitude
IR beam from
spectrometer

“coupled”
wave

EM oscillating
wave
from bond
vibration
 Introduction cont…
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Each stretching and bending vibration of bond occurs with a

certain frequency
🞑 If a compound is bombarded with radiation of
frequency that exactly matches the frequency of
the vibration of one of its bonds, the vibrating
bond will absorb energy
🞑 This allows the bond to stretch and bend a bit more
🞑 In other words, the absorption of energy increases
the amplitude of the vibration but does not change
its frequency
17

By experimentally determining the wavelengths of light that are

absorbed by a particular compound, we can determine what kinds of
bonds it has
🞑 e.g. stretching vibration of carbon oxygen double bond absorbs light with
wave number ~1700 cm-1, whereas the stretching vibration of oxygen-
hydrogen bond absorbs light with a wave number of ~3450 cm-1
 IR spectrum
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o It is a graph of % transmittance
vs wave number or frequency.
o The y-axis on an IR spectrum is
in units of % transmittance
o The x-axis of the IR spectrum is
in units of wave numbers,
o which is the number of waves per
centimeter in units of cm-1
(Remember E = hν or E = hc/λ)
 IR spectrum cont…
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⮚ Infrared spectra are usually

plotted ‘upside down’ so that
o zero absorbance is at the
top of the spectrum

o 100% absorbance is at the

bottom
 IR spectrum cont…
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In regions where the EM

field of an osc. bond
interacts with IR light of the
same ν – transmittance is
low (light is absorbed)
In regions where no osc. bond
is interacting with IR light,
transmittance nears 100%

V (cm-1)
 IR spectrum region
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⮚ IR spectrum can be
divided into two areas
1. Functional group
region:- Left-hand two-
third, (4000-1000 cm-1)
2. Finger print region:-
the right-hand third
(~1000-400 cm-1)

⮚ Each compound shows a

unique pattern
 IR spectrum region
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Example
• 2-pentanol and 3-pentanol have the same functional group,
so they show the same bonds between 4000-1000 cm-1
region but the finger print regions are different (Fig. 2.3 next
slide)
 IR spectrum region
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 Factors affecting vibration
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The intensity of an absorption

1. change in dipole moment
◻ The greater the difference in
electronegativity between the
atoms involved in bonding, the
larger the dipole moment
◻ The greater the change in dipole
moment, the more intense the
absorption
 Factors affecting vibration
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2. Conjugation
◻ The intensity of the stretching of carbon–carbon double
bonds is increased when they are conjugated to a polar
double bond

3. number of bonds responsible for the absorption.

4. The concentration of the sample
🞑 Concentrated samples have greater numbers of absorbing
molecules and, therefore, more intense absorption bands.
 Factors affecting vibration
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◻ It is important to make note of peak intensities to show

the effect of these factors:
🞑 Strong (s) – peak is tall, transmittance is low (0-35 %)
🞑 Medium (m) – peak is mid-height (75-35%)
🞑 Weak (w) – peak is short, transmittance is high (90-75%)
🞑 * Broad (br) –abnormally broad
 Factors affecting vibration
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The position of an absorption

◻ The amount of energy required to stretch a bond depends on

1. the strength of the bond

🞑 The stronger the bond, the greater the energy required to stretch it,
🞑 Triple bonds > double bonds > single bonds in energy
2. Conjugation
🞑 by resonance, conjugation lowers the energy of a double or triple bond. The
effect of this is readily observed in the IR spectrum
3. the masses of the bonded atoms.
🞑 The frequency of the vibration is inversely related to the mass of the atoms
attached to the spring, so heavier atoms vibrate at lower frequencies.
🞑 Lighter atoms will allow the oscillation to be faster – higher energy
🞑 – C-H, N-H and O-H
28 Infrared Group Analysis
The primary use of the IR is to detect functional groups
Remember all organic functional groups are made of
multiple bonds and therefore show up as multiple IR bands
(peaks)
 Infrared Group Analysis
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■ The four primary regions of the IR spectrum

Bonds to Triple Double Single
H Bonds Bonds Bonds

Fingerprint
Region

O-H C≡C C=O C-C

N-H C≡N C=N C-N
C-H C=C C-O
 Octane

1.Alkanes
• sp3 C-H between 2800-3000 cm-1

(w – (m
s) )

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Infrared
Spectroscopy 1-Octene
2. Alkenes – addition of the C=C and vinyl C-H bonds
• C=C stretch at 1620-1680 cm-1 weaker as substitution increases

• vinyl C-H stretch occurs at 3000-3100 cm-1

• The difference between alkane, alkene or alkyne C-H is important!

If the band is slightly above 3000 it is vinyl sp2 C-H or alkynyl sp
C-H if it is below it is alkyl sp3 C-H

(w –
m) (w –
m)

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Infrared
Spectroscopy 1-Octyne

3. Alkynes – addition of the C=C and vinyl C-H bonds

• C≡C stretch 2100-2260 cm-1;
• C-H for terminal alkynes occurs at 3200-3300 cm-1

(w-
m)

(m –
s)

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Infrared
Spectroscopy Ethyl benzene
4. Aromatics
• Due to the delocalization of e- in the ring, C-C bond order is 1.5, the
stretching frequency for these bonds is slightly lower in energy than
normal C=C
• These show up as a pair of sharp bands, 1500 & 1600 cm-1, (lower
frequency band is stronger)

• C-H bonds off the ring show up similar to vinyl C-H at 3000-3100 cm-
1

(w – (w –
m) m)

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Infrared
Spectroscopy Diisopropyl ether
6. Ethers – addition of the C-O-C asymmetric band and vinyl C-H
bonds
• Show a strong band for the antisymmetric C-O-C stretch at
1050-1150 cm-1

• Otherwise, dominated by the hydrocarbon component of the rest

of the molecule

(s
)

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Infrared
Spectroscopy 1-butanol

7. Alcohols
• Strong, broad O-H stretch from 3200-3400 cm-1

• Like ethers, C-O stretch from 1050-1260 cm-1

(m–
s)
br

(s
)

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Infrared
Spectroscopy 2-aminopentane
8. Amines - Primary
• Shows the –N-H stretch for NH2 as a doublet between 3200-
3500 cm-1 (symmetric and anti-symmetric modes)
• -NH2 has deformation band from 1590-1650 cm-1

(w (w
) )

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Infrared
Spectroscopy Cyclohexyl carboxaldehyde
10. Aldehydes
• C=O (carbonyl) stretch from 1720-1740 cm-1
• A highly unique sp2 C-H stretch appears as a doublet, 2720 &
2820 cm-1

(w-
m)

(s
)

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Infrared
Spectroscopy 3-methyl-2-pentanone
11. Ketones
• Simplest of the carbonyl compounds as far as IR spectrum –
carbonyl only

• C=O stretch occurs at 1705-1725 cm-1

(s
)

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Infrared
Spectroscopy Ethyl pivalate
12. Esters
• C=O stretch at 1735-1750 cm-1

• Strong band for C-O at a higher frequency than ethers or

alcohols at 1150-1250 cm-1

(s
) (s
)

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Infrared
Spectroscopy 4-phenylbutyric acid
13. Carboxylic Acids:
• Gives the messiest of IR spectra

• C=O band occurs between 1700-1725 cm-1

• The highly dissociated O-H bond has a broad band from 2400-3500 cm-1 covering
up to half the IR spectrum in some cases

(w – (s (s
m) ) )
br
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 Summary of IR Stretching
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 Summary of IR Stretching
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 Summary of IR Stretching
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 Types of Instrumentation
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◻ The instrument used to obtain an infrared spectrum is

called an IR spectrometer.
◻ Two types of instrument are commonly used for
obtaining IR spectra:
1. Dispersive instruments
2. Fourier transform instruments,
 Types of Instrumentation
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1. Dispersive instruments
◻ Use a monochromator to select each wavenumber in
turn in order to monitor its intensity after the radiation
has passed through the sample
 Types of Instrumentation
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Dispersive Type
 Types of Instrumentation
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2. A Fourier transform IR (FT-IR) spectrometer,

◻ has several advantages.

◻ Sessitivity

🞑 Its sensitivity is better because, instead of scanning through the

frequences, it measures all frequencies simultaneously.
◻ Fast
🞑 With a conventional IR spectrometer, it can take 2 to 10 minutes to scan
through all the frequencies.
🞑 In contrast, FT-IR spectra can be taken in 1 to 2 seconds.
◻ Automated
🞑 The information is digitized and Fourier transformed by a computer to
produce the FT-IR spectrum.
 Sample preparation
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LIQUID
🞑 The sample is run as a film sandwiched between two NaCl
or potassium chloride (KCl) discs.
🞑 IR spectra of liquids or solutions in an organic solvent,
commonly chloroform
 Sample preparation
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Solid
🞑 The sample is ground to a powder with KBr or KCl
🞑 This is the procedure used in pharmacopoeial methods to prepare a
drug for analysis by IR
🞑 Gas – expanded into an evacuated cell

Note
◻ KBr discs and NaCl or KBr cells do not absorb IR radiation because

they have no covalent bond

◻ When solvents are used, they must have few absorption bands in

the region of interest e.g. CCl4, CHCl3, CS2

 Application of IR spectrophotometry
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◻ Qualitative analysis
🞑 Identification
🞑 Structural elucidation
■In conjunction with other instruments; MS and NMR
🞑 Follow the progress of chemical rxns
 PROBLEMS 1

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 PROBLEMS 2

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 PROBLEMS 3

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 PROBLEMS 4

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 PROBLEMS 5

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Thank you