It is normal practice to refer the index of refraction to that of a vacuum which is arbitrarily defined

as having a refractive index of unity; reference to air introduces less than 3 parts in 104 error. The
refractive index n, therefore, is a dimensionless constant whose value for light of given wave
length is determined by the character and state of the liquid or solid medium and of the reference
medium, air. If the refractive index of various liquids or liquid solutions is to be compared with
each other, then it is necessary to specify the state of the reference medium m well as to control
other variables which affect the velocity of light in the sample to be measured. The symbol n20D for
example, means the refractive index for the D lines of sodium measured at 20C. Most refractive
index values given in the handbooks have been measured under these conditions and are so
referenced.

Types of Refractometers

Two types of refractometers are commercially available, the differential and the critical-angle. In
the differential refractometer, a light beam is transmitted through a partitioned cell which refracts
the beam at an angle which depends on the difference in refractive index between the sample
liquid in one part and a standard liquid in the other. Differential refractometers can be accurate to
1 X 10-7 units of refractive index difference between the two liquids. In the critical-angle
refractometer the light incident on the surface of the solution changes sharply from reflected lo
trasnsmitted light at a critical angle. Several different versions of the differential and critical-angle
refractometers are commercially available for the laboratory and for continuous process
monitoring.

A. Critical-Angle Refractometers

Critical-angle refractometers measure the refractive index of liquids at an interface with air or,
more commonly, with a glass prism. As shown in Fig. 2, a light, beam is directed at the interface at
various angles in the vicinity of the critical angle. The critical angle is the angle from the
perpendicular at which the beam changes from light transmitted into the liquid to light totally
reflected at the liquid surface. At angles smaller than the critical angle the light is transmitted into
the liquid. The critical angle depends not only on the solution composition hut also on the prism
material. The refractive index can he calculated from:

i, = arc sin ng /ni

where

i, = critical angle in radians within the glass

ng =index of refraction of the glass

ni = index of refraction of the liquid

The significant feature of a critical angle refractometer is that, it measures the refractive index at
the surface of a solution. Since surface reflection requires no penetration of the light beam into
the solution, this instrument may he used for highly opaque samples and various murky solutions
and suspensions, as well as transparent samples
8. Differential Refractometers

Differential refractometers are intended primarily for the analysis of liquid mixtures. They are
applicable to any mixture whose refractive index is a single-valued function of the composition;
this includes nearly all simple binary systems. In refractive index measurements, the temperature
control has always been a major problem. The designs of new instruments indicate that this
problem is reconigzed and precautions are taken to minimize the temperature effect.

Each of the instruments employs a sample cell through which a light beam is transmitted. The
beam is refracted through an angle whose size depends on the refractive index difference
between the sample and a standard which constitutes a part of the cell. The angle of refraction is
measured with a photoelectric pickup.

The applicability of a refractometer to the analysis of liquids is usually determined empirically.

Samples of known chemical composition are passed through the instrument, and a calibration
curve of composition versus refractometer reading is plotted. Various rangess and nominal values
of refractive index can be accommodated by the various instruments, and some of them will
provide any range down to n = 10-5 at any nominal value.

The minimum detectable index difference for sustained periods of operation is '/100 of the range
or 10-7 units of refractive index for the best of the new instruments. In the most precise
instruments sensitivity is limited to this value mainly by mechanical deformation of the instrument
caused by changes in ambient and sample temperature.

The principle of the differential refractometer is very simple. First consider the passage of a beam
of light through a simple right-angled prism of refractive index n, and a second prism of identical
composition in close proximity to the first but with the refracting surfaces reversed (Fig. 3a); the
beam will pass through the combination without net refraction. If, however, the second prism is
made of material having a very slightly different refractive index from the first n + dn, then the
beam will be deflected through the angle (Fig. 3b). An even higher ultimate sensitivity is possible
with sulfuric acid solutions (Fig. 6).

The separation of aromatics from saturates is an outstanding example of the possibility of using
refractive index to follow a process, since the change in refractive index between aromatics and
saturates is quite marked. The aromatics have a refractive index of about 1.50, and the saturates
about 1.40. Since these measurements can be made to one in the fourth place, a precision of
about 0.1% is easily obtained. Alcohol-water analyses are also carried out by this method. Water
has a refractive index of 1.33299, while methanol is 1.32920, ethanol 1.36176, and isopropanol
1.37757 (Fig. 7). I t is possible to detect changes of s few tenths to a few hundredths of 1% in the
concentrations of these various alcohols in water.

Many applications of continuous refractometry are carried out in fractionating tower control. One
example of such an application is the separation of cyclohexane and n-hexane. The respective
refractive indices of these components are 1.42623 and 1.37486. This difference is sufficient to
give measurement of composition changes of less than 0.1%. Another typical fractionating column
application is the determination of normal butane in isobutane. These two components in the
liquid phase have a refractive index difference of approximately 0.0100. It is possible to detect
changes of the order of 0.1% in this case.
While refractometry has been applied to many process streams there was a limitation in the scope
of these applications until the development of the in-line critical-angle refractometers. Many
processes are amenable to monitoring and control by refractive index, but these streams may
often he opaque or contain a large concentration of solid materials such as catalyst fines, pipe
scale, undissolved solid product, polymers, etc. For example, in the manufacturing of high boiling
petroleum products a relation between refractive index and quality exists.

These streams are too dark to be analyzed by the differential refractometer hut they can he easily
handled with the critical angle reflectance type refractometer. The Anacon in-line refractometer
(schematic diagram, Fig. 8) has the prism mounted in the pipeline itself. The prism is in intimate
contact with the process fluid because its surface is flush with the wall of the pipeline. The entire
optical system other than the prism is mounted in an explosion proof housing, clamped to the
pipe.

The Pulfrich uses monochromatic light, requires more of the sample than the Abbe type, and is
therefore less commonly employed. These instruments have been used extensively in the
laboratory for many years. Accurate measurements can be made over a fairly wide range of
refractive indices. Same typical accuracies and ranges are shown in Table I.
The Abbe Refroctometer

The range of the Abbe is normally 1.3000 to 1.7000, the maximum precision attainable being
0.0001. It reads the refractive index directly, and requires only a drop of sample. White light is
used, and to prevent R colored, indistinct boundary between the light and dark fields two direct-
vision prisms, called Amici prisms, are placed one above the other between the objective and
eyepiece of the telescope. These are constructed of different varieties of glass and are so designed
as not la deviate a ray of light of the wavelength of the sodium D line. Rays of other wavelengths
are, however, deviated, and by rotating the Amici prisms it is possible to counteract the dispersion
of light at the liquid interface. A typical Abbe refractometer is shown in Figure 9.

Refractometers in Liquid Chromatography

The chromatography of colorless liquid compounds has long been burdened with tedious
methods of fraction collection and estimation. Various analytical techniques such as ultraviolet
and infrared absorption, colorimetry, and refractometry have been adapted in an effort to obtain
continuous flowing chromatographs which would greatly simplify fraction collection and analysis.
An instrument which would continually monitor the refractive index of the column effluent, has
always appeared to be the most desirable for this application (Fig. 12). Various instruments along
these lines have been described in the literature since Tiselius, Claesson and their collaborators
first described the use of an optical system registering changes in refractive index based on the
"Schlieren method.

Refractometry is appealing as a, continuous monitor for liquid cromatography, and one can say
that refractive index is to liquid chromatography as thermal conductivity is to gas chromatography.
Refractameters will respond to any change in the liquid effluent and therefore can be used as a
universal detector. The other analytical techniques mentioned above are specific rather than
universal and consequently are limited to particular classes of material. With such instruments it is
necessary to know what material is being eluted from the column and at what wavelength it
absorbs radiation or what reagent must be used to cause a color reaction. If the material does not
absorb radiation at the frequency for which the detector is set the peak will be missed entirely or
if the reagent is wrong a color change will not occur and again a peak will be missed. A
refractometer responds to any change in the liquid effluent and is therefore a universal, highly
sensitive detector.

When to Use a Refractometer

Whenever the sample to be analyzed is simple binary mixture, such as alcohol in water, the first
choice analyzer is a refractometer. Density-measuring analyses are applicable when the range of
compositions is broad. But when the range is narrow, down to about 0.4%, and certainly when an
analysis of the liquid phase of a suspcnsion or slurry is required, a refractometer again is first
choice.

Batch Analysis: Ketchup, Jams, Jellies

There are also a variety of applications for batch analysis wherein very viscous food products are
being cooked to a desired soluble solids content. A typical example is continuous measurement of
soluble solids in ketchup (Fig. 13).

It was felt that it would be impossible to analyze these products continuously, because of large
quantities of entrained metal catalysts, such as nicked, platinum, etc.

The maintenance problems involved in filtering and cleansing these sample streams for
measurement by a differential refractometor or other analytical instruments presented such
severe problems that analysis could seldom be made on a continuous basis. The in-line
refractometer has been applied to these hydrogenation problems as well as to measurement of
waxes in oils, measurement of catalytic cracking-unit feed stock, measurement of octane numbers
of gasoline, and detection of interfaces in pipelines. It provides an immediate, simple analysis
without a very elaborate, highly complicated, sampling system. In a number of eases the
elimination of a sampling system in itself mare than justifies installation of the refractometer.

The field of in-line measurements is becoming more and mare important with the advent of
completely controlled automatic processes. Figure 15 shows an automatic control system for
applesauce processing and Figure 16 a monitor for a paper mill recovery bailer. To obtain true
automatic control in many eases, analysis must be extremely fast and extremely reliable. The more
important factors in analysis instrumentation are reliability and simplicity. In order to simplify the
complicated analysis measurements it is virtually essential in many cases that the unit become an
in-line measuring device.

By measuring within the actual process, many of the problems of analysis are eliminated and the
unreliability of complicated sampling systems is removed. The in-line measurement provides a
very high degree of reliability and a very high speed of response. It is anticipated that in the next
few years we will see more and more analytical devices applied to direct in-line measurement,.

In summary, refractometers have been used for almost 100 years for the measurement of liquid
solutions. Continual improvements are being made, particularly in the continuous process type
refractometers. No significant changes have been made in laboratory refractometers in recent
years but the advent of solid state circuitry probably will cause some major changes in these
instruments in the very near future. Refractometers are reliable, simple analytical tools for the
laboratory, continuos monitoring, and liquid chromatography.