Refractometry

Refractometry. Introduction
It is an analytical technique that consists of measuring the refractive index of a
liquid in order to investigate its composition whether it is a solution or its
pureza si es un compuesto único. La medida continua en una columna cromatrográfica
Can you indicate the composition or purity of the eluent.
Refractometers have changed little since the original design by Abbé (1874) and Pulfrich.
(1887).

Theory
A ray of light that passes obliquely from one medium to another of different
density changes its direction when it crosses the surface. This change in the
the direction will be called refraction. When the second medium is denser than the first
First, the ray approaches the perpendicular drawn on the surface.
divider at the point of impact. The fundamental cause of this change in the
The direction is due to the change in the speed of light, which becomes slower the more
the medium through which the beam passes. The yellow light of the sodium lamp
decreases its speed from 3x1010cm/s in a vacuum up to 2.25x1010cm/s in water.
The angle formed between the ray in the first medium and the perpendicular is called the angle.
of incidence, i, while the corresponding angle in the second medium is
denotes the angle of refraction, r. The refractive index, n, is the ratio of the
light speeds in both media. Snell's law represents this index as the
ratio of the sines of the angles of incidence and refraction

i n=
air you

liquid
r

It is common practice to refer the index of refraction to vacuum, which is defined arbitrarily.
as refractive index unit. If it refers to air, the error made is 3 parts in
104It is a dimensionless constant, therefore, whose value for a light of a
a certain wavelength is determined by the characteristics of the medium
liquid or solid and air as a reference medium. If the indices are going to be compared
liquids or solutions should indicate the reference medium as well as other variables
that affect the speed of light in the sample to be measured. The symbol nD, for example,
20

It refers to the measurement at 20 °C of the index for the D lines of sodium. Most of the
Refractive indices collected in the literature refer to these conditions.
Ejemplos: Agua, 1,33; vidrio ‘crown’, 1,50; CS2, 1.63; glass 'flint', 1.75; diamond, 2.42;
rutile (TiO2)2), 2.60-2.90.

Refractometers
The most important devices are based on two principles: angle refractometers.
limit or critical and the image displacement refractometers.

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Limit angle refractometers
In these devices, the field of the eyepiece is observed to be divided into a dark area and another.
clara. The separation between the two corresponds to the limit ray. The limit ray can be
visualize in the following scheme. The light passes through a thin layer of
sample (0.1 mm) and enters the diffraction prism P2. The prism P1 is for diffusion of
way that shows a rough surface and acts as a source of an infinite number
of rays that enter the sample in all directions. The radiation that only
it touches the surface of prism P2 penetrating into it forming an angleIccalled angle
limit or critical and its value depends on the wavelength and refractive indices
from the sample and the prism. No ray can form an angle greater than the limit already
that the source of such rays does not penetrate the prism and all the other rays that
they penetrate the prism and refract according to smaller angles (to the right), than the angle
limit, and they will illuminate the right side of the eyepiece. The area on the left remains
obscure since rays are not refracted at angles greater than the limit.
The measurement of this angle allows for measuring the refractive index of the sample. In a
Abbé apparatus, what is measured isDwhat is the complementary ofIcand it is the angle with
the rays emerge from the prism P2. Most refractometers use this
principle and the most important are those of Abbé, Pulfrichy and those of immersion.

Abbe refractometer
A diagram appears showing two articulated prisms between which the
sample. Through the center of the prisms passes an axis that allows the prism to move.
refraction P2 and thus measure 'a' on a graduated scale that is projected in the eyepiece and that
graduated in units denDup to 0.001. The amplifier allows determining the
next figure, 0.0001. Indices are measured between 1.3 and 1.7.
The so-called compensators are made up of prisms (prisms of
Friends), and allow the use of white light as a source. These glass prisms allow
dispersar todas las longitudes de onda excepto el color amarillo en le vecindad de la
Sodium's D line, which is the only one that passes through the prism. That is to say, it acts like a.
monochromator, but the resolution is not perfect.

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 Refractometer of
immersion

Immersion refractometer
It is the simplest of all. It only requires 10-15 ml of sample. It goes in a simple prism.
mounted on a telescope that contains the compensator and the eyepiece. The scale is located
beneath the eyepiece inside the tube. The bottom surface of the prism is immersed in a
small cup that holds the sample, with a mirror underneath to reflect light towards
up through the liquid.

Abbé Refractometer
and immersion

Pulfrich Refractometer
It is mainly used for precise measurements in solutions or very volatile liquids.
reactives or hygroscopic, for solid plates, differential studies and for measuring
Dispersion. The absolute values obtained are not reliable in the fifth decimal place.
but a comparison at two wavelengths or with two substances can give a
precision of 1x10-5The solids or liquids with indices between 1.33 and 1.86 can be
determined over a wide range of temperatures. The refractive index n does not

3
it can be determined directly, but only after a series of observations. A
Once the device is stabilized, it is possible to obtain the index in about five minutes.

Image displacement refractometers

In these devices, the displacement of the refracted ray is measured in relation to the ray.
incident, instead of measuring the displacement of the dividing line between the area
clear and dark due to the limiting angle. A prism is constructed with the sample and the
The index is calculated based on the angular displacement of light as it passes through the sample. If
the sample is liquid and is placed in a prism-shaped container. The precision is
twice that obtained with the Abbe refractometer. There is no limit in the
determination of refractive indices and it can work on a greater number of
wavelengths, including areas of ultraviolet or near-infrared, if used
quartz prisms. Among these devices are differential refractometers.

Differential refractometers
They are primarily used for the analysis of liquid mixtures. They are applied to any
a mixture whose refractive index is a simple function of the composition; this includes
approximately to all binary systems. In the measure of the indices of
refraction is always a problem the temperature that must be controlled
carefully. These instruments use a single cell through which light
is transmitted.

A n

Refractometer-
the differential
B n+dn
T
x

The ray is diffracted at an angle whose value depends on the difference in the index of
refraction between the sample and a standard sample that constitutes a part of the
cell. The angle of refraction is measured with a photoelectric device.
The applicability to liquid analysis is through an empirical procedure.
Samples of known chemical composition are passed through the instrument.
thus obtaining a composition curve against refractometer readings. Some
instruments can provide value ranges up to'n= 10-5to any nominal value.
The minimum detectable index difference is 1% for a range of 10.-7units of
refractive index for the most precise instruments. Precision comes
conditioned by changes in temperature and deformations of the device.

Applications

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To monitor the purity of butadiene and styrene for rubber manufacturing. The
The indices of these ingredients are 1.5434 and 1.4120, respectively. A change of 0.1%
it is detectable by refractometry.
In the food industry for soy seed or cottonseed oil.
with indices of 1.47. The final product for producing margarine has 1.43.
Other applications relate to the variation of the concentration of solutions.
Thus, the concentration of sugar, brines, and acids is easy to monitor through
refractometry. For example, the refractive index of a sucrose solution
increases by 0.0002 units for an increase in concentration of 0.1%. It also
detect changes of 0.02% in the concentration of nitric acid by the same
procedure, and even greater sensitivity can be achieved in the measurements of the
concentrations of sulfuric acid.

Refractive index against the

concentration

There is a big difference between the refractive indices of aromatic compounds and the
saturated; the first have indices of around 1.50 and the second, 1.40.
Alcohol-water mixtures can also be measured. Water has an index of
1.33299, methanol, 1.32920, ethanol 1.36176 and isopropanol 1.37757; it can be
determine aqueous concentrations of these alcohols.
For the control of fractional distillation towers as in the separation of
cyclohexane of n-hexane, with indices 1.42623 and 1.37486 respectively. They can
detect changes in composition of up to 0.1%. Likewise, this method is used
in the fractional separation of butane and isobutane.
Critical angle refractometers are suitable for inline installation for
monitor the measures especially in those opaque fluids, with particles of
catalyst or polymers.
Critical angle refractometers must measure representative fluid since the index
The measured refraction is of the interface layer. The agitation or turbulence
they contribute to the homogeneity of the fluid and to the cleanliness of the glass at the interface;
but when the agitation is small or, in the case of the fluid being very viscous, it
they can produce reading errors.

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Inline critical angle refractometers
They measure the refractive index of liquids at the interface with air or, more commonly,
a glass prism.

a e
a) Líquido; b) interfase;
["c) prism;","d) lens;"]
b c e)fotodetector; f) fuente de luz.

f
g Critical Angle Refractometry

The light is sent to the interface at various angles close to the critical angle. The critical angle is
the angle formed by the perpendicular at which the beam changes from transmitted light
in the liquid to light totally reflected on the surface of the liquid. At greater angles
small that the critical light is transmitted in the liquid. The critical angle does not depend
not only from the composition of the solution but also from the material of the prism. The index of
refraction can be calculated like this:
ic= arcsin(ng/nl),
Wherecit is the critical angle in radians in glass; ng refractive index of glass,
nlthe refractive index of the liquid.
The main notable fact of this technique is that the refractive index is measured in the
surface of the solution. Since the reflective surface does not require penetration of the
Ray in the solution, this instrument can be used for quite opaque samples.
and suspensions in addition to transparent samples.

Refractometers in liquid chromatography

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In the chromatography of a colorless liquid, the different fractions are detected with
various methods such as ultraviolet or infrared spectrum, colorimetry, and refractometry.
It is desirable to continuously monitor the refractive index of the effluent of the
column. Refractometers respond to any changes that occur in the
liquid effluent as they constitute universal and highly sensitive detectors.

When to use a refractometer

To analyze a simple mixture like the
binary mixture alcohol/water, the best method
it is refractometry. The density measurements
are applicable if the composition range is
great. When this composition varies only in
0.4% and especially when it comes to a phase
liquid or a suspension, refractometry is
the technique of choice.

Analysis of ketchup, jams, juices

There is a wide application for food.
viscous liquids with some content in
solids. An example is the continuous analysis of
the solids soluble in the ketchup. A sample
it is pumped from the bottom of the tank,
taken to a refractometer placed inline and
returned later to the deposit. When the
product reaches the desired composition it
discharges and fills with a new load.

Carbonated drinks and other industrial processes

The sugar concentration is measured after being
carbonated and just before packaging. Other applications
they are measurements of the glycerin-water mixtures,
formaldehyde-methanol, processes in synthetic rubber,
foods like coffee or tea. An important application
it is in the hydrogenation of fats and oils whose
Continuous analysis is hindered by the quantities.
metal variables used as catalysts such as
like nickel or platinum.
Generally, the installation of inline refractometers
provides quick and accurate analysis in a multitude of
industrial processes.

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Interferometry
In interferometry, the difference between the refractive indices of the sample is measured.
and a pattern making use of the phenomenon of interferences.
The basic principles of an interferometer are explained according to the following scheme.
When a parallel monochromatic radiation reaches two slits S1 and S2,
produce the diffraction phenomenon in each of them. If there is no bucket with the
shows (C), a bright line is produced at O, because both reach that point.
you make it in phase, the S1-O path is equal to the S2-O. Bright lines also appear in Q1
and Q2 because the difference in paths corresponds to a wavelength, S2Q1-S1Q1
= OTherefore, constructive interferences appear at O, Q1, Q2 as well as in others.
points for which the optical paths differ by integer numbers of the length
of wave (1O, 2O, 3O... Between these points destructive interference takes place.
dark areas appear. Thus, the points P1 and P2 appear when the paths
optical differ by half the wavelength.

Interference phenomenon and interferometer

Now we place bucket C with a substance of slightly varying refractive index.

superior to the air. In this case, the speed of light in the bucket decreases which
produce an increase in the optical path of the S2O beam by an amount'defined as
'l=l(n-no)
Where: l = length of the cuvette, n is the refractive index of the substance in C, no=
refractive index of air.
Under these conditions, both waves will not reach phase until O but until O’ now.
is optimally equidistant from S1 and S2. If we call N the number of strips (each
fringe is formed by a bright line and a dark one), which appear between O and O’,
for a certainThewe can write
N ='l/The=l(n-no)/O
With monochromatic light, it is difficult to count the number of bands between both points.
because all the bands are the same. If white light is used, the central band is the only one
that is white, the others are bluish towards the inside and reddish towards the ends with it
it is easier to differentiate them. From the previous expression, n is calculated and above all
differences between refractive indices.

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Interferometer
The drawing shows a Zeiss interferometer. The source S is a small bulb.
of 4 V tungsten filament that provides white light. A lens L directs the light
towards two glass plates P1 and P2, and two cuvettes C1 and C2. The light reaches two openings
rectangles R1 and R2 and they reflect in the mirror M, reflecting upon themselves,
passing again over the buckets. Finally, the lens focuses the rays at point O,
where a series of interference fringes are formed.
The P plates are used to align these stripes through a rotation.
interference with the reference ones which gives a measure of the displacement
interferometric. Initially, P1 and P2 form a 45º angle with the beam. Normally, P2 is fixed and
P1 moves with a micrometer screw. If solvent is placed in the cuvette C1 and the
dissolution to measure in C2, the plate P1 must be turned until the stripes match
interference of the sample (upper) with the reference (lower). The reading of the
micrometer is directly proportional to the difference in the refractive indices of the
solvent and dissolution. This reading is converted into concentration through curves of
calibrated and is rarely used for the determination of the refractive index. It can be
achieve an accuracy in the refractive index of 1x10-7with a thermostat of 0.5 ºC
of precision.