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Specific rotation is an intensive property, distinguishing it from the more general phenomenon of optical rotation. As such, the observed rotation ( α ) of a sample of a compound can be used to quantify the enantiomeric excess of that compound, provided that the specific rotation ( [α] ) for the enantiopure compound is known.
Optical rotation, also known as polarization rotation or circular birefringence, is the rotation of the orientation of the plane of polarization about the optical axis of linearly polarized light as it travels through certain materials. Circular birefringence and circular dichroism are the manifestations of optical activity.
Determination of specific rotation: In order to determine a specific rotation of an optically active substance (say, sugar), the polarimeter tube is first filled with pure water and the analyzer is adjusted for equal darkness (both the halves should be equally dark) point. The position of the analyzer is noted with the help of the scale.
The observed rotation of the sample is the weighted sum of the optical rotation of each anomer weighted by the amount of that anomer present. Therefore, one can use a polarimeter to measure the rotation of a sample and then calculate the ratio of the two anomers present from the enantiomeric excess, as long as one knows the rotation of each pure anomer.
The same phenomenon is observed after an angle of 180°. The specific rotation of the sample may then be calculated. Temperature can affect the rotation of light, which should be accounted for in the calculations. [] = / where: [α] λ T is the specific rotation. T is the temperature.
the specific rotation of (S)-2-ethyl-2-methyl succinic acid is found to be dependent on concentration; in what is known as the Horeau effect [3] the relationship between mole based ee and optical rotation based ee can be non-linear i.d. in the succinic acid example the optical activity at 50% ee is lower than expected.
In all materials the rotation varies with wavelength. The variation is caused by two quite different phenomena. The first accounts in most cases for the majority of the variation in rotation and should not strictly be termed rotatory dispersion. It depends on the fact that optical activity is actually circular birefringence.
Finding the Jones matrix, J(α, β, γ), for an arbitrary rotation involves a three-dimensional rotation matrix. In the following notation α , β and γ are the yaw, pitch, and roll angles (rotation about the z-, y-, and x-axes, with x being the direction of propagation), respectively.