Pharmaceutical Chemistry V (Analytical Chemistry), Pabitra Subedi

Unit VI : Polarimetry
Polarized light:
-Natural light cannot be employed directly for polarimetric measurement.
-In this ,electric vectors vibrate in all planes.
-Hence,
Its necessary to isolate light whose net electric vector vibrates in a single plane(Linearly
polarized light).
-The electric vectors vibrating in all planes can be resolved into two planes perpendicular to each
other.

-So, unpolarized light can be represented as

-Process of polarization is separating natural light into its mutually perpendicular components
and the separation can be accomplished with a polarimeter.

Optical Activity:

-Phenomenon of rotating the plane polarized light by certain substances is known as optical
activity.
-Genarally a chiral /assymmetric molecules rotate the plane of polarized light.
-Assymmetric compounds possess non-superimposable mirror images.

-Optical activities lie in

i) Crystal structure ii)Molecular structure
i) Crystal structure

-Quartz exhibits the phenomenon of optical activity.

-It exists in two crystalline enatiomeric forms.
-When crystals are fused, vaporised or dissolved in the solvent, the optical activity is lost.
-Other examples are, crystals of sodium chloride, benzil, zinc sulphate, hydrazine sulphate,
barium formate etc.

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ii)Molecular structure

-A necessary inflexible & sufficient condition :

The geometric structure of the molecule should not superimpose on its mirror image.
-A compound exists in enantiomeric form if it is devoid of the elements of symmetry i.e.

i) A plane of symmetry,
ii)A center of symmetry,
iii)An alternating axis of symmetry.
If any compound possesses elements of symmetry other than the mentioned is called a
dissymmetric molecule.

Specific Optical Rotation:

-It is the intensity of optical rotation(α).

-It is like a physical property of a compound like boiling point, melting point etc.
[α]25D= 100α./l.c
For a liquid substance the relation becomes,
[α]25D= α./l.d25
-The two enantiomers have the same physical & chemical properties but differ only in their
action on plane polarized light.
-One of the species rotates the plane polarized light to the right[Dextrorotatory(+)]& the other
to same extent but to the left[Laevorotatory(-)].
-Upon mixing the both in equimolecular quantities, the resulting product becomes optically
inactive due to the mutual compensation.
-Such optically inactive mixture or compound is known as racemic modification(±).
Derivation of specific optical rotation:
Optical rotation(α) is dependent upon the nature of the substance, length of the column of
solution through which the light passes, the temperature, concentration of the solution &
the wavelength of the light used.

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α is measured at 20◦C or at 25◦C & with necessarily using monochromatic light source.

The rotation(α) , is thus given by:

α = [α]tλ.l. m/v

Where,
‘l’ = the length of the column of the solution in decimeter(dm) through which the light passes,
‘m/v’ is weight in ‘g’ of the substance dissolved in a volume in ‘ml’.
‘[α]tλ’ is a constant and called specific optical rotation. It depends upon the nature of substance,
temperature and wavelength of light. It is generally expressed at 20◦C or at 25◦C using sodium D-
line(589.3nm), hence the relationship becomes,

[α]25D= α.v/l.m
The constant is expressed in degree of rotation per decimeter per gram, ml(deg dm-1,g-1ml) but
when l= 1dm, v=1ml, m=1g, then optical rotation becomes equal to Sp. optical rotation.
[α]25D= α ,

If ‘c’ is g of substance is dissolved in 100ml of water or solvent, the relation becomes,

[α]25D= 100α./l.c

For a liquid substance the relation becomes,

[α]25D= α./l.d25,where d25 is the specific gravity of the liquid sample at 25◦C.
Polarimeter:
An instrument which is a mean to generate or isolate plane polarized light & to detect,
measure the extent of rotation of the plane of polarized light is called polarimeter.
Where this effect is large enough for measurement, it may serve as the basis for identifying or
assaying a substance.
Instrumentation for a simple visual polarimeter:

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Brief description of the components:
-The light source is the sodium vapour lamp.
-The light is made parallel by lens L1, & polarized by the Nicol prism P1(Polarizer).
-The third prism, P2 (or a half wave plate) is to generate the half- shaded view, A & C.
(It enhances the sharpness in the measurement of optical rotation)
- Tube is to hold the sample solution(it is generally 1 & 2 dm length)
-First, a blank solution is kept in the sample tube, then prism P3 (analyzer) is rotated to obtain the
field view ‘B’
(equal illumination on both sides) and a vernier reading ( O0 suppose).
-Then , an optically active sample solution is kept in the tube, field view A or C appears and
prism P3 is rotated to obtain the field view ‘B’ again.
-Measurement is confirmed by the calibrated circular vernier scale.
Detail operational description:

-Usual light source is sodium vapour lamp.

-The light is made parallel by lens L1, & polarized by the Nicol prism P1( possesses different
refractive indices for the mutually perpendicular components (↕,↔) of unpolarised light.
- P3 is rotated for the measurement of the optical rotation.
-In the absence of sample and when the planes of P1 & P3 are parallel, a bright field view
appears.
-Principal planes of P1& P3 are mutually at right angles to each other.
-Result is: no light is transmitted through P3 .
-So, the dark field view is the consequence.
-P1& P3 are said to be crossed.
-Upon filling the sample tube with an optically active substance, the light again begins to
emerge from P3 .
-The extinction again restored by rotating P3 through an angle.
-The angle is measured ona calibrated circular vernier scale which will be equal in
magnitude & sign to the rotation of the sample.
-But , it is very difficult to determine the angular position for the field of minimum
illumination.
-A third prism, P2 (or a half wave plate) is therefore inserted to cover half the field.
-It causes two polarised rays to pass through the tube differing in phase by half a wavelength.
-When the analyser is crossed with the unobstructed part of the field, the part is darkened.(Field
view A)
-In the same time, some light is present in the obstructed half.
-The rotation of analyser in correct direction gives a field as in B.
-In the B, both the beams are almost completely extinguished.
-Both areas of the field seem of equal intensity.

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-Further rotation gives the field view C in which , the light from the obstructed half is eliminated,
but some rays from the unobstructed half pass through.
-The phase B is the balance point.
(Both areas illuminate with equal intensity)
Applications:
i)Used in the determination of the unknown solution concentration.
ii)Used in the identification of several compounds.
iii)Used in quantitative determination in sugar industry.
iv)Used in proteomics.
v)Used in the determination of the optical purity of substances.
vi)Used in the determination of chiral compounds.
Advantages:
i)Simple
ii)Random analysis
iii)Simple in sample preparation

Disadvantages:
i)Only optically active substances can be measured.
ii)Less accurate
iii)High interferences
Circularly polarised light:

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-The linearly polarised light is the resultant of two rays of circularly polarised light rotating in
opposite directions.
-Two circularly polarized components are like left- and right-handed springs.
-Frequency of rotation is related to the frequency of the light.
-The two oppositely rotating vectors, may be absorbed or refracted to different extent by a
matter.
-The extent of absorption & refraction is represented by constants absorptivity(є) & refractive
index(η).
-The characterisation of interaction of right & left circularly polarise light is possible with єL, єR,
ηL, ηR.

Refraction effect:
ηL = c/vL
ηR = c/vR
vL&vRare velocities of the corresponding rays.
-If nL>nR, then, vR>vL then , the right vector travels faster than the left.

-Vector addition continues to yield a linearly polarised light.

-But the velocity difference brings about the change in the direction of rays after passing
through the matter.
-The angle of rotation of the plane linearly polarised light is denoted as α.
-If the rotation is clockwise, then the substance is said to be dextrorotatory, & (+) sign is given.
-If the rotation is anticlockwise(nL<nR ), then the substance is said to be laevorotatory, & (-) sign
is given.
Circular birefringence:
-The phenomenon of the difference in velocity of left & rightcircularly polarised light is called
circular birefringence.
-If the medium is optically active, the left & right circularly polarised components are retarded
to different extents.

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-It is because ηL&ηR differ for left & right circularly polarised components.
Hence, circular birefringence (Δn)=ηL- ηR
Optical rotatory dispersion(ORD):

-The change in optical activity with respect to wavelength is called optical rotatory
dispersion(ORD)

-It is a plot of [α] or [Φ] against a range of polarized light wavelength λ.

Where, [Φ] is molecular rotation, ie [Φ] = α x Molecular Wt./ l . c

-ORD is a dispersive effect.

-Clockwise rotation is plotted positively; counterclockwise rotation is plotted negatively.

-A substance may be dextro. &laevorotatory at diff. WL.s

Cotton effect:
-A so-called plain curve in the ORD for a chiral compound lacks a chromophore.

-Chiral compounds containing a chromophore can give anomalous (Cotton effect) curves.

-Positive Cotton effect is where the peak is at a higher WL than the trough.
-Negative Cotton effect is the opposite

-Optically pure enantiomers always display opposite Cotton effect of ORD curves of identical
magnitude

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-Zero crossover point between the peak and the trough of ORD or cotton effect closely
corresponds to the normal UV λmax

Photoelectric spectropolarimeter:

-The light source is usually a xenon arc lamp which emits continuously between 190nm and
700nm.
-The light passes through a monochromator and the monochromatic beam then pssses through
the polariser, sample cell and analyser as in the visual polarimeter.
-In the beginning of analysis, the polariser is caused mechanically to oscillate through a small
angle( say 2º).
-The plane of polarisation of the beam passing through the sample is thus modulated through the
same angle.
-To position the analyser at its extinction angle it is rotated until the intensity of the light
reaching the photomultiplier ( and hence the photocurrent) is the same for both extreme
positions of the polariser.