INFRARED ABSORPTION

SPECTROSCOPY

Prof. Dr. A. V. Patil

Smt. S. S. Patil College of Pharmacy, Chopda
 LEARNING OUTCOMES
 By the end of this topic, students should be able to:

 Explain the principles and the working mechanism of infrared

(IR) absorption spectroscopy
 Identify the molecular species that absorb IR radiation
 Interpret IR spectrum
 Explain stretching and bending vibrations in relation to IR
absorption
 Determine unknown qualitatively using IR absorption
 Draw a schematic diagram of a conventional IR instrument
and a fourier transform IR instrument and explain the
function of each component of the instrument
 Differentiate between a dispersive IR instrument and a FTIR
spectrometer 2
 INFRARED SPECTROSCOPY
 Mostly for qualitative analysis
 Absorption spectra is recorded as transmittance spectra
 Absorption in the infrared region arise from molecular
vibrational transitions
 Absorption at specific wavelengths
 Thus, IR spectra provides more specific qualitative
information
 IR spectra is called “fingerprints”- because no other
chemical species will have identical IR spectrum

3
COMPARISON BETWEEN TRANSMITTANCE (UPPER) VS
ABSORBANCE (LOWER) PLOT

The transmittance
spectra provide better
contrast btw
intensities of strong
and weak bands
compared to
absorbance spectra

4
 ELECTROMAGNETIC SPECTRUM

 Energy of IR photon insufficient to cause electronic 5

excitation but can cause vibrational excitation
Here is the key to molecular spectroscopy: a given molecule will
specifically absorb only those wavelengths which have energies that
correspond to the energy difference of the transition that is
occurring. Thus, if the transition involves the molecule jumping
from ground state A to excited state B, with an energy difference of
ΔE, the molecule will specifically absorb radiation with wavelength
that corresponds to ΔE, while allowing other wavelengths to pass
through unabsorbed.
By observing which wavelengths a molecule absorbs, and to what
extent it absorbs them, we can gain information about the nature of
the energetic transitions that a molecule is able to undergo, and thus
information about its structure.
 INTRODUCTION
 Comparison between UV-vis and IR

 Energy: UV > vis > IR

 Frequency: UV > vis > IR
 Wavelength: UV < vis < IR

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9
 INFRARED SPECTROSCOPY

 Infrared (IR) spectroscopy deals with the interaction of

infrared radiation with matter

 IR spectrum provides:
 Important information about its chemical nature
and molecular structure

 IR applicability:
 Analysis of organic materials
 Polyatomic inorganic molecules
10
 Organometallic compounds
 IR region of EM spectrum:
 λ: 780 nm – 1000 μm
 Wavenumber: 12,800 – 10cm-1

 IR region subdivided into 3 subregions:

N
1. Near IR region (Nearest to the visible) E
A
- 780 nm to 2.5 μm (12,800 to 4000 cm-1) R

2. Mid IR region M

infrared
- 2.5 to 50 μm (4000 – 200 cm-1) I
D
3. Far IR region F
- 50 to 1000 μm (200 – 10cm-1) A
R

11

11
 When IR absorption occur?

1.IR absorption only occurs when IR radiation interacts

with a molecule undergoing a change in dipole
moment as it vibrates or rotates.

2.Infrared absorption only occurs when the incoming IR

photon has sufficient energy for the transition to the
next allowed vibrational state

Note: If the 2 rules above are not met, no absorption

can occur
12
WHAT HAPPEN WHEN A MOLECULE ABSORBS
INFRARED RADIATION?

 Absorption of IR radiation corresponds to energy

changes on the order of 8 to 40 kJ/mole.
- Radiation in this energy range corresponds to stretching
and bending vibrational frequencies of the bonds in
most covalent molecules.

 In the absorption process, those frequencies of IR

radiation which match the natural vibrational
frequencies of the molecule are absorbed.

 The energy absorbed will increase the amplitude

of the vibrational motions of the bonds in the
molecule. 13
 NOT ALL bonds in a molecule are capable of absorbing
IR energy. Only those bonds that have change in
dipole moment are capable to absorb IR radiation.

 The larger the dipole change, the stronger the

intensity of the band in an IR spectrum.

14
 What is a dipole moment?

 is a measure of the extent to which a separation exists

between the centers of positive and negative charge within
a molecule.

δ-
O

H H
δ+ δ+
15
 Inheteronuclear diatomic molecule, because
of the difference in electronegativities of the
two atoms, one atom acquires a small positive
charge (q+), the other a negative charge (q-).

 This
molecule is then said to have a dipole
moment whose magnitude, μ =qd

distance of separation of the charge

q: electrical charge, d: directed distance of that

charge from some defined origin of coordinates
from the molecule.
16
 MOLECULAR SPECIES THAT ABSORB
INFRARED RADIATION

 Compound absorb in IR region

Organic compounds, carbon monoxide

 Compounds DO NOT absorb in IR region

O2, H2, N2, Cl2

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18
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 Theory

 Covalent bonds in organic molecules are not rigid sticks – rather, they behave
more like springs.
At room temperature, organic molecules are always in motion, as their bonds
stretch, bend, and twist. These complex vibrations can be broken down
mathematically into individual vibrational modes.
 The energy of molecular vibration is quantized rather than continuous,
meaning that a molecule can only stretch and bend at certain 'allowed'
frequencies.
 If a molecule is exposed to electromagnetic radiation that matches the
frequency of one of its vibrational modes, it will in most cases absorb energy
from the radiation and jump to a higher vibrational energy state – what this
means is that the amplitude of the vibration will increase, but the vibrational
frequency will remain the same.
 The difference in energy between the two vibrational states is equal to the
energy associated with the wavelength of radiation that was absorbed. It turns
out that it is the infrared region of the electromagnetic spectrum which contains
22
frequencies corresponding to the vibrational frequencies of organic bonds.
 The power of infrared spectroscopy - that different functional groups have
different characteristic absorption frequencies.
 Some bonds absorb infrared light more strongly than others, and some bonds
do not absorb at all.
 In order for a vibrational mode to absorb infrared light, it must result in a
periodic change in the dipole moment of the molecule. Such vibrations are said
to be infrared active.
 In general, the greater the polarity of the bond, the stronger its IR
absorption.
 The carbonyl bond is very polar, and absorbs very strongly. The carbon-
carbon triple bond in most alkynes, in contrast, is much less polar, and thus a
stretching vibration does not result in a large change in the overall dipole
moment of the molecule. Alkyne groups absorb rather weakly compared to
carbonyls.
 Some kinds of vibrations are infrared inactive. The stretching vibrations of
completely symmetrical double and triple bonds, do not result in a change in
dipole moment, and therefore do not result in any absorption of light (but other
bonds and vibrational modes in these molecules do absorb IR light).
23
 On the horizontal axis we see IR wavelengths expressed in terms of a unit called
wavenumber (cm-1), which tells us how many waves fit into one centimeter. On
the vertical axis we see ‘% transmittance’, which tells us how strongly light
was absorbed at each frequency (100% transmittance means no absorption
occurred at that frequency).
 You will notice that there are many additional peaks in this spectrum in the
longer-wavelength 400 -1400 cm-1 region. This part of the spectrum is called the
fingerprint region. The pattern of absorbance peaks in the fingerprint region is
unique to every molecule, meaning that the data from an unknown sample can be
compared to the IR spectra of known standards in order to make a positive
identification.

24
IR VIBRATIONAL MODES

25
 Molecular vibration

divided
back & into involves
forth change in
movement bond angles

stretching bending

wagging
scissoring

symmetrical asymmetrical rocking twisting

in-plane out of
vibration plane
vibration
26
STRETCHING

27
BENDING

28
Vibrational spectra (I): Harmonic oscillator model
• Infrared radiation in the range is absorbed and converted by an organic molecule into
energy of molecular vibration, this absorption is quantized:
Consider diatomic molecule A and B with mass m1 and m2
Two atoms connected by covalent bond as a spring,stiffness of bond is force constant k
If spring struck with force,vibrations are produced described by HOOKS law of simple
harmonic motion

A simple harmonic oscillator is a mechanical system consisting of a point mass

connected to a massless spring. The mass is under action of a restoring force 29
proportional to the displacement of particle from its equilibrium position and the
force constant f (also k in followings) of the spring.
The vibrational frequency is increasing with:
1.Bond Strength: increasing force constant f = increasing bond
strength
2. Mass: decreasing atomic mass 30
• Example: f cc > f c=c > f c-c
31
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39
40
 Fundamental Vibrations

Polyatomic molecule-atoms and bonds are not rigid-fundamental and overtone

bands.
No. of fundamental bands depends on degree of freedom ie three coordinates
X.Y,Z
Besides fundamental mode non fundamental modes-called overtone or
combination tones 41
 SAMPLE HANDLING TECHNIQUES
 Gases
 evacuated cylindrical cells equipped with suitable windows

 Liquid
 sodium chloride windows
 “neat” liquid

 Solid
 Pellet (KBr)
 Mull

Factors influencing vibrational frequency

1.Effect of another bonding in molecule

2. Change in force constant of bond due to electronic structure
3. Due to different state of substance solid,liq.,gas 42
 LIQUID

 a drop of the pure (neat) liquid is squeezed between two

rock-salt plates to give a layer that has thickness 0.01mm
or less
 2 plates held together by capillary mounted in the beam
path

What is meant by “neat” liquid?

 Neat liquid is a pure liquid that do not contain any solvent or
water.

 This method is applied when the amount of liquid is small

or when a suitable solvent is unavailable
43
 SOLID SAMPLE PREPARATION
 There are three ways to prepare solid sample for IR
spectroscopy.

 Solid that is soluble in solvent can be dissolved in a

solvent, most commonly carbon tetrachloride CCl4.

 Solid that is insoluble in CCl4 or any other IR solvents

can be prepared either by KBr pellet or mulls.

44
 PELLETING
(KBr PELLET)

 Mixing the finely ground solid sample with

potassium bromide (KBr) and pressing the
mixture under high pressure (10,000 – 15,000 psi)
in special dye.
 KBr pellet can be inserted into a holder in the

spectrometer.

45
 MULLS

 Formed by grinding 2-5 mg finely powdered

sample, presence 1 or 2 drops of a heavy
hydrocarbon oil (Nujol)
 Mull examined as a film between flat salt plates

 This method applied when solid not soluble in an

IR transparent solvent, also not convenient
pelleted in KBr
46
What is a mull
 A thick paste formed by grinding an insoluble solid
with an inert liquid and used for studying spectra of
the solid

What is Nujol
 A trade name for a heavy medicinal liquid paraffin.
Extensively used as a mulling agent in spectroscopy

47
INSTRUMENTATION

48
 IR INSTRUMENT
 Dispersive spectrometers
 sequential mode

 Fourier Transform spectrometers

 simultaneous analysis of the full spectra range using
inferometry

49
 IR INSTRUMENT (DISPERSIVE)
 Important components in IR dispersive
spectrometer

1 2 3 4 5
source sample λ signal processor
detector & readout
lamp holder selector

Detector:
Source:
- Thermocouple
- Nernst glower
- Pyroelectric transducer
- Globar source
- Thermal transducer
- Incandescent wire
50
 RADIATION SOURCES
 generate a beam with sufficient power in the
λ region of interest to permit ready detection
& measurement
 provide continuous radiation; made up of all
λ’s with the region (continuum source)
 stable output for the period needed to
measure both P0 and P

51
SCHEMATIC DIAGRAM OF A DOUBLE BEAM
INFRARED SPECTROPHOTOMETER

52
 FTIR
FOURIER TRANSFORM INFRARED

53
 FTIR
Why is it developed?

 to overcome limitations encountered with the

dispersive instruments
 especially slow scanning speed; due to individual
measurement of molecules/atom
 utilize an interferometer

54
  Interferometer
 Special instrument which can read IR frequencies
simultaneously
 faster method than dispersive instrument
 interferograms are transformed into frequency spectrums
by using mathematical technique called Fourier
Transformation

FT
Calculations

interferograms
IR spectrum
55
COMPONENTS OF FOURIER TRANSFORM INSTRUMENT

- majority of commercially available Fourier transform infrared

instruments are based upon Michelson interferometer

5 2

56
Instrumentation
Perkin ElmerTM
Spectrum One

BRUKE TENSORTM
Series
Advantages (over dispersive instrument)

 high sensitivity
 high resolution
 speed of data acquisition ( data for an entire spectrum can
be obtained in 1 s or less)

58
C) Instrumentation
1.) Basic Design
- normal IR instrument similar to UV-vis
- main differences are light source & detector

59
i.) Light Source:
- must produce IR radiation
- can’t use glass since absorbs IR radiation
- several possible types

a) Nernst Glower
Zr, Ce, Th

- rare earth metal oxides (Zr, Ce, Th) heated electrically

- apply current to cylinder, has resistance to current flow
generates heat (1200o – 2200o C).
- causes light production similar to blackbody radiation
- range of use ~ 670 – 10,000cm-1
- need good current control or overheats and damaged

b) Globar
- similar to Nernst Glower but uses silicon carbide rod
60
instead of rare earth oxides
- similar range
c) Incandescent Wire Source

- tightly wound nichrome or rodium wire that is electrically heated

- same principal as Nernst Glower
- lower intensity then Nernst Glower or Globar, but longer lifetime
d) CO2 Laser
- CO2 laser gas mixture consists of 70% He, 15% CO2, and 15% N2
- a voltage is placed across the gas, exciting N2 to lowest vibrational levels.
- the excited N2 populate the asymmetric vibrational states in the CO2 through
collisions.
- infrared output of the laser is the result of transitions between rotational
states of the CO2 molecule of the first asymmetric vibrational mode to
rotational states of both the first symmetric stretch mode and the second
bending mode
- gives off band of ~ 100 cm-1’s in range of 900-1100 cm-1
- small range but can choose which band used & many compounds have IR
absorbance in this region
- much more intense than Blackbody sources

e) Others
- mercury arc (l > 50 mm) (far IR) 61
- tungsten lamp (4000 -12,800cm-1) (near IR)
ii.) Detectors:
- two main types in common IR instruments

a) Thermal Detectors
1.) Thermocouple
- two pieces of dissimilar metals fused together at the ends
- when heated, metals heat at different rates
- potential difference is created between two metals that varies
with their difference in temperature
- usually made with blackened surface (to improve heat
absorption)
- placed in evacuated tube with window transparent to IR (not
glass or quartz)
- IR “hits” and heats one of the two wires.
- can use several thermocouples to increase sensitivity.

metal1 metal2
hn

- + 62
IR transparent
material (NaCl)
V
2.) Bolometer
- strips of metal (Pt, Ni) or semiconductor that has a large change in
resistance to current with temperature.
- as light is absorbed by blackened surface, resistance increases and
current decreases
- very sensitive

hn

A
b) Photoconducting Detectors
- thin film of semiconductor (ex. PbS) on a nonconducting glass surface
and sealed in a vacuum.
- absorption of light by semiconductor moves from non-conducting to
conducting state
- decrease in resistance  increase in current hn
-1
- range: 10,000 -333 cm at room temperature

semiconductor 63

glass
c) Pyroelectric Detectors
- pyroelectric (ceramic, lithium tantalate) material get polarized
(separation of (+) and (-) charges) in presence of electric field.
- temperature dependent polarization
- measure degree of polarization related to temperature of crystal
- fast response, good for FTIR

64
iii.) Other Components
a.) Sample Cell
- must be made of IR transparent material (KBr pellets or NaCl)

Liguid Sample Holder

NaCl plates
b.) monochromator
- reflective grating is common
- can’t use glass prism, since absorbs IR

65
 v.) Fourier Transfer IR (FTIR) – alternative to Normal IR
- Based on Michelson Interferometer

Principal:
1) light from source is split by central mirror into 2 beams of equal intensity
2) beams go to two other mirrors, reflected by central mirror, recombine and
pass through sample to detector
3) two side mirrors. One fixed and other movable
a) move second mirror, light in two-paths travel different distances
before recombined 66
b) constructive & destructive interference
c) as mirror is moved, get a change in signal
Remember
Destructive Interference can be created when two waves from the
same source travel different paths to get to a point.

This may cause a difference in the phase between the two waves.
• If the paths differ by an integer multiple of a wavelength, the waves will also be in
phase.
67
• If the waves differ by an odd multiple of half a wave then the waves will be 180
degrees out of
phase and cancel out.
- observe a plot of Intensity vs. Distance (interferograms)
- convert to plot of Intensity vs. Frequency by doing a Fourier
Transform
- resolution Dn = 1/Dd (interval of distance traveled by mirror)

68
Advantages of FTIR compared to Normal IR:
1) much faster, seconds vs. minutes
2) use signal averaging to increase signal-to-noise (S/N)
increase S / N  number scans

3) higher inherent S/N – no slits, less optical equipment, higher light intensity

4) high resolution (<0.1 cm-1)

Disadvantages of FTIR compared to Normal IR:

1) single-beam, requires collecting blank
2) can’t use thermal detectors – too slow
In normal IR, scan through frequency range. In
FTIR collect all frequencies at once.

69
Application of IR

70
 Application of IR
Qualitative and quantitative analysis

INTERPRETATION
INFRARED SPECTRA

71
72
73
 INFRARED SPECTRA

 IR spectrum is due to specific structural

features, a specific bond, within the molecule,
since the vibrational states of individual
bonds represent 1 vibrational transition.

 e.g.
IR spectrum can tell the molecule has an
O-H bond or a C=O or an aromatic ring

74
INFRARED SPECTRA

75
HOW TO INTERPRET INFRARED SPECTRA?

76
 How to analyze IR spectra

1. Begin by looking in the region from 4000-1300.

Look at the C–H stretching bands around 3000:

Indicates:
alkyl groups (present in most organic
Are any or all to the right of 3000?
molecules)
a C=C bond or aromatic group in the
Are any or all to the left of 3000?
molecule

77
 2. Look for a carbonyl in the region 1760-1690.
If there is such a band:

Indicates:
Is an O–H band also present? a carboxylic acid group
Is a C–O band also present? an ester
Is an aldehyde C–H band also
an aldehyde
present?
Is an N–H band also present? an amide
Are none of the above present? a ketone

(also check the exact position of the carbonyl band for clues as to the type 78
of carbonyl compound it is)
 3. Look for a broad O–H band in the region 3500-3200 cm-1.
If there is such a band:

Indicates:
Is an O–H band present? an alcohol or phenol

4. Look for a single or double sharp N–H band in the region 3400-3250
cm-1.
If there is such a band:

Indicates:
Are there two bands? a primary amine
Is there only one band? a secondary amine
79
5. Other structural features to check for:

Indicates:
an ether (or an ester if there is a
Are there C–O stretches?
carbonyl band too)
Is there a C=C stretching band? an alkene
Are there aromatic stretching bands? an aromatic
Is there a C≡C band? an alkyne
Are there -NO2 bands? a nitro compound

80
 How to analyze IR spectra

 If there is an absence of major functional group bands in the

region 4000-1300 cm-1 (other than C–H stretches), the compound
is probably a strict hydrocarbon.

 Also check the region from 900-650 cm-1. Aromatics, alkyl halides,
carboxylic acids, amines, and amides show moderate or strong
absorption bands (bending vibrations) in this region.

 As a beginning, you should not try to assign or interpret every

peak in the spectrum. Concentrate on learning the major bands
and recognizing their presence and absence in any given
spectrum.
81
82
83
 ALKANE

H H H

H C C C H

H H H
n

84
C-H Stretch for sp3 C-H around 3000 – 2840 cm-1.
CH2 Methylene groups have a characteristic bending absorption
at approx 1465 cm-1
CH3 Methyl groups have a characteristic bending absorption at
approx 1375 cm-1
CH2 The bending (rocking) motion associated with four or more 85
CH2 groups in an open chain occurs at about 720 cm-1
ALKENE

H H
C C
H H
86
 ALKENE

=C-H Stretch for sp2 C-H occurs at values greater than 3000 cm-1.
=C-H out-of-plane (oop) bending occurs in the range 1000 – 650 cm-1
C=C stretch occurs at 1660 – 1600 cm-1; 87
often conjugation moves C=C stretch to lower frequencies
and increases the intensity
 ALKYNE

HC CH

88
 ALKYNE

CH Stretch for sp C - H occurs near 3300 cm-1.

C C Stretch occurs near 2150 cm-1; conjugation moves

stretch to lower frequency. 89
 AROMATIC RINGS

C H Stretch for sp2 C-H occurs at values greater than 3000 cm-1.

Ring stretch absorptions occur in pairs at 1600 cm-1 and

C C 1475 cm-1.

C H Bending occurs at 900 - 690cm-1.

90
AROMATIC RINGS

91
 C-H Bending ( for Aromatic Ring)

The out-of-plane C-H bending is useful in order to assign the positions

of substituents on the aromatic ring.

Monosubstituted rings
this substitution pattern always gives a strong absorption near 690
cm-1. If this band is absent, no monosubstituted ring is present. A
second strong band usually appears near 750 cm-1.

Ortho-Disubstituted rings
one strong band near 750 cm-1.

Meta- Disubstituted rings

gives one absorption band near 690 cm-1 plus one near 780 cm-1. A
third band of medium intensity is often found near 880 cm-1.

Para- Disubstituted rings

92
one strong band appears in the region from 800 to 850 cm-1.
 Ortho-Disubstituted rings

C H Bending observed as one strong band near 750 cm-1.

93
 Meta- Disubstituted rings

- gives one absorption band near 690 cm-1 plus one near 780 cm-1.
C H A third band of medium intensity is often found near 880 cm-1.

94
 Para- Disubstituted rings

C H - one strong band appears in the region from 800 to 850 cm-
1.

95
 ALCOHOL
H H
H OH H
H C C OH
H C C C H
H H
H H H
Primary alcohol 10
Secondary alcohol 20
CH3
H3C C OH
CH3 Tertiary alcohol 30
96
 ALCOHOL

O-H The hydrogen-bonded O-H band is a broad peak at 3400 – 3300 cm-1.
This band is usually the only one present in an alcohol that has not
been dissolved in a solvent (neat liquid).
C-O-H Bending appears as a broad and weak peak at 1440 – 1220 cm-1 often
obscured by the CH3 bendings.
C-O Stretching vibration usually occurs in the range 1260 – 1000 cm-1.
This band can be used to assign a primary, secondary or tertiary 97
structure to an alcohol.
PHENOL

OH

98
PHENOL

99
100
 ETHER

R O R'
C-O The most prominent band is that due to C-O stretch, 1300 – 1000 cm-1.

Absence of C=O and O-H is required to ensure that C-O stretch

is not due to an ester or an alcohol.

Phenyl alkyl ethers give two strong bands at about 1250 – 1040 cm-1,
while aliphatic ethers give one strong band at about 1120 cm-1.
101
102
 CARBONYL COMPOUNDS

cm-1

1810 1800 1760 1735 1725 1715 1710 1690

Anhydride Acid Anhydride Ester Aldehyde Ketone Carboxylic
Amide
(band 1) Chloride (band 2) acid

Normal base values for the C=O stretching vibrations for carbonyl groups

103
 A. ALDEHYDE

R C H
O
R C H C=O stretch appear in range 1740-1725 cm-1 for normal
O aliphatic aldehydes

Ar C H Conjugation of C=O with phenyl; 1700 – 1660 cm-1 for

C=O
O and 1600 – 1450 cm-1 for ring (C=C)

C-H Stretch, aldehyde hydrogen (-CHO), consists of weak

bands, one at 2860 - 2800 cm-1 and
104
the other at 2760 – 2700 cm-1.
105
 B. KETONE

R C R'
O
R C R' C=O stretch appear in range 1720-1708 cm-1 for
O normal aliphatic ketones

Ar C R' Conjugation of C=O with phenyl; 1700 – 1680 cm-1 for C=O
O and 1600 – 1450 cm-1 for ring (C=C)

106
107
C. CARBOXYLIC ACID

R C OH
O

108
109
 D. ESTER

R C O R
O
R C O R C=O stretch appear in range 1750-1735 cm-1 for normal
O aliphatic esters

Ar C O R Conjugation of C=O with phenyl; 1740 – 1715 cm-1 for C=O

O and 1600 – 1450 cm-1 for ring (C=C)

C–O Stretch in two or more bands, one stronger and broader than
the other, occurs in the range 1300 – 1000 cm-1 110
111
 E. AMIDE

O O O
H H R
R C N R C N R C N
H R R
10 20 30

112
AMIDE

113
 F. ACID CHLORIDE

O
R C Cl
Stretch appear in range 1810 -1775 cm-1 in conjugated
C O chlorides. Conjugation lowers the frequency to 1780 – 1760
cm-1

C Cl Stretch occurs in the range 730 -550 cm-1

Acid chloride show a very strong band for the C=O group. 114
 F. ANHYDRIDE

O O
R C O C R

Stretch always has two bands, 1830 -1800 cm-1 and 1775 – 1740 cm-1,
C O with variable relative intensity.
Conjugation moves the absorption to a lower frequency. Ring strain
(cyclic anhydride) moves absorptions to a higher frequency.

C O Stretch (multiple bands) occurs in the range 1300 -900 cm-1

115
 AMINE

H H R N R
R N R N R
H R
10 20
30

116
 AMINE
Stretching occurs in the range 3500 – 3300 cm-1.
Primary amines have two bands.
N–H Secondary amines have one band: a vanishingly weak one for
aliphatic compounds and a stronger one for aromatic secondary
amines.
Tertiary amines have no N – H stretch.

N–H Bending in primary amines results in a broad band in the range

1640 – 1560 cm-1.
Secondary amines absorb near 1500 cm-1

N–H Out-of-plane bending absorption can sometimes be observed

near 800 cm-1

C–N Stretch occurs in the range 1350 – 1000 cm-1

117
PRIMARY AMINE

Secondary Amine

118
TERTIARY AMINE

Aromatic Amine

119