Polarimetry: Theory & Principle Instrumentation Applications Disadvantages

Polarimetry
Theory & Principle

Instrumentation
Applications
Disadvantages
Definition
 Polarimetry
An instrumental method using rotation of

polarized light by some substances as a
measure of their concentration
Theory
Recall - Isomerism of Molecules

Theory
Stereoisomerism of Molecules
 Have the same structure and bond order but
their atom and group of atom are arranged
differentially.
 Different spatial arrangements and their

molecules are not superimposable
Theory
 Geometric isomerism
Involves a double bond, usually C=C, that does not
allow free rotation about the double bond (unlike a
C-C single bond). They are not superimposable.
e.g. cis-but-2-ene and trans-but-2-ene

Theory
 Optic isomerism
Involves an atom, usually carbon, bonded to four

different atoms or groups of atoms. They exist in
pairs, in which one isomer is the mirror image of
the other. These isomers are referred to as
enantiomers.
e.g. glyceraldehyde
Theory
Chiral Carbon
Two enantiomers of glyceraldehyde

Theory
Optical Isomerism / Rotation

 A property exhibited by any compound whose
mirror images are not superimposable
 Enantiomers interact with plane polarized light
to rotate the plane of the light in opposite
directions
 This interaction with polarized light is called
optical activity
 Measuring angle of rotation (α) - the
concentration of a substance in a solution can
be determined.
Principle
A plane polarized light is that which

essentially has its vibration in only one
direction or one plane as shown below (C)
A - the light waves propagating in all directions or planes (multidirectional)

B - the Nicol prism which cuts all the planes of light and allows the light to
come out with vibration in only one plane or direction (unidirectional)
C - the resultant light which is said to be a plane polarized light.
 Polarimetry measures the extent to which a substance interacts
with plane polarized light (light which consists of waves that
vibrate only in one plane); whether it rotates plane polarized light
to the left, to the right, or not at all.
 If the substance rotates plane polarized light to the left or to the

right, it is called optically active. To be optically active, a
compound must have a chiral center. A chiral center is a carbon
that has 4 different groups attached to it.
 The number of degrees and the direction of rotation are

measured to give the observed rotation. The observed rotation
must be corrected for the length of the cell used and the solution
concentration.
Instrumentation - Polarimeter
Polarized filter (Analyzer)
Monochromatic mounted on circular dial
light (Sodium rotated to give maximum
vapor lamp) Polarized filter amount of transmitted light
- polarizer
Sample tube
α
Unpolarized Plane-polarized
light light Rotated plane-
polarized light
α – degree of rotation measured
http://scholar.hw.ac.uk/site/chemistry/activity5.asp
 Unpolarized light from the light source is first
polarized and passes through a sample cell.
 An optically active substance in a sample
tube, rotates the plane polarized light.
 The rotation is noticed through the analyzer as
a change in intensity of illumination.
 To reach the same illumination as was
without an optically active sample, the
analyzer must be turned around for an angle.
 Readings are taken in degrees (angle) a or
sugar degrees °Z.
Rotation of polarized light plane by a sample with an

optical active substance and the influence of the length of
sample tube.
Conventional
polarimeter
Digital polarimeter
Half-shadow
polarimeter
The Relationship Between Molecular Structure
and Optical Activity
 When enantiomers in a solution is placed in
the polarimeter, the plane polarized light is
rotated by;
 One isomer always rotates light in a clockwise (+)
direction (D-dextrorotatory isomer)
 The other isomer rotates the light in a anticlockwise
(-) direction (L-levorotatory isomer)
at the same degree but opposite direction
Instrumentation – Polarimeter
 Magnitude of rotation depends upon:

 The nature of the compound
 The length of the tube (cell or sample container)
usually expressed in decimeters (dm)
 The wavelength of the light source employed;
usually either sodium D line at 589.3 nm or mercury
vapor lamp at 546.1 nm
 Temperature of sample
 Concentration of compound in grams per 100 ml
Applications – Sugar Analysis
Principle
 Sugars with optically active molecules are
capable of rotating plane polarized light.
 The rotation is directly proportional to the
number of the molecules in the light path.
 Specific rotation of a sugar, [α]DT, is 100 × the
angle of rotation of plane polarized light (α) of
wavelength D after passing through 1 dm of a
1g/100 mL solution of the sugar at temperature T.
 observed x 100
[]DT =
lxc
D = wavelength of the light source (Na)
T = temperature oC, normally 20°C
α obs = observed rotation in degree
(specify solvent)
l = length of tube in decimeter
c = concentration in grams/100ml
[α]DT = specific rotation (from references)
 Therefore, measurements (unknown) can be
either;
 Sugar concentration or
 Specific rotation of sugar
 Types of sugar
 D-glucose +52.7
 D-fructose - 92.4
 D-galactose +80.2
 L-arabinose +104.5
 D-mannose +14.2
Specific rotation of
 D-arabinose -105.0 various carbohydrates
 D-xylose +18.8 at 20°C (Equilibrium
 Lactose +55.4 after mutarotation)
 Sucrose +66.5
 Maltose+ +130.4
 Invert sugar -19.8
 Dextrin +195
Applications – Determination of Starch
Content
Principle
 1st, sample is treated with hot dilute HCl.
After clarification and filtration, the optical
rotation of the solution is measured.
 2nd, sample is extracted with 40 % ethanol.
After acidifying the filtrate with HCl, clarifying
and filtering, the optical rotation is measured.
 The difference between the two
measurements, multiplied by a known factor,
gives the starch content of the sample.
Starch concentration 2000 (P – P’)
(%) =
20°
[α]D
P = total optical in angle degrees

P’ = optical rotation in angle degrees of
the substances soluble in 40% ethanol
20°
[α]D = specific optical rotation of pure starch. The
numerical values conventionally accepted for
factor are the following;
Disadvantages
 Requires the samples only in solution form.

 The solution should be free of bubble or any
free particle, otherwise the light path will be
affected and hence the accuracy.
 The sample holder should be thermostatted,
since the optical activities of the substances
vary with temperature.

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Polarimetry

Theory & Principle

An instrumental method using rotation of

Recall - Isomerism of Molecules

 Different spatial arrangements and their

e.g. cis-but-2-ene and trans-but-2-ene

Involves an atom, usually carbon, bonded to four

Two enantiomers of glyceraldehyde

Optical Isomerism / Rotation

A plane polarized light is that which

A - the light waves propagating in all directions or planes (multidirectional)

 If the substance rotates plane polarized light to the left or to the

 The number of degrees and the direction of rotation are

Rotation of polarized light plane by a sample with an

 Magnitude of rotation depends upon:

P = total optical in angle degrees

 Requires the samples only in solution form.

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