Chapter 27

Refractometry
and Polarimetry

REFRACTOMETRY

When a ray of electromagnetic radiation strikes a flat surface at an angle,

the ray may be bent upward (rejlected) or bend downward (refracted) as
illustrated in Fig. 27.1. Notice that the ray does not go straight through the
material.
The amount of refraction is a characteristic of every substance. It is com-
monly expressed by the refractive index (RI) n, defined as

n = sin i/sin r (27.1)

Refractive index measurements have long been used for the qualitative
identification of unknown compounds by comparing the RI of the unknown

Fig. 27.1. Reflection and refraction.

reflected incident
roy roy

I
I
I
I
refrocted
roy

430
Y. Pomeranz et al., Food Analysis
© Chapman & Hall, Inc. 1994
 Refractometry 431

with literature values of various known substances. When density measure-

ments also are considered, a certain amount of information about the struc-
ture of a compound can be obtained. Each atom, bond, or group contributes
to the overall RI. When these individual contributions (atomic refractions)
are taken together, the result is the specijic refractivity. If the specific re-
fractivity is multiplied by the molecular weight of a compound, then the
molecular refractivity, R, is obtained. The Lorentz-Lorenz equation shows
this relation:

(n 2 - I) M
R=--- (27.2)
(n 2 + 2) d

where n is the RI, M the molecular weight, and d the density.

The relation is particularly useful in the identification of unknown ma-
terials. Suppose you have isolated a new compound and suspect that it may
be one of several possible structures. Using the atomic refractions listed in
Table 27.1, 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 (CH 30CH20CH3 ;
M = 76.10, d = 0.8560) as folIows. First, we calculate the molecular re-
fractivity from the atomic refractions:

3C: 3 x 2.42 = 7.26

8H: 8 x 1.10 = 8.80
2 ether 0: 2 x 1.64 = 3.28
R = 19.34
Then, we substitute into Eq. 27.2:

19.34 = (-
n2
- x--
- 1) 76.10
n2 + 2 0.8560
(n 2 - 1)/(n2 + 2) = 0.21754

n2 - 1 = 0.2175n2 + 0.4351
0.7825n 2 = 1.4351
n2 = 1.834

n = 1.354
The value reported in the literature is 1.3534.