Polarimetry

• The tendency of the molecules to rotate the plane of plane polarized light (clockwise or
anticlockwise) and the extent of rotation is measured.

• It’s a type of qualitative and quantitative technique, used mostly for optically active
compounds.

• These properties are unique for a molecule, thus polarimetry can be used to identify and
estimate the compounds.

Unpolarized light

A light wave is an electromagnetic wave. Electromagnetic wave is a transverse wave that has both an
electric and a magnetic component that oscillate perpendicular to the direction of propagation.

A light wave that is vibrating in more than one plane is referred to as unpolarized light.

Polarized light: light waves in which the vibrations occur in a single plane.

Polarization

The process of transforming unpolarized light into polarized light.

The most common method of polarization involves the use of a Polaroid filter. Polaroid filters are
made of a special material that is capable of blocking one of the two planes of vibration of an
electromagnetic wave.

The filter can be thought of as having long-chain molecules that are aligned within the filter in the
same direction. The alignment of these molecules gives the filter a polarization axis. This polarization
axis extends across the length of the filter and only allows vibrations of the electromagnetic wave
that are parallel to the axis to pass through. Any vibrations that are perpendicular to the polarization
axis are blocked by the filter.

Plane-polarized light

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

Optically active substance

An optically active substance is one that rotates the plane of polarized light. In general, organic
molecule having a certain carbon atom to which are attached four different moieties, as C (WXYZ)
thereby, rendering the molecule asymmetric (chiral carbon), are all optically active. Such types of
molecules usually exist in two stereoisomeric forms as mirror images of each other. For example:
Lactic acid.

✔ The rotation of the plane of polarization is to the right, the lactic acid is dextrorotatory
designated by ‘d’ (Latin: Dexter = right) or “positive”

✔ the rotation is to the left, is levorotatory designated by ‘l’ (Latin : Laevus = left) or “negative”

When both d- and l- isomers are present in equal amounts, the mixture is called a racemic mixture. A
racemic mixture is optically inactive.
Instrumentation
An instrument used to measure the angle of rotation caused by passing polarized light through an
optically active substance.

The components of polarimeter are:

1. A light source: usually a sodium lamp

2. A polarizer: Unpolarised light gets converted into a plane-polarized light by simply passing it
through a lens called a Nicol Prism (after William Nicol, the inventor).

A Nicol Prism consists of two pieces of calcite (CaCO3) or Iceland spar glued together. It generates two
polarized rays (O-Ray and E-Ray) from unpolarized impinging light. The angle of the glued surfaces
causes one of the rays to be internally reflected and lost. The result is that only the plane-polarized
E-Ray is emitted from the opposite end.

3. A sample tube: contains optically active substances in a solution (usually 10cm long).

4. An analyzer: a rotatable Nicol prism. Two situations arise when the analyzing rotator prism is
put into action. Firstly, the prism being parallel to the plane of polarization of the incident
light, the net result is that the intensity of light reaching the detector is maximum. Secondly,
the prism being perpendicular to the plane of the polarized light, the net result is observed by
the intensity of light reaching the detector as minimum.

5. A graduated circle: to measure the rotation of plane polarized light.

[Link]
Principle:

At first, the unpolarized light from the source is polarized, and then passed through a sample cell. The
analyzer is rotated until maximum brightness of the light (i.e. 100% transmittance) is reached. This
reading is noted on the graduated scale.

If an optical active substance is in a sample tube, it will rotate the plane polarized light. The analyzer
is rotated until the original bright condition is restored. The rotation is observed by looking through
the analyzer. Difference between the two readings gives the amount in degrees by which the
polarized light has been rotated by the optically active solution.

Factors affecting magnitude of rotation

✔ Nature of the substance

✔ Concentration of the sample

✔ Nature of the solvent

✔ Temperature

✔ Length of the sample tube or cell

✔ Wavelength of the light passing through the sample

Specific rotation
The standard measurement of rotation for a specific chemical compound is called the specific
rotation, defined as an angle measured at a path length of 1 decimeter and a concentration of 1g/ml.
The specific rotation of a pure substance is an intrinsic property.

Where,

● [α] = specific rotation (The correct unit is deg mL g−1 dm−1, but are usually just given as deg)
● λ = wavelength of light (usually 589 nm, the D-line of a sodium lamp)
● T = temperature in degrees
● α = measured angle of rotation of a substance
● l = path length in decimetres
● c = concentration in g/ml

[α]D25 = +3.12°
Means D-line of a sodium lamp (λ=589 nm) is used for the light at a temperature of 25°C, and that a
sample containing 1 g/ml of the optically active substance, in a 1 dm tube, produces a rotation of
3.12° in a clockwise direction.

Applications

1. 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 etc.
2. Flavor Industry: Polarimetry is an important step for incoming raw materials (camphors,
gums, natural acids and natural oils) inspection.
3. Food Industry: Polarimeters ensure product quality by measuring the concentration and
purity of the following compounds in sugar-based foods, cereals and syrups.
4. Chemical Industry: Analyzing optical rotation as a means of identifying and characterizing
chemicals is an application for polarimeters.

Example 1: Suppose that the observed rotation of an optically active isomer is +13°. The sample had
a concentration of 1000g/liter and the length of the sample tube was 20 cm in length. What would be
the reported specific rotation of this dextrorotatory isomer?

Solution: Convert the concentration to g/ml, 1000g/liter = 1 g/ml

• Convert the length of the tube to decimeters, 20 cm = 2 dm

• Specific Rotation [α]λT = +13° / (1 × 2) = +6.50°

Example 2: Calculate the observed rotation of a solution of 0.5245g of (S)-1-amino-1-phenylethane

dissolved in a volume of 10 mL with methanol at 20°C, using the D line of a sodium lamp and a 1 dm
tube. Specific rotation of this material: [α]D23 = -30.0°.

Solution: Concentration of the sample = 0.5245 g/ 10 mL = 0.05245 g/mL

α = [α]λT lc = -30.0° × 1 × 0.05245 = -1.57°

Determination of optical rotation of pharmaceutical substances

Ibuprofen:

Materials: 2.5 % (w/v) solution of ibuprofen and a polarimeter.

Procedure: First and foremost it is absolutely necessary to check the linearity of the scale of a
polarimeter either using certified quartz plates or using known solution of sucrose.

The sample tube of the polarimeter is rinsed with the drug solution (2.5 % w/v) and filled up with the
same solution. The end glass-windows are closed properly. The angle of rotation of ibuprofen is now
measured using the D-line of polarized sodium light. Take at least five measurements and determine
the mean value.