Polarimetry

Introduction
Most physical properties of enantiomers i.e., melting point, boiling point, refractive index, etc.
are identical. However, they differ in a property called optical activity, in which a sample rotates
the plane of polarization of a polarized light beam passing through. This effect was first
discovered in 1808 by E.L. Malus (1775-1812), who passed light through reflective glass
surfaces. Four years later, J.B. Biot (1774-1862) found that the extent of rotation of the light
depends on the thickness of the quartz plates that he used. He also discovered that other
compounds i.e., turpentine and sucrose solutions were capable of rotating the light. He attributed
this "optical activity" to certain features in their molecular structure (asymmetry). Based on his
research, he designed one of the first polariscopes, and formulated the basic quantitative laws of
polarimetry. In 1850, Wilhelmy used polarimetry to study the reaction rate of the hydrolysis of
sucrose. In 1874, van't Hoff proposed that a tetrahedral environment of the carbon atom could
explain the phenomenon of optical activity. Today, polarimetry is used routinely in quality and
process control in the pharmaceutical industry, the flavor, fragrance and essential oil industry, the
food industry, and the chemical industry. The optical purity of the product can be determined by
measuring the specific rotation of compounds like amino acids, antibiotics, steroids, vitamins,
lemon oil, various sugars, and polymers and comparing them with the reference value (if the
specific rotation of the pure enantiomer is known).
Compound [α]D (in o)
(1R)-(+)-Camphor +44.26
Sucrose +66.47
Cholesterol -31.50
D-(+)-Glucose +52.70
D-(-)-Fructose -92.00
Morphine -132.00
L-Proline (in
-84.00
water)

Experiment: Determine the angle of rotation and hence the specific rotation of an optically
active compound.
Theory
A polarimeter consists of two Nicols termed as polariser and analyser. These can be rotated about
a common axis and the substance, for which the rotation is to be determined, is placed in a tube
in between these two. The half shade plate is placed between the polariser and the solution tube.
This polarizer consists of a circular plate, one half of which is made of quartz plate cut parallel to
the optic axis. It is of such a thickness that it produces a retardation of half-a-wave- length of
sodium light between the ordinary and extraordinary rays. The other half of the plate is made-up
of the glass and of such a thickness that the transmitted light is of the same intensity as that
coming out from the quartz. Therefore, there will be two plane polarized light beams. One will
be passing out of the glass portion and other pass out of the quartz. If these two beams of the
polarized light of the same intensity are inclined on the principle section of the analyser then the
two halves of the field-of-view (as observed through the eyepiece) will appear equally bright.

However, in between the polarizer and analyzer, we fill the sugar solution tube which causes the
rotation of the plane of the polarization of incident lights. We estimate this property of the
optically active compound by measuring the specific rotation () which is a property of a chiral
chemical compound. It is defined as the change in orientation of monochromatic plane-polarized
light, per unit distanceconcentration product, as the light passes through a sample of a compound
in the solution. Compounds which rotate light clockwise are said to be dextrorotary, and
correspond with positive specific rotation. On contrary, the compounds which rotate light
counterclockwise are said to be levorotary, and correspond with negative values of specific
rotation. The specific rotation can be estimated as

where l is the tube length, and c is the concentration. c is defined as the dissolved mass (gm)
of the compound per unit volume (c.c).
A slight rotation in the plane of polarization in the clockwise or anticlockwise direction causes
one component greater than the other. Therefore, either the quartz portion appears brighter than
the glass or vice-versa. Thus, the analyzer can be set accurately so that the two halves of the field
become equally bright.

Apparatus: Polarimeter, Solution tube filled with the given solution of optically active
compound
Procedure
1. Switch on the power of the polarimeter instrument.
2. Illuminate the sodium lamp (yellow light) at maximum emission. The light will pass
through the solution tube.
3. Make an experiment with the distilled water. It will be filled in the tube.
 4. Rotate the polarimeter using the rotating nob. It also rotates the circular scale.
5. First keep the eyepiece focused on the maximum intense yellow strip, and after rotation
of the polarizer check the appearance of the intense black-strip at the same place. You
will not note the corressponding scales of these two positions. This is just to examine the
focus of the eyepience for the incoming polarized light.
6. Now again keep the eyepiece focused on the position where yellow or black strip was
seen with maximum contrast, and then slightly rotate the analyzer. Once the yellow or
black strip disappears, i.e., fades against the background and less intense and almost
uniform field-of-view appears, note the reading of circular scale as well as vernier scale.
7. The polarizer plate consists of equal brightness of two component of polarized light at
this point, so the field-of-view appears almost uniform. By slightly rotating it either in
clock-wise or anti-clockwise direction, the deviation from this condition will be
observed.
8. Fill the solution tube now with a given concentration of sugar (10 %; 5 %; 2.5 %) and
perform the above experiment again and note down the corresponding readings of the
circular scale.
9. The Vernier scale has markings from 0 to 10, however, it has 20 divisions. It resembles
with the 20 divisions of the circular scale (in degree). Therefore, the least count of the
Vernier scale is 0.05o. It should be noted that the circular scale ranges from 0o to 180o.
10. The circular scale reading is that how many its divisions already passed from the zeroth
of the Vernier scale. Note that reading in the table. While, for the reading of Vernier scale
we see the division of this scale which matches exactly with the division of circular scale.
We multiply that division of Vernier scale with its least-count and add in the reading of
the main circular scale.
11. θ1 is the difference between the reading of the first position on the circular scale for the
sugar solution to the same for the distilled water. Similarly, θ 2 is the difference between
the readings of the second position on the circular scale for the sugar solution to the same
for the distilled water.
12. Mean θ is estimated as (θ1+θ2)/2, which is the angle of the rotation of the plane of
polarization of the light, when it passes through the solution.
Observations
1. Room temperature = .... oC.
2. Length of the solution tube = ...... dm.
3. Mass of the sugar dissolved = ......gm.
4. Volume of the solution = ......in c.c.
5. Least count of the circular scale = .....o
6. Least count of the vernier scale = ..... o = .....
 Table of Observations
Results
1. The formula to calculate the specific rotation () is given by :

where  = Specific rotation; l = Length of the solution tube in dm; V = Volume of the
solution in c.c.; x = weight of the dissolved sugar in gm; ѳ= Rotation in degrees.
2. The specific rotation () of the cane sugar (for a given concentration per decimeter)
solution at .....oC is ........
3. Estimate the same parameter  for the different concentrations of cane sugar.
4. Error estimation as per the general instruction.
5. Draw a graph between rotation vs concentration of the soutions.

Precautions
1. There should be no air-bubble in the tube while filling it with solution or distilled water.
2. While taking one set of the observations, the polarizer should not be disturbed.
3. The cap of the tube should not be tightened beyond a limit as it may strain the glass.
Strained
1. glass may produce elliptically polarized light which might interfere with the setting.
4. Two positions at ±90o may appear where the equal illumination remains for a long range.
2. These readings should not be taken.
5. Switch off the lamp after completing the experiment.
Experiment: To study the kinetics of inversion of cane sugar, catalyzed by acid,
polarimetrically.

Theory:
A solution of sucrose is optically active, that is, it has the ability to rotate the plane of
polarization. It is dextro-rotatory, which means that it can rotate the plane of polarization of the
plane polarized light in a clockwise manner. Fructose is laevo-rotatory, which means that it can
rotate the plane of polarization of the plane polarized light in an anticlockwise manner. Glucose
is dextro-rotatory, and the mixture of products has the resultant laevo-rotatory. The angle of
rotation depends on : (a) temperature ; (b) wavelength of light used; (c) length of the liquid
column through which the light passes ; (d) nature of the substrate. In order to indicate the
rotatory power of the liquid or solution, we have to define a quantity known as SPECIFIC
ROTATION. The specific rotation of a substance (solute in solution) is given by :
[ α ] λ = 100 α / c l
where 'α' is the angle of rotation, 't' is the temperature, 'λ' is the wavelength of light used, 'l' is the
length of the liquid column (in decimeters), 'c' is the concentration of the solution (i.e., 'c' gram
of substance present in 100 ml of solution).

MATERIALS REQUIRED: Polarimeter with polarimeter tube ; sodium vapour lamp; hot
water bath; standard volumetric flasks (100ml, 50 ml); 100 ml measuring cylinders; 250 ml
stoppered reagent bottles; 250 ml stoppered conical flasks; Burette (50 ml); Pipette (10 ml, 20
ml); sucrose (20%); fructose (5%); 2N HCl solution.

PART – I
(Determination of Specific Rotation)

PROCEDURE
1. A stock solution of 5% fructose is prepared (5 g in 100 ml water).
2. The polarimeter is set up with the sodium vapour lamp.
3. The polarimeter tube is cleaned and filled with distilled water, taking care to exclude any
air bubbles.
4. The “analyzer” of the polarimeter is rotated using the rough and fine adjustments, until
the field of view is uniformly dark. This reading is taken. Readings in both the semi-
circles of the scale are taken, and the mean of the readings are taken, after applying the
correction. Let this reading be taken as ‘a’.
5. The distilled water is removed from the polarimeter tube. The tube is rinsed and filled
with 5 % fructose solution. Step (4) is repeated. Let this reading be taken as ‘b’.
6. Step (5) is repeated with 1 %, 2 %, 3 % , 4% solutions, and for the unknown solution. 7.
The angle of rotation (α) would correspond to (b – a). That is, α = (b – a).
OBSERVATIONS AND CALCULATIONS
1. Room Temperature = ……. oC
2. Wavelength of light = 5893 Ao ;
3. Length of Polarimeter Tube (l) = 2. 0 dm
4. Zero-reading with water, 'a' = ……...... deg ;
5. Instrumental error = .............. deg

Table: Determination of Specific Rotation of Fructose

(MS = Main Scale ; VS = Vernier Scale ; T = Total Reading)

Average Specific rotation, [ α ] = _________________

Plot a graph of concentration (c) versus angle of rotation (α ).
Slope = [α] l / 100 ⇒ [α] = (slope x 100) / l
From the rotation of the unknown solution, the concentration of the unknown solution can be
determined.

RESULTS
1. Specific Rotation of Fruit Sugar at …... oC = ……........ degree
2. Concentration of Unknown Solution = ………… %

PART – II
(Determination of Specific Rate Constant)
Experiment: To determine the specific rate constant for the hydrolysis of sucrose, in the
presence of acid, using polarimetry.
THEORY
Sucrose is dextro-rotatory. In the presence of acid (e.g. HCl), sucrose is hydrolysed to give an
equimolar mixture of glucose (d-) and fructose (l-) :
The course of the reaction (inversion of sucrose) is followed by observing the change in optical
rotation of sucrose, as a function of time. Since water is taken in large excess, the active mass of
water remains constant. Hence, the concentration of sucrose changes during the reaction.

Therefore, the reaction is a pseudo first order reaction.

dx/dt = k1[H2O][Sucrose] = k[Sucrose]

If ‘a’ is initial concentration of sucrose, ‘x’ the amount decomposed, then (a – x) is the fraction of
sucrose remaining after time t .Therefore,
dx/dt = k(a - x)
Rearranging and integrating eq. (4), we get
2.303 a
k= log
t (a - x)
If αo : initial angle of rotation; αt : angle of rotation at time t, α∞ : angle of rotation after
completion of the reaction, then
a  ( α o - α ∞)
x  ( αo - αt ) and
(a – x)  ( αt – α∞)

PROCEDURE
The Specific Rotation of 20% sucrose is determined by using part – I.
1. 50 ml of 20 % sucrose solution is taken in a 250 ml stoppered reagent bottle.
2. 50 ml of 2N HCl solution is added. The mixture is shaken well.
3. The polarimeter tube is rinsed quickly with this solution, and then filled. The reading is
taken which corresponds to αo.
4. Readings are taken at regular intervals of time (2, 5, 10, 15, 25, 35, 45, 60 minutes). Each
reading corresponds to αt.
5. The remaining solution is taken in a stoppered conical flask, heated to 60oC, for 5 min.
6. The solution is allowed to cool to room temperature for 5-10 min, and is taken into the
polarimeter tube and the reading is taken. This reading corresponds to α∞.
7. Steps (5), (6) and (7) are repeated till concurrent values of α∞ are obtained.
OBSERVATIONS AND CALCULATIONS
Room Temperature = ……. oC Concentration of HCl = ............
 Table: Determination of Specific Rate Constant (k) for the hydrolysis of Sucrose

Then, α = (b-a) = .......................................

where 'a' is the zero reading for water and 'b' is the reading for 20 % sucrose solution.
Mean Value of 'k' = .................................
Graphical Value of 'k' = .........................
Specific Rotation of Sucrose solution, [α] = ......................
Plot a graph of log {( αo - α∞)/( αt - α∞)}versus time (t).
From the graph, slope = k / 2.303
RESULTS
1. Specific Rotation of Sucrose at ……..... oC = ……........ degrees.
2. Rate Constant (k) for the hydrolysis of Sucrose, in the presence of 2 N HCl, at ……. oC,
Theoretical value of k = ……………… min-1 .
Graphical value of k = ……………… min-1 .
3. Comment on the nature of the graph(s) and the result.

VIVA VOCE
1. What is a light wave?
2. What is polarized light?
3. How is it possible to polarize the light?
4. What is a polaroid and Nicol prism?
5. What is the intensity of the light?
6. Formulate Malus’ law and substantiate it.
7. What is the construction and work principle of a half shade polarimeter?
8. What is specific rotation of a dilution?
 9. What does the specific rotation depend on?
10. Give the physical explanation to the rotation of the plane of polarization in an optically
active substance

Appendix - Density of Aqueous Sugar Water Solutions

Wt% density (g/mL) at 20oC

0.0 0.998234
1.0 1.002120
2.0 1.006015
3.0 1.009934
4.0 1.013881
5.0 1.017854
6.0 1.021855
7.0 1.025885
8.0 1.029942
9.0 1.034029
10.0 1.038143
11.0 1.042288
12.0 1.046462
13.0 1.050665
14.0 1.054900
15.0 1.059165
16.0 1.063460
17.0 1.067789
18.0 1.072147
19.0 1.076537
20.0 1.080959