INFRARED (IR) & ULTRAVIOLET-VISIBLE

(UV-VIS) SPECTROSCOPY
Theory and Interpretation of Spectra

By:
Dr. Sunny Manohar
(Assistant Professor of Chemistry)
Deen Dayal Upadhyaya College
University of Delhi
 Layout of the Chapter

Application of Spectroscopy to Simple Organic Molecules

Application of visible, ultraviolet and Infrared spectroscopy in organic molecules.
Electromagnetic radiations, electronic transitions, λmax & εmax, chromophore,
auxochrome, bathochromic and hypsochromic shifts. Application of electronic
spectroscopy and Woodward rules for calculating λmax of conjugated dienes and α,β
– unsaturated compounds.
Infrared radiation and types of molecular vibrations, functional group and fingerprint
region. IR spectra of alkanes, alkenes and simple alcohols (inter and intramolecular
hydrogen bonding), aldehydes, ketones, carboxylic acids and their derivatives (effect
of substitution on >C=O stretching absorptions).

12 Lectures
 Suggested Readings
For elementary IR spectroscopy:
™ Organic Chemistry by Paula Y. Bruice
™ Organic chemistry by L. G. Wade
™ Elementary Organic Spectroscopy by Y. R. Sharma

For advanced IR spectroscopy:

™ Spectroscopy by Pavia
™ Organic Spectroscopy by William Kemp
™ Spectroscopy of Organic Compounds by P. S. Kalsi
 Spectroscopy: Introduction and Importance
• Spectroscopy is the study of the interaction of electromagnetic radiation (also known as light) with matter. When
the matter concerned is an organic compound it leads to the field of organic spectroscopy.
• Organic spectroscopy is particularly used to determine the structure of unknown organic compound. It has various
advantages over traditional way of structure determination through chemical means (like qualitative organic
compound analysis). Some of the advantages are summarized below:

S. Structure determination through qualitative organic Structure determination through organic

No. compound analysis (Chemical technique)
1. Time consuming as series of tests (Flame test, extra element
test, functional group test etc.) and measurements
(Elemental analysis, mol. wt. Determination, B.Pt./M.Pt.
determination etc.) has to be done.
2. Needs relatively large amount of sample (Minimum 2
grams). Hence, impractical to do the analysis with
compounds that are difficult to obtain.
3. Destroys the sample during analysis.
3 Dangerous to execute as most of the times the chemist has
to deal with explosive reactions, toxic fumes, hazardous
chemicals etc.
4. The procedure sometimes are insufficient to determine the
structure of complex unknown organic compound.
5. Relatively inexpensive.
spectroscopy (Analytical technique)
Time saving as measurements through
different spectrophotometer can be done in
matter of few minutes.
Needs very little quantity of sample
(Maximum 20-25mg).
Apart from mass spectrometry, other
spectroscopic techniques are non-destructive
and samples can be recovered after analysis.
Easy to execute with no such danger.
Structure of complex unknown organic
compounds can be determine.
Only expensive in terms of cost of
instruments.
Electromagnetic Radiations (EMRs): Properties
• Before we learn more about spectroscopy it is important to know what is electromagnetic radiation
(EMRs)? what are the properties of EMRs? how different types of EMRs characterized? what is the
nature of matter?

• EMRs (also known as light) travels in the form of waves involving both electrical and magnetic fields
and carries energy in the form of small packets known as photons (see Fig A). Each photon has
quanta of energy. EMRs has no detectable mass component and can be referred as “pure energy”.
(alpha rays which consist of helium nuclei having both mass and energy component are not termed
as EMR).

• The description of EMRs is best made by taking consideration of two theories; wave theory and
particle theory. Each of the theories explains some of the properties of EMRs, however they fail to
completely account for all the properties of EMRs.

• We can assume EMRs as if they are made up of small mass less particles (called photons) travelling in
a wave like motion in the direction of propagation of EMR.
A

The perpendicular oscillating,

electric and magnetic
fields associated with
electromagnetic radiation.
 Electromagnetic Radiation (EMR): Characterization
• Because electromagnetic radiation has wave-like properties, it is characterized by either its frequency (ν) or
its wavelength (λ). All the EMRs travel with the same speed (3 × 108 m/sec also known as speed of light),
however they differ in frequency or wavelength.
• Frequency is the number of wave crests that pass by a given point A crest
in one second; frequency has units of sec-1 or hertz (Hz).

• Wavelength is the distance from any point on one wave to the

corresponding point on the next wave. Or it can simply be distance
between corresponding crests (or trough). Wave-length is generally
measured in nanometers; 1 nm = 10-9 m (See Fig. A).

• Accordingly, a long wavelength corresponds with a low frequency,

and a short wavelength corresponds with a high frequency. This trough
relationship is summarized by the equation where frequency (ν)
B
and wavelength (λ) are inversely proportional. The constant of
proportionality is the speed of light (c) (See Fig. B).

• Energy of each photon is associated to the frequency and

C
wavelength of the light wave by the equation: (where h is planck’s
constant = 6.6 × 10-34 J.sec.) (See Fig. C).

• Frequency of the electromagnetic radiation can also be represented as wavenumber, which is the number of
waves in 1 cm. Wavenumbers, therefore, have units of reciprocal centimeters (cm-1).
• High frequencies, large wavenumbers, and short wavelengths are associated with high energies.
 Electromagnetic Spectrum

When the EMRs of all possible frequency are arranged in the order of increasing/decreasing wavelength
or frequencies, a continuum known as electromagnetic spectrum is obtained (see Fig A).

A
Electromagnetic Radiation: Size and Source
 Nature of Matter
• Matter (say molecule), like electromagnetic radiation, also exhibits both wave-like properties and
particle-like properties. According to the principles of quantum mechanics, the energy of a molecule is
“quantized.”

• The stored energy in the molecule rotates the molecule in space (rotational energy), vibrate their
bonds like springs (vibrational energy), excite the electrons to a number of possible molecular orbitals
(electronic energy), and so on. Each of these forms of energy is quantized.

• For example, a molecule can only rotate at specific energy levels (shown in Fig. A). The horizontal lines
in the diagram represent allowed rotational energy levels for a particular molecule. The molecule is
restricted to these energy levels and cannot rotate with an energy in between the allowed levels. The
difference in energy (ΔE) between allowed energy levels is determined by the nature of the molecule.
A
High-energy rotational state

Rotational Energy Levels

Low-energy rotational state

An energy diagram showing the energy gap between allowed rotational states.
 Interaction between EMR and Matter

• If a photon of EMR possesses exactly the amount of energy (ΔE); the energy gap
between two rotational levels; the molecule can absorb the photon to promote a
rotational excitation (see Fig. A). The energy of the photon is temporarily stored as
rotational energy until it is released back into the environment (see Fig. B).

A B Molecule at high energy level

Incident photon
striking the molecule
E2 E2

Energy ΔE = E2-E1
Ephoton = hν
Ephoton = hν
Photon is released
E1 E1 to the environment
Molecule at low energy level

Absorption process Emission process

Upward transition (excitation Downward transition from E2 to
of molecule) from E1 to E2 E1 showing release of photon
happens only when ΔE = hν
Absorption and Emission Process
 Spectroscopy: Basic Principle
A E2

E1
Physical Response Detecting
Molecule
Stimulus instrument
(in the form of EMR)
Visual information or
Spectrum

• Upon stimulating (irradiating) with EMR, molecule make a response. The instrument
detects this response and translates it into a visual information called a spectrum (see
Fig. A)

• Depending upon what kind of information is needed, the molecule is irradiated with
different kind of EMR. Different forms of spectroscopy depends upon what kind of EMR
is used as physical stimuli.
 Different Forms of Spectroscopy

Each form of spectroscopy uses a different region of the electromagnetic spectrum and
involves a different kind of excitation.
Name of Radiation Relative What it does to the What information is
Spectroscopy Used Energy atom/molecule deduced about the nature
of atom/molecule
Photoelectron X rays (0.01-10 Very High Ionization Atomic structure, how tightly
spectroscopy nm) (formation of the electrons are held by the
ions) nucleus, identity of an element

UV-Visible spectroscopy UV (50-400 nm) High Electrons Extent of π electron system,

Visible (400-800 promoted to presence of conjugated
nm) higher energy unsaturation and conjugation
state with non-bonding electrons.

IR spectroscopy IR (2.5-50 μm) Medium Induces stronger Detection of functional groups

vibrations of and types of bonds
bonds in the
molecule
Electron Spin Resonance Microwaves Low Induces spin change of unpaired Detection of free radicals and
(ESR) or Electron (0.3mm-0.1m) electron the interaction of electron with
Paramagnetic Resonance nearby nuclei
(EPR) spectroscopy

NMR spectroscopy Radiowaves Very Low Electrons flipping Hydrogens and carbon atoms in
(0.1m-103m) magnetic spin different environments can be
detected and counted
Infrared (IR) Spectroscopy
 Infrared (IR) Spectroscopy

• IR spectroscopy is the study of the interaction of IR radiation with a molecule.

• IR radiations (particularly from mid-IR region having wavenumbers between 4000-400 cm-
1) has just the right amount of energy to induce stronger vibrations in the bonds of an

organic molecule. Once the bonds of a molecule absorbs IR radiation of certain frequency,
it will undergo excitation from low energy vibrational state to high energy vibrational
state and in turn vibrates more strongly.

Incident photon of IR
radiation striking the E2 (High-energy vibrational state)
molecule

Energy ΔE = E2-E1
Ephoton = hν
E1 (Low-energy vibrational state)
Bond of a molecule at low energy level
Absorption of IR radiation
Upward transition (excitation of bond) from
E1 to E2 happens only when ΔE = hν

• But what do you mean by vibration of bonds in a molecule?

 Vibration of Bonds in a Molecule
• A covalent bond in an organic molecule can be viewed as a
vibrating spring holding two balls together. If the bond is stretched,
a restoring force pulls the two atoms together toward their A
equilibrium bond length. If the bond is compressed, the restoring
force pushes the two atoms apart. If the bond is stretched or
compressed and then released, the atoms vibrate (Fig. A, B & C).
B
• The covalent bonds can vibrate with stretching and bending
motions.
a. A stretch is a vibration occurring along the line of the bond;
a stretching vibration changes the bond length.
C
b. A bend is a vibration that does not occur along the line of
the bond; a bending vibration changes the bond angle.
c. The stretch and bend are also known as types or modes of D
vibration.

• A diatomic molecule such as H-Cl can undergo only a stretching E Stretching Vibrations
vibration because it has no bond angles (Fig. D).

• The vibrations of a molecule containing three or more atoms are

more complex because they include stretches and bends. The
stretching and bending vibrations, moreover, can be symmetric or Symmetric stretch Asymmetric stretch
asymmetric, and the bending vibrations can be either in-plane or
out-of-plane (see figure for -CH2- vibration; ‘C’ is in yellow and ‘H’ Bending Vibrations
is in blue) (Fig. E).

• Bending vibrations are often referred to by the

terms rock, scissor, twist and wag (Fig. E). Symmetric in-plane Asymmetric in-plane Symmetric out-of-plane Asymmetric
Bend (scissor) Bend (rock) Bend (twist) out-of-plane Bend (wag)
Calculation of Number of Fundamental Modes of Vibration for a Molecule

• Each atom has 3 degree of freedom (x, y, z)

• A molecule of n atoms therefore has 3n degrees of freedom.
• Since degree of freedom of a molecule = Translational degree of freedom + rotational
degree of freedom + vibrational degree of
freedom
• For a linear molecule such as CO2 A O C O symmetrical stretch: 1367 cm-1
The translation degree of freedom = 3
The rotational degree of freedom = 2 O C O asymmetrical stretch: 2349 cm-1

Therefore, the vibrational degree of freedom = 3n-5

bending
Since no. of atoms in a molecule of CO2 = 3 O C O

Hence, the vibrational degree of freedom = 3 × 3 – 5 = 4 degenerate: 667 cm-1

So, a molecule of CO2 has 4 modes of vibration (Fig. A). O C O bending

Modes of Vibration in CO2

B
• For a non-linear molecule such as H2O H H symmetrical stretch: 3657 cm-1
The translation degree of freedom = 3 O

The rotational degree of freedom = 3 H H asymmetrical stretch: 3756 cm-1

Therefore, the vibrational degree of freedom = 3n-6 O
Since no. of atoms in a molecule of H2O = 3
H H bending (scissoring): 1595 cm-1
Hence, the vibrational degree of freedom = 3 × 3 – 6 = 3
O
So, a molecule of H2O has 3 modes of vibration (Fig. B).
Modes of Vibration in H2O
Importance of IR Spectroscopy in Structure Determination

• Depending upon the nature of the bonds, the stored energy in the molecule vibrate the
bonds with a characteristic frequency (known as fundamental frequency).

• When a molecule is bombarded with IR radiation of a frequency that exactly matches

the frequency of the vibration of one of its bonds, the molecule absorbs energy. This
allows the bond to vibrate a bit more (increases the amplitude of the vibration of
bonds) (Fig. A and B). B
A

Absorption of IR radiation increases the amplitude of the stretching vibration (ie increases
back and forth motion of atoms connected by a bond). The frequency of the stretching
vibration remains same (i.e. the number of vibrations per sec.)
• By experimentally determining the wavenumbers of the energy absorbed by a
particular compound, we can ascertain what kinds of bonds it has. For example, the
stretching vibration of a C-O bond absorbs energy with wavenumber ≈ 1700 cm-1,
whereas the stretching vibration of an O-H bond absorbs energy with wavenumber ≈
3400 cm-1.
 IR Spectrophotometer: Working
• IR spectrophotometer (or IR spectrometer) is the instrument which records the interaction of
IR radiations with a compound.

A typical IR
spectrophotometer

• A sample is irradiated with different frequencies of IR radiation. Depending on the nature of

bonds in a molecule, some of the individual frequencies are completely absorbed (and
nothing transmitted), partially absorbed (and partially transmitted) or completely transmitted
(and nothing absorbed). Some of the of the frequencies of the radiation can also be reflected
back to the source.
Transmitted
IR Chemical radiation
Detector
source sample
A chemical substance may absorb some of the
individual frequency and transmits rest
• The detector detects how much of an individual frequency of IR radiation is transmitted (or
absorbed).
• The spectrophotometer then plot a graph between transmitted (or absorbed) frequencies vs.
intensity of the transmission (or absorption). The graph is known as IR spectrum that shows
which of the frequencies were absorbed by the sample..
 IR Spectrum in Absorption Mode
Frequencies is depicted as wavenumbers on the x-axis in units of cm-1, and
intensities are plotted on the y-axis in % units.

The graph above shows a spectrum in absorption mode.

 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.
 A Typical IR Spectrum of 1-Butanol

Each signal as downward peak is The position of each signal on the

known as absorption band. The spectrum can be specified by the
presence of absorption bands tells corresponding frequency (in
that absorption has taken place wavenumbers) with units cm-1.

• Every absorption band in an IR spectrum has three characteristic features: position,

intensity and shape.
 Position of Absorption Bands

• The fundamental vibration of a stretching bond (Fig. A) A

(assumed as a vibrating spring connecting two masses
together) can be calculated using Hooks law (Fig. B). B
• As mred appears in the denominator. This means that
smaller atoms give bonds that vibrate at higher
frequencies, thereby corresponding to a higher
wavenumber of absorption. For example, the C−H
bond involves the smallest atom (H) and therefore C
appears at the highest wavenumber (Fig. C and D).

• The force constant (f) appears in the numerator. This

means that stronger bonds will vibrate at higher D
frequencies, thereby corresponding to a higher
wavenumber of absorption. For example, compare the
following bonds. The C≡N bond having highest bond
order is the strongest of the three bonds and
therefore appears at the highest wavenumber (Fig. E).

• Bending a bond needs less energy than stretching a

bond. Hence bending vibrations appears at smaller E
wavenumber (approx. 1400-400 cm-1) than stretching
vibrations (approx. 4000-1250 cm-1).
 Division of IR Spectrum: on the basis of Bond Strength and
Atomic Mass

X-H are generally strongest bonds due single bonds except X-H
to smaller H and appear on the left side are generally weakest
of spectrum bonds and appear on the
right side of spectrum

An IR absorbance spectrum divided into regions based on bond strength and atomic mass.
 Division of IR Spectrum: on the basis of Functional Group
Region and Fingerprint Region

(Functional group region)

Most of the functional group absorption bands Each compound has a unique pattern of bands
arises in this region. In the analysis, we have to in this region, much the way each person has a
focus on this region as they are less complex unique fingerprint. This region is complex and
and easy to interpret reliably difficult to interpret reliably.
An IR absorbance spectrum divided into diagnostic (functional group) region and fingerprint region

Very different
Very similar functional IR spectra for 2-butanol and 2-propanol. fingerprint region.
group region.
 Position of Absorption Band: Effect of Hybridization

• As the order of electronegativity is:

C (sp3) > C (sp2) > C (sp) A
109 ppm 108 ppm 106 ppm
The electron density is more attracted towards
the nucleus of C (sp3) than C (sp2) followed by
C (sp).
Hence Csp3-H has the shortest bond length and
is therefore strongest bond and give
absorption band at larger wavenumber. This is
followed by absorption band of Csp2-H and B
then Csp-H (see fig. A).

• An alkane can be distinguished from an

alkene or an alkyne by analyzing the
spectra. An alkane does not have any band
to the left of 3000 cm-1. An alkene has a
band at 3100 cm−1, and an alkyne has a
band at 3300 cm−1 (see fig. B).

• The absence of a signal to the left of 3000 cm−1 does not necessarily C
indicate the absence of a double bond or triple bond in the compound.
Tetrasubstituted double bonds do not possess any Csp2−H bonds, and
internal triple bonds also do not possess any Csp−H bonds (see fig. C).
 Position of Absorption Band: Effect of Resonance
• Resonance (delocalization of π electron)
affects position of absorption bands. A

• A single bond is weaker than a double bond,

so a carbonyl group with significant single-
bond character due to electron A
delocalization is weaker and stretches at a
lower frequency than one with little or no
single-bond character. Consequently it B B
appears at smaller wavenumber (see fig. A).

• Putting an atom other than carbon next to

the carbonyl group also causes the position
of the carbonyl absorption band to shift.
Whether it shifts to a lower or to a higher
frequency depends on whether the C
predominant effect of the atom is to donate
electrons by resonance or to withdraw
electrons inductively (see fig. B).

• The predominant effect of the nitrogen of an amide is electron donation by resonance. In contrast,
oxygen is less able than nitrogen to accommodate a positive charge because of oxygen’s greater
electronegativity, so the predominant effect of the oxygen of the OR group of an ester is inductive
electron withdrawal. As a result, the carbonyl group of an ester has less single-bond character, it is
stronger and shows band at (1740 cm-1) than the carbonyl group of an amide (1660 cm-1) (see fig. C).
 Intensity of Absorption Band

• Some bonds absorb IR radiation more efficiently and A

appear as strong absorption bands.

• Various absorption band is abbreviated as:

a) Strong: s
b) Medium: m
c) Weak: w

• The intensity of absorption bands depends on change in

dipole moment. The greater the change in dipole B
moment, the more intense the absorption (see fig. A).

• Dipole moment of a bond; μ = e × d

Where e = magnitude of charge on either of
connecting atoms.
d = distance between the atoms.
• As a bond vibrates, the distance between the partial charges is constantly changing, which means that
the strength of the dipole moment also changes with time. A plot of the dipole moment as a function
of time shows an oscillating dipole moment (see fig. B).

• The dipole moment is an electric field surrounding the bond. So as the dipole moment oscillates, the
bond is essentially surrounded by an oscillating electric field, which serves as an antenna (so to speak)
for absorbing IR radiation. Since electromagnetic radiation itself is comprised of an oscillating electric
field, the bond can absorb a photon because the bond’s oscillating electric field interacts with the
oscillating electric field of the IR radiation.
 Intensity of Absorption Band Contd.
• The efficiency of a bond at absorbing IR radiation therefore A
depends on the strength of the dipole moment (or polarity).

• As the carbonyl group (C=O) has much more dipole moment than
C=C. The change in dipole moment associated with C=O is much
more than C=C. The oscillating electric field associated with the
carbonyl group is much stronger than the oscillating electric field
associated with the C=C. Therefore, the C=O group functions as a
better antenna for absorbing IR radiation. Consequently, the B
carbonyl group is more efficient at absorbing IR radiation,
producing a stronger absorption band (see fig. A and B).

• The stretching vibration of an O-H bond is associated with a

greater change in dipole moment than that of an N-H bond,
because the O-H bond is more polar. Consequently, an O-H bond
shows more intense absorption than an N¬H bond. Similarly, an
N-H bond shows more intense absorption than a C-H bond,
because the N-H bond is more polar (see fig. C).

• The intensity of an absorption band also depends on the number

of bonds responsible for the absorption. For example, the C
absorption band for a C-H stretch is 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.
• 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. In the chemical literature, you will find intensities referred to as strong (s), medium (m),
weak (w), broad, and sharp.
IR In-Active Bonds(Vibrations): Absence of Absorption Bands

• Some alkenes do not even produce any C=C band A

at all. For example, consider the IR spectrum of
2,3-dimethyl-2-butane (see Fig. A). This alkene is
symmetrical and the C=C bond has no dipole
moment at all. As the C=C bond vibrates, there is
no change in dipole moment, which means that
the bond cannot function as an antenna for
absorbing IR radiation.

• Symmetrical C=C bonds as well as symmetrical

C≡C bonds are completely inefficient at absorbing
IR radiation, and no bands is observed.

• Bonds with zero dipole moments sometimes produce absorptions (usually weak) because
molecular collisions, rotations, and vibrations make them unsymmetrical part of the time.

• It may be noted that absence of absorption bands are also attributed to other factors apart for
bond (vibration) being IR in-active. These are:
a) Fundamental frequencies that fall outside the 4000-400 cm-1 region.
b) Fundamental bands that are too weak to be observed.
c) Fundamental bands that are so close that they overlap.
d) The occurrence of a degenerate band from several absorptions of the same frequency in
highly symmetrical molecules.
 Overtone Bands, Combination Bands, Difference Bands and Fermi
Resonance Bands

• IR spectrum looks complicated because apart from

fundamental absorption bands arising from A
fundamental stretching and bending vibrations, 4th excited vibrational state
they also shows bands arising from overtones,
combinations, differences and Fermi-resonance.
3rd excited vibrational state
• Weak overtones absorption bands result from
excitation of vibration from the ground state to 2nd 2nd excited vibrational state
excited state or higher (Fig. A). Overtones
corresponds to integral multiples of the frequency
1st excited vibrational state
of the fundamental vibrations. They are observed in
(Lowest energy excited state)
the bonds having very high dipole moments (such
as C=O) which very efficiently absorbs radiation. Ground vibrational state

• Combination bands arises when vibration of one An energy diagram showing

bond (ṽ1) couple with vibration of another bond (ṽ2) the energy gap between
to give rise a new infrared active vibration (ṽ3(comb.) = allowed vibrational states.
ṽ1 + ṽ2). Not all possible combinations occur.

• Difference bands are similar to combination bands. The observed frequency in this case results
from the difference between the two interacting vibrations (ṽ3(diff) = ṽ1 - ṽ2). Not all possible
differences occur.

• Fermi-resonance bands occur when fundamental vibration couples with an overtone or

combination bands. Again, only certain combinations are allowed.
 Shape of Absorption Bands
• In IR spectrum, some absorption bands are very broad (br) A
while others are very narrow or sharp (sh) (Fig. A).

• Hydrogen bonding affects the shape of absorption bands. It

leads to bond weakening (Fig. B).

• In a concentrated solution of alcohol having extensive H-

bonding, different O-H bond making varying extent of H-
bonding will get weakened to different extent.
Consequently different O-H bond will absorb at slightly
different wavenumber giving rise to broad absorption band. B
Also, due to bond weakening, absorption band appear at
smaller wavenumber (Fig. C and D).
Intensity of Absorption Band
• On the other hand, in a very dilute solution of alcohol with
no H-bonding, all the O-H bond will be in same C
environment and will get weakened to same extent. E
Consequently all O-H will be absorbed at same
wavenumber giving rise to narrow absorption band. Also,
since there is no bond weakening, absorption band appear
at larger wavenumber (Fig. E and F). R R
Distinct bond has a
D F well-defined length
O H O CCl4
Many kinds of OH bonds of different and strength.
H CCl4
lengths and strengths. This leads to a H Solvent molecules R O CCl4
R O O H
broad absorption. R O surround but do not
H R CCl4
H hydrogen bond. CCl4
Longer bonds are weaker and O
leads to smaller wavenumber. R H
Occurs in dilute solutions of
Hydrogen bonding occurs in concentrated alcohol in an “inert” solvent like
solutions ( for instance, undiluted alcohol ) CCl4.
 Shape of Absorption Bands Contd.

• When the solution is neither very concentrated nor very dilute, two signals are
observed. The molecules that are not participating in H bonding will give rise to
a narrow signal (due to free O-H), while the molecules participating in H
bonding will give rise to a broad signal (due to H-bonded O-H). For example see
the IR spectrum (from 3700-3000 cm-1) of 2-butanol (in fig.).

broadening

shifting
 Shape of Absorption Bands
• Intramolecular H-bonding leads to narrow absorption bands at larger wavenumber while intermolecular H-
bonding leads to broad absorption bands at relatively smaller wavenumber.

• Carboxylic acids shows even more broad absorption band at smaller wavenumber due to more extensive
hydrogen bonding. Notice the very broad signal on the left side of the spectrum, extending from 2200 to
3600 cm−1. This signal is so broad that it extends over the usual C−H signals that appear around 2900 cm−1.

• The effect is more pronounced than alcohols, because

molecules of the carboxylic acid can form two strong
hydrogen-bonding interactions, resulting in a dimer.

• The IR spectrum of a carboxylic acid is easy to recognize,

because of the characteristic broad signal that covers
nearly one-third of the spectrum. This broad signal is also
accompanied by a broad C=O signal just above 1700 cm−1.
 Interpretation of a Spectrum: How to do analysis

Spectrum interpretation process mainly contains three step:

1. Recognizing a pattern.

2. Associating patterns with physical parameters.

3. Identifying 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.
 Interpreting IR Spectrum
1. Keep in mind some of the of the useful signals in the functional group region (diagnostic region)
and in the fingerprint region of IR spectrum (Fig. A and B).
A
 Interpreting IR Spectrum Contd.
B

2. Draw a line at 1500 cm−1. Focus on any bands to the left of this line (the
diagnostic region). In doing so, it will be extremely helpful if you can C
identify the following regions:
• Double bonds: 1600-1850 cm−1
• Triple bonds: 2100-2300 cm−1
• X−H bonds: 2700-4000 cm−1

3. Remember that each signal appearing in the diagnostic region will have
three characteristics (position, intensity, and shape). Make sure to
analyze all three characteristics.

4. When looking for X−H bonds, draw a line at 3000 cm−1 and look for
signals that appear to the left of the line (Fig. C).
IR Spectrum of Common Compounds
 IR Spectrum of Alkanes

Alkanes have no functional groups. Their IR spectrum displays only C-C and C-H bond
vibrations. Of these the most useful are the C-H bands, which appear around 3000 cm-1.
Since most organic molecules have such bonds, most organic molecules will display those
bands in their spectrum.
 IR Spectrum of Alkenes

Besides the presence of C-H bonds, alkenes also show sharp, medium bands corresponding
to the C=C bond stretching vibration at about 1600-1700 cm-1. Some alkenes might also
show a band for the =C-H bond stretch, appearing around 3080 cm-1 as shown below.
However, this band could be obscured by the broader bands appearing around 3000 cm-1
(see next slide)
 IR Spectrum of Alkenes Contd.

This spectrum shows that the band appearing around 3080 cm-1 can be obscured by the
broader bands appearing around 3000 cm-1.
 IR Spectrum of Alkynes
• The most prominent band in alkynes corresponds to the carbon-carbon triple bond.
It shows as a sharp, weak band at about 2100 cm-1. The reason it’s weak is because
the triple bond is not very polar.

• Terminal alkynes, where the triple bond is at the end of a carbon chain, have C-H
bonds involving the sp carbon (the carbon that forms part of the triple bond).
Therefore they may also show a sharp band at about 3300 cm-1 corresponding to the
C-H stretch.
 IR Spectrum of Alkynes Contd.

• In some cases, such as in highly symmetrical alkynes, C≡C may not show at all due
to the no or neglible polarity of the triple bond associated with those alkynes.

• Internal alkynes, that is those where the triple bond is in the middle of a carbon
chain, do not have C-H bonds to the sp carbon and therefore lack C-H basorption
band.
 IR Spectrum of Alcohols

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 sheer size and broad
shape of the band dominate the IR spectrum and make it hard to miss.
 IR Spectrum of Aldehydes and Ketones

• Carbonyl compounds are those that contain the C=O functional group. In aldehydes,
this group is at the end of a carbon chain, whereas in ketones it’s in the middle of the
chain. As a result, the carbon in the C=O bond of aldehydes is also bonded to another
carbon and a hydrogen, whereas the same carbon in a ketone is bonded to two other
carbons.

• Aldehydes and ketones show a strong, prominent, stake-shaped band around 1710 -
1720 cm-1 (right in the middle of the spectrum). This band is due to the highly polar
C=O bond. Because of its position, shape, and size, it is hard to miss.

• Because aldehydes also contain a C-H bond to the sp2 carbon of the C=O bond, they
also show a pair of medium strength bands positioned about 2700 and 2800 cm-1.
These bands are missing in the spectrum of a ketone because the sp2 carbon of the
ketone lacks the C-H bond.

• The following slide shows a spectrum of an aldehyde and a ketone. Study the
similarities and the differences so that you can distinguish between the two.
IR Spectrum of Aldehydes and Ketones Contd.
 IR Spectrum of Carboxylic Acids
A carboxylic acid functional group combines the features of alcohols and ketones
because it has both the O-H bond and the C=O bond. Therefore carboxylic acids show a
very strong and broad band covering a wide range between 2800 and 3500 cm-1 for the
O-H stretch. At the same time they also show the narrow-shaped band in the middle of
the spectrum around 1710 cm-1 corresponding to the C=O stretch.
 IR Spectrum of Amides

The amide functional group combines the features of amines and ketones because it has
both the N-H bond and the C=O bond. Therefore 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 1650 cm-1 for the C=O stretch. As with amines, primary amides show
two spikes, whereas secondary amides show only one spike.
 IR Spectrum of Amines
The most characteristic band in amines is due to the N-H bond stretch, and it appears as a
weak to medium, somewhat broad band (but not as broad as the O-H band of alcohols). This
band is positioned at the left end of the spectrum, in the range of about 3200 - 3600 cm-1.

Primary amines have two N-H bonds, therefore they typically show two spikes that make this
band resemble a molar tooth. Secondary amines have only one N-H bond, which makes them
show only one spike, resembling a canine tooth. Finally, tertiary amines have no N-H bonds,
and therefore this band is absent from the IR spectrum altogether. The spectrum below shows
a secondary amine.
 Summary

• Organic IR Spectroscopy is interaction of IR radiation (having wavenumber

between 4000-400 cm-1) with organic compound.

• IR radiation stimulates vibration (stretching and bending) of the bonds in the

molecule.

• IR spectrophotometer is the instrument used to detect the interactions. It

generates information in the form of IR spectrum. IR spectrum is a plot between
%transmittance and wavenumbers and has two important regions know as
functional group region (4000-1500 cm-1) and fingerprint region (1500-400 cm-1).

• IR spectroscopy mainly provides information about the presence or absence of

certain func onal groups (such as C=C, C≡C, C=O, O-H etc. ) in an organic
compound and is used in conjunction with other spectroscopic technique to
determine complete molecular structure of an organic compound.

• IR spectroscopy is also used as an analytical tool to differentiate between

stereoisomers (except enantiomers).
Ultraviolet-Visible (UV-Vis) Spectroscopy
 UV-Vis Spectroscopy
• UV-Vis spectroscopy is the study of the interaction of Ultraviolet and Visible radiation with a molecule.

• Ultraviolet radiations (having wavelength between 180-400 nm) and visible radiations (having
wavelength between 400-780 nm) has just the right amount of energy to induce electronic transition in
an organic molecule. Once the electron absorbs UV-Vis radiation of certain wavelength, it will undergo
transition from low energy electronic state (occupied orbital) to high energy electronic state
(unoccupied orbital).
electron at higher energy level after
electronic transition (Excited State)
Incident photon of UV-
Vis radiation striking E2 (High-energy electronic state) E2
the electron

Energy ΔE = E2-E1
Ephoton = hν
E1 (Low-energy electronic state) E1
electron at low energy level (Ground State)
BEFORE TRANSITION AFTER TRANSITION
Absorption of UV-Vis radiation
Upward transition (excitation of electron) from E1 to E2 happens only when ΔE = hν

• We should know what are different electronic states and possible transitions in a molecule.
 Electronic States in a Molecule
• Usually three kinds of electrons are present in a organic molecule composed of covalent bonds.
These are σ electrons present in the σ molecular orbital of a σ bond, π electrons present in the π
molecular orbital of a π bond and n electrons known as non-bonded electrons present in the non-
bonding orbitals on an atom (see the structure of acetone; fig A).

• For most molecules, the lowest-energy occupied molecular orbitals are the σ orbitals. The π orbitals
lie at somewhat higher energy levels, and nonbonding (n) orbitals, lie at even higher energies. The
unoccupied or antibonding orbitals (π* and σ*), are the orbitals of highest energy. Figure B shows a
typical progression of electronic energy levels.

B σ* antibonding MO These are normally empty

π* antibonding MO

non bonding MO These contain lone pair of

electrons

π bonding MO These contain bonding

σ bonding MO pair of electrons

Electronic energy levels

 Possible Transitions in a Molecule
• In all compounds other than alkanes, the electrons may undergo several possible transitions of
different energies. These are illustrated in figure A.

Types of transitions

• Some of the most important transitions in different types of compounds are:

σ → σ* In alkanes
σ → π* In carbonyl compounds
Increasing π → π* In alkenes, carbonyl compounds, alkynes, azo compounds, and so on
Energy
n → σ* In oxygen, nitrogen, sulfur, and halogen compounds

n → π* In carbonyl compounds

• Generally, the most probable transition is from the highest occupied molecular orbital (HOMO) to
the lowest unoccupied molecular orbital (LUMO).
 Forbidden Transitions

• Apart from transitions shown in previous slide, other transitions (like σ → π or π → n)

are not allowed due to certain restrictions called selection rules, must be considered.

• One of the important selection rule states that transitions that involve a change in the
spin quantum number of an electron during the transition are not allowed to take
place. Other selection rules deal with the numbers of electrons that may be excited at
one time, with symmetry properties of the molecule and of the electronic states, and
with other factors that are beyond the scope of the syllabus.

• Transitions that are not allowed to take place by the selection rules are known as
forbidden transitions. Theoretically, forbidden transitions are not observed.

• However, in certain cases forbidden transitions are observed, although the intensity of
the absorption tends to be much lower than for transitions that are allowed by the
selec on rules. The n → π* transition is the most common type of forbidden
transition.
 Importance of UV-Vis Spectroscopy in Structure Determination

• By experimentally determining the wavenumbers of the ultraviolet-visible radiation

absorbed by a particular compound, we can determine certain information about the
structure of an organic compound, particularly, extent of conjugation present in an
organic compound.

• UV-Vis spectroscopy is also used in other qualitative and quantitative analysis of an

organic compound such as:
• Determination of impurity present in an organic compound.
• Determination of molar concentration of organic compound under study.
• Determination of certain isomers.
• Determination of molecular weight of an organic compound using Beer’s law.
• Determination of acidity of an organic compound.
• Determination of reaction rate of an organic reaction etc.

• UV-Visible spectroscopy is used in conjunction with other spectroscopic techniques to

determine complete structure of an organic compound.

• UV-Vis spectroscopy has application in diverse field of science including pharmaceuticals,

biotechnology, environmental, food and beverages etc.
 UV-Vis Spectrophotometer: Working
• UV-Vis spectrophotometer (or UV-Vis spectrometer) is
the instrument which records the interaction of UV-Vis A
radiations with a compound (Fig A).

• A typical UV-Vis spectrophotometer works in the range of

200-800 nm. A sample is irradiated with different A modern UV-Vis spectrophotometer
wavelengths of UV-Vis radiation. Depending on the
nature of a molecule, some of the individual wavelengths
are completely absorbed (and nothing transmitted), B
partially absorbed (and partially transmitted) or IR Chemical Transmitted
Detector
completely transmitted (and nothing absorbed). Some of source sample radiation
the of the wavelengths of the radiation can also be A chemical substance may absorb some of the
reflected back to the source (Fig B). individual wavelengths and transmits rest

• The detector detects how much of an individual C

wavelength of UV-Vis radiation is absorbed.

• The spectrophotometer then plot a graph between

wavelength vs. absorbance. The graph is known as UV
spectrum if the molecule absorbs ultraviolet light, and Vis
spectrum if it absorbs visible light. A UV-Vis spectrum
shows which of the wavelengths were absorbed by the
sample. Fig. C shows a typical UV-Vis spectrum of Wavelength is depicted on the x-axis in units of nm,
butadiene. and absorbance is plotted on the y-axis.
 Lambert-Beer Law
• Like other absorption spectroscopy, UV-Vis spectroscopy obeys Lambert-Beer’s Law when a single
species gives rise to the observed absorption.

A = log ( ) = εcl {for a given wavelength}

Where, A = absorbance
IO = intensity of light incident upon sample cell
I = intensity of light leaving sample cell
c = concentration of solute (moles/litre)
l = length of sample cell (cm)
ε = constant known as molar absorptivity (or molar extinction coefficient) (mol-1Lcm-1)

• If the sample absorbs light at a particular wavelength, I is less than the Io and the ratio is greater than 1.
The ratio is equal to 1 when there is no absorption. The absorbance (the logarithm of the ratio) is
therefore greater than zero when the sample absorbs, and is equal to zero when it does not.

• As absorbance α concentration of solute, it means, greater the number of molecules capable of

absorbing radiation of a given wavelength, the greater the extent of radiation absorption.

• Also as absorbance α length of sample cell, it means, longer the length of sample cell, greater is the
possibility of radiation encountering more number of molecules capable of absorbing radiation of a
given wavelength, hence greater the extent of radiation absorption.

• Furthermore, molar absorptivity (ε) is a measure of how effectively the molecule absorbs light of a
given wavelength. Hence, greater the molar absorptivity of a molecule, the greater the extent of light
absorption.
 Lambert-Beer Law Contd.

• Molar absorptivity (ε) is a inherent or characteristic property of the molecule

undergoing an electronic transition and is not a function of the variable parameters
involved in preparing a solution (e.g. change in concentration do not affect molar
absorptivity).

• Molar absorptivity depends on transition probability as well as on area of absorbing

part of molecule.

• Molar absorptivity changes with change in solvent. Therefore the solvent in which the
sample is dissolved is always reported while showing UV-Vis spectrum.

• Molar absorptivity, ranges from 0 to 106. Values above 104 are termed high-intensity
absorptions, while values below 103 are low-intensity absorptions. Forbidden
transitions have absorptivity in the range from 0 to 1000.

• Lambert-Beer law is not followed when different forms of the absorbing molecule are
in equilibrium, when solute and solvent form complexes through some sort of
association, when thermal equilibrium exists between the ground electronic state and
a low-lying excited state, or when fluorescent compounds or compounds changed by
irradiation are present.
 Salient Features of a UV-Vis Spectrum
• As, A = log , the value of absorbance on y-axis can vary from 0 A
to 1 (Fig. A).
• Absorbance can also be depicted in terms of log ε on y-axis (Fig. B).
As, log ε = log
• λmax (pronounced lambda max), indicates the wavelength of
maximum absorption (Fig. A).
• εmax , indicates molar absorptivity at λmax . B
• A typical UV-Vis spectrum generally ranges from 200-800nm.
Hence very high energy transitions such as σ → σ* or σ → π*
transitions are not seen. The most important transitions that lie in
this region are n → π* and π → π*. For this reason, it is said that
molecule should contain π bonds to produce UV-Vis spectrum.
• UV-Vis spectrum consist of broad absorption bands as
opposed to relatively narrow bands observed in IR
spectrum. This is because each electronic state consist of
overlapping closely spaced vibrational and rotational C
energy levels (Fig. A). As various molecules of a
compound can occupy different rotational and vibrational
levels within an electronic state, many possible
transitions can take place from and to these different
levels, each differing from the others by only a slight
amount (Fig. C). Spectrophotometer cannot resolve vast
number of lines arising due to these transitions , rather it
traces an envelope over the entire region, seen as broad Electronic transitions with vibrational transitions
absorption band centred near the wavelength of the superimposed. (Rotational levels, which are very closely
major transition. spaced within the vibrational levels, are omitted for clarity.)
 Choice of Solvent for Obtaining UV-Vis Spectrum
• Choice of solvent is very important in obtaining desired UV-Vis spectrum and is usually based on
three criteria:

1. The good solvent is the one that should not absorb ultraviolet radiation in the same region as the
substance whose spectrum is being determined. Usually, solvents that do not contain conjugated
systems are most suitable for this purpose. Table A given below lists some common ultraviolet
spectroscopy solvents and their cut-off points or minimum regions of transparency. Water, 95%
ethanol, and hexane are most commonly used. Each is transparent in the regions of the ultraviolet
spectrum in which interesting absorption peaks from sample molecules are likely to occur.
A B

Solvents with their λmax values

2. A second criterion for a good solvent is its effect on the fine
structure of an absorption band. Fig. B illustrates the effects
of polar and nonpolar solvents on an absorption band. A
nonpolar solvent does not hydrogen bond with the solute,
and the spectrum of the solute closely approximates the
spectrum that would be produced in the gaseous state, in
which fine structure is often observed. In a polar solvent, Ultraviolet spectra of phenol in
the hydrogen bonding forms a solute–solvent complex, and ethanol and in isooctane.
the fine structure may disappear.
Choice of Solvent for Obtaining UV-Vis Spectrum Contd.

3. A third criterion for a good solvent is its ability to influence the wavelength of ultraviolet light that
will be absorbed via stabilization of either the ground or the excited state. Polar solvents do not
form hydrogen bonds as readily with the excited states of polar molecules as with their ground
states, and these polar solvents increase the energies of electronic transitions in the molecules.
Polar solvents shift transitions of the n → π* type to shorter wavelengths. On the other hand, in
some cases the excited states may form stronger hydrogen bonds than the corresponding ground
states. In such a case, a polar solvent shifts an absorption to longer wavelength since the energy of
the electronic transition is decreased. Polar solvents shift transitions of the π → π* type to longer
wavelengths. Table A illustrates typical effects of a series of solvents on an electronic transition.

Solvent shifts on the n → π* transition of acetone

 Chromophore
• A chromophore is the part of a molecule (consisting of group of atoms) that absorbs UV
or visible radiation and give absorption bands in UV-Vis spectrum.
Compound Transitions Important Chromophore Remarks
taking place Transition w.r.t. w.r.t. UV-Vis
UV-Vis spectrum spectrum

Alkanes σ → σ* None (as σ → σ* No chromophore

transition is not
seen in UV-Vis
spectrum)

Saturated σ → σ* and None (as σ → σ* No chromophore

Alcohols, Ethers, n → σ* and n → σ*
Amines, Alkyl transition are also
Halides (RF, RCl, generally not seen
RBr) and Sulfur in UV-Vis
Compounds spectrum)

Alkenes and σ → σ*, π → π* C=C (conjugated),

Alkynes σ → π* and (only C≡C (conjugated)
π → π* when π bond is in
conjugation)
 Chromophore Contd.
Compound Transitions Important Chromophore Remarks
taking place Transition w.r.t. w.r.t. UV-Vis
UV-Vis spectrum spectrum
Carbonyl σ → σ*, π → π* (only C=O
Compounds σ → π*, when π bond is (conjugated)
π → π* and in conjugation)
n → π* and
n → π*

The following four compounds all have the

same chromophore, so they all have
approximately the same λmax.
 Effect of Conjugation on λmax
• As stated before, the most probable electronic transition
A
take place from highest occupied molecular orbital
(HOMO) to lowest unoccupied molecular orbital (LUMO).

• Ethylene, for example, has two pi orbitals: the bonding

orbital (π, the HOMO) and the antibonding orbital (π*,
the LUMO). The ground state has two electrons in the
bonding orbital and none in the antibonding orbital. A
photon with the right amount of energy (E = 686 kJ/mol
corresponding to λ = 171 nm) can excite an electron from B
the bonding orbital to the antibonding orbital (Fig A). This
transition from a bonding orbital to a antibonding orbital
is called a π → π* transition. This transition is not seen by
typical UV spectrophotometer.

• When the π bond of ethylene is in conjugation with

another π bond such as in the case of buta-1,3-diene, it
leads to formation of newer molecular orbitals (π1, π2,
π3*, π4*) where there is decrease in the energy of HOMO
(π2) and increase in the energy of LUMO (π3*) as
compared to energies of HOMO (π) and LUMO (π*) of
ethylene (Fig B). Both differences reduce the relative
energy of the π2 → π3* transition. The resulting
absorptionis at 217 nm (540 kJ/mol), which can be The two double bonds can interact with each
measured using a standard UV spectrophotometer. other which in turn move the electronic
energy levels of a chromophore closer together.
 Effect of Conjugation on λmax Contd.
A
• Hexa-1,3,5-triene, comprised of 3
conjugated double bonds have even
more closer HOMO (π3) and LUMO (π4*)
(Fig. A). It absorbs at a longer
wavelength (258 nm).

• Hence, as the conjugation increases, the

energy difference between HOMO and
LUMO decreases and the wavelength of
absorption increases.

• A general rule can be stated as: A

compound that contains a longer chain
of conjugated double bonds absorbs
radiation at a longer wavelength (Fig.
B). The extent of conjugation present in
the compound can hence be predicted
by the λmax value. Each additional B
conjugated double bond adds between
30 and 40 nm (Fig. B).

• Isolated double bonds do not interact

with each other and hence do not C
contribute to shifting the UV absorption
to longer wavelengths (Fig. C).
 Colored Compounds
• If a compound has enough conjugated double bonds, it will absorb visible radiation
(radiation with wavelengths > 400 nm) and the compound will be coloured.

• For example, β-carotene, a precursor of vitamin A with a λmax = 455 nm, is an orange
substance found in carrots, apricots, and the feathers of flamingos. Lycopene with a
λmax = 474 nm, found in tomatoes, watermelon, and pink grapefruit is red.
 Effect of Conjugation on εmax
• On increasing conjugation, the number of chromophores increases i.e. the area of radiation
absorbing part of the molecule increases. This leads to more absorption of a particular
wavelength of radiation. Hence molar absorptivity εmax increases (Table A).
A

B
• Figure B is depicting the increase in εmax and λmax
value of alkenes having general formula CH3-
(CH=CH)n-CH3, as the number of double bonds
increases. A is having n= 3, B is having n=4 and C is
having n=5.
 Auxochromes

• An auxochrome is a substituent that does not itself absorb in the UV region above 200 nm, but
when attached to a chromophore, alters both its λmax and the intensity of the absorption (εmax),
usually increasing both. For example, OH and NH2 groups are auxochromes (Fig. A). The lone-
pair of electrons on oxygen and nitrogen in the compounds shown below are available to
interact with the π electron cloud of the benzene ring by electron delocalization; such an
interaction increases the λmax.

• Removing a proton from phenol increases the λmax because the phenolate ion has an additional
lone pair. Protonating aniline decreases the λmax because the lone pair is no longer available to
interact with the π cloud of the benzene ring. Because the anilinium ion does not have an
auxochrome, its λmax is similar to that of benzene (Fig. A).
 Absorption and Intensity Shifts
As we have seen in previous slides, the shift of both λmax and εmax can take place on increasing or
decreasing conjugation or change in the polarity of solvent. These shifts are more commonly known
as hypsochromic shift (blue shift), bathochromic Shift (red shift), hyperchromic shift and
hypochromic shift as explained below.

(Hypsochromic Shift) (Bathochromic Shift)

 Woodward-Fieser Rule
• Woodward-Fieser rules can be used to make simple predictions about the λmax of a compound,
particularly those containing conjugated π systems. Woodward-Fieser rules only provides with an
estimate for λmax. In some cases, the estimate will be very close to the observed value, and in other
cases, there will be a discrepancy. The rules are only meant as a rough guide for making meaningful
predictions, and they do not work well for compounds that contain more than six double bonds in
conjugation.

• Before applying Woodward-Fieser rules, we should know what are various kinds of double bonds in
conjugation with each other.
1. Alicyclic conjugated double bonds: These are conjugated double A
bonds contained in an open chain system where basic unit is
butadiene system (Fig A).

2. Homo-annular conjugated double bonds: These are the conjugated

B
double bonds present in the same ring (Fig B).

3. Hetero-annular conjugated double bonds: These are the conjugated

C
double bonds which are not present in the same ring (Fig C).

4. Exocyclic conjugated double bonds: Exocyclic double bond is part of D

the conjugated system, formed by any carbon atom of any ring but is
present outside the ring (Fig D & E).
E
5. Endocyclic conjugated double bonds: Endocyclic double bond is part
of the conjugated system, formed by any carbon atom of any ring and
is present inside the ring (Fig D & E).
Woodward-Fieser Rule for Conjugated Alkenes (in EtOH)

Feature to look for: λmax (nm) Example Calculation

Conjugated diene Base value 217 nm
= 217
Each additional double bond +30 Base: 217
extending conjugation + 2 × 30
Two additional 277 nm
double bonds (observed = 290 nm)
Each auxochromic +5 Base: 217
alkyl group (or ring residue) +3×5
232 nm
Three alkyl groups (observed = 232 nm)
connected to chromophore
Each exocyclic double bond (a double +5 Base: 217
bond where one vinylic position is + 2 × 5 alkyl groups
part of a ring and the other vinylic + 5 exocyclic double bonds
position is outside the ring) Exocyclic double bond 232 nm
(observed = 230 nm)
Homoannular diene—both double +39 Base: 217
bonds are contained in one ring, so + 4 × 5 alkyl groups
the diene is locked in an s-cis + 39 homoannular diene
conformation Homoannular diene 276 nm
present (observed = 269 nm)
 Woodward-Fieser Rule for Enones (in EtOH)
Feature to look for: λmax (nm) Example Calculation
1) Six-membered ring or acyclic Base value α 215 nm
parent enone = 215
β
2) Five-membered ring parent enone = 202
3) Acyclic dienone = 245
Each additional double +30 γ α Base: 215
bond extending conjugation δ β + 30 double bond extend. conjug.
One additional 245 nm
double bond (observed = 247 nm)
Each auxochromic alkyl group (or ring α +10 Base: 215
α
residue) β +12 + 10 (α CH3)
γ & higher +18 β + 2 × 12 (β CH3)
Four alkyl groups 249 nm
connected (observed = 249 nm)
Each exocyclic double bond +5 Base: 202
O + 2 × 12 (2 × β alkyl groups)
+ 5 exocyclic double bond
α β 231 nm
Exocyclic double (observed = 226 nm)
bond present
Homoannular diene—both double +39 Base: 215
bonds are contained in one ring, so α + 30 double bond extend. conjug.
the diene is locked in an s-cis + 39 homoannular diene
β
conformation γ δ + 18 (δ alkyl group)
Homoannular 302 nm
diene present (observed = 300 nm)
 Summary

• Organic UV-Vis Spectroscopy is interaction of UV-Vis radiation (having

wavelength usually between 200-800 nm) with organic compound.

• UV-Vis radiation stimulates electrons in the molecule and excite them to higher
electronic energy levels.

• UV-Vis spectrophotometer is the instrument used to detect the interactions. It

generates information in the form of UV-Vis spectrum. UV-Vis spectrum is a plot
between absorbance and wavelength and has two important regions know as
UV region (200-400 nm) and visible region (400-800 nm).

• UV-Vis spectroscopy mainly provides information about the conjugation (such as

conjugated C=C, C=O etc. ) present in the molecule and is used in conjunction
with other spectroscopic technique to determine complete molecular structure
of an organic compound.

• UV-Vis spectroscopy is extensively used in scientific research and industries for

various qualitative and quantitative analysis.
Thank You