Asst. Prof. Dr.

Salam Ghafour Taher

https://sites.google.com/a/koyauniversity.org/salam-taher/

ORGANIC SPECTROSCOPY
• how atoms are connected together? How many C and H
atoms? Total identification?
• What is the molecular mass of the molecule?
• Which bonds are single, double, or triple?
• What functional groups exist in the molecule?
• How to determine a specific stereoisomer?
The field of organic identification aims to answer
1
these questions..
Why this course?
• Finding structures of new
molecules, synthesized or
natural is critical !!

• To get a good idea of the

range of structural
techniques available and
how they should be used

2
The general steps to determine the structure of an
organic compound

3
 INSTRUMENTAL METHODS OF ORGANIC STRUCTURE
IDENTIFICATION

• Different regions of the electromagnetic spectrum are used to

probe for different aspects of molecula r structure:

Mass electrons Bombardment molecular mass

4 spectrometry
 INSTRUMENTAL METHODS OF ORGANIC
STRUCTURE IDENTIFICATION
1. Infrared Spectroscopy (IR) – Triggering molecular vibrations through
irradiation with infrared light. Provides mostly information about the
presence or absence of certain functional groups.
2. Nuclear Magnetic Resonance (NMR) – Excitation of the nucleus of atoms
through radiofrequency irradiation. Provides extensive information about
molecular structure and atom connectivity.
3. Mass spectrometry – Bombardment of the sample with electrons and
detection of resulting molecular fragments. Provides information about
molecular mass and atom connectivity.
4. Ultraviolet spectroscopy (UV) – Promotion of electrons to higher energy
levels through irradiation of the molecule with ultraviolet light. Provides
mostly information about the presence of conjugated p systems and the
5 presence of double and triple bonds.
IR Mass

HNMR

UV

CNMR

6
 SPECTRUM INTERPRETATION PROCESS

1. Recognize a pattern.
2. Associate patterns with physical parameters.
3. Identify possible meanings, i.e. propose explanations.

Once a spectrum is obtained, the main challenge is to extract the

information it contains in abstract, or hidden form. This requires
the recognition of certain patterns, the association of these patterns
with physical parameters, and the interpretation of these patterns in
terms of meaningful and logical explanations.

7
 Introduction to Spectroscopy
Spectroscopy is a general term referring to the interactions of
various types of electromagnetic radiation with matter.

Upon irradiation with different sources, certain bonds, atoms, or

molecules responds. This response can be detected and translated
into a visual representation called a spectrum.

Physical response Detecting

Molecule
stimulus instrument

Visual (most common)

representation, or
Spectrum
8
 Spectroscopy
Electromagnetic radiation: is a form of energy which exhibits
both wave and particle properties. It is supposed to travel as a
wave.
Wave number: (Ū= 1/λ) is the number of waves per unit of
length.
Frequency (V): is the number of waves (cycles) per unit of
time(second).

9
 • Frequency, is the number of wave cycles that pass through
a point in one second. It is measured in Hz, where 1 Hz = 1
cycle/sec.
• Wavelength, λ (lambda), is the length of one complete
wave cycle. It is measured in cm (centimeters).
Wavelength and frequency are inversely related:
• Wave number: (Ū= 1/λ) is the number of waves per unit
of length.

10
 EFFECT OF ELECTROMAGNETIC RADIATION
ON MOLECULES

11
 Infra-red Spectroscopy (IR)
An important tool of the organic chemist is Infrared Spectroscopy, or IR. IR
spectra are acquired on a special instrument, called an IR spectrometer.
IR is used both to gather information about the structure of a compound and as
an analytical tool to assess the purity of a compound. Arises from absorption
of IR radiation by organic compounds. Causes atoms and groups of atoms of
organic compounds to vibrate with increased amplitude about the covalent
bonds that connect them.

12
 Infrared Spectroscopy (IR)
•IR deals with the interaction of infrared radiation with
matter. The IR spectrum of a compound can provide
important information about its chemical nature and
molecular structure.
•Most commonly, the spectrum is obtained by measuring the
absorption of IR radiation, although infrared emission and
reflection are also used.
•Widely applied in the analysis of organic materials, also
useful for polyatomic inorganic molecules and for
organometallic compounds.
13
 Infrared Spectroscopy (IR)
• Some night vision goggles can detect IR light that is emitted
• IR or thermal imaging is also used to detect breast cancer

14
 Infrared Spectroscopy (IR)
When a chemical sample is exposed to the action of IR LIGHT, it can absorb
some frequencies and transmit the rest. Some of the light can also be reflected
back to the source.

Transmitted
IR Chemical light
Detector
source sample

From all the frequencies it receives, the chemical sample can absorb
(retain) specific frequencies and allow the rest to pass through it
(transmitted light).

The detector detects the transmitted frequencies, and by doing so also

reveals the values of the absorbed frequencies.
15
 Infra-red Spectroscopy/ theory

E = h

16
 IR Spectroscopy
• Molecular bonds can vibrate by stretching or by bending in a
number of ways

• This chapter will focus mainly on stretching frequencies

17
There are three well defined infrared regions; each of them has the
potential to provide different information:
* Far-Infrared (400-33 cm-1): vibrations of molecules containing
heavy atoms, molecular skeleton vibrations and crystal lattice
vibrations
* Mid-Infrared (4000-400 cm-1): useful for organic analysis
* Near Infrared (12820-4000 cm-1): overtones; very useful for
quantitative analysis

18
 Infra-red Spectroscopy/ theory

• In order for IR absorbance to occur four conditions must be met:

1. There must be a change in the dipole moment of the

molecule as a result of a molecular vibration (or
rotation). The change (or oscillation) in the dipole
moment allows interaction with the alternating
electrical component of the IR radiation wave.
Symmetric molecules (or bonds) do not absorb IR
radiation since there is no dipole moment.
2. If the frequency of the radiation matches the natural
frequency of the vibration (or rotation), the IR photon
is absorbed and the amplitude of the vibration
increases.
19
 3. The energy absorption must occure
between 400-4000 cm-1 (The region of
wavelengths)
4. The intensity of the absorption should be
strong enough to be detected.

20
 Infrared Spectroscopy

Infrared (IR) spectroscopy: based on IR absorption by molecules as undergo

vibrational and rotational transitions.

rotational transitions
Potential Energy (E)

Vibrational transitions

Interatomic Distance (r)

Potential energy resembles classic Harmonic Oscillator

21
 Modes of vibrations
There are two types of molecular vibrations, stretching and
bending. A molecule consisting of n atoms has a total of 3n
degrees of freedom. In a nonlinear molecule, 3 of these
degrees are rotational and 3 are translational and the
remaining correspond to fundamental vibrations; in a linear
molecule, 2 degrees are rotational and 3 are translational. The
net number of fundamental vibrations for nonlinear and
linear molecules is therefore:

22
 Modes of vibrations
• Among the several factors that may contribute to their absence
are the following:
• The absorption may be too weak to be observed.
• The absorption may combine with another absorption.
• The absorption may occur outside the region of the spectrum.
For instance, the C–I stretching vibration appears between 602–
500 cm −1 (16.0–20.0 μm) which is outside the range of some
infrared instruments.
• Two or more absorptions may be degenerate (of the same
energy), thus, occurring at the same frequency.
• There may be no net change (or very little change) in the dipole
moment of the bond during vibration.

23
 3756 3652 1596 cm-1
24
Carbon dioxide,CO2, is linear and hence has four fundamental
vibrations.The asymmetrical stretch of CO2 gives a strong band
in the IR at 2350cm–1. Since CO2 is present in the atmosphere.
The two scissoring or bending vibrations are equivalent and
therefore, have the same frequency and are said to be
degenerate, appearing in an IR spectrum at 666 cm –1

25
The symmetrical stretch of CO2 is inactive in the IR because this
vibration produces no change in the dipole moment of the
molecule. In order to be IR active, a vibration must cause a change
in the dipole moment of the molecule. Of the following linear
molecules, carbon monoxide and iodine chloride absorb IR
radiation, while hydrogen, nitrogen, and chlorine do not. In
general, the larger the dipole change, the stronger the intensity of
the band in an IR spectrum.

Why only two IR bands (2350 and 666 cm–1 ) are seen for
carbon dioxide, instead of four?

26
27
 CO2

28
 Modes of vibrations
Fundamental: stretching, bending
Non-fundamental: Overtone, Combination, Difference, Fermi resonance
1. Stretching - the rhythmic movement along a bond axis wit a subsequent
increase and decrease in bond length.

2. Bending - a change in bond angle or movement of a group of atoms with

respect to the rest of the molecule.

29
 Modes of vibrations
Stretching can be viewed as springs holding together two masses, or atoms.

30
 Modes of vibrations

Symmetrical stretching : -

Asymmetrical stretching : -

31
 Modes of vibrations

Bending (scissoring) : - two modes

Behind paper

Out of paper

32
Symmetrical stretching Asymmetrical stretching In plane:rocking In plane:scissoring

Out plane:Wagging Out plane:Twisting

33
 Non fundamental absorption
Usually, the spectrum is complicated because of the presence
of weak overtone, combination, and difference bands.
• Overtone: results from excitation from the ground state to
higher energy states, which correspond to integral
multiples of the frequency of the fundamental.
• Combination band: This band is the sum of the two
interacting bands. Combination bands are observed when
more than two or more fundamental vibrations are excited
simultaneously
• Difference band: results from the difference between the
two interacting bands.
• Fermi resonance: results from combination of
fundamental with non-fundamental vibration (overtone,
combination). Fermi resonance is often observed in
34
carbonyl compounds.
 overtone
• The energy required for the first overtone is twice the
fundamental, assuming evenly spaced energy levels. Since
the energy is proportional to the frequency absorbed and
this is proportional to the wavenumber, the first overtone
will appear in the spectrum at twice the wave number of
the fundamental.

35
 • Let's say you run an IR spectrum of acetone (CH3)2C=O:
you'll get a huge absorption at ~1720 cm-1. This
corresponds to the excitation of the molecule from its
ground state (νo) to the first C=O vibrationally excited
state (ν1)

If you look at around twice this frequency (i.e., ~3440 cm-

1) at high conc you will observe a weak absorption due to
excitation of acetone to the second next C=O vibrationally
excited state ν2. This is called the first overtone band for
the C=O stretch. Third (~5160 cm-1) and fourth (6880 cm-
1) overtone bands can also be observed: need synchrotron
radiation and special near IR detectors. The bands get
progressively weaker because the probability of their
occurrence gets lower.
36
 combination
Two vibrational frequencies (v1 and v2) in a molecule
couple to give rise to a new infrared active frequency. This
band is the sum of the two interacting bands (v
combination = v1 + v2).
• The energy levels mix, hence resulting in the same number
of vibrational modes, but at different frequencies, and
bands can no longer be assigned to one bond. This is very
common and occurs when adjacent bonds have similar
frequencies. Coupling commonly occurs between C–C
stretching, C stretching, C–N stretching, C–H rocking and
C–H wagging motions. A further requirement is that to be
strongly coupled, the motions must be in the same part of
37 the molecule.
38
 Difference band

A difference band, occurs between excited states of two different

vibrations. The frequency is approximately equal to the difference
between the fundamental frequencies. The molecule already
existing in one excited vibrational state absorbs enough additional
energy to raise into another vibrational level in differecnt
vibrational mode. The measured absorption is the difference
between two.

39
 Fermiresonace
• Fermi resonance results in the splitting of two vibrational bands that
have nearly the same energy and symmetry in IR. The two bands are
usually a fundamental vibration and either an overtone or combination
band. The wavefunctions for the two resonant vibrations mix
according to the harmonic oscillator approximation, and the result is a
shift in frequency and a change in intensity in the spectrum. As a
result, two strong bands are observed in the spectrum, instead of the
expected strong and weak bands. It is not possible to determine the
contribution from each vibration because of the resulting mixed wave
function.

40
41
 Calculation of vibrational frequency

The stretching frequency of a bond can be approximated

by Hooke’s Law. In this approximation, two atoms and the
connecting bond are treated as a simple harmonic
oscillator composed of 2 masses (atoms) joined by a
spring:

The frequency of the vibration of the spring is related to the

mass and the force constant of the spring, k , by the following
formula:

42
 Mechanical Model of Stretching Vibrations
1. Simple harmonic oscillator.
• Hooke’s Law (restoring force of a spring is proportional to the
displacement)

F = -ky

Where: F = Force
k = Force Constant
(stiffness of spring)
y = Displacement

• Natural oscillation frequency of a mechanical oscillator depends

on:
a) mass of the object
b) force constant of the spring (bond)
• The oscillation frequency is independent of the amount of energy
43
imparted to the spring.
• Vibrational Frequency: The natural
frequency of the oscillation is

1 k
m 
2p m
m = natural frequency
m = mass of the attached body
k = force constant of the spring (related to the
44
strength of the spring (bond))
 The equation may be modified to describe the
behavior of a system consisting of two masses
m1 and m2 connected by a spring. Here, it is only
necessary to substitute the reduced mass  for the
single mass m where
m1m2

m1  m2
Thus, the vibrational frequency for such a system
is given by
1 k 1 k (m1 . m2)
m  
2p  2p m1  m2
45
The radiation in wave numbers,

1 k k
  5.3  10
2p c  

K= 5X105 dyne/cm for single bonds

K=10X105 dyne/cm for double bonds
K=15X10
46 5 dyne/cm for triple bonds
47
 Bond strength 
k
k
ν 
 μ
C – C < C = C < C  C
1200 cm-1 1650 cm-1 2150 cm-1

Increasing frequency of vibration

48
Comparison of wavelength, stretching frequency, and wavenumber
of bonds with different strengths (i.e. single C-N =1145 cm-1,
double
49 C=N = 1619, and triple bonds = 1983).
 Masses of bonding atoms 
k

ν 
 μ
C–H < C-C < C-Cl
3000 cm-1 1200 cm-1 800 cm-1

Increasing Masses of bonding atoms

50
 AN IR SPECTRUM IN ABSORPTION MODE
The IR spectrum is basically a plot of transmitted (or absorbed)
frequencies vs. intensity of the transmission (or absorption). Frequencies
appear in the x-axis in units of inverse centimeters (wave numbers), and
intensities are plotted on the y-axis in percentage units.

51 The graph above shows a spectrum in absorption mode.

 AN IR SPECTRUM IN TRANSMISSION MODE

The graph above shows a spectrum in transmission mode.

This is the most commonly used representation and the one found in most chemistry
and spectroscopy books. Therefore we will use this representation.
52
 CLASSIFICATION OF IR BANDS
IR bands can be classified as strong (s), medium (m), or weak (w), depending
on their relative intensities in the infrared spectrum. A strong band covers most
of the y-axis. A medium band falls to about half of the y-axis, and a weak band
falls to about one third or less of the y-axis.

53
• The more polar the bond, the greater the opportunity for
interaction between the waves of the electrical field and the IR
radiation
• Greater bond polarity = stronger IR signals

54
 INFRARED ACTIVE BONDS
Not all covalent bonds display bands in the IR spectrum. Only polar bonds do
so. These are referred to as IR active.
The intensity of the bands depends on the magnitude of the dipole moment
associated with the bond in question:
• Strongly polar bonds such as carbonyl groups (C=O) produce strong bands
around 1700 cm-1.
• Medium polarity bonds and asymmetric bonds produce medium bands.
• Weakly polar bond and symmetric bonds produce weak or non observable
bands.

55
 INFRARED BAND SHAPES
Infrared band shapes come in various forms. Two of the most common are
narrow and broad. Narrow bands are thin and pointed, like a dagger. Broad
bands are wide and smoother.

A typical example of a broad band is that displayed by O-H bonds, such as

those found in alcohols and carboxylic acids, as shown below.

56
Infrared Spectroscopy
E. The IR Spectrum – The detection of different bonds
7. As opposed to chromatography or other spectroscopic
methods, the area of a IR band (or peak) is not directly
proportional to concentration of the functional group
producing the peak

8. The intensity of an IR band is affected by two primary

factors:
Whether the vibration is one of stretching or bending

Electronegativity difference of the atoms involved in

the bond

57
 • For both effects, the greater the change in
dipole moment in a given vibration or
bend, the larger the peak.

• The greater the difference in

electronegativity between the atoms
involved in bonding, the larger the dipole
moment

• Typically, stretching will change dipole

moment more than bending

58
 Absorption Regions

59
 Factors influencing vibrational frequencies

 Vibrational coupling
 Hydrogen bonding
 Electronic effect
a. Mesomeric effect
b. Inductive effect
c. Field effect
 Bond angels
 Hybridization

60
 Vibrational coupling
• Interaction between vibrations can occur (coupling) if the
vibrating bonds are joined to a single, central atom.
Vibrational coupling is influenced by a number of factors;
• Strong coupling of stretching vibrations occurs when there
is a common atom between the two vibrating bonds
• Coupling between fundamental and non-fundamental
(Fermi Resonance)
• Coupling between a stretching vibration and a bending
vibration occurs if the stretching bond is one side of an
angle varied by bending vibration
• Coupling is greatest when the coupled groups have
approximately equal energies
• No coupling is seen between groups separated by two or
61 more bonds
 An isolated C-H bond has only one stretching vibration at 2890
cm-1.
 In CH2, C-H vibrations are combined together to produce two
coupled vibrations of different frequencies.
1. symmetric frequencies νsymm 2853 cm-1
2. anti symmetric frequencies. νanti. 2926 cm-1
 The equivalent coupled vibrations of CH3 groups have
different frequencies from CH2 groups, and appear at (2872,
2926 cm-1). All of the vibrations can be seen in high resolution
spectra of compounds containing both CH2 and CH3 groups.
 Vibration coupling occurs between two bonds similar
frequency provided the bonds are reasonably close in
molecule.
62
63
  Q/ Amides shows two absorption bands around 1600-1700 cm-1
corresponding mainly to C=Ostr. and N-Hdef. (bending) However,
the two bands are not pure C=Ostr neither N-Hdef ?

Ans. Because of the vibrational coupling, the original characters

of the two vibrations are modified. The two bands are usually
referred as amide I and amide II bands. Moreover, amide I may be
as High as 80% of C=Ostr in character, while amide II is strongly
coupled interaction between the two (C=Ostr and N-Hdef).

64
 IR SPECTRUM OF AMIDES
Amides show a very strong, somewhat broad band at the left end
of the spectrum, in the range between 3100 and 3500 cm-1 for the
N-H stretch. At the same time they also show the stake-shaped
band in the middle of the spectrum around 1710 cm-1 for the
C=O stretch. As with amines, primary amides show two bands

65
 In aldehydes the C-Hstr absorption usually
appears as a doublet around 2800 cm-1.
Why?
Ans. Because of interaction between the C-Hstr
fundamental and the overtone of C-Hdef .
C-Hstr 2850 cm-1 C-Hdef 1425 x 2 = 2850 cm-1

66
 IR SPECTRUM OF ALDEHYDES AND KETONES

67
Graphics source: Wade, Jr., L.G. Organic Chemistry, 6th ed. Pearson Prentice Hall Inc., 2006
 Hydrogen bonding:
• HYDROGEN BONDING (Intra Molecular Hydrogen bonding Inter Molecular
Hydrogen bonding)

• Inter molecular H-bonding : -leads to broadening of bands in concentrated

solutions. In dilute solutions a sharp peak is obtained. Eg : alcohols & phenols
in condensed phases. Hydrogen bonding involves lengthening of the original
OH bond, the bond is consequently weakened (force constant is reduced & the
frequency is lowered). The concentrated amines show bonded N-Hstr around
3300 cm-1, while the diluted amines show a new band around 3600 cm-1
corresponds to free N-Hstr.
Intra molecular H-bonding:

• Intra molecular H-bonding Eg ; H-bonding persists even at very low

concentrations.

 The effect of intramolecular hydrogen bonding can be clearly seen for hydroxy
68
benzoic cids.
 Intra-molecular hydrogen bonding

69
70
P-Hydroxy benzoic acid
 IR SPECTRUM OF AN ALCOHOL
The most prominent band in alcohols is due to the O-H bond, and it
appears as a strong, broad band covering the range of about 3000 -
3700 cm-1. The size and broad shape of the band dominate the IR
spectrum and make it hard to miss. This could be an example of
Inter molecular H-bonding

71
 Electronic effect
a. Mesomeric effect: conjugation lowers the frequency of
C=Ostr and C=Cstr, whether the conjugation is brought
about by α,β-unsaturation or by an aromatic ring.

νC=O≈ 1720 cm-1 1700 cm-1 1700 cm-1 νC=C≈ 1650 cm-1 1610 cm-1

72
• The more delocalized the pi electrons, the weaker the pi bond, and
the lower the stretching frequency

1700
1700
73
  any substituent that enhance the mesomeric shift will
decrease the band order of the C=O band and lead to to
lower C=Ostr frequency.

I II III IV
ν ≈ 1720 cm-1 1700 cm-1 1680 cm-1 >1720 cm-1

• Electron donating group such as p-MeO in (III) will led to

lower frequency too. Whereas, electron withdrawing group
such as p-NO2 (IV) will appose the trend and lead to
higher frequencies.
74
 b. Inductive effect
 Inductive effects are usually small, unless coupled with a resonance
contributor

 In some molecules Inductive Effect (I) is more important than

Mesomeric Effect (M), nevertheless, the opposite is true in some
cases.

 Inductive effects (+I effect)—weakening of the bond-absorption at

lower wave number. Absorption frequency shifts from the normal
value because of electronic effects. Eg: HCHO- 1750cm-1
,CH3CHO-1745 Cm-1 Introduction of electronegative group:
inductive effect (-I effect) increases wave no. of absorption. Eg:
75
CH3COCH3 1715cm-1 ClCH2 COCH3 1725cm-1 :
 Inductive and mesomeric effect

76
 Field effect:
 c. Two groups often influence each others vibrational
frequencies by a through space interaction, which may be
electrostatic and/or steric in nature.
 C=O stretching frequencies is higher when chlorine in
equatorial than when it is axial. It may be due to repulsive
force of non bonding electron of oxygen and chlorine in
the Molecule.

 Equatorial conformation axial conformation

1750 cm-1 1725 cm-1

77
 Strain effects (Bond angels)
Strain effects – changes in bond angle forced by the constraints of a ring will

cause a slight change in hybridization, and therefore, bond strength. As bond

angle decreases, carbon becomes less sp2 hybridized (bond angle < 120°)

In ketones, the vibrational frequency increases with the bond strain, and it

reaches its highest in cyclobutanone and cyclopropanone.

This can be explained in terms of bond angular strain. when the C—CO—C .

bond angle is reduced below 1200 leads to increase S character C=O bond.

Moreover, the C=O bond is shortened, therefore, the bond is strengthened and
78
νc=o increases.
 Hybridization
C-Hstr. Shifts to higher frequency in the sequence alkane,
alkene, alkyne.
The S character of the C–H bond increases in the sequence
sp3, sp2, sp, and the bond strength increases, therefore, the
vibrational frequency increases.

79
 IR Instrumentation

• Dispersive instruments: with a monochromator to be

used in the mid-IR region for spectral scanning and
quantitative analysis.
• Fourier transform IR (FTIR) systems: widely applied
and quite popular in the far-IR and mid-IR spectrometry
for both quantitative and qualitative analysis.
• Nondispersive instruments: use filters for wavelength
selection or an infrared-absorbing gas in the detection
system for the analysis of gas at specific wavelength. For
quantitative analysis.

80
Instrumentation
Perkin ElmerTM
Spectrum One

BRUKE TENSORTM
Series
81
 Dispersive IR spectrophotometers
Modern dispersive IR spectrophotometers are invariably double-
beam instruments, but many allow single-beam operation via a
front-panel switch.

Simplified diagram of a double beam infrared spectrometer

Double-beam operation allows a stable 100% T baseline in the

spectra. The optical efficiency of the mirrors and grating, and the
detector instability, which are serious in the IR region.single-
82
beam instruments not practical.
 Dispersive spectrophotometers Designs

83
 Components of dispersive spectrophotometers
1. IR source: Nernst Glower, Globar, W filament lamp, Hg arc
lamp.
2. Detector: (Thermocouple, Bolometer, Pyroelectric,
Photoconducting ) which converts IR energy to electrical
energy
3. Reflection gratings ( made from various plastics): the groove
spacing is greater (e.g. 120 grooves/mm). To reduce the effect
of overlapping orders and stray radiation, filters or a
preceding prism are usually employed. Two or more gratings
are often used with several filters to scan a wide region.
4. Mirrors consists of a rotating segmented mirrors, which are
used to focus the IR radiation. Generally made from Pyrex.
Front surfaces coated with a vacuum-deposited thin metal
film of Al, Ag, or Au.
84
 Components of dispersive spectrophotometers

1. IR source

Nernst Glower heated rare earth oxide rod 1-50 µm

(~1500 K) (mid- to far-IR)
Globar heated SiC rod (~1500 K) 1-50 µm
(mid- to far-IR)
W filament lamp 1100 K 0.78-2.5 µm
(Near-IR)
Hg arc lamp plasma 50 - 300 µm
(far-IR)
CO2 laser stimulated emission lines 9-11 µm

85
 2. Detector: converts IR energy to electrical energy
Thermocouple thermoelectric effect - cheap, slow,
dissimilar metal junction insensitive

Bolometer Ni, Pt resistance Highly sensitive

thermometer (thermistor) <400 cm-1

Pyroelectric Tri glycine sulfate fast and sensitive

piezoelectric material (mid IR)

Photoconducting PbS, CdS, Pb Se light fast and sensitive

sensitive cells (near IR)

86
 3. Optical system

87
•Windows are used for sample cells and to permit various
compartment to be isolated from the environment.
 transparent to IR over the wavelength region
 inert to the various chemicals analyzed
 capable of being shaped, ground, and polished to the
desired optical quality

88
 Fourier transform IR
• Fourier transform is to
transform the signal from the
time domain to its
representation in the
frequency domain.
• FT – IR can take wavelength
readings across the whole IR
region simultaneously and
smoothly, making this a very
rapid technique.
• Greater wavenumber
accuracy. Most FT
instruments have an accuracy
of +/- 0.01 cm -1.
89
Multiplexing (FT) Spectrometers
• Collect data in the time domain and convert to the frequency domain by
Fourier Transform.

200 scans

50 scans

1 scan
90
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.

91
 Advantages of FTIR
• very high resolution (< 0.1 cm –1 )
Two closely spaced lines only separated if one complete "beat" is recorded.
As lines get closer together, d must increase.
D(cm-1)  1/d
Mirror motion is 1/2 d
Resolution governed by distance movable mirror travels

• very high sensitivity (nanogram quantity)

can be coupled with GC analysis (–> measure IR spectra in gas-phase)

• High S/N ratios - high throughput

Few optics, no slits mean high intensity of light

• Rapid (<10 s)

• Reproducible and • Inexpensive

92
 Sample preparation techniques
Infrared spectra may be obtained for gases, liquids or solids (neat
or in solution)

The preparation of samples for infrared spectrometry is often the

most challenging task in obtaining an IR spectrum. Since almost all
substances absorb IR radiation at some wave length, and solvents
must be carefully chosen for the wavelength region and the sample
93
of interest.
 Gas samples
• A gas sample cell consists of a cylinder of glass or sometimes a metal.
The cell is closed at both ends with an appropriate window materials
(NaCl/KBr) and equipped with valves or stopcocks for introduction of
the sample.

• Long pathlength (10 cm) cells – used to study dilute (few molecules)
or weakly absorbing samples.
• Multipass cells – more compact and efficient instead of long-path
length cells. Mirrors are used so that the beam makes several passes
94
through the sample before exiting the cell. (Effective path length  10
m).
 Liquid samples
•The sample is most often in the form of liquid films (―sandwiched‖ between
two NaCl plates)

95
 Solid samples
• Spectra of solids are obtained as alkali halide discs
(KBr), mulls (e.g. Nujol, a highly refined mixture of
saturated hydrocarbons) and films (solvent or melt
casting)

Alkali halide discs:

1. A milligram or less of the fine ground sample mixed with about 100 mg
of dry KBr powder in a mortar or ball mill.
2. The mixture compressed in a special cell to form transparent disc.
Mulls
1. Grinding a few milligrams of the powdered sample with a mortar or with
pulverizing equipment. A few drops of the mineral oil added (grinding
continued to form a smooth paste).
2. The IR of the paste can be obtained as the liquid sample.
96
 Infrared Group Analysis
General
1. The primary use of the IR is to detect functional groups

2. Because the IR looks at the interaction of the EM spectrum

with actual bonds, it provides a unique qualitative probe into
the functionality of a molecule, as functional groups are
merely different configurations of different types of bonds

3. Since most ―types‖ of bonds in covalent molecules have

roughly the same energy, i.e., C=C and C=O bonds, C-H and
N-H bonds they show up in similar regions of the IR
spectrum

4. Remember all organic functional groups are made of multiple

bonds and therefore show up as multiple IR bands (peaks)
5. Library Database Computer Search can help…..
97
 iv.) Computer Searches
- many modern instruments have reference IR spectra on file (~100,000
compounds)
- matches based on location of strongest band, then 2nd strongest band, etc
overall skeletal structure of a compound
- exact interpretation of this region of spectra seldom possible because of
complexity
- complexity  uniqueness

Bio-Rad SearchIT database

of ~200,000 IR spectra

98
Infrared Spectroscopy
II. Infrared Group Analysis
A. General
5. The four primary regions of the IR spectrum
Bonds to H Triple bonds Double bonds Single 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

4000 cm-1 2700 cm-1 2000 cm-1 1600 cm-1 600 cm-1

99
 iii.) Fingerprint Region (1200-700 cm-1)
- region of most single bond signals
- many have similar frequencies, so affect each other & give pattern
characteristics of overall skeletal structure of a compound
- exact interpretation of this region of spectra seldom possible because of
complexity Fingerprint Region
- complexity  uniqueness

100
Infrared Spectroscopy
Octane
1. Alkanes – combination of C-C and C-H bonds
• C-C stretches and bends 1360-1470 cm-1

• CH2-CH2 bond 1450-1470 cm-1

• CH2-CH3 bond 1360-1390 cm-1

• sp3 C-H between 2800-3000 cm-1

(w – s) (m)

101
102
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)

103
Infrared Spectroscopy
1-Octyne
3. Alkynes – addition of the C=C and vinyl C-H bonds
• C≡C stretch 2100-2260 cm-1; strength depends on
asymmetry of bond, strongest for terminal alkynes,
weakest for symmetrical internal alkynes

• C-H for terminal alkynes occurs at 3200-3300 cm-1

• Internal alkynes ( R-C≡C-R ) would not have this band!

(w-m)

(m – s)

104
105
• Alkyl C-H bonds come just under 3000 cm-1, while alkenyl and
alkynyl C-H bonds are over 3000 cm-1

106
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 – m) (w – m)

107
Mononuclear Aromatics

Overtone bands
2000-1650 cm–1

Aromatic
C-H Stretches out of
3087, 3062, Aromatic C-H in plane bends plane
3026 cm–1 1300-1000 cm–1 ring
bending
Aromatic 428 cm–1
C-H out of
Plane bends
Aromatic C-C Stretches 728 cm–1
1600-1585; 1500-1400 cm–1 694 cm-1

108
 CH3

CH3 795 cm-1

CH3

CH3

768 cm-1 691 cm-1

CH3
CH3

742 cm-

109
C–O stretching Vibrations
• Alcohols (1260-1000 cm–1) • Phenols (1260-1800 cm–1)
primary alcohol: 1050-1085 cm-1
secondary alcohol: 1085-1125-1
tertiary alcohol: 1125-1200 cm-1

OH

1073 cm-1

OH

1110 cm–1

OH

1202 cm–1
110
 Broad band with peak
at about 3300 cm-1

No aliphatic C-H
stretching

111
 weak

Several peaks 3300

(2840-3000 cm-1)
due to
different modes
of Symmetrical
& asymmetrical
stretching 3100 medium

Different
modes of C-H
bending
(~1400 cm-1)

112
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)

113
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
• Additionally there is a “wag” band at 780-820 cm-
1 that is not diagnostic

(w) (w)

114
 No C-H stretching
 No C=C-H
above 3000 cm-1

1 amine N-H
bending
H

115
 H
1 amine
C

116
117
Infrared Spectroscopy
Cyclohexyl carboxaldehyde
10. Aldehydes
• C=O (carbonyl) stretch from 1720-1740 cm-1

• Band is sensitive to conjugation, as are all

carbonyls (upcoming slide)

• A highly unique sp2 C-H stretch appears as a

doublet, 2720 & 2820 cm-1 called a “Fermi
doublet”

(w-m)

(s)

118
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)

119
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)

120
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 – m) (s) (s)
br

121
122
Infrared Spectroscopy
Propionyl chloride
O
15. Acid halides
• Clefted band at 1770-1820 cm-1 for C=O
Cl
• Bonds to halogens, due to their size (see
Hooke’s Law derivation) occur at low
frequencies, only Cl is light enough to have a
band on IR, C-Cl is at 600-800 cm-1

(s)

(s)

123
Infrared Spectroscopy
pivalamide
O
16. Amides
• Display features of amines and carbonyl
NH2
compounds
• C=O stretch at 1640-1680 cm-1

• If the amide is primary (-NH2) the N-H stretch

occurs from 3200-3500 cm-1 as a doublet

• If the amide is secondary (-NHR) the N-H stretch

occurs at 3200-3500 cm-1 as a sharp singlet

(m – s) (s)

124
Infrared Spectroscopy
2-nitropropane
17. Nitro group (-NO2) O
O

• Proper Lewis structure gives a bond order of 1.5 N

from nitrogen to each oxygen

• Two bands are seen (symmetric and

asymmetric) at 1300-1380 cm-1 and 1500-1570
cm-1

• This group is a strong resonance withdrawing

group and is itself vulnerable to resonance
effects

(s) (s)

125
 H

126
 Broad band with peak
at about 2900 cm-1

C O

127