Refractive Index
Measurement Principle
Refractive index measurement principle
Introduction
Detection of liquid concentrations by optical means was already known in antiquity. The law of
refraction was mathematically formulated first by Ibn Sahl in 984. His discovery was not known in
Europe, and usually the discovery is attributed to Dutch astronomer and mathematician Willebrord
Snellius (Snell), who rediscovered the law and published it in 1621. The first laboratory instrument
to accurately measure the refractive index of liquids was developed by Ernst Abbe in 1874.
Speed of light
Refractive index measurement is actually a measurement of the speed of light in a medium. The
speed of light (usually denoted by c) is 299 792 458 m/s in vacuum. In other media the speed of
light is lower than this value, and the refractive index, R.I., of a medium is a measure of how
much the speed of light is reduced in the medium. The refractive index (n) of a medium is
defined as the ratio of speed of light in vacuum (c) in to that in the medium (v):
(1)
As the speed of light is highest in vacuum, n is always greater than 1.
The speed of light in a medium depends on the medium itself, temperature and wavelength. Due to
the wavelength dependency, the refractive index is measured with monochromatic light. The
common practice is to use the sodium D-line wavelength 589 nm. The refractive index measured
at this wavelength is usually denoted by nD. The temperature is usually 20 C or 25 C.
Huygens principle
When studying the wave nature of light, Dutch physicist Christiaan Huygens developed the theory
of wavefronts.
When a wavefront of parallel light rays enters the interface between an optically denser material (
A) and an optically less dense material (B) at the angle () one side of the wavefront meets the
interface earlier than the other side. Figure 1 depicts this situation. Because the material A is
optically denser and the speed of light in it lower than in material B, the left side of the wavefront
travels a longer distance (SB) than the right side (SA). This difference in the distance forces the ray
to change its direction.
Figure 1. Bending of a light ray at an interface
The distances SA and SB are proportional to the velocities:
(2)
This ratio is the relative refractive index between the two media (n).
As the absolute refractive indexes (relative to vacuum) of the media are:
(3)
the relative refractive index can be written as the ratio between the absolute refractive indexes:
(4)
The significance of this result lies in the fact that practical refractive index measurement
instruments use some optical glass material instead of vacuum as the reference material instead.
The angle of refraction can be calculated by using the simple geometric relations (Fig. 1):
(5)
These equations can be divided by each other, and the Snells law is obtained by substituting the
relations given in eq. 4:
3
(6)
or:
(7)
Critical angle
If the medium A is optically denser than B, the angle is always greater than . Be reorganizing
the equation 7, the angle can be calculated:
(8)
When the angle is increased, reaches 90 at some point, and the bent rays travel along the
surface (see figure 2). If the angle is further increased, the light cannot enter material B. Instead,
it reflects back to A. This phenomenon is called total internal reflection.
Figure 2. Ray at the critical angle
The angle c at which sin = 1 is called the critical angle of refraction, and it can be calculated
as:
(9)
The refractometer measure the angle c. As nA is the well-known refractive index of the
measurement prism, the refractive index nB of the sample can be easily calculated by using eq. 9.
Measuring prism
The measuring prism provides the interface between the instrument and the medium which is
measured. The geometry of the optical system is such that light rays at a certain selection of
angles are projected onto the prism surface. The actual angles are chosen so that the desired
refractive index range can be measured, i.e., the critical angle is always within this selection.
The measuring prism acts as the refractive index reference. The refractive index of the prism has
to be higher than that of the medium under measurement, as otherwise there will be no total
internal reflection. In practice, the difference of refractive indexes has to be relatively high.
The prism material has to be chemically and mechanically as durable as possible. The material
has to be optically homogeneous and preferable isotropic (similar to all direction). These
requirements limit the choice of materials considerably, and different applications may require
different prism materials.
Optical image
Figure 3 depicts the analyzer part of the optical system in a typical refractometer. All light rays
coming from the prism and entering the optical system at the same angle are focused onto a
single point on the image detector (CCD). The distance d between this point and the axis of the
optical system depends only on the angle of the incoming light. This way the angular distribution of
the light can be converted to light position distribution on the CCD.
Figure 3. Analyzer optics of a refractometer
All modern refractometers convert the optical image into digital information. Figure 4 shows a
typical optical image. On the left side of the critical angle all light undergoes total internal reflection,
and the intensity of light is high. On the right side of the critical angle the intensity falls rapidly, as
most light enters the sample and is not reflected back.
Figure 4. Optical image of a critical angle refractometer
The digital image analysis algorithm determines the point on the CCD corresponding to the critical
angle. It may also determine some diagnostic values related to the image quality.
R.I. measurement
After the critical angle position d is determined, the angle has to be calculated. As the relation
between d and depends only on the geometry of the optics, this angle is straightforward to
calculate. The actual formula depends on the optical system itself. The equation 9 gives directly
the refractive index when the critical angle is known.
Precision of the measurement can be verified by measuring R.I. standard liquids. Accuracy of the
refractive index measurement carried out with this principle is typically 0.0001 in refractive index.
Concentration
In most solutions, the concentration of solute in a solvent can be determined by measuring the
refractive index nD. The relation between the refractive index and the concentration depends on the
solvent and solute, temperature, and wavelength.
In practice, the wavelength-dependency (dispersion) is avoided by using monochromatic light. The
temperature dependency is eliminated in laboratory measurements by thermostating the sample,
but in process measurements it has to be compensated by using a compensation formula.
The actual numbers vary between different solutions, but usually one percent of concentration
corresponds to approximately 0.002 in nD. One centigrade in temperature corresponds to 0.0001 in
nD in aqueous solutions. The temperature dependency is usually higher with other solvents. These
numbers show the need of temperature measurement and compensation, as a change of one
centigrade corresponds typically to a change of 0.05 % in concentration.
6
The temperature compensation is not a linear function. Both the temperature and the concentration
change the amount of temperature compensation required. Also, the relationship between
concentration and refractive index in nonlinear.
The concentration can be calculated from the refractive index and temperature when these
nonlinear functions are known. There are several possible temperature compensation algorithms.
In practical use, a simple 3rd degree polynomial in both temperature and concentration (total 16
coefficients) is sufficient.
