Polarimetry

In analytic chemistry, Polarimetry is the measurement of the angle of rotation of

the plane of polarized light (that is, a beam of light in which the vibrations of the
electromagnetic waves are confined to one plane) that results upon its passage
through certain transparent materials. Polarimetry is of interest to the chemist
because the ability of a substance to affect polarized light in this way is closely
related to its chemical structure.

The term Polarimetry may be referred as the study of the rotation of polarised light
by transparent optically active substance.

The optically· active substances are of two types:

(i) Dextro rotatory or right handed. The substance which rotates plane of
polarization of light towards right or in clockwise Direction are called dextro
rotatory or right handed.
(ii) Laevo rotatory or left handed. The substance which rotates plane of
polarization of light towards left or in anticlockwise directions are called laevo
rotatory or left handed. Ex: Lactic acid

A polarimeter is a scientific instrument used to measure the angle of rotation

caused by passing polarized light through an optically active substance

A polarimeter consists of a

 polarized Light source – Sodium vapor lamp,

  Polarizer – A polarizer or polariser is an optical filter that can convert a
beam of light of undefined or mixed polarization into a beam of well-defined
polarization, that is polarized light. The common types of polarizers are
linear polarizers and circular polarizers

Example : quartz prism material

 Analyzer – Nicol prism aligned to intercept the linearly polarized ray as it

emerges from the sample solution, a

 graduated circle- to measure the rotation angle, and sample tubes

Optical activity :- Optical activity is the ability of a chemical substance to rotate

the plane of vibration of polarized light to the right or left. The optical rotation is
the angle by which the plane of linear polarized light is rotated when passing
through the sample.

Magnitude of rotation depend upon the following factors:

1. Nature of Substance
2. Length of liquid column ( l ) through which light passes.
3. Concentration of the solution.
4. Nature of the solvent.
5. Temperature of the solution (t)
6. Wavelength of the light used

Specific rotation, [α], is a fundamental property of “chiral” substances that is

expressed as the angle to which the material causes polarized light to rotate at a
particular temperature, wavelength, and concentration.

The specific rotation ([α]) is an intensive property of a chemical compound,

defined as the change in orientation of the plane of linearly polarized light as this
light passes through a sample with a path length of 1 decimeter and a sample
concentration of 1 gram per 1 millilitre
Plane polarized light

A polarized light vibrating in a single plane perpendicular to the direction of

propagation is called plane polarised light.
Plane polarized light is 3 types :

1. Linearly polarized light

2. Circularly polarized light
3. Elliptically polarized light

1. Linearly polarized light

A plane electromagnetic wave is said to be linearly polarized. The transverse

electric field wave is accompanied by a magnetic field wave
2. Circularly polarized light

It consists of two perpendicular electromagnetic plane waves of equal

amplitude and 90° difference in phase. The light illustrated is right-
circularly polarized.

If light is composed of two plane waves of equal amplitude but differing in

phase by 90°, then the light is said to be circularly polarized. If you could
see the tip of the electric field vector, it would appear to be moving in a
circle as it approached you. If while looking at the source, the electric vector
of the light coming toward you appears to be rotating counterclockwise, the
light is said to be right-circularly polarized. If clockwise, then left-circularly
polarized light. The electric field vector makes one complete revolution as
the light advances one wavelength toward you. Another way of saying it is
that if the thumb of your right hand were pointing in the direction of
propagation of the light, the electric vector would be rotating in the direction
of your fingers.
 3. Elliptically polarized light

It consists of two perpendicular waves of unequal amplitude which differ in phase

by 90°. The illustration shows right- elliptically polarized light.
Depending on how the electric field is oriented, we classify polarized light into
three types of polarizations:
 Linear polarization: the electric field of light is confined to a single plane
along the direction of propagation.
 Circular polarization: the electric field of light consists of two linear
components that are perpendicular to each other, equal in amplitude, but
have a phase difference of π/2. The resulting electric field rotates in a circle
around the direction of propagation and, depending on the rotation direction,
is called left- or right-hand circularly polarized light.
 Elliptical polarization: the electric field of light describes an ellipse. This
results from the combination of two linear components with differing
amplitudes and/or a phase difference that is not π/2. This is the most general
description of polarized light, and circular and linear polarized light can be
viewed as special cases of elliptically polarized light.
Optical rotatory dispersion

Optical rotatory dispersion is the variation in the optical rotation of a substance

with a change in the wavelength of light. Optical rotatory dispersion can be used to
find the absolute configuration of metal complexes. For example, when plane-
polarized white light from an overhead projector is passed through a cylinder of
sucrose solution, a spiral rainbow is observed perpendicular to the cylinder.

When white light passes through a polarizer, the extent of rotation of light depends
on its wavelength. Short wavelengths are rotated more than longer wavelengths,
per unit of distance. Because the wavelength of light determines its color, the
variation of color with distance through the tube is observed.This dependence of
specific rotation on wavelength is called optical rotatory dispersion.

The combination of both (circular birefringence and circular dichroism) effects in

the region in which optically active absorption bands are observed gives rise to a
phenomenon called cotton effect.
They are of two types-

1. Plain Curves
2. Anamolous Curves
a. Single cotton effect curves
b. multiple cotton effect curves

Plain curves
• These are normal or plain curves.
• These curves occur at absorption maximum.
• These curves obtained for compounds which don’t have any absorption in
wavelength where optically active

Cotton effect curves

• These curves will show the high peaks & troughs which depends on the
absorbing groups.
• These curves will obtain for the compounds which are having asymmetric carbon
& chromophore which absorbs near UV region.
• These are again divided into 2 types, they are
1. Single cotton effect curves
2. Multiple cotton effect curves.

Single cotton effect curves

• These single cotton curves will show both maximum & minimum curves at
maximum absorption.
• From the longer wavelength towards the cotton effect region if crest passes first
through it then the trough it is called as +ve cotton effect.
• In the same manner if it happens in opposite way it is called as –ve cotton effect.

Multiple cotton effect curves

• These are a little different from the single cotton effect curves. Here more than
two crests & troughs are obtained. Ex: camphor etc.
Circular birefringence :The difference in indices of refraction for right circularly
polarized light (RCPL) & left circularly polarized light (LCPL) is know as circular
birefringence.

Circular dichroism:
Circular dichroism (CD) spectroscopy measures differences in the absorption of
left-handed polarized light versus right-handed polarized light which arise due to
structural asymmetry. The absence of regular structure results in zero CD intensity,
while an ordered structure results in a spectrum which can contain both positive
and negative signals.

linearly polarized light is transformed into elliptically polarized light upon

traveling through matter. Enantiomeric molecules exhibit besides different
refractive indices for left and right circular polarized light also different absorption
coefficients

Optical rotation: the rotation of linearly polarized light by the sample

Optical rotary dispersion: the variation of optical rotation as a function of

wavelength. The spectrum of optical rotation.

Circular Dichroism: the difference in absorption of left and right circularly light.

Correlation between ORD and CD:

 ORD is based on the different refractive indices of left and right

circular polarized light (nR ≠ nL )

 CD results from the different absorption behavior for left and right
circular polarized light (eR ≠ eL)
Advantages and Disadvantages of CD and ORD

1. Simple and quick experiments

2. No extensive preparation
3. Relatively low concentrations/amounts of sample
4. Microsecond time resolution
5. Any size of macromolecule
6. Better resolution
7. Better sensitivity
8. Easier to assign

Differences between ORD and CD

Research Applications for Polarimetery

Research applications for polarimetry are found in industry, research institutes and
universities as a means of:
 Isolating and identifying unknowns crystallized from various solvents or
separated by high performance liquid chromatography (HPLC).
  Evaluating and characterizing optically active compounds by measuring
their specific rotation and comparing this value with the theoretical values
found in literature.
 Investigating kinetic reactions by measuring optical rotation as a function of
time.
 Monitoring changes in concentration of an optically active component in a
reaction mixture, as in enzymatic cleavage.
 Analyzing molecular structure by plotting optical rotatory dispersion curves
over a wide range of wavelengths.
 Distinguishing between optical isomers.

Quality and Process Control Applications

1. Quality and process control applications, both in the laboratory or on-line in

the factory, are found throughout the pharmaceutical, essential oil, flavor,
food and chemical industries. A few examples are listed below.
2. Pharmaceutical Industry - Polarimeters can be used to determine product
purity by measuring specific rotation and optical rotation of compounds such
as amino acids, antibiotics, tranquilizers and antibiotics.
3. For pharmaceutical testing, most work is done using 589 nm light (sodium D
line). For electronic (automatic) polarimeters, total accuracies of 0.01° are
possible.
4. Flavor, Fragrance, and Essential Oil Industry - Polarimetry is an
important step for incoming raw materials (camphors, gums, natural acids
and natural oils) inspection.
5. Food Industry - Polarimeters ensure product quality by measuring the
concentration and purity of the following compounds in sugar-based foods,
cereals and syrups: carbohydrates, sucrose, glucose, fructose, various
starches, etc.)
6. Chemical Industry - Analyzing optical rotation as a means of identifying
and characterizing chemicals, including bio, natural and synthetic polymers
is an additional application for polarimeters.

References
1. https://www.edmundoptics.com/resources/application-
notes/optics/introduction-to-polarization/
2. Techniques and Experiments For Organic Chemistry By Addison Ault
3. Organic spectroscopy by William kemp 3 rd edition pages no 279-280.
4. Instrumental method of Chemical Analysis by Chatwal G.R. and Anand S.K.
5. Instrumental method of Analysis by Willard H.H.,Merritt L.L., Dean J.A.,
Settle F.A., 6 th edition.
6. Instrumental methods of Chemical Analysis by B.K. Sharma.

Md.Nazmul Islam (ABIR)

#151330 (2ND Batch)
Contact: 01766388247
Abir140044@gmail.com
Department of Pharmacy
Pabna University of Science and Technology