Embed Doc
Copy Link
Readcast
Collections

CommentGo Back

Download

optics

) The calculated rotation of light passing through a solution as related to the solutionvolume and depth, the amount of solute, and the observed optical rotation at a given wavelengthand temperature.

(

Symbol

α)The arc of rotation, expressed in angular degrees, through which the plane of polarized lightmoves when it is in a light path onedecimeter in length passing through a solution containingone gramof a compound per one milliliter water. The

specific rotation

of achemical compound[α] is defined as the observed angle of optical rotationα when plane-polarized light is passed through a sample with a path length of 1decimeter and a sample concentration of 1gramper 1millilitre.The specific rotation of a pure material is an intrinsic property of that material at a given wavelength and temperature. Valuesshould always be accompanied by the temperature at which the measurement was performed andthe solvent in which the material was dissolved. Often the temperature is not specified; in thesecases it is assumed to be room temperature. The formal unit for specific rotation values is degcm² g

-1

but scientific literature uses justdegrees. A negative value meanslevorotatoryrotation and a positive value meansdextrorotatoryrotation. Some examples:

•

Sucrose+66.47°

•

Lactose+52.3°

•

cholesterol−31.5°

•

Camphor +44.26°

•

PenicillinV +223°

•

taxol−49°

•

(S)-bromobutane +23.1°

•

(R)-bromobutane −23.1°

•

(+)-cavicularin+168.2°Optical rotation is measured with an instrument called a polarimeter . There is a linear relationship between the observed rotation and the concentration of optically active compoundinthe sample. There is a non-linear relationship between the observed rotation and the wavelengthof light used. Specific rotation is calculated using either of two equations, depending on thesample you are measuring:For pure liquids:In this equation,

is the path length in decimeters, and

is the density of the liquid in g/mL, for asample at a temperature

(given in degrees Celsius) and wavelength

(in nanometers). If thewavelength of the light used is 589nanometer (the sodium D line), the symbol “D” is used. Thesign of the rotation (+ or -) is always given.°For solutions, a different equation is used:

In this equation,

is the path length in decimeters and

is the concentration in g/100mL, for asample at a temperature

(given in degrees Celsius) and wavelength

(in nanometers). If thewavelength of the light used is 589nanometer (the sodium D line), the symbol “D” is used. Thesign of the rotation (+ or -) is always given. When using this equation, the concentration and thesolvent are always provided in parentheses after the rotation. The rotation is reported usingdegrees, and no units of concentration are given (it is assumed to be g/100mL).For example:° (c 1.0, EtOH)This solution equation is incorrectly represented in many textbooks and on many websites as:(concentration in g/mL)Mathematically, the two forms seems to be similar, also chemically they are similar. From thechemical point of view, also a pure compound have some concentration (dependent on itsnature), and this concentration in g/ml is the same as density, so for the pure liqiud samples, their concentration (in g/ml) is the same as their density, which means, that both equations meanssame, but should be used in different situations. Using the incorrect form of the equation will produce problems because the concentration will have the incorrect units. Because the units areusually not reported, this can produce difficulties for those trying to use the data later. Butgenerally the specific optical rotation is given for pure compounds (thus problem of concentration is solved) and the length of pathway of light through the sample is the only unitthat should be reported; but almost all the polarimetric measuremnts are done in 1 dm cuvetteand due to lazy spectroscopic people, this get to be a kind of convence and all given opticalrotations are for 1 dm optical pathway (if not explictly staten otherwise).If a compound has a very large specific rotation or a sample is very concentrated, the actualrotation of the sample may be larger than 180°, and so a single polarimeter measurement cannotdetect when this has happened (for example, the values +270° and –90° are not distinguishable,nor are the values 361° and 1°). In these cases, measuring the rotation at several differentconcentrations allows one to determine the true value. Another method would be to use shorter pathlengths.In cases of very small or very large angles, one can also use the variation of specific rotation withwavelength to facilitate measurement. Switching wavelength is particularly useful when theangle is small. Many polarimeters are equipped with a mercury lamp (in addition to the sodiumlamp) for this purpose.The variation of specific rotation with wavelength is the basis of optical rotary dispersion (ORD)that can be used to elucidate the absolute configuration of certain compounds.