POLARIMETRY
DR. JOOHEE PRADHAN
MLSU
UDAIPUR
OUTLINE
Introduction
Optical activity
Specific Rotation
Polarimeter
Applications
INTRODUCTION
Polarimetry is a type of qualitative and quantitative
technique, used for optically active compounds
• the tendency of the molecules to rotate the plane
of plane polarized light (clockwise or
anticlockwise) and the extent of rotation is
measured
• these properties are unique for a molecule, thus
polarimetry can be used to identify and estimate
the compounds
DEFINITION
Polarimetry is one of the important instrumental methods
employed in analysis. This measures the rotation of the
polarized light as it passes through an optically active
compound. This technique involves the measurement of
change in the direction of vibration of polarized light when
interact with an optically active compound. A substance is
said to be optically active if it rotates the plane of the
polarized light.
PLANE POLARIZED LIGHT
According to wave theory of light, an ordinary ray
light is considered to be vibrating in all planes at
right angle to the direction of propagation. If this
ordinary ray of light is passed through a Nicol prism,
the emergent ray has its vibration only in one plane.
This light having wave motion in only one plane is
known as Plane Polarised Light.
NICOL Prism –
Iceland Spar
Calcite ( CaCO3 form )
(or) Polaroid
PLANE POLARIZED LIGHT
A plane polarized light consists of two components of
fixed magnitude rotating in opposite directions to
one another: The right circulatory polarized light and
The left circulatory polarized light
Plane polarized light is the vector sum of these two
components
OPTICAL ACTIVITY
It is the property of a chemical substance to rotate
the plane of polarization of plane-polarized light.
Example: Lactic acid
Dextro= right designated by ‘d’, (+), clockwise
Levo= left designated by ‘l’, (-), counterclockwise
OPTICAL ACTIVITY
Displayed by solutions of some compounds, notably
many sugars.
The 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
The Rotatory Power of a given solution is generally
expressed as specific rotation.
It is the number of degrees of rotation of plane polarized
light produced by one gram of the substance per ml. The
measurements is carried out at temp (T) using sodium
light (D line). The Specific rotation can be Calculated by
the following relation:
[α] = specific rotation, T = temperature, λ = wavelength, θ=
optical rotation, c = concentration in g/100ml, l = optical
path length in dm.
SPECIFIC ROTATION
• [α] depends on the temperature and the wavelength of the
light used
• These quantities are also incorporated while reporting [α]
[α]D25 = +3.12o
• means D line of a sodium lamp (λ=589.6nm) is used for the
light at a temperature of 25oC, and that a sample containing
1.00g/ml of the optically active substance, in a 1-dm tube,
produces a rotation of 3.12o in a clockwise direction
Types of molecules analyzed by Polarimetry
Molecule must be Optically active: Optically Active
molecule contain asymmetric carbon atom, i.e.
ENANTIOMERS
Specific rotation of Enantiomers of 2-butanol
INSTRUMENTATION:POLARIMETER
The Polarimeter is a device used to measure the effect of
plane-polarized light on optically active compounds
The components of polarimeter are:
• A light source : usually a sodium lamp
• A polarizer: Nicol Prism
• A tube for holding sample in the light beam: sample cell
• An analyzer: Nicol prism aligned to intercept the linearly
polarized ray as it emerges from the sample solution , and
• A scale: to measure the rotation of plane polarized light
POLARIMETER: Outline
POLARIMETER: Detailed
POLARIMETER: Working
• if no or optically inactive sample is present in the
tube and the instrument is reading zero (0o), the
axes of plane polarized light and the analyzer is
exactly parallel
• the observer will detect maximum amount
(100 % transmittance) of light passing through.
• if the sample is optically active the plane of PPL
will be rotated as it pass through the tube
POLARIMETER: Working
• in order to detect the maximum brightness of the
light (ie. 100% transmittance) observer will have to
rotate the axis of the analyzer in either clockwise or
counterclockwise direction
• if the analyzer is rotated in a clockwise
direction, the rotation (α in degree) is said to be
positive (+), and such substance are c/a
dextrorotatory
• if the rotation is counterclockwise, the α is –ve,
and such substances are c/a levorotatory
POLARIMETER: Working
APPLICATIONS
polarimetric method is a simple and accurate
means for determination of structure in micro
analysis of expensive and non-duplicable samples.
• it is employed in quality control, process control
and research in the pharmaceutical, chemical,
essential oil, flavor and food industries.
• it is so well established that the United States
Pharmacopoeia and the Food & Drug
Administration include polarimetric
specifications for numerous substances.
RESEARCH APPLICATIONS
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 HPLC.
• evaluating and characterizing optically active
compounds by measuring their specific rotation
and comparing this value with the theoretical
values found in literature.
RESEARCH APPLICATIONS
• 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 (ORD) curves over a wide
range of wavelengths.
• distinguishing between optical isomers.
PHARMACEUTICAL APPLICATIONS
To determine product purity by measuring
specific rotation and optical rotation of: Amino
acids, Amino sugars, Analgesics, Antibiotics
Cocaine, Dextrose, Diuretics, Serums, Steroids,
Tranquilizers, Vitamins etc.
For raw materials inspection of: Camphors,
Citric acid, Glyceric acid Gums Lavender oil,
Lemon oil Orange oil Spearmint oil
SUMMARY
Definition
Plane Polarized Light
Optical Rotation
Specific Rotation
Polarimeter
Applications
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