.

 Fundamentals Of ORD.
 Optical Rotatory Dispersion.
 Cotton Effect.
 The ORD Curve.
 Circular Dichroism.

 Octant Rule.

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• ORD refers to the change in optical rotation with
the change in wavelength of light source. i.e. applied
only in optically active compounds.
• Optical rotation caused by compound changed with
wavelength of light was first noted by Biot in 1817.
• ORD curves in recent years are made use in
structural determination by comparing the curve
obtain from compound believed to have related
structures particularly applied to carbonyl
compounds.

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Natural light is having two components electric
component and magnetic component, and both are
perpendicular to each other in different planes.

Both these electric component and magnetic

components are also perpendicular to the direction of
propagation of light.

28 March 2019 M.M.C.P. 4

UNPOLARISED LIGHT
NATURAL LIGHT

POLARISED LIGHT

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I. Linear or plane polarized light.

II. Circular polarized light.

III. Elliptically polarized light.

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 A polarized light vibrating in a single plane
perpendicular to the direction of propagation
is called plane polarised light.
 A light wave is characterized by an electric
field vector Ē and a magnetic field vector Ĥ
which are perpendicular to each other and in
phase. The two vectors are also perpendicular
to the direction of propogation.

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 When vibration of light are along a circle lying in
a plane perpendicular to the direction of
propagation the light is called circular polarized
light.
 Represent a wave in which the electrical
component & the magnetic component spirals
around the direction of propagation (vibration) of
the ray, either clockwise (or right handed or
dextrorotatory.) OR counterclockwise (or left
handed or levorotary).

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 Linearly polarized light can be regarded as the resultant
of two equal and opposite beams of circularly polarized
light i.e.., as a combination of left and right circularly
polarized light.
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 When vibration are along a ellipse lying in a plane
perpendicular to the direction of propagation the light is called
elliptically polarized light

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 The difference in indices of refraction for right
circularly polarized light (RCPL) & left circularly
polarized light (LCPL) is know as circular
birefringence.

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 The specific rotation of a chemical compound
[α] is defined as the observed angle of optical
rotation α when plane-polarized light is passed
through a sample with a path length of 1
decimeter and a sample concentration of 1 gram
per 1 millilitre

 where,
α – Angle of Rotation in degrees
l –path length is in decimeters
d – density of liquid is in g 100 ⁄ ml 1
T–Temperature.

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 A negative value means levorotatory rotation and a
positive value means dextrorotatory rotation.
 Some examples:
 Sucrose +66.47°
 cholesterol −31.5°
 Camphor +44.26°
 Penicilin V +223

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 FARADAY EFFECT :-
Any liquid or solution, when placed in a
magnetic field , rotates the plane of polarized light
because of the effect of magnetic field upon the motion of
electrons in the molecule.

 INDEX OF REFRACTION (η) :-

The ratio of velocity of ray of light in
vacuum (c) to its velocity in medium (v) i.e. η= C/V

 Small differences in the refractive indices for right & left

circularly polarized light cause an appreciable rotation of
the plane polarized light.

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 Optical activity :-
Ability to rotate plane of polarized light .

 Optically active compound :-

Certain organic compound when placed in a path of
a plain polarized light, it rotates the plain polarized light
through a certain angle. This property of the compound
to rotate plane polarized light is called optical activity.
For a compound to be optically active, it must be chiral
in nature(Asymmetric character).

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 Optical activity is not seen in symmetrical molecules
due to equal rotation in opposite directions getting
cancelled. The isomer that rotates the plane of
polarization to the left is called levo isomer (-) and to the
right is called dextro isomer (+).

 To be optically active , a molecule must not possessed

any one of following symmetry elements :
1) Centre of symmetry
2) Plane of symmetry
3) An Proper axis

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 The specific rotation [α] changes with
wavelength is called optical rotatory
dispersion (ORD) .
OR

 The rate of change of specific rotation with

wavelength is called Optical rotatory
dispersion (ORD) .

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 The rate of change of specific rotation with
wavelength is known as optical rotary dispersion .
 Drude has shown that the specific rotation may be
expressed as a function of wavelength by an equation,
[α] = k1 + k2 + k3 +-----
λ2 – λ12 λ2 – λ22 λ2 – λ23
 where
 λ- Wavelength of measurement
 k1,k2 ,k3 – constants that can be identified with the
wavelength of maximum absorption of optically active
absorption bands.

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Specific
Rotation
α

Wavelength λ

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 From graph,
 A-Represents the plain positive ORD curve :
The specific Rotation
increases with decreasing wavelength.
 B – Represents the plain negative ORD curve :

 Plain – implies that there exist no maximum or minima

in the curve.

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28 March 2019 M.M.C.P. 24
 The combination of circular birefringence and circular
dichroism in which the optically active bands are observed ,
such phenomenon called as cotton effect.
 Optically active bands are absorption bands of the
chromophores which are either intrinsically asymmetric or
which becomes asymmetric because of the interaction with
asymmetric environment.
 E.g.. 1) Hexahelicene molecule which itself act as
chromophore.
 2) Carbonyl group which is symmetric but becomes optically
active in an asymmetric environment.

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 They are of two types

 1) Plain curves

 2) Anamolous (cotton effect ) curves

a) Single cotton effect curves
b) Multiple cotton effect curves

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 The curves obtained do not contain any peak and
that curve do not cross the zero rotation line

 Such waves are obtained for compounds which

do not have absorption in the wavelength region
where optical activity is being examined

 E.g. .compounds exhibiting such plane curves are

alcohols and hydrocarbons

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 These curve on the other hand shows a
number of extreme peaks and troughs
depending on the number of absorbing groups
and therefore known as anomolous dispersion
of optical rotation.

 This type of curve is obtained for compounds

,which contain an asymmetric carbon atom
and also contains chromophore.
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 These are anomolous dispersion curves which
shows maximum and minimum, both of them
occurring in the region of maximum absorption.

 If an approaching the region of cotton effect from

the long wavelength ,one passes first through
maximum (peak) and then a minimum (trough)
,the cotton effect said to be positive . (Positive
Cotton effect is where the peak is at a higher
wavelength than the trough).

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 If the trough is reached first and the peak it is called a
negative cotton effect curves.

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 The vertical distance between ‘peak’ and ‘trough’ is
called amplitude ‘a’ and is convently expressed in
hundreds of degrees.
 Molecular amplitude, a =ǿ2 - ǿ1
100
 Where,
 ǿ2 – molar rotation of extreme peak or trough from
large wavelength.

 ǿ1 - molar rotation of extreme peak or trough from

shorter wavelength.

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 In this type of curves two or more peaks and
trough are obtained .

 E.g. functional group i.e. Ketosteriods ,

Camphor etc exhibits such curves .

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Some materials posses special properties of absorption of the left
circulary polarised light to different extent than the right circularly
polarised light.This phenomenon is called as circularly dichroism.

The electric field of a light beam causes a linear displacement of

charge when interacting with a molecule, whereas the magnetic field of it
causes a circulation of charge.

These two motions combined result in a helical displacement when

light impinges on a molecule (both field vectors in the same place are of
the same direction but at different moments of time).

The magnitude of circular dichroism is expressed by the ellipticiy.

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 An ordinary spectrophotometer can be adapted
to measure circular dichroism. It is only
necessary to provide some means of production
r and l circularly polarized radiation.

 Forthis purpose a plane polarized beam can be

passed through a quartz-wave plate. If the plate
is rotated from -45o to +45o , first r and l
circularly polarized light is produced
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APPLICATIONS OF CIRCULAR DICHROISM (CD) SPECTROSCOPY

PROTEIN CONFORMATION:-

The CD spectrum of a protein can provide a information about the relative amounts of
the major types of secondary structure within the protein in solution.

CD spectra of the α-helix β conformation and the random coil of poly-L-amino acids
are distinctly different form each other.

NUCLEIC ACID CONFORMATION:-

The CD spectrum of a single stranded nucleic acid may be calculated fairly accurately
form a knowledge of its nearest neighbor frequency. Thus any differences between the
calculated and measured CD spectrum must be due to variation in structure, such as
double-strandness.

The CD spectra are frequently used to study changes in the structure of nucleic acids
such as: the los of helicity of single stranded nucleic acids as a function of temperature
or pH structural changes on binding cation and proteins.
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 DIFFERENECES BETWEEN ORD AND CD
OPTICAL ROTATORY DISPERSION CIRCUALR DICHROISM
(ORD) (CD)
ORD is If the refractive indices of the Circular dichroism is the differential
sample for the left and right handed absorption of left and right handed
polarized light are different, when the circularly polarized light
components are recombined , the plane
polarized radiation will be rotated through
and angle α

ORD spectra are dispersive CD spectra are absorptive

In ORD the circular polarized light is used In CD the circular polarized lgiht is used
is not converted to elliptical light and is converted to elliptical light

ORD graphs are obtained by plotting CD graphs are obtained by ploting molar
specific rotation vs wavelength ellipticity vs wavelength.

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A. Chetwal GR & Anand SK, Instrumental method
of chemical analysis, 5TH edition page no:-
2.468-2.481.
B. Kalsi PS, Spectroscopy Of Organic Compounds,
New age international limited, sixth edition:611-
627.
C. Jag Mohan, Organic Spectroscopy Principles
And Applications, Narosa publishing hose:482-
496.
D. Sharma BK, Instrumental method of chemical analysis,
26TH edition:-M-286 to M-307.

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1. What is meant by ORD ? Discuss the principle and
application of ORD .(Nov 98).
2. What is optical rotatory dispersion & how is it useful
in characterization of substances.(Jul 98).
3. ORD & Circular Dicroism.(2000).

4. Cotton effect .(2004).

5. Note on the principle & application of ORD &

Circular Dicroism .(2004,Oct 08).
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6. Write an account on fundamental principles of
ORD.(2005).
7. Explain Circular Dicroism.(2006).
8. Describe the instrumentation used for measuring
circular dichroism.(Oct 09).
9. Explain the phenomena of optical rotation & circular
polarization. Giving a schematic diagram, write
about an ORD instrument. What are the applications
of ORD & CD.(May 10 & 12).
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