IR Spectroscopy

2.5

1
 Wavelength & Frequency
• Frequency () is inversely proportional to wavelength (  = c/
c is the speed of light (3x108 ms-)1

λ E = hν = hc
λ
E = energy (J) of 1 photon
h = Plank's constant (6.63x10–34Js)
c = speed of light (3x108ms–)1
ν = frequency (Hz)
λ = wavelength (m)

long wavelength = low energy

short wavelength = high energy 4
 Introduction

• IR frequencies are usually expressed in units of wavenumbers (  ) whose unit is the reciprocal
centimeter (cm−;)1

• E.g. 2.5 µm = 2.5 x 10-4 cm 1/2.5x 10-4 cm = 4000 cm-1

15µm = 15 x 10-4 cm 1/15x 10-4 cm = 666 cm-1

• Wavenumbers (in cm−1) are directly proportional to frequency (in Hertz), and the two are related by
the speed of light; therefore, higher frequency vibrations correspond to higher wavenumbers.

3
 Introduction
• Three typical spectral regions for IR spectroscopy:

1.Near-IR: excites overtones or harmonics of fundamental vibrations (multiple level

transition.)
2. Mid-IR: excites the fundamental vibrations (single level transition). This region is the
most widely used for IR spectroscopy, because it generates spectral fingerprints in
which most of organic molecules.

3. Far-IR: excites low-energy vibrations and higher energy rotations. The far-IR is a
difficult spectral region for IR spectroscopy, and thus has few analytical uses.
Region Energy (kJ/mol) Wavenumber (cm-)1 Wavelength )µm)
Near IR 50-150 4000-12,800 2.5-0.78
Mid IR 2.5-50 400-4000 25-2.5
Far IR 0.1-2.5 10-400 1000-25
• Higher wavenumber corresponds to a higher energy absorption 4
 Introduction

• Spectroscopy provide the information about molecular structure. As IR is very useful

in identifying functional groups.

• A peak-by- peak correlation is excellent evidence for identity. Any two compounds,
except enantiomers, are unlikely to give exactly the same IR spectrum.

• IR spectra usually used in conjunction with other spectral data in order to

determine or confirm molecular structure.

• Even a very simple molecule can give an extremely complex spectrum.

5
 Theory

• Infrared radiation is absorbed and converted by an organic molecule into

energy of molecular vibration. And the vibrational spectra appear as bands.
• The vibrational–rotational bands occurring between 4000 cm−1 and 400 cm−.1

;
• The frequency or wavelength of absorption depends on th e
1. the relative masses of the atoms,
2. the force constants of the bonds,
3. the geometrical arrangement of the atoms (i.e., the molecular structure.)

6
 Theory

• Two of the most important types of molecular vibrations are stretching and bending.

• A stretching vibration is a rhythmical movement along the bond axis such that the interatomic
distance is increasing or decreasing.
CH2
• Stretching can be symmetrical or asymmetrical.

• A bending vibration may consist of a change Symmetrical Asymmetrical In-plane bending

stretching (vs CH)2 stretching (vas CH)2 or scissoring ( s CH)2
2853~cm–1 2926~cm–1 1465~cm–1
in angle between bonds

• For example, scissoring, rocking,

wagging, or twisting, vibrations involve a
Out-of-plane bending Out-of-plane bending In-plane bending
or wagging ( CH)2 or twisting ( CH)2 or rocking ( CH)2
change in bond angles within the molecule. 1350cm–1 to 1150 cm–1 1350cm–1 to 1150 cm–1 720~cm–1

7
 Theory

• Only those vibrations that result in a change in the net dipole

moment of the molecule are observed in the IR spectrum.

• The alternating electric field, produced by the changing

charge distribution accompanying a vibration, couples the
molecular vibration with the oscillating electric field of the
electromagnetic radiation.
• The positions and relative sizes of the peaks (also called bands) give clues about
the structure of a compound.

• Functional groups that have a strong dipole give rise to strong absorptions in the IR.
8
 Theory

• Band intensities can be expressed either as transmittance (T) or absorbance (A.)

• Transmittance : T= I/I0 (Intensity of light out/intensity of incident light)

• Absorbance: A= log10 (1/T)

9
 Theory

• A molecule has as many degrees of freedom as the total degrees of freedom of its
individual atoms.

• Each atom has three degrees of freedom corresponding to the Cartesian coordinates (x, y,
z) necessary to describe its position relative to other atoms in the molecule.

10
 Theory

• For nonlinear molecules, three degrees of freedom describe rotation and three describe translation; the
remaining 3n −6 degrees. H2O has (3X3)-6 = 3 fundamental vibrations
H2O

Symmetrical Asymmetrical Scissoring

stretching (vs OH) stretching (vas OH) ( s OH)
3652 cm–1 3756 cm–1 1596 cm–1

• Linear molecules have 3n −5 vibrational degrees of freedom, since only two independent degrees of
freedom are required to describe rotation. H2O has (3X3)-5 = 4 fundamental vibrations
CO2

)2(Asymmetrical )4(Scissoring (bending)

stretching (vas CO)2 ( s CO)2
)1(Symmetrical 2350cm–1 )3(Scissoring (bending) 665cm–1
stretching (vs CO)2 ( s CO)2
1340cm–1 665cm–1

11
 Theory

• The the observed vibrations might be larger than the theoretical number of fundamental vibrations
because of overtones.

• The following will reduce the number of observed bands:

1.Fundamental wavenumbers that fall outside of the 4000 cm−1 to 400 cm−1 region.

2.Fundamental bands that are too weak to be observed.

3.Fundamental vibrational wavenumbers that are so close that the bands coalesce.

4.The occurrence of a degenerate band from several absorptions of the same frequency in highly
symmetrical molecules.

5. The failure of certain fundamental vibrations to appear in the IR because of the lack of change in
molecular dipole.
12
 Theory

• Assignments for stretching frequencies can be approximated by

the application of Hooke’s law.
• Hooke’s law calculate the relationship between wavenumber of
oscillation, atomic masses, and bond force constant.
-y
Mass Displacement y
m
+y

single bond 5 x105 dyne/cm

double bond 10 x105 dyne/cm
triple bond 15 x105 dyne/cm

.The calculation is not highly accurate because effects arising from the molecule environment.
13
 IR Instrumentation

• Fourier-Transform Infrared (FT-IR) instrument uses a system called an interferometer.

• The interferometer consists of a source, beam-splitter, two mirrors, and a detector.

• This interferogram goes from the beam-splitter to the sample, the energy either absorbed or
transmitted. Then the transmitted portion reaches the detector.
• The detector reads information about every wavelength in the infrared range.
• The detector signal is sent to the computer, and an algorithm called a Fourier transform is
performed on the interferogram to convert it into a single beam spectrum.
b Interferogram:
Moving the signal the
Mirror computer receives.

Detector

Computer
Beam Sample Cell
Fixed splitter FT Transform
Mirror

Infrared 16
source FT-IR Printer
 Advantages of FT-IR

• High S/N ratios, so it is excellent spectra from very small samples can be obtained.

• Rapid (<10 s). The entire radiation range is passed through the sample simultaneously and much
time is saved.

• Reproducible.

• High resolution (<0.001 cm-)1

• Inexpensive

• FT-IR can be interfaced with chromatographic instrumentation,

17
 Sample preparation
Infrared spectra may be obtained for gases, liquids, or
solids.

• Gases fill cell

(a) transparent windows (NaCl/KBr)

(b) long pathlength (10 cm) - few molecules

• Liquids fill cell

(a) solute in transparent solvent - not water (attacks

windows)

(b) short pathlength (0.1-1 mm) - solvents absorb

(c) Solvent may be used is CCl4

(d) (NaCl/AgCl) used as diluents 18

 Sample preparation

• Solids

(a) make semi-transparent pellet with KBr

(b) grind and mix with Nujol (hydrocarbon oil) to form mull. One drop between NaCl plates.

Slight penetrations of the

• The best method of determining a spectrum of samples is to sample by the reflected beam
are made at the surface.
Sample
make use of an Attenuated Total Reflectance (ATR) accessory.
(Multiple Reflections)
• The ATR method provides a powerful sampling technique that
ATR Crystal

virtually eliminates sample preparation with both liquids and

solids, thus leading to rapid analysis of samples. Infrared source beam Attenuated infrared beam
exiting crystal

17
 IR Spectroscopy
Factors Affecting Group Frequencies
• Hydrogen bonding
• Ring strain
• Electronic effects
• Isomerism
• structural
• stereoisomerism

• Symmetry
• Fermi coupling

18
 Factors Affecting Group Frequencies

Hydrogen Bonding

• Hydrogen bonding takes place between a hydrogen atom bonded to an

electronegative element and an atom with a non-bonding electron pair.

• X-H….Y

• The effect of hydrogen bonding is to cause increasing the intensities,

broadening peaks and a shift peaks to lower frequencies in IR.

19
 Factors Affecting Group Frequencies
Effect of Ring Strain

1714cm-1
• Increasing ring strain causes a shift in
the carbonyl stretching to higher wave
numbers.
• This increase in frequency with increasing
1746cm-1
angle strain is observed for exocyclic
double bonds

1783cm-1
20
 Factors Affecting Group Frequencies

Electronic Effects - Effect of Conjugation

• Effects due to the change in the distribution of electrons in a molecule

produced by a substituent atom or group can often be detected in vibrational
spectra. Include inductive and resonance effects as well as conjugation of
double bonds.

• Conjugation tends to lower the double bond character and

increase the bond order of the intervening single bond.

• As a consequence, the C=O stretching frequency is lowered by 20-30 cm-1 in

this conjugated aldehyde.

21
 CHARACTERISTIC GROUP ABSORPTIONS OF ORGANIC MOLECULES

• The characteristic group absorptions expressed as ranges of absorption bands.

• These values have been assigned following the examination of many compounds in
which the groups occur.
• Although the ranges are quite well defined, the precise frequency or wavelength at
which a specific group absorbs is dependent on its environment within the molecule
and on its physical state.

22
 IR for Functional Groups
 Alkanes
• The spectra of normal alkanes is based on the stretching and bending of C⏤H and C⏤C bonds.
• The C⏤C bending vibrations occur at very low frequencies (below 500 cm−1) and therefore do not
appear in spectra.

• The bands assigned to C⏤C stretching vibrations are weak and appear in the broad region of 1200
cm−1 to 800 cm−1; they are generally of little value for identification.

• The most characteristic vibrations are those arising from C⏤H stretching and bending.
• The vibrational modes of alkanes are common to many organic molecules. Although the positions of
C⏤H stretching and bending frequencies of methyl and methylene groups remain nearly constant in
hydrocarbons, the attachment of CH3 or CH2 groups to atoms other than carbon, or to a carbonyl group
or aromatic ring, may result in appreciable shifts of the C⏤H stretching and bending frequencies.

• C⏤H stretching in the alkanes occurs in the general region of 3000 cm−1 to 2840 cm−.1
9
23
 Alkanes IR for Functional Groups
• C⏤H Bending Vibrations.
• Methyl Groups. Two bending vibrations can occur within a methyl group. The first of these, the
symmetrical bending vibration, involves the in-phase bending of the C⏤H bonds (I). The second,
the asymmetrical bending vibration, involves out-of-phase bending of the C⏤H bonds (II.)
H H
H H H H

I II

• The symmetrical bending vibration (very stable in position) occurs near 1375 cm−1, and the
asymmetrical bending vibration near 1450 cm−.1
• For methyl group, two distinct bands occurring at approximately 2962 cm−1 and 2872 cm−1. The first
of these results from the asymmetrical stretching mode in which two C⏤H bonds of the methyl group
are extending while the third one is contracting. The second arises from symmetrical stretching in which
all three of the C⏤H bonds extend and contract in phase.
10 24
 Alkanes

100

CH3 CH3
CH3 CH CH2 C CH3
%Transmittance

50
CH3

1370
1478
0
2882
2905
2959

4000 3000 2000 1000

Wavenumber (cm–)1

25
 IR for Functional Groups
• Alkenes (olefinic) structures introduce several new modes of vibration into a hydrocarbon molecule:
a C⏤C stretching vibration, C⏤H stretching vibrations in which the carbon atom is present in the
alkene linkage, and in-plane and out- of-plane bending of the alkene C⏤H bond.

• C⏤C Stretching Vibrations Unconjugated Linear Alkenes. The C⏤C stretching mode of
unconjugated alkenes usually shows moderate to weak absorption at 1667 cm−1 to 1640 cm−.1

• C⏤C Stretching Vibrations conjugated Systems. The alkene bond stretching vibrations in
conjugated dienes without a center of symmetry interact to produce two C⏤C stretching bands.

• The spectrum of an unsymmetrical conjugated diene, shows absorption near 1650 cm−1 and
1600cm−1. The symmetrical molecule diene shows only one band near 1600 cm−.1

• Alkene C⏤H Stretching Vibrations. In general, any C⏤H stretching bands above 3000 cm−1
result from aromatic, heteroaromatic, alkyne, or alkene C⏤H stretching.

• The most characteristic vibrational modes of alkenes are the out-of-plane C⏤H bending vibrations
14 28
between 1000 cm−1 and 650 cm−.1
 Alkenes

100

1640
1794

1378
1439
%Transmittance

CH2

2951
3090

992
H3C C CH CH2
2982
50

1601

899
4000 3000 2000 1000
Wavenumber (cm–)1

27
 Alkynes

• The two stretching vibrations in alkynes (acetylenes) involve C C and C⏤H

stretching

• The C C stretching band of alkyne molecules occurs in the region of 2260 cm−1 to 2100 cm−.1
• Because of symmetry, no C C band is observed in the IR for symmetrically substituted
alkynes.
• When the substituents are similar in mass, or produce similar inductive and resonance
effects, the band may be so weak as to be unobserved in the IR spectrum.
• The C⏤H stretching band of monosubstituted alkynes occurs in the general region of 3333 cm−1
to 3267 cm−.1
• The C⏤H bending vibration of alkynes or monosubstituted alkynes leads to strong, broad absorption in the
700cm−1 to 610 cm−1 region.

28
 Alkynes

100

2126
%Transmittance

1247
50

HC C (CH2)4CH3

1463
2866
3314

637
2959

4000 3000 2000 1000

Wavenumber (cm–)1

29
 IR for Functional Groups
• Aromatic Hydrocarbons

• The most prominent and most informative bands in the spectra of aromatic compounds occur in the
low-frequency range from 900 cm−1 to 675 cm−.1

• Skeletal vibrations, involving carbon–carbon stretching within the ring (aromatic C=C), absorb in the
1600cm−1 to 1585 cm−1 and 1500 cm−1 to 1400 cm−1 regions.

• Aromatic C⏤H stretching bands occur between 3100 cm−1 and 3000 cm−. 1

• Weak combination and overtone bands appear in the 2000 cm−1 to 1650 cm−1 region.
• Out-of-Plane C⏤H Bending Vibrations. The in-phase, out-of-plane bending. The bands are
frequently intense and appear at 900 cm−1 to 675 cm−.1

30
 IR for Functional Groups
• The =C-H oops bands are usually intense
• monosubstitution
• 690cm-1 (st) second band at 750 cm-1
• ortho-disubstituted
• One band at 750 cm-1 (st)
• meta-disubstituted
• 690cm-1 (st), one band at 780 cm-1, third at 880 cm-1
• para-disubstituted
• 850-800cm-1 (st)
• Combination and overtones
• mono, di, tri, tetra, penta or hexsubstitutes

Note/ The aim of this slide is to show students that different phenyl substitution
leads to different IR absorption at area 900-675 cm-1 33
 Aromatic Hydrocarbon

100

Overtone or combination bands

1605
CH3

1050
1381

1019
%Transmittance

50

2878
CH3

2970

1497
3017

1466
2940

741
0
4000 3000 2000 1000
Wavenumber (cm–)1

32
 Important Rules
Stronger bonds vibrate at a higher frequency than weaker bonds
HC CH H2C CH2 H3C CH3

2150cm-1 1650cm-1 1200cm-1

Bending modes occur at lower frequencies than stretching

stretch bend
C H C H

3000cm-1 1400
1240 cm-1
cm-1

Hybridization changes the force constant (values are for the C-H stretch)
sp3
sp sp2
H2
HC C H H2C C H H3C C H
H
23
3300cm-1 3100cm-1 2900cm-1

33