10 REFRACTOMETRY

Theory

Refractive index
The speed of electromagnetic waves in vacuum c = 2,99792458⋅108 m s-1, is one of the most
important constants in physics. A human’s eye is able to detect electromagnetic waves in the
range from 360 nm (violet colour) to 750 nm (red colour). It is called a visible range of light.
When light waves travel through a medium (optical medium), its electric part interacts with
the electrons of that medium, causing them to vibrate. The electrons of the medium thus
become radiating light waves as the secondary sources. However, the speed of new waves
(v), changes accordingly to the optical properties of the particular medium. It is always
smaller than the speed of light in vacuum, v < c. All materials are characterized by their
ability to slow down the light waves, known as optical refractive index (n):
c
n (1)
v
The refractive index is a unitless parameter, equal to 1 for a vacuum and larger than 1 for
any other material (e.g. n =1.33 for water). The speed of light in air is only slightly less than
c, resulting into the refractive index of 1.0003. Typically, it is truncated to 1.

Figure 1 Refraction of light

The difference between a light speed in different media results into the change of direction
along which the light propagates, refraction (Figure 1). Refraction occurs when the light
passes from one medium to a medium with a different index of refraction, except the light
that approaches the boundary between the two media perpendicularly. Accordingly, to the
properties of an optical medium, some portion of light approaching the interface at an
incident angle (α) is reflected back to the first medium while the rest propagates into the
other medium at an angle of refraction (β). The angles of incident, reflection and refraction
are defined as angles between the particular ray and the interface normal (see Figure 1).
Note, that the reflection angle is always equal to the incident angle.
On the other hand, the refractive angle is determined by the Snell's law:
n1 sin   n2 sin  (2)
where n1 is the refractive index of medium 1 and n2 is the refractive index of medium 2. It
is possible to define an optical density for the media of different refractive indices. Medium
1 has a higher optical density than medium 2, if its refractive index is higher than that of
medium 2. According to the Snell's law, the light ray is "bending towards the normal" (β<α),
if it enters the medium with a higher optical density (Figure1). When it enters the medium
with a lower optical density, it is "bending away from the normal “:
(β > α).
Refractive index can be measured by the refractometer. We will use the double prism system
called the Abbe's refractometer, shown in Figure 2.

Figure 2 The schematic of the Abbe's refractometer

It consists of the two optical prisms (illuminating and refracting) with the thin layer of a
liquid sample between them. The measuring prism is made of a glass with a high refractive
index (n2 >1.75), which allows this refractometer to measure refractive indices up to
n1<1.75. The light enters the refractometer from the left side of the illuminating prism at
many different angles. The bottom part of this prism (AB') is rough, i.e. it consists of many
small areas oriented in different directions. As such, this surface can be imagined as a source
shining the light into all directions. Part of this light passes through the sample into the
refracting prism, where the biggest possible angle of incident, αmax, corresponds to the ray
that propagates from point A to point B (Figure 2). According to the Snell's law, the
refraction of this ray is then described by the maximum angle of refraction βmax. All other
rays enter the refracting prism at smaller angles and thus end up to the left of point C.
Consequently, detector located at the bottom of the refracting prism detects the illuminated
region to the left of point C and a dark region to the right of this point. Since the maximum
angle (αmax), and the refractive index of the refracting prism, n2, are known constants, it is
straightforward to determine the refractive index of a measured liquid (n1). The interface
between an illuminated and dark region (position of point C) changes as a function of angle
βmax, which is different for samples with different refractive indices n1. The simple readout
from the scale of refractometer then provides the refractive index directly, or it can be readily
determined using a conversion table.
The refraction index depends on the wavelength of light, because the speed of light waves
in materials depends on their wavelength. Light of different colours (different wavelengths)
is bending at different angles even if it comes at the same angle of incident (dispersion). As
a result, the white light, that comprises all the wavelengths, produces a rainbow after passing
through the optical prism (or droplets of moisture in the atmosphere). However, despite the
beauty of a rainbow, this is an unwanted effect in refractive index determination. It causes
the smearing of an interface between the illuminated and dark regions in the Abbe's
refractometer. To increase the precision of a measurement, it is therefore preferable to use a
monochromatic light (light of a single wavelength). The most commonly used source is a
sodium light of a wavelength equal to 589 nm. The refractive index depends also on the
density of the measured sample, which is affected by its temperature. Typically, refractive
index decreases with the decreasing density (increasing temperature). The measurement of
a refractive index is therefore reported together with the temperature and the wavelength of
light used. Symbol nD20 then represents the refractive index measured at t = 20 °C using the
sodium line D light (low pressure sodium lamp). The refractive index is an important
physical parameter, which is widely used in chemistry. It is commonly used to identify the
liquid, or its purity. Often, it is used to determine the concentration of solutions.

The determination of the refractive index of a methanol-ethanol solution

The task consists of the determination of the refractive index of methanol (CH3OH), ethanol
(CH3CH2OH) and their mixtures described by the volumetric percentage of methanol ( %
CH3OH). The measurement results into calibration curve (refractive index as a function of
 % CH3OH). This curve will be then used to determine the composition of an unknown
mixture of methanol and ethanol.

Equipment
Abbe's refractometer, pipette, thermometer, different mixtures of methanol and ethanol at
known compositions, mixture of methanol and ethanol at an unknown composition, filter
paper

Experimental procedure
1. Turn on the light source.
2. Open the double-prism of the refractometer, clean both glass surfaces with a filter
paper, and close the double-prism.
Use a pipette to fill the space between the two prisms with methanol. Turn the
refractometer scale knob to get a clear interface between the illuminated and dark
regions. Use the micrometric screw for the additional refinement of the scale, until
the clear interface appears.
Read refractive index of solution.
3. Open the double-prism and dry out glass surfaces using the filter paper. Repeat the
measurement for all methanol-ethanol mixtures of known and unknown compositions.
Write down all measured values to the Table 1.
4. Use MSExcel to create a calibration curve (i.e. dependence n = f( % CH3OH)). Fit
the experimental points with a straight line and write down its coefficients A and B
from equation:
n  B CH 3OH  A
 5. Determine the composition of an unknown solution using its refractive index and the
calibration curve.

Table 1 Measured and calculated values for prepared composition

Measurement methanol : ethanol (%) n
number
1 100 : 0
2 90 : 10
3 75 : 25
4 50 : 50
5 25 : 75
6 10 . 90
7 0 : 100
Unknown
composition

References
1. Kopecký, F.: Physics for Students of Pharmacy I. Bratislava, UK 1999. 184 s. (in
Slovak)
2. Edition of Department of Physical Chemistry: Laboratory Practice in Physics for
Students of Pharmacy. Faculty of Pharmacy, Comenius University, Bratislava, UK
1991.
3. Oremusová J., Vojteková M., Sarka K.: Fyzika – laboratórne cvičenia pre
farmaceutov UK Bratislava 2009 (in Slovak).

Manual written
RNDr. Alexander BÚCSI, PhD., doc. RNDr. Jana GALLOVÁ, CSc., Ing. Jarmila
OREMUSOVÁ, CSc., prof. RNDr. Daniela UHRÍKOVÁ, CSc.