INTRODUCTION TO SPECTROSCOPY

I Spectroscopy and the Electromagnetic Spectrum

Spectroscopy is the study of the interaction of matter and electromagnetic
radiation.
Electromagnetic radiation is radiant energy having the properties of both
particles and waves. An electromagnetic spectrum consists of a range of all
different types of electromagnetic radiation—each type associated with a
particular energy range.
The arrangement of all types of electromagnetic radiations in order of
their wavelength or frequencies is known as electromagnetic spectrum.
Visible light is the type of electromagnetic radiation with which we are most
familiar, but it represents only a fraction of the range of the entire
electromagnetic spectrum. X-rays and radio waves are other types of familiar
electromagnetic radiation.

The electromagnetic spectrum is made up of the following components: (High

energy (Frequency) to low energy (Frequency).
• Cosmic rays, which consist of radiation discharged by the sun, have the
highest energy, the highest frequencies, and the shortest wavelengths.

1
• (gamma rays) are emitted from the nuclei of certain radioactive elements and,
because of their high energy, can severely damage biological organisms.
• X-rays, somewhat lower in energy than are less harmful, except in high doses.
Low-dose X-rays are used to examine the internal structure of organisms. The
denser the tissue, the more it blocks X-rays.
• Ultraviolet (UV) light is responsible for sunburns, and repeated exposure can
cause skin cancer by damaging DNA molecules in skin cells.
• Visible light is the electromagnetic radiation we see.
• Infra Red (IR). We feel infrared radiation as heat.
• Micro waves. We cook with microwaves and use them in radar.
• Radio waves have the lowest energy (lowest frequency). We use them for radio
and television communication, digital imaging, remote controls, and wireless
linkages for laptop computers. Radio waves are also used in NMR spectroscopy
and in magnetic resonance imaging (MRI)
II Both Particle and Wave nature: A particle of electromagnetic radiation
is called a photon. We may think of electromagnetic radiation as photons
traveling at the speed of light. Because electromagnetic radiation has both
particle-like and wave-like properties, it can be characterized by either its
frequency or its wavelength
III Frequency: Frequency is defined as the number of wave crests that pass
by a given point in one second. Frequency has units of hertz (Hz).
IV Wavelength: Wavelength is the distance between two successive crusts or
troughs. Wavelength is generally measured in micrometers or nanometers. One
micrometer is 10-6 of a meter; one nanometer (nm) is 10-9 of a meter.
The frequency of electromagnetic radiation, therefore, is equal to the speed of
light (c) divided by the radiation’s wavelength:
υ(Neu) = C/λ
So wavelength has invers relation with frequency and energy. Short
wavelengths have high frequencies and high energy, and long wavelengths have
low frequencies and low energy.

2
The relationship between the energy (E) of a photon and the frequency (or the
wavelength) of the electromagnetic radiation is described by the equation
E= hυ(neu)=hc/λ
where h is the proportionality constant called Planck’s constant, named after the
German physicist who discovered the relationship.
V Wavenumber is another way to describe the frequency of electromagnetic
radiation, and the one most often used in infrared spectroscopy. It is the
number of waves in one centimeter, so it has units of reciprocal
centimeters. Scientists use wavenumbers in preference to wavelengths because,
unlike wavelengths, wavenumbers are directly proportional to energy. The
relationship between wavenumber and wavelength is given by the equation:

Neu Bar (cm-1) = 1/λ

So high frequencies, large wavenumbers, and short wavelengths are associated
with high energy.
VI Absorption and Emission Spectra
VIA Absorption Spectra:
When electromagnetic radiations are passed through an organic compound,
these induce electronic, vibrational and rotational transitions in the molecule.
The energy required for each of these transitions is quantized.
Thus only the radiation supplying the required quantum (Photon) of energy is
absorbed and the remaining portion of the incident radiation is transmitted. The
wavelength or the frequencies of the absorbed radiations are measured with the
help of spectrophotometer. Generally a spectrometer records an absorption
spectrum as a plot of intensity versus their wave length or frequency. Such
spectra which are obtained by absorption of electromagnetic radiations are called
as absorption spectra. UV, Visible, IR and NMR all are examples of absorption
spectra. Absorption band in absorption spectrum can be characterized by the
wave length at which max absorption occurs.

3
VIB Emission spectra
The spectra which are obtained by the emission of electromagnetic radiations
from the excited substances are known as Emission spectra
, like atomic emission spectra. The excitation is caused by heating the substance
to a high temperature either thermally or electrically. The excited substance
emits certain radiations when it comes to the ground state and a spectrometer
records these radiations as an emission spectrum.

4
 CHAPTER NO. 2 INFRARED SPECTROSCOPY
1. Infrared Spectroscopy

IR spectroscopy is a very useful for the detection of different functional groups

through their absorption of infrared light. All the bonds in a molecule are
constantly vibrating. When these bonds absorb radiation in the IR region, their
amplitude of vibration increases which is called vibrational excitement. IR
spectroscopy measures this vibrational excitation of atoms around the bonds
that connect them. The positions of the absorption lines associated with this
excitation depend on the types of functional groups present, and the IR spectrum
as a whole displays a pattern unique for each individual substance.
2.1 Stretching and Bending Vibrations
The covalent bonds in molecules are constantly vibrating. The bond between two
atoms behaves like a vibrating spring.
There are two types of vibrating motions of covalent bonds.
1) Stretching vibration 2) Bending vibration
2.1 A stretch is a vibration that occurs along the line of the bond and changes
the bond length.
2.2 A bend is a vibration that does not occur along the line of the bond, but
changes the bond angle.

In general, stretching vibrations occur at higher frequencies than bending

vibrations. Also asymmetric stretching vibrations occur at higher
frequencies than symmetric stretching vibration.
A diatomic molecule such as H-Cl can undergo only a stretching vibration since
it has no bond angles.
The vibrations of a molecule containing three or more atoms are more complex.
Such molecules can have two types of stretching vibrations, symmetric and
asymmetric.

5
Their bending vibrations can be either in-plane or out-of-plane. Bending
vibrations can be divided into for main types rocking, scissoring (in plane),
wagging, and twisting (out of plane).

2.2 Absorption of IR Radiations:

Each stretching and bending vibration of a bond in a molecule occurs with a
characteristic frequency. When a compound is bombarded with radiation of a
frequency that exactly matches the frequency of one of its vibrations, the
molecule will absorb energy. This allows the bonds to stretch and bend a bit
more. Thus, the absorption of energy increases the amplitude of the
vibration, but does not change its frequency. By experimentally determining
the wavenumbers of the energy absorbed by a particular compound, we can
determine the type of bonds it has. For example, the stretching vibration of a
C=O bond absorbs energy of wavenumber 1700 cm-1 whereas the stretching
vibration of an O-H bond absorbs energy of wavenumber 3450 cm-1.
C=O ∼1700 cm−1 O-H ∼3450 cm−1
The amount of energy needed for stretching and bending individual bonds,
corresponds to rather shorter wavelengths. These wavelengths lay in the
infrared, that is, heat radiation just to the long wavelength side of visible light.
6
When the carbon skeleton of a molecule vibrates, all the bonds stretch and relax
in combination and these absorptions are unhelpful. However some bonds
stretch essentially independently of the rest of the molecule. This occurs if the
bond is either:
• much stronger or weaker than others nearby, or
• between atoms that are much heavier or lighter than their neighbors.
2.2.1 The Position of Absorption Bands
In IR Spectroscopy, it is very important to know the exact vibrational absorption
of different functional groups. According to Hooke’s law for a simple harmonic
oscillator, there is a relationship between the frequency of the bond vibration,
the mass of the atoms, and the strength of the bond.
The natural frequency of vibration of a bond is given by the equation

1
𝜐= √𝐾/µ
2𝜋𝑐
which is derived from Hooke’s Law for vibrating springs. µ is called as the
reduced mass m of the system which is given as
𝑚1𝑚2
µ= 𝑚1+𝑚2

In above equation, K is a constant that varies from one bond to another and it is
directly proportional to the vibrating frequency. But the reduces mass is
inversely proportional to the vibrating frequency.
Two things should be noticeable immediately.
One is that stronger bonds have a larger force constant K and vibrate at higher
frequencies than weaker bonds. In general, triple bonds are stronger than double
or single bonds between the same two atoms and have higher frequencies of
vibration (higher wavenumbers).
Given Values chiefly affected by bond strength (stronger bond, higher frequency)
C≡ O, C=O, C–O, 2143 cm–1, 1715 cm–1, 1100 cm–1.

The second is that bonds between atoms of higher masses (larger reduced mass,
m) vibrate at lower frequencies than bonds between lighter atoms.
7
e.g., As the atom bonded to carbon increases in mass, the reduced mass (m)
increases, and the frequency of vibration decreases (wavenumbers get smaller).
For example, these values chiefly affected by mass of atoms: (lighter atom, higher
frequency) C–H, C–D, C–O, C–Cl, 3000 cm–1, 2200 cm–1, 1100 cm–1, 700 cm–1.
2.2.2 The Intensity of Absorption Bands
Dipole moment
The intensity of an absorption band depends on the size of the change in dipole
moment associated with the vibration: The greater the change in dipole
moment, the more intense the absorption.
As we know the dipole moment of a bond is equal to the magnitude of the charge
on one of the bonded atoms, multiplied by the distance between the two charges.
When the bond stretches, the increasing distance between the atoms
increases the dipole moment. The stretching vibration of an O-H bond will be
associated with a greater change in dipole moment than that of an N-H bond
because the O-H bond is more polar. Consequently, the stretching vibration of
the bond will be more intense. Likewise, the stretching vibration of an N-H bond
is more intense than that of a C-H bond because the N-H bond is more polar.
No. of bonds
The intensity of an absorption band also depends on the number of bonds
responsible for the absorption. For example, the absorption band for the C-H
stretch will be more intense for a compound such as octyl iodide, which has 17
C-H bonds, than for methyl iodide, which has only three C-H bonds.
Concentration of Sample
The concentration of the sample used to obtain an IR spectrum also affects the
intensity of the absorption bands. Concentrated samples have greater numbers
of absorbing molecules and, therefore, more intense absorption bands.
Intensities can be strong (s), medium (m), weak (w), broad, and sharp.
2.3 Fundamental vibrations and overtones
The vibrations we have been discussing are called fundamental absorptions.
They arise from excitation from the ground state to the lowest-energy excited

8
state. Usually, the spectrum is complicated because of the presence of weak
overtone, combination, and difference bands.
2.3.1 Overtones: This result from excitation from the ground state to higher
energy states, which correspond to integral multiples of the frequency of the
fundamental (υ). For example, you might observe weak overtone bands at 2υ, 3
υ, . . . . An absorption in the infrared at 500 cm−1 may well have an
accompanying peak of lower intensity at 1000 cm−1 an overtone.
2.3.2 Combination Bands: When two vibrational frequencies (n-1 and n-2) in
a molecule couple to give rise to a vibration of a new frequency within the
molecule, and when such a vibration is infrared active, it is called a combination
band. This band is the sum of the two interacting bands (υcomb = υ-1 + υ-2). Not
all possible combinations occur.
2.3.3 Difference Bands: There are similar to combination bands. The observed
frequency in this case results from the difference between the two interacting
bands (ndiff = υ1- υ2).
2.3.4 Fermi Resonance: When a fundamental vibration couples with an
overtone or combination band, the coupled vibration is called Fermi resonance.
Again, only certain combinations are allowed. Fermi resonance is often observed
in carbonyl compounds.
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.

2.4 The infrared spectrophotometer

The instrument that determines the absorption spectrum for a compound is
called an infrared spectrometer or, more precisely, a spectrophotometer. Two
types of infrared spectrometers are in common use in the organic laboratory:
dispersive and Fourier transform (FT) instruments. Both of these types of
9
instruments provide spectra of compounds in the common range of 4000 to 400
cm−1. Although the two provide nearly identical spectra for a given compound,
FT infrared spectrometers provide the infrared spectrum much more rapidly than
the dispersive instruments.
2.4.1 Dispersive Infrared Spectrometers

Figure below schematically illustrates the components of a simple dispersive

infrared spectrometer.
1. IR source: The instrument produces a beam of infrared radiation from a hot
wire and, by means of mirrors, divides it into two parallel beams of equal-
intensity

radiation. The sample is placed in one beam, and the other beam is used as a
reference.
2.Monocharomator: The beams then pass into the monochromator, which
disperses each into a continuous spectrum of frequencies of infrared light. The
monochromator consists of a rapidly rotating sector (beam chopper) that passes
the two beams alternately to a diffraction grating (a prism in older instruments).
The slowly rotating diffraction grating varies the frequency or wavelength of
radiation reaching the thermocouple detector.
3. Detector: The detector senses the ratio between the intensities of the
reference and sample beams. In this way, the detector determines which
frequencies have been absorbed by the sample and which frequencies are
unaffected by the light passing through the sample.

10
4.Amplifier & Recorder: After the signal from the detector is amplified, the
recorder draws the resulting spectrum of the sample on a chart. It is important
to realize that the spectrum is recorded as the frequency of infrared radiation
changes by rotation of the diffraction grating. Dispersive instruments are said
to record a spectrum in the frequency domain.
5. IR Graph: A detector generates a plot of percent transmission of radiation
versus the wavenumber (or wavelength) of the radiation transmitted. At
100% transmission, all the energy of the radiation passes through the molecule.
Lower values of percent transmission mean that some of the energy is being
absorbed by the compound. Each downward spike in the IR spectrum represents
absorption of energy. The spikes are called absorption bands. Most chemists
report the location of absorption bands using wavenumbers.

2.4.2 Fourier Transform Infrared (FT-IR) Spectrophotometers

A newer type of IR spectrometer, called a Fourier transform IR (FT-IR)

spectrometer, has several advantages.
1-Its sensitivity is better because With this, a spectrum with a better signal-to-
noise ratio can be plotted.
2-It is very fast. Instead of scanning through the frequencies one by one, it
measures all frequencies simultaneously. With a conventional IR spectrometer,
it can take 2 to 10 minutes to scan through all the frequencies. In contrast, FT-
IR spectra can be taken in 1 to 2 seconds.
3- The information is digitized and Fourier transformed by a computer to produce
the FT-IR spectrum.

11
The most modern infrared spectrometers (spectrophotometers) operate on a
different principle. The design of the optical pathway produces a pattern called
an interferogram. The interferogram is a complex signal, but its wave-like
pattern contains all the frequencies that make up the infrared spectrum. An
interferogram is essentially a plot of intensity versus time (a time-domain
spectrum). However, a chemist is more interested in a spectrum that is a plot of
intensity versus frequency (a frequency-domain spectrum). A mathematical
operation known as a Fourier transform (FT) can separate the individual
absorption frequencies from the interferogram, producing a spectrum virtually
identical to that obtained with a dispersive spectrometer. This type of instrument
is known as a Fourier transform infrared spectrometer, or FT-IR. The advantage

12
of an FT-IR instrument is that it acquires the interferogram in less than a second.
It is thus possible to collect dozens of interferograms of the same sample and
accumulate them in the memory of a computer. An FT-IR instrument is therefore
capable of greater speed and greater sensitivity than a dispersion instrument.

A schematic diagram of an FT-IR is shown above.

1-The FT-IR uses an interferometer to process the energy sent to the sample. In
the interferometer, the source energy passes through a beam splitter, a mirror
placed at a 45° angle to the incoming radiation, which allows the incoming
radiation to pass through but separates it into two perpendicular beams, one
undeflected, the other oriented at a 90° angle. One beam, the one oriented at 90°
in Figure above, goes to a stationary or “fixed” mirror and is returned to the beam
splitter. The undeflected beam goes to a moving mirror and is also returned to
the beam splitter. The motion of the mirror causes the path length that the
second beam traverses to vary. When the two beams meet at the beam splitter,
they recombine, but the path length differences (differing wavelength content) of
the two beams cause both constructive and destructive interferences. The
combined beam containing these interference patterns is called the
interferogram. This interferogram contains all of the radiative energy coming
from the source and has a wide range of wavelengths.
2-The interferogram generated by combining the two beams is oriented toward
the sample by the beam splitter. As it passes through the sample, the sample
simultaneously absorbs all of the wavelengths (frequencies) that are normally
found in its infrared spectrum.
3-The modified interferogram signal that reaches the detector contains
information about the amount of energy that was absorbed at every wavelength
(frequency).
4-Detector: The computer compares the modified interferogram to a reference
laser beam to have a standard of comparison. The final interferogram contains

13
all of the information in one time-domain signal, a signal that cannot be read by
a human.
5-Fourier transformation: A mathematical process called a Fourier transform
must be implemented by computer on interferogram. This method converts time
domain spectra to frequency domain spectra which is similar to typivcal IR and
can be understandable by humans.
To obtain a spectrum of a compound, the chemist first obtains an
interferogram of the “background,” which consists of the infrared-active
atmospheric gases, carbon dioxide and water vapor (oxygen and nitrogen
are not infrared active.

2.5 PREPARATION OF SAMPLES FOR INFRARED SPECTROSCOPY

To determine the infrared spectrum of a compound, one must place the
compound in a sample holder, or cell. In infrared spectroscopy, this immediately
poses a problem. Glass and plastics absorb strongly throughout the infrared
region of the spectrum. Cells must be constructed of ionic substances—
typically sodium chloride or potassium bromide. Potassium bromide plates
are more expensive than sodium chloride plates but have the advantage of
usefulness in the range of 4000 to 400 cm−1. Sodium chloride plates are used
widely because of their relatively low cost. The practical range for their use in
spectroscopy extends from 4000 to 650 cm−1. Sodium chloride begins to absorb
at 650 cm−1, and any bands with frequencies less than this value will not be
observed. Since few important bands appear below 650 cm−1, sodium chloride
plates are in most common use for routine infrared spectroscopy.
2.5.1 Liquids
A drop of a liquid organic compound is placed between a pair of polished
sodium chloride or potassium bromide plates, referred to as salt plates. When
the plates are squeezed gently, a thin liquid film is formed between them. A
spectrum determined by this method is referred to as a neat spectrum since no
solvent is used. Salt plates break easily and are water soluble. Organic
14
compounds analyzed by this technique must be free of water. The pair of plates
is inserted into a holder that fits into the spectrometer.
2.5.2 Solids
There are at least three common methods for preparing a solid sample for
spectroscopy.
1-The first method involves mixing the finely ground solid sample with powdered
potassium bromide and pressing the mixture under high pressure. Under
pressure, the potassium bromide melts and seals the compound into a matrix.
The result is a KBr pellet that can be inserted into a holder in the spectrometer.
The main disadvantage of this method is that potassium bromide absorbs
water, which may interfere with the spectrum that is obtained. If a good pellet
is prepared, the spectrum obtained will have no interfering bands since
potassium bromide is transparent down to 400 cm−1.
2-The second method, a Nujol mull, involves grinding the compound with
mineral oil (Nujol) to create a suspension of the finely ground sample dispersed
in the mineral oil. The thick suspension is placed between salt plates. The main
disadvantage of this method is that the mineral oil obscures bands that
may be present in the analyzed compound. Nujol bands appear at 2924,
1462, and 1377 cm−1.

3- The third common method used with solids is to dissolve the organic
compound in a solvent, most commonly carbon tetrachloride (CCl4). Again,
as was the case with mineral oil, some regions of the spectrum are obscured by

15
bands in the solvent. Although it is possible to cancel out the solvent from the
spectrum by computer or instrumental techniques, the region around 785 cm−1
is often obscured by the strong CI-Cl stretch that occurs there.
2.6 Different Regions of IR spectra
An IR spectrum can be divided into two main areas.
1-The left-hand two-thirds of an IR spectrum is where most of the functional
groups show absorption bands. This region is called the functional group region.
2-The right-hand one third of the IR spectrum is called the fingerprint region
because it is characteristic of the compound as a whole, just as a fingerprint is
characteristic of an individual. Even if two different molecules have the same
functional groups, their IR spectra will not be identical, since the functional
groups are not in exactly the same environment; this difference is reflected in
the pattern of absorption bands in the finger print regions. Each compound
shows a unique pattern in this region. For example, 2-pentanol and 3-
pentanol have the same functional groups, so they show similar absorption
bands in the functional group region. Their fingerprint regions are different,
however, because the compounds are different. Thus a compound can be
positively identified by comparing its fingerprint region with the
fingerprint region of the spectrum of a known sample of the compound. The
useful information from this spectrum is the presence of the CN and C=O groups
and the exact position of the C=O absorption.
However, it is actually the left-hand half of the spectrum (Functional group
region) that is more useful. It can be further divided into three regions.
A-X-H Region: The first region, from about 4000 to about 3000 cm–1 is the region
for C–H, N–H, and O–H bond stretching. Most of the atoms in an organic molecule
(C, N, O, for example) are about the same weight. Hydrogen is an order of
magnitude lighter than any of these and so it dominates the stretching frequency
by the large effect it has on the reduced mass. The reduced mass of a C–C bond
is (12 × 12)/(12 + 12), i.e. 144/24 = 6.0. If we change one of these atoms for H,
the reduced mass changes to (12 ×1)/ (12 + 1), i.e. 12/13 = 0.92, but, if we

16
change it instead for F, the reduced mass changes to (12 × 19)/ (12 + 19), i.e.
228/31 = 7.35. There is a small change when we increase the mass to 19 (F),
but an enormous change when we decrease it to 1 (H).
B-Even the strongest bonds—triple bonds such as C≡C or C≡N—absorb at
slightly lower frequencies than bonds to hydrogen: these are in the next region
from about 3000 to 2000 cm–1. All regions of the spectrum follow in logical order
of bond strength as the reduced masses are all about the same:
C-Third region consists of double bonds such as C=C and C=O from about 2000–
1500 cm–1. Single bonds are at the right- hand end of the spectrum (finger print
region).

2.6.1 The X–H IR stretches are very different in these four

compounds.
The X–H region distinguishes C–H, N–H, and O–H bonds. The reduced masses of
the C–H, N–H, and O–H combinations are all about the same. Any difference
between the positions of the IR bands of these bonds must then be due to bond
strength. In practice, C–H stretches occur at around 3000 cm–1 (though they
are of little use as virtually all organic com- pounds have C–H bonds), N–H
stretches occur at about 3300 cm–1, and O–H stretches higher still. We can

17
immediately deduce that the O–H bond is stronger than N–H which is stronger
than C–H. IR is a good way to measure such bond strengths.
Shapes of X-H groups: The IR peak of an NH group is different from that of an
NH2 group. A group gives an independent vibration only if both bond strength
and reduced mass are different from those of neighboring bonds. In the case of
N–H, this is likely to be true and we usually get a sharp peak at about 3300 cm–
1, whether the NH group is part of a simple amine (R2NH) or an amide (RCONHR).
The NH2 group is also independent of the rest of the molecule, but the two
NH bonds inside the NH2 group have identical force constants and reduced
masses and so vibrate as a single unit. Two equally strong bands appear, one
for the two N–H bonds vibrating in phase (symmetric) and one for the two N–H
bonds vibrating in opposition (antisymmetric). The antisymmetric vibration
requires more energy and is at slightly higher frequency.
The O–H bands occur at higher frequency, sometimes as a sharp absorption
at about 3600 cm–1. However in most cases O-H bond forms hydrogen bonding
so, you will see a broad absorption at anywhere from 3500 to 2900 cm–1.
This is because OH groups form strong hydrogen bonds that vary in length and
strength. The sharp absorption at 3600 cm–1 is the non-hydrogen-bonded
OH and the lower the absorption the stronger the H bond.
Alcohols form hydrogen bonds between the hydroxyl oxygen of one molecule and
the hydroxyl hydrogen of another. These bonds are variable in length (though
they are usually rather longer than normal covalent O–H bonds) and they slightly
weaken the true covalent O–H bonds by varying amounts. When a bond varies
in length and strength it will have a range of stretching frequencies distributed
about a mean value. Alcohols typically give a rounded absorption at about 3300
cm–1 (contrast the sharp N–H stretch in the same region).

18
Carboxylic acids (RCO2H) form hydrogen-bonded dimers with two strong H
bonds between the carbonyl oxygen atom of one molecule and the acidic
hydrogen of the other. These also vary considerably in length and strength and
usually give very broad V-shaped absorbances.
Good examples are paracetamol and BHT. Paracetamol has a typical sharp peak
at 3330 cm–1 for the N–H stretch and then a rounded absorption for the
hydrogen-bonded O–H stretch from 3300 down to 3000 cm–1 in the gap between
the N–H and C–H stretches.

19
By contrast, BHT has a sharp absorption at 3600 cm–1 as the two large and
roughly spherical t-butyl groups prevent the normal H bond from forming.

The IR spectrum of a terminal alkyne, R–C≡C–H, will show a strongish sharp

peak at around 3300 cm–1 that looks just like an N–H stretch. The displacement
of this peak from the usual C–H stretch at about 3000 cm–1 cannot be due to a
change in the reduced mass, Actually it is due to a marked increase in bond
strength. As R–C≡C–H has “sp” hybridized carbon as compared to sp3 in alkane,
so more “s” character is more near to nucleus and will be shorter and stronger
than alkane C–H bonds.

20
2.6.2 The double bond region is the most important in IR
spectra
In the double bond region, there are three important absorptions, those of the
carbonyl (C=O), alkene (C=C), and nitro (NO2) groups. All give rise to sharp
bands: C=O to one strong (i.e. intense) band anywhere between 1900 and 1500
cm–1; C=C to one weak band at about 1640 cm–1; and NO2 to two strong (intense)
bands in the mid-1500s and mid-1300s cm–1. The number of bands is easily
dealt with. Just as with OH and NH2, it is a matter of how many identical bonds
are present in the same functional group.

Carbonyl and alkene clearly have one double bond each. The nitro group at first
appears to contain two different groups, N+–O– and N=O, but delocalization
means they are identical and we see absorption for symmetrical and anti-
symmetrical stretching vibrations. As with NH2, more work is needed for the anti-
symmetrical vibration which occurs at higher frequency (>1500 plus cm–1).

2.6.2.1 Strength of IR absorption

The strength of an IR absorption depends on dipole moment. Now what about
the variation in strength (i.e. intensity, the amount of energy absorbed)? The
strength of an IR absorption varies with the change of dipole moment when the
bond is stretched. If the bond is perfectly symmetrical, there is no change in
dipole moment and there is no IR absorption. Obviously, the C=C bond is less
polar than either C=O or N=O and is weaker in the IR. Indeed, it may be absent
altogether in a symmetrical alkene. By contrast the carbonyl group is very
polar and stretching it causes a large change in dipole moment and C=O
stretches are usually the strongest peaks in the IR spectrum. You may also have
noticed that O–H and N–H stretches are stronger than C–H stretches (even

21
though most organic molecules have many more C–H bonds than O–H or N–H
bonds): the reason is the same.

2.6.3 Single bond region

The single bond region is used as a molecular fingerprint. Single bond vibration
occur below 1500 cm–1. However individual bonds may not vibrate independently
of the rest of the molecule. The atoms C, N, and O all have about the same atomic
weight and C–C, C–N, and C–O single bonds all have about the same strength.
In addition, C–C bonds are likely to be joined to other C–C bonds with virtually
identical strength and reduced mass, and they have essentially no dipole
moments. The only one of these single bonds of any value is C–O which is polar
enough and different enough (Table 3.7) to show up as a strong absorption at
about 1100 cm–1. Some other single bonds such as C–Cl (weak and with a large
reduced mass) are quite useful at about 700 cm–1. Otherwise the single bond
region is usually crowded with hundreds of absorptions from vibrations of all
kinds used as a ‘fingerprint’ characteristic of the molecule but not really open to
interpretation. Among the hundreds of peaks in the fingerprint region, there are
some of a quite different kind. Stretching is not the only bond movement that
leads to IR absorption. Bending of bonds, particularly C–H and N–H bonds, also
leads to quite strong peaks. These are called deformations. Bending a bond is

22
easier than stretching it (which is easier, stretching or bending an iron bar?).
Consequently, bending absorptions need less energy and come at lower
frequencies than stretching absorptions for the same bonds. These bands may
not often be useful in identifying molecules, but you will notice them as they are
often strong (they are usually stronger than C=C stretches for example) and may
wonder what they are.

2.7 Carbonyl compounds IR absorption

The carbonyl group is present in aldehydes, ketones, acids, esters, amides, acid
chlorides, and anhydrides. This group absorbs strongly in the range from 1850
to 1650 cm−1 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. Below we provide 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.
Anhydride (band 1) 1810---acid chloride 1800---- anhydride (Band 2) 1760--
------ Ester 1735------ Aldehyde 1725-----ketone 1715-----Carboxylic acid
(dimeric) 1710--------- amide 1690

23
The range of values given in Figure above may be explained through the use of
electron-withdrawing effects (inductive effects, resonance effects, and
hydrogen bonding). The first two effects operate in opposite ways to influence
the C=O stretching frequency.
ESTERS: First, an electronegative element may tend to draw in the electrons
between the carbon and oxygen atoms through its electron-withdrawing effect,
so that the C=O bond becomes somewhat stronger. A higher-frequency (higher-
energy) absorption result. Since oxygen is more electronegative than carbon,
this effect dominates in an ester to raise the C=O frequency above that of
a ketone.
AMIDE: Second, a resonance effect may be observed when the unpaired
electrons on a nitrogen atom conjugate with the carbonyl group, resulting in
increased single-bond character and a lowering of the C=O absorption frequency.
This second effect is observed in an amide. Since nitrogen is less
electronegative than an oxygen atom, it can more easily accommodate a positive
charge. The resonance structure shown here introduces single-bond character
into the C=O group and thereby lowers the absorption frequency below that of a
ketone.

24
ACID CHLORIDES: In acid chlorides, the highly electronegative halogen atom
strengthens the C=O bond through an enhanced inductive effect and shifts the
frequency to values even higher than are found in esters.
ANHYDRIDES: Anhydrides are likewise shifted to frequencies higher than are
found in esters because of a concentration of electronegative oxygen atoms. In
addition, anhydrides give two absorption bands that are due to symmetric and
asymmetric stretching vibrations.
CARBOXYLIC ACID: A carboxylic acid exists in monomeric form only in very
dilute solution, and it absorbs at about 1760 cm−1 because of the electron-
withdrawing effect just discussed. However, acids in concentrated solution, in
the form of neat liquid, or in the solid state (KBr pellet and Nujol) tend to dimerize
via hydrogen bonding. This dimerization weakens the C=O bond and lowers the
stretching force constant K, resulting in a lowering of the carbonyl frequency of
saturated acids to about 1710 cm−1.

ALDEHYDES: Ketones absorb at a lower frequency than aldehydes because of

their additional alkyl group, which is electron donating (compared to H) and
supplies electrons to the C=O bond. This electron-releasing effect weakens the
C=O bond in the ketone and lowers the force constant and the absorption
frequency.
2.8 Factors that Effect C=O stretching vibration:
2.8.1 Conjugation Effects.
The introduction of a C=C bond adjacent to a carbonyl group results in
delocalization of the p electrons in the C=O and C=C bonds. This conjugation
increases the single-bond character of the C=O and C=C bonds in the resonance
hybrid and hence lowers their force constants, resulting in a lowering of the
frequencies of carbonyl and double-bond absorption. Conjugation with triple
bonds also shows this effect.

25
Generally, the introduction of an alpha, Beta double bond in a carbonyl
compound results in a 25- to 45-cm−1 lowering of the C=O frequency from the
base value given in Figure above. A similar lowering occurs when an adjacent
aryl group is introduced. Further addition of unsaturation (gamma, delta) results
in a further shift to lower frequency, but only by about 15 cm−1 more. In
addition, the C=C absorption shifts from its “normal” value, about 1650 cm−1,
to a lower-frequency value of about 1640 cm−1, and the C=C absorption is
greatly intensified. Often, two closely spaced C=O absorption peaks are observed
for these conjugated systems, resulting from two possible conformations, the s-
cis and s-trans. The s-cis conformation absorbs at a frequency higher than the
s-trans conformation. In some cases, the C=O absorption is broadened rather
than split into the doublet.
The following examples show the effects of conjugation on the C=O frequency.
α ,β-unsaturated ketones--------1715-1690, Aryl substituted aldehyde---1725-
1700, aryl susbstituted acids---1710-1680
Conjugation does not reduce the C=O frequency in amides. The introduction of
a,b unsatu- ration causes an increase in frequency from the base value given in
Figure 2.35. Apparently, the introduction of sp2-hybridized carbon atoms
removes electron density from the carbonyl group and strengthens the bond
instead of interacting by resonance as in other carbonyl examples. Since the
parent amide group is already highly stabilized (see p. 53), the introduction of
the C=C unsaturation does not overcome this resonance.
Ring-Size Effects.
Six-membered rings with carbonyl groups are unstrained and absorb at about
the values given in Figure 2.35. Decreasing the ring size increases the frequency
of the C=O absorption for the reasons discussed in Section 2.10 (C=C stretching
vibrations and exocyclic double bonds; p. 41). All of the functional groups listed

26
in Figure 2.35, which can form rings, give increased frequencies of absorption
with increased angle strain. For ketones and esters, there is often a 30-cm−1
increase in frequency for each carbon removed from the unstrained six-
membered ring values. Some examples are
In ketones, larger rings have frequencies that range from nearly the same value
as in cyclohexanone (1715 cm−1) to values slightly less than 1715 cm−1. For
example, cycloheptanone absorbs at about 1705 cm−1.
a-Substitution Effects. When the carbon next to the carbonyl is substituted with
a chlorine (or other halogen) atom, the carbonyl band shifts to a higher
frequency. The electron-withdrawing effect removes electrons from the carbon of
the C=O bond. This removal is compensated for by a tightening of the p bond
(shortening), which increases the force constant and leads to an increase in the
absorption frequency. This effect holds for all carbonyl compounds.
In ketones, two bands result from the substitution of an adjacent chlorine atom.
One arises from the conformation in which the chlorine is rotated next to the
carbonyl, and the other is due to the conformation in which the chlorine is away
from the group. When the chlorine is next to the carbonyl, nonbonded electrons
on the oxygen atom are repelled, resulting in a stronger bond and a higher
absorption frequency. Information of this kind can be used to establish a
structure in rigid ring systems, such as in the following examples:
Axial chlorine ~1725 cm–1
Equatorial chlorine ~1750 cm–1
Hydrogen-Bonding Effects. Hydrogen bonding to a carbonyl group lengthens the
C=O bond and lowers the stretching force constant K, resulting in a lowering of
the absorption frequency. Examples of this effect are the decrease in the C=O
frequency of the carboxylic acid dimer (p. 53) and the lowering of the ester C=O
frequency in methyl salicylate caused by intramolecular hydrogen bonding:
C OCH3 O H O • • • Methyl salicylate 1680 cm–1

27
HOW TO APPROACH THE ANALYSIS OF A SPECTRUM (OR WHAT YOU CAN
TELL AT A GLANCE)
When analyzing the spectrum of an unknown, concentrate your first efforts on
determining the presence (or absence) of a few major functional groups.
The C=O, O-H, N-H, C-O, C=C, C=-C, C=-N, 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 absorptions near 3000 cm−1;
almost all compounds have these absorptions. Do not worry about subtleties of
the exact environment in which the functional group is found. Following is a
major checklist of the important gross features.
1. Is a carbonyl group present? The C=O group gives rise to a strong absorption
in the region 1820–1660 cm−1. The peak is often the strongest in the spectrum
and of medium width. You can’t miss it.
2. If C=O is present, check the following types (if it is absent, go to step 3):
ACIDS Is O-H also present?
• Broad absorption near 3400–2400 cm−1 (usually overlaps C-H).
AMIDES Is N-H also present?
• Medium absorption near 3400 cm−1; sometimes a double peak with equivalent
halves. ESTERS Is C-O also present?
• Strong-intensity absorptions near 1300–1000 cm−1.
ANHYDRIDES Two C=O absorptions near 1810 and 1760 cm−1.
ALDEHYDES Is aldehyde C-H present?
• Two weak absorptions near 2850 and 2750 cm−1 on right side of the aliphatic
C-H absorptions.
KETONES The preceding five choices have been eliminated.
1. If C=O is absent:
ALCOHOLS, PHENOLS Check for O-H.
• Broad absorption near 3400–3300 cm−1.
• Confirm this by finding C-O near 1300–1000 cm−1.
AMINES Check for N-H.
• Medium absorption(s) near 3400 cm−1.
28
 ETHERS Check for C-O near 1300–1000 cm−1 (and absence of O-H near
3400 cm−1).
2. Double bonds and/or aromatic rings
•C=C is a weak absorption near 1650 cm.
• Medium-to-strong absorptions in the region 1600–1450 cm−1; these
often imply an aromatic ring.
• Confirm the double bond or aromatic ring by consulting the C-H region;
aromatic and vinyl C-H occur to the left of 3000 cm−1 (aliphatic C-H
occurs to the right of this value).

5. Triple bonds
•C=-N is a medium, sharp absorption near 2250 cm−1. •C=-C is a weak, sharp
absorption near 2150 cm−1. • Check also for acetylenic C=-H near 3300 cm−1.
6. Nitro groups
• Two strong absorptions at 1600–1530 cm−1 and 1390–1300 cm−1.
7. Hydrocarbons
• None of the preceding is found. • Major absorptions are in C-H region near
3000−1. • Very simple spectrum; the only other absorptions appear near 1460
and 1375 cm−1.
The beginning student should resist the idea of trying to assign or interpret every
peak in the spectrum. You simply will not be able to do it. Concentrate first on
learning these major peaks and recognizing their presence or absence. This is
best done by carefully studying the illustrative spectra in the sections that follow.

29