Refractometry

REFRACTOMETRY
principle
measures the extent to which
light is bent (i.e. refracted)

when it moves from air into a
sample and is typically used to
determine the index of
refraction, (refractive index, (RI) or n)
of a liquid sample.
Figure (1)
The refractive index is a unitless
number, between 1.3000 and 1.7000

for most compounds, and is normally
determined to five digit precision.
RI, measurements have been used for
the qualitative identification of unknown

compounds by comparing the RI of the
unknown with literature values of
various known substances.
Since the density of a liquid usually
decreases with temperature, it is not

surprising that the speed of light in a liquid
will normally increase as the temperature
increases. (when density measurements are considered, a
certain amount of information about the structure of a compound can
be obtained)
Thus, the index of refraction normally

decreases as the temperature increases
for a liquid. For many organic liquids the
index of refraction decreases by

approximately 0.0005 for every 1 C increase
in temperature
Factor s affecting refracting index:
1-temperature of the sample .

2-wavelength of light used .
(increase
decrease
Variation of with called optical dispersion
Ref. index measurement is carried at the same
which is 589.3 nm by using sodium lamp.
Ex.:
The italicized n denotes refractive index, the

superscript indicates the temperature in degrees
Celsius, and the subscript denotes the wavelength of
light (in this case the D indicates the sodium D line at
589 nm).
Whenever light changes speed as it
crosses a boundary from one medium into

another it is refracted (Figure 1).
The relationship between light's speed in
the two mediums (vA and vB), the angles
of incidence (A) and refraction ( B) and
the refractive indexes of the two mediums
(nA and nB) is shown below:
Each atom, bond, or group contributes to the overall RI.

When these individual contributions (atomic refractions) are
taken together, the result is the specific refrativity.

If the specific refractivity is multiplied by the molecular weight
of a compound, then the molecular refractivity, MR, is

obtained.
The Lorentz-Lorenz equation shows this relation:
where M, is the molecular weight expressed in ml.mol,

n, it is the refraction index and p, the density.
The relation is particularly useful in the
identification of unknown materials.

Suppose you have isolated a new compound
and suspect that it may be one of several

possible structures.
Using the atomic refractions listed in the
table you can calculate the expected RI for

each possible structure and then see which
matches the experimental RI.
Example:
We calculate the RI of dimethoxymethane
(CH3OCH2OCH3, M= 76.1, d= 0.8560) as
follows.
3C: 3x 2.42 = 7.26

8H: 8 x 1.10 = 8.80
2 ether O: 2 x 1.64 = 3.28
MR= 19.34
Substitution eq.
19.34 = (n2 1/ n2 +2) x 76.1/ 0.8560
n = 1.354
The value reported in the literature is 1.3534.
Instruments,(refractometers)
The instruments for obtaining RIs will be
examined.
In order to standerdize measurements, the RI
is usually determined at 20oC with the sodium
D line (the yellow doublet at 589nm).
The symbol used to indicate these standard
conditions is n20D
Several refractometers use the crirtical ray
approach
Three rays of monochromatic radiation strike a medium of

different density. (increase incidence angle lead to increase refractive angle)
Two of these rays are refracted and would produce light on
the other side of the medium.
The third ray and all other rays having an angle of incidence
equal to or greater than 2 are not refracted.
Thus, no light get through the medium at this point and
dark field is produced.
This critical ray is utilized in refractometer
to measure the RI of various substances,

If the angle of incidence is made to equal 90
(called grazing angle) and the angle of
refraction achieves its maximum value

which is called critical angle of refraction
since the critical angle is different for each substance.
Each wavelength of incident radiation has a

critical angle, and if white light were used, no
sharp division would occur between the light and
dark field, and there would be a light field
followed by a rainbow of color and the dark field.
We can eliminate the rainbow of color by the
Amici prism (optical compensator)
Sharpen the boundary and yield critical ray with white
light that equivalent to the ray that would be obtained with
the sodium D line.The rays of other wavelengths are then
disposed of an Amici prism
The refractive index measured with the Abe refractometer
therefore is nD.
Notice that only the sodium D line through in the same direction
as the incident light.
This permits the use of white light since all the rays , other than
the one of interest, an out of the optical path.
Abbe Refractometer
Cross hair:
figure (3)
figure(4)
the cross hair should be half dark & half light if not
adjust it using the knob.
Why the refracting prism would show

a light region to the left and a
dark region to the right?
Figure(5)
Inspection the Figure(5) shows that light
traveling from point A to point B will have the

largest angle of incidence (qi) and hence the
largest possible angle of refraction (qr) for
that sample. All other rays of light entering
the refracting prism will have smaller qr and
hence lie to the left of point C
This refractometer cover the RI range from 1.3 to

1.7.
It can be used for direct reading and requires only
one or two drops of sample.
Place the sample between the two lower prisms
Rotate the connecting arm until the critical ray is
centered in the eyepiece.
If the division line between the light and dark
field is colored, turn the Amici prism(the
compensator) until a sharp division appears.
Dont use ether or acetone to clean off the
sample from the prism; these solvents evaporate
quickly and change the temperature of the
prism???????
What is dispersion?
dispersion would result in the light and dark
borderline being in different places for

different wavelengths of light (appears as
"fuzziness" of the borderline)
How to over come dispersion?

"compensating prisms" into the optical path
after the refracting prism. These

compensating prisms are designed so that
they can be adjusted to correct (i.e.,
compensate for) the dispersion of the sample
Advantage of Abee refractometer

1- Simple
Easy to manipulate
Small amount of sample is used

Wide range of measured ref. index
Can use with ordinary white light.
Applications:
Qualitative analysis: in which the refractive
index of each element is constant.

Quantitative analysis: we can get the
concentration of an element from the
refractive index.
HPLC: as a detector.
In the testing the purity of a solvent.
RI of mixtures
20 ml of amixture of xylene and carbon tetrachloride hade a density of 1.2156

and RI = 1.4338. pure xylene has a density of 0.8570 and RI = 1.4915. Pure carbon
tetrachloride has a density of 1.5816 and RI = 1.4562.
Calculate the wt.% of this mixture.
r = (n2 1 / n2 + 2) 1/d
For xylene:
r = (1.4915)2 - 1/ (1.4915)2 + 2 X 1 / 0.8570 = 0.3382
For carbon tetrachloride:
r = (1.4562)2 - 1 / (1.4562)2 + 2 X 1/1.5816 = 0.1719
For the mixture:
r= (1.4738)2 - 1 / (1.4738)2 + 2 X 1 / 1.2156 = 0.2311
Then calculate the wt. of the mix. Z, in gm Z = volume x density
Z = 20 x1.2156 = 24.31 g
Let X be the weight of carbon tetrachloride and Y the weight of xylene
X + Y = 24.31g
0.1719 X + 0.3382Y = 24.31 X 0.2311
Solving the two eq.
X = 15.66g
Y = 8.65g
= 64.4%
= 8.65%

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REFRACTOMETRY

light is bent (i.e. refracted)

The refractive index is a unitless

number, between 1.3000 and 1.7000

RI, measurements have been used for

the qualitative identification of unknown

Since the density of a liquid usually

decreases with temperature, it is not

Thus, the index of refraction normally

index of refraction decreases by

Factor s affecting refracting index:

1-temperature of the sample .

The italicized n denotes refractive index, the

Whenever light changes speed as it

crosses a boundary from one medium into

Each atom, bond, or group contributes to the overall RI.

taken together, the result is the specific refrativity.

of a compound, then the molecular refractivity, MR, is

where M, is the molecular weight expressed in ml.mol,

The relation is particularly useful in the

identification of unknown materials.

and suspect that it may be one of several

table you can calculate the expected RI for

3C: 3x 2.42 = 7.26

Three rays of monochromatic radiation strike a medium of

This critical ray is utilized in refractometer

to measure the RI of various substances,

refraction achieves its maximum value

since the critical angle is different for each substance.

Each wavelength of incident radiation has a

Why the refracting prism would show

Inspection the Figure(5) shows that light

traveling from point A to point B will have the

This refractometer cover the RI range from 1.3 to

borderline being in different places for

How to over come dispersion?

after the refracting prism. These

Advantage of Abee refractometer

Small amount of sample is used

index of each element is constant.

20 ml of amixture of xylene and carbon tetrachloride hade a density of 1.2156

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