INFRARED SPECTROSCOPY

Imad Abu Reid 1

 Learning Objectives
To know analytical uses of infrared spectroscoy
To understand the origin of electromagnetic radiation.
To determine the frequency, wavelength,
wavenumber and energy change associated with an
infrared transition.
To appreciate the factors governing the intensity of
bands in an infrared spectrum.
To predict the number of fundamental modes of
vibration of a molecule.

Imad Abu Reid 2

 Uses of Infrared Spectrum
The infrared spectrum can be used for molecules
much as a fingerprint can be used for humans. By
comparing the infrared spectra of two substances
thought to be identical, you can establish whether
they are, in fact, identical. If their infrared spectra
coincide peak for peak (absorption for absorption), in
most cases the two substances will be identical.(i.e.
identification)

Imad Abu Reid 3

 A second and more important use of the infrared
spectrum is to determine structural information about a
molecule. The absorptions of each type of bond (NH,
C-H, O-H, C-X, C=O, C-O, C-C,C=C, C C, C N, and so
on) are regularly found only in certain small portions of
the vibrational infrared region. A small range of
absorption can be defined for each type of bond.
Outside this range, absorptions are normally due to
some other type of bond. (i.e. structure elucidation)
Imad Abu Reid 4
 Thirdly the principles underlying quantitative
ultraviolet spectroscopy apply also to IR work
(quantitative)

Imad Abu Reid 5

The infrared (IR) region of the electromagnetic
spectrum extends from 0.8 m(800 nm) to 1000
m(1 mm) (Figure 1)and subdivided to three
regions (see table 1).The fundamental region
between 2 and 15 m is the region that provides
the greatest information for elucidation of
molecular structure.

Imad Abu Reid 6

Figure 1:THE ELECTROMAGNETIC SPECTRUM

Imad Abu Reid 7

Table 1.

Imad Abu Reid 8

 Visible wavelengths typically expressed in
nanometers (1 nm = 1 x 10-9 m)
Infrared region wavelengths longer than
visible
Infrared wavelengths typically expressed in
micrometers (1 m = 1 x 10-6 m)
Typical infrared spectrum covers between 2.5
m to 25 m (2500 nm to 25000 nm)
Energy is inversely related to wavelength, so
infrared light has less energy than visible light

Imad Abu Reid 9

 Typical units in infrared spectroscopy are
wavenumbers () - the reciprocal of the
wavelength (in centimeters)
2.5 m = 2.5 x 10-4 cm =4000 cm-1
25 m = 2.5 x 10-3 cm =400 cm-1
Thus your typical IR spectrum runs from 4000
to 400 cm-1

Imad Abu Reid 10

 Infrared Absorption Process
As with other types of energy absorption, molecules are
excited to a higher energy state when they absorb
infrared radiation. The absorption of infrared radiation
is, like other absorption processes, a quantized process.
A molecule absorbs only selected frequencies (energies)
of infrared radiation. The absorption of infrared
radiation corresponds to energy changes on the order
of 8 to 40 kJ/mole.

Imad Abu Reid 11

Radiation in this energy range corresponds to
the range encompassing the stretching and bending
vibrational frequencies of the bonds in most covalent
molecules. In the absorption process, those frequencies
of infrared radiation that match the natural vibrational
frequencies of the molecule in question are absorbed,
and the energy absorbed serves to increase the
amplitude of the vibrational motions of the bonds in
the molecule.
Imad Abu Reid 12
Note, however, that not all bonds in a molecule
are capable of absorbing infrared energy, even if
the frequency of the radiation exactly matches
that of the bond motion. Only those bonds that
have a dipole moment that changes as a
function of time are capable of absorbing
infrared radiation.

Imad Abu Reid 13

DIPOLE MOMENTS

Imad Abu Reid 14

 The following illustrates an example of an
infrared-active molecule, a heteronuclear
diatomic molecule. The dipole moment of such a
molecule changes as the bond expands and
contracts.
By comparison, an example of an infrared-inactive
molecule is a homonuclear diatomic molecule
because its dipole moment remains zero no matter
how long the bond.

Imad Abu Reid 15

Symmetric bonds, such as those of H2 or Cl2 , do not
absorb infrared radiation. A bond must present an
electrical dipole that is changing at the same
frequency as the incoming radiation for energy to
be transferred. The changing electrical dipole of the
bond can then couple with the sinusoidally changing
electromagnetic field of the incoming radiation.

Imad Abu Reid 16

Thus, a symmetric bond that has identical or
nearly identical groups on each end will not
absorb in the infrared.
For the purposes of an organic chemist, the
bonds most likely to be affected by this restraint
are those of symmetric or pseudosymmetric
alkenes (C=C) and alkynes (C C).(Figure 2.)

Imad Abu Reid 17

 Only bonds which have significant dipole moments will
absorb infrared radiation.

Bonds which do not absorb infrared include:

Symmetrically substituted alkenes and alkynes
R R
R C C R
R R

Many types of C-C Bonds

Symmetric diatomic molecules

H-H Cl-Cl

Imad Abu Reid 18

Figure 2.

Imad Abu Reid 19

 THE MODES OF STRETCHING AND
BENDING

The simplest types, or modes, of vibrational motion in a

molecule that are infrared activethose, that give rise
to absorptionsare the stretching and bending modes.

Imad Abu Reid 20

However, other, more complex types of stretching and
bending are also active. The following illustrations
of the normal modes of vibration for a methylene group
introduce several terms. In general, asymmetric
stretching vibrations occur at higher frequencies than
symmetric stretching vibrations; also, stretching
vibrations occur at higher frequencies than bending
vibrations. The terms scissoring, rocking, wagging, and
twisting are commonly used in the literature to describe
the origins of infrared bands.

Imad Abu Reid 21

Figure 4.

Imad Abu Reid 22

 http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/InfraRed/infrared.htm#ir1

Imad Abu Reid 23

In any group of three or more atoms, at least two
of which are identical, there are two modes of
stretching: symmetric and asymmetric. Examples
of such groupings are -CH3, -CH2,-NO2, -NH2, and
anhydrides. The methyl group gives rise to a
symmetric stretching vibration at about 2872 cm1
and an asymmetric stretch at about 2962 cm1.

Imad Abu Reid 24

The anhydride functional group gives two
absorptions in the C=O region because of the
asymmetric and symmetric stretching modes. A
similar phenomenon occurs in the amino group,
where a primary amine (NH2) usually has two
absorptions in the N-H stretch region, while a
secondary amine (R2NH) has only one absorption
peak. Amides exhibit similar bands.
Imad Abu Reid 25
There are two strong N=O stretch peaks for a
nitro group, with the symmetric stretch
appearing at about 1350 cm 1 and the
asymmetric stretch appearing at about
1550 cm 1.

Imad Abu Reid 26

Although rotational frequencies of the whole
molecule are not infrared active, they often couple
with the stretching and bending vibrations in the
molecule to give additional fine structure to these
absorptions, thus further complicating the
spectrum. One of the reasons a band is broad rather
than sharp in the infrared spectrum is rotational
coupling, which may lead to a considerable amount
of unresolved fine structure.
Imad Abu Reid 27
BOND PROPERTIES AND ABSORPTION
TRENDS
The energy of the stretch decreases as the
mass of the atoms is increased
C-H 3000 cm-1
C-C 1200 cm-1
C-O 1100 cm-1
C-Cl 750 cm-1
C-I 500 cm-1

Imad Abu Reid 28

 The energy of the stretch is related to the
hybridization in the order sp > sp2 > sp3
C-H sp 3300 cm-1
C-H sp2 3100 cm-1
C-H sp3 2900 cm-1

Imad Abu Reid 29

For instance, any absorption in the range 3000
150 cm1 is almost always due to the presence of a
C-H bond in the molecule; an absorption in the range
1715 100 cm 1 is normally due to the presence of a
C=O bond (carbonyl group) in the molecule. The
same type of range applies to each type of bond. Figure
3, illustrates schematically how these are spread
out over the vibrational infrared. Try to fix this general
scheme in your mind for future convenience.

Imad Abu Reid 30

Figure 3.

Imad Abu Reid 31

 Learning Objectives
To understand how an infrared spectrum is obtained
To recognize the different methods of sample
preparation and sample handling techniques which are
used for preparing samples in infrared spectroscopy.
To select appropriate sample preparation methods for
different types of samples.

Imad Abu Reid 32

 Infrared Spectrometer
The instrument that determines the absorption
spectrum for a compound is called infrared
spectrophotometer:
Dispersive
Fourier transform

Imad Abu Reid 33

 Dispersive IR Spectrophotometer
Beam from an IR source is split into two halves
using a mirror
One beam is passed through a reference cell; the
other is passed through a sample cell
The two beams are alternately passed to the
diffraction grating using a beam chopper
Absorption of radiation is detected by comparing
the two signals
Light is dispersed (spread into constituent
wavelengths) by a grating much as it would by be
by a prism
Imad Abu Reid 34
 The grating is slowly rotated, which changes
the angle if diffraction and which wavelengths
are passed to the detector
Spectrum recorded in the frequency domain

Imad Abu Reid 35

 Fourier Transform IR
Most modern IR spectrometers are of this type
Spectrum obtained as a function of time
rather than frequency; a Fourier transform is
used to convert from time domain to
frequency domain
Most are single-beam spectrometers
A background scan is first performed, then
scan of the sample, and the background scan
is detected from the sample scan by computer
Imad Abu Reid 36
Imad Abu Reid 37
 Sample Preparation
1.Nujol Mull:
Sample is mixed with a mulling agent such mineral oil and
pressed between plates made of sodium chloride Sodium
chloride is used because it has no IR absorptions; glass or
plastic plates would have IR absorptions of their own
Sodium chloride plates are good from 4000 to 650 cm-1;
below 650 cm-1 they begin to absorb
Potassium bromide plates can be used in place of sodium
chloride and are transparent to 400 cm-1, but they are more
expensive.

Imad Abu Reid 38

 Downside of this method is absorptions due to the
mineral oil
Used to identify different crystal forms(polymorphs)
,to avoid the high pressure exerted to prepare KBr disc,
as this results in polymorphs interconversion.

Imad Abu Reid 39

2. KBr disc:
The sample is ground to a powder with KBr or
KCl. Usually KBr is used unless a hydrochloride
salt is being analyzed in which KCl is used to
avoid halogen exchange. Hydraulic press with
the aid of vacuum is used to make a thin disc of
the mix.
Only works for solids

Imad Abu Reid 40

3. Solution:
IR spectra of liquids or solutions in organic
solvent, commonly chloroform may be obtained
by putting the liquid into a short pathlength
cell with width of approximately 1mm.The cells
are constructed of sodium or potassium chloride.

Imad Abu Reid 41

4.Gases:
Gases have densities which are several orders of
magnitude less than liquids, and hence pathlengths
must be correspondingly greater, usually 10 cm or
longer.
A typical gas cell is shown next. The walls are of glass
or brass, with the usual choice of windows. The cells
can be filled by flushing or from a gas line.

Imad Abu Reid 42

Schematic of a typical infrared gas cell

Imad Abu Reid 43

 Spectra
The IR spectrum is a plot of the absorption of IR
light with variation of wavelength () or,
alternatively, wavenumber (cm-1).
The ordinate may be linear in % transmittance
(%T) or absorbance.

Imad Abu Reid 44

The presentation of spectral regions may be in terms of
wavelength as metres or sub-multiples of a metre. The
following units are commonly encountered in
spectroscopy:

Imad Abu Reid 45

Another unit which is widely used in infrared
spectroscopy is the wavenumber, -, in cm 1 . This is the
number of waves in a length of one centimetre and is
given by the following relationship:

Imad Abu Reid 46

Imad Abu Reid 47
 Learning Objectives
To recognize the characteristic bands that appear in
the infrared regions.
To understand how hydrogen bonding affects an
infrared spectrum.
To assign the infrared bands of the main classes of
organic molecules.
To identify the structures of organic molecules by
using the infrared spectra of such molecules.
To develop a strategy for the interpretation of
infrared spectra.

Imad Abu Reid 48

 Correlation Charts & Tables
Interpretation of absorption spectra is considerably
simplified by charts and tables which correlate the
frequency at which a band occur with molecular
structure.

Imad Abu Reid 49

Although the entire IR spectrum can be used as a fingerprint
for the purposes of comparing molecules, the 600 - 1400
cm-1 range is called the fingerprint region.
This is normally a complex area showing many bands,
frequently overlapping each other. This complexity limits its
use to that of a fingerprint, and should be ignored by
beginners when analyzing the spectrum.
As a student, you should focus your analysis on the rest of
the spectrum, that is the region to the left of 1400 cm-1.

Imad Abu Reid 50

 1. Hydrocarbons: Alkanes, Alkenes &
Alkynes
1.1 Alkanes:
C-H stretch occurs at 3000 2840 cm-1
CH2 bending modes at 1465 cm-1
CH3 bending absorption at 1375 cm-1
CH2 (four or more CH2 groups) rocking at 720
cm-1

Imad Abu Reid 51

Decane (neat liquid, KBr plates)

Imad Abu Reid 52

Cyclohexane (neat liquid, KBr plates)

Note lack of long-chain bend and CH3 bend in above

spectrum
Imad Abu Reid 53
Imad Abu Reid 54
 2. Alkenes
C-H stretch occurs in region of 3095 3010 cm-1
(note higher wavenumber relative to alkanes)
C=C stretch occurs in region of 1670 1640 cm-1
Can be used to determine type of substitution:
Symmetrically substituted does not absorb at all
A cis isomer absorbs more strongly than a trans
isomer (cis is less symmetrical than trans)
Simple monosubstituted absorbs at 1640 cm-1
Simple 1,1-disubstituted absorbs at 1650 cm-1
Imad Abu Reid 55
 C-H out of plane bending (oop) absorbs at 1000 650
cm-1
Often very strong absorptions
Can be used to determine type of substitution:
Monosubstituted gives two peaks near 990 and 910
cm-1
1,2-disubstituted (cis) gives one strong band near 700
cm-1
1,2-disubstitued (trans) gives on band near 970 cm-1

Imad Abu Reid 56

 1,1-disubstituted gives one strong band near
890 cm-1
A trisubstituted double bond absorbs near 815
cm-1
A tetrasubstituted double bond does not
absorb at all

Imad Abu Reid 57

Imad Abu Reid 58
1-hexene (neat liquid, KBr plates)

A monosubstituted alkene gives two strong

peaks near 990 and 910 cm -1
Imad Abu Reid 59
cyclohexene (neat liquid, KBr plates)

A cis 1,2-disibstiuted alkene gives one strong band near 700 cm-1
Note that the C=C stretch is much less intense than for the
monosubstituted example

Imad Abu Reid 60

The strength of the C=C stretch can serve to
differentiate between cis and trans isomers

The cis isomer more intense C=C stretch

Note the single large peak at 700 cm-1 (indicates cis
isomer) Imad Abu Reid 61
The trans isomer less intense C=C stretch
Note the band near 970 cm1 (indicates trans
isomer)

Imad Abu Reid 62

 3. Alkynes

C-H stretching frequency is approximately 3300 cm-1

(still higher than for alkanes or alkenes)
C-C stretch occurs at approximately 2150 cm-1
(but not observed if alkyne is symmetric) .

Imad Abu Reid 63

octyne (neat liquid, KBr plates)

An asymmetric alkyne

Imad Abu Reid 64

4-octyne (neat liquid, KBr plates)

A symmetric alkyne (no C-C stretch)

Imad Abu Reid 65
 Example Problem 1

Shown below are spectra for cis and

trans 3-hexen-1-ol. Assign a structure
to each

Imad Abu Reid 66

Imad Abu Reid 67
 Example Problem 2

Which of the following structures

matches the spectrum shown below?

Imad Abu Reid 68

Imad Abu Reid 69
 Example Problem 3

Which of the following structures matches

the spectrum shown below?

Imad Abu Reid 70

Imad Abu Reid 71
 4. Aromatic rings
C-H stretch occurs between 3050 and 3010 cm-1
C-H out-of-plane bending occurs at 900 690
cm-1
(useful for determining type of ring substitution)
C=C stretching often occurs in pairs at 1600 cm-1
and 1475 cm-1
Overtone and combination bands occur between
2000 and 1667 cm-1

Imad Abu Reid 72

toluene (neat liquid, KBr plates)

Imad Abu Reid 73

 styrene
(neat liquid, KBr plates)

Imad Abu Reid 74

 ortho-diethylbenzene
(neat liquid, KBr plates)

Imad Abu Reid 75

 meta-diethylbenzene
(neat liquid, KBr plates)

Imad Abu Reid 76

 para-diethylbenzene
(neat liquid, KBr plates)

Imad Abu Reid 77

(a) The C-H out-of-plane bending vibrations for substituted benzenoid
compounds.(b) The 2000 -1667 cm-1 region for substituted benzenoid
compound

Imad Abu Reid 78

 Problem
Examine the IR spectra of three isomeric disubstituted
benzenes presented below in Figures A, B and C.
Which of these is 1,2-, which 1,3- and which 1,4-
disubstituted?

Imad Abu Reid 79

Spectrum A

Imad Abu Reid 80

Spectrum B

Imad Abu Reid 81

Spectrum C

Imad Abu Reid 82

 5. alcohols & phenols
Hydrogen-bonded O-H stretching occurs as a very
broad and intense peak at 3400-3300 cm-1
Free O-H stretching (only observed when dilute)
occurs at 3600 3650 cm-1
C-O-H bending - a broad and weak peak at 1550-
1220 cm-1
C-O stretching occurs in range 1260 1000 cm-1
The position of the C-O stretch can be used to
determine the type of alcohol

Imad Abu Reid 83

Imad Abu Reid 84
 1-hexanol
(neat liquid, KBr plates)

Imad Abu Reid 85

 2-butanol
(neat liquid, KBr plates)

Imad Abu Reid 86

 para-cresol
(neat liquid, KBr plates)

Imad Abu Reid 87

 6.Ethers
C-O stretch most important, occurs at 1300-1000
cm-1
In dialkyl ethers occurs as a strong band at 1120
cm-1
Aryl alkyl ethers give two peaks; asymmetric C-O-
C stretch near 1250 cm-1 and a symmetric stretch
near 1040 cm-1
Vinyl alkyl ethers give two peaks, a strong
asymmetric stretch at 1220 cm-1 and a weak
symmetric stretch near 850 cm-1

Imad Abu Reid 88

 C-O stretches also occur in alcohols and esters,
so look for O-H or C=O stretches before
concluding a compound is an ether

Imad Abu Reid 89

 Dibutyl ether
(neat liquid, KBr plates)

Imad Abu Reid 90

 Anisole
(neat liquid, KBr plates)

Imad Abu Reid 91

 7. Carbonyl compounds
The carbonyl group is present in aldehydes, ketones,
acids, esters, amides, acid chlorides, & anhydrides.
This group absorbs strongly in the range from 1850
to 1650 cm1 because of its large change in dipole
moment. Since the C=O stretching frequency is
sensitive to attached atoms, the common functional
groups already mentioned absorb at characteristic
values.
Imad Abu Reid 92
The figure below, provides the normal base values
for the C=O stretching vibrations of the various
functional groups. The C=O frequency of a ketone,
which is approximately in the middle of the range, is
usually considered the reference point for
comparisons of these values.

Imad Abu Reid 93

 aldehydes
Contains a C=O stretch at:
1740 1725 cm-1 for normal aliphatic aldehyde
1700 1680 cm-1 for conjugation with double
bond
1700 1660 cm-1 for conjugation with phenyl
group
Conjugation decreases the C=O bond order and
therefore decreases the stretching frequency

Imad Abu Reid 94

 The (CO)-H stretch occurs as a pair of weak
bands at 2860 2800 cm-1 and 2760 2700
cm-1; the higher-frequency bands are often
masked by alkane C-H absorptions
Above band can help to differentiate between
aldehydes and ketones as these both have a
carbonyl group

Imad Abu Reid 95

 nonanal
(neat liquid, KBr plates)

Imad Abu Reid 96

 crotonaldehyde
(neat liquid, KBr plates)

Imad Abu Reid 97

 benzaldehyde
(neat liquid, KBr plates)

Imad Abu Reid 98

 ketones
Contains a C=O stretch at:
1720 1708 cm-1 for normal aliphatic aldehyde
(slightly lower frequency than for aldehydes)
1700 1675 cm-1 for conjugation with double bond
1700 1680 cm-1 for conjugation with one phenyl
group
1670 1600 cm-1 for conjugation with two phenyl
groups
~ 1716 cm-1 for 1,2 diketones (not conjugated)
~ 1680 cm-1 for 1,2 diketones (conjugated)

Imad Abu Reid 99

Ring strain moves the absorption to a higher frequency
in cyclic ketones.

Imad Abu Reid 100

Imad Abu Reid 101
 mesityl oxide
(neat liquid, KBr plates)

Imad Abu Reid 102

 acetophenone
(neat liquid, KBr plates)

Imad Abu Reid 103

 cyclopentanone
(neat liquid, KBr plates)

Imad Abu Reid 104

 carboxylic acids
Carboxylic acids occur as hydrogen-
bonded dimers unless in dilute solution

Imad Abu Reid 105

C=0 stretch occurs in the following regions:
1730 1700 cm-1 for simple aliphatic acids in dimeric
form
Occurs at lower frequencies if conjugated with an
alkene or aromatic
O-H stretch occurs as a very broad peak at 3400 to
2400 cm-1, may partially obscure C-H stretching
bands
C-O stretch of medium intensity observed at 1320
1210 cm-1
Imad Abu Reid 106
 Isobutyric acid
(neat liquid, KBr plates)

Imad Abu Reid 107

benzoic acid (nujol mull, KBr plates)
(dots indicate the paraffin oil absorption bands)

Imad Abu Reid 108

 Esters
C=O stretch occurs at:
1750 1735 cm-1 for normal aliphatic esters
(example ethyl butyrate, 1738 cm-1)
1740 1750 cm-1 if carbonyl carbon conjugated with
an alkene
(example methyl methacrylate, 1725 cm-1)
1740 1715 cm-1 if carbonyl carbon conjugated with
aromatic
(example methyl benzoate, 1724 cm-1)
Imad Abu Reid 109
 1765 1762 cm-1 if oxygen atom conjugated with
alkene or aromatic (note that this is a shift to
higher frequency)
(example phenyl acetate, 1765 cm-1)
(example vinyl acetate, 1762 cm-1)
The C-O stretch occurs as two bands, one stronger
and broader than the other, at 1300 1000 cm-1
Ring strain moves the C=O absorption to a
higher frequency in cyclic esters (lactones)

Imad Abu Reid 110

 ethyl butyrate
(neat liquid, KBr plates)

simple aliphatic ester

Imad Abu Reid 111
 methyl methacrylate
(neat liquid, KBr plates)

alkene group adjacent to C=O group

Imad Abu Reid 112
 vinyl acetate
(neat liquid, KBr plates)

oxygen atom conjugated with alkene

Imad Abu Reid 113
 methyl benzoate
(neat liquid, KBr plates)

aromatic group adjacent to C=O group

Imad Abu Reid 114
 methyl salicylate
(neat liquid, KBr plates)

Imad Abu Reid 115

 amides
Amides show a very strong band for C=O group that
appears in the range of 1680-1630 cm-I.The N-H
stretch is observed in the range of 3475-3150 cm-I.
Unsubstituted (primary) amides, R-CO-NH2, show
two bands in N-H region while monosubstituted
(secondary) amides, CO-NH-R , show only one band.
The presence of N-H bands plus an unusually low
value for the C=O would suggest the presence of
amide functional group.

Imad Abu Reid 116

Disubstituted (tertiary) amides , R-CO-NR2, will
show the C=O in the range of 1680-1630 cm-I,but
will not show an N-H stretch.

Imad Abu Reid 117

propionamide (nujol mull, KBr plates)
(dots indicate the paraffin oil absorption bands)

Imad Abu Reid 118

 N-methylacetamide
(neat liquid, KBr plates)

Imad Abu Reid 119

 anhydrides
Anhydrides show two strong bands for the C=O
group .Simple alkyl substituted anhydrides generally
give bands near 1820 and 1750 cm-1.Anhydrides
and acid chlorides are most common functional
groups that have C=O peak appearing at such a
high frequency.Cojugation shifts each of the bands
to lower frequencies ( about 30 cm-1 each) .Simple
five membered ring anhydrides have bands at near
1780 cm-1.Ring strain shifts the absorption to higher
frequencies.

Imad Abu Reid 120

Imad Abu Reid 121
 Problem
Assign the following pairs of carbonyl stretching
wavenumbers to the corresponding structures shown
below : 1815 and 1750 cm 1 , and 1865 and 1780 cm 1
.

Imad Abu Reid 122

 8.Amines

N-H stretch occurs at 3500 3300 cm-1

Primary amines two bands
Secondary amines one band; weak for
aliphatic amines but stronger for aromatic
Tertiary amines have no absorption in this
region (no N-H bonds)

Imad Abu Reid 123

N-H bending
Broad band at 1640 1560 cm-1 for primary
amine
Secondary amines absorb at 1500 cm-1
N-H out of plane bending occurs at 800 cm-1
C-N stretching occurs at 1350 1000 cm-1

Imad Abu Reid 124

 butylamine
(neat liquid, KBr plates)

Imad Abu Reid 125

 dibutylamine
(neat liquid, KBr plates)

Imad Abu Reid 126

 tributylamine
(neat liquid, KBr plates)

Imad Abu Reid 127

Imad Abu Reid 128
 9. Nitro compounds
Nitro compounds show two strong bands in the
infrared spectrum. One appears near 1550 cm-1
and the other near 1350 cm-1 .Although these
two bands may partially overlap the aromatic
ring region, 1600-1450 cm-1 , it is usually easy to
see the nitro peaks.

Imad Abu Reid 129

 1-nitrohexane
(neat liquid, KBr plates)

Imad Abu Reid 130

 nitrobenzene
(neat liquid, KBr plates)

Imad Abu Reid 131

 Example 4
27

Imad Abu Reid 132

Imad Abu Reid 133
 Example 5

Match each spectrum to the

appropriate structure

Imad Abu Reid 134

Imad Abu Reid 135
 How to approach the analysis of
a spectrum
When analyzing the spectrum of an unknown,
concentrate your first effort on determining the
presence or absence of a few major functional
groups. The C=O ,O-H, N-H, C-O C=C ,CC,
CN, and NO2 peaks are the most conspicuous
and give immediate structural information if they
are present . Do not try to make a detailed analysis
of the C-H absorption near 3000 cm-1, almost all
compounds have these absorptions

Imad Abu Reid 136

Imad Abu Reid 137
Imad Abu Reid 138
Imad Abu Reid 139