How Do You Know if You Have Clockwise or Counterclockwise Rotation in Polarimeter

updated Friday, April 01, 2016

Polarimeter

Most concrete properties of enantiomers i.e., melting point, humid point, refractive index, etc. are identical. However, they differ in a property called optical activity, in which a sample rotates the plane of polarization of a polarized calorie-free axle passing through. This effect was start discovered in 1808 by Due east.L. Malus (1775-1812), who passed light through reflective glass surfaces. 4 years subsequently, J.B. Biot (1774-1862) constitute that the extent of rotation of the light depends on the thickness of the quartz plates that he used. He also discovered that other compounds i.e., turpentine and sucrose solutions were capable of rotating the calorie-free. He attributed this "optical activity" to certain features in their molecular structure (asymmetry). Based on his research, he designed one of the first polariscopes, and formulated the bones quantitative laws of polarimetry. In 1850, Wilhelmy used polarimetry to report the reaction rate of the hydrolysis of sucrose. In 1874, van't Hoff proposed that a tetrahedral environment of the carbon atom could explain the phenomenon of optical activity. Today, polarimetry is used routinely in quality and process command in the pharmaceutical industry, the flavor, fragrance and essential oil industry, the food industry, and the chemic industry. The optical purity of the product can exist adamant by measuring the specific rotation of compounds similar amino acids, antibiotics, steroids, vitamins, lemon oil, various sugars, and polymers and comparing them with the reference value (if the specific rotation of the pure enantiomer is known).

Compound

[α] D (in o )

(1R)-(+)-Camphor

+44.26

Sucrose

+66.47

Cholesterol

-31.50

D-(+)-Glucose

+52.seventy

D-(-)-Fructose

-92.00

Morphine

-132.00

L-Proline (in water)

-84.00

How does it piece of work? Normal monochromatic light contains light that possesses oscillations of the electrical field in all possible planes perpendicular to the direction of propagation. When light is passed through a polarizer (i.east., Nicol prism, Polaroid film) but calorie-free aquiver in ane aeroplane will leave the polarizer ("picket contend model"). This linear polarized light can be described every bit a superposition of two counter-rotating components, which propagate with different velocities in an optical active medium. If one component interacts stronger than the other with a chiral molecule, information technology volition slow down and therefore get in afterwards at the observer. The result is that the aeroplane of the calorie-free appears to be rotated because the two vectors are not canceling each other anymore due to the phase shift.

In a polarimeter (figure 2), aeroplane-polarized light is introduced to a tube (typically 10 cm in length, figure 3) containing a solution with the substance to be measured. If the substance is optical inactive, the plane of the polarized calorie-free volition non change in orientation and the observer will read an angle of [α] = 0o. If the compound in the polarimetry cell was optical active, the aeroplane of the light would exist rotated on its mode through the tube. The observed rotation is a upshot of the different components of the plane polarized light interacting differently with the chiral center. In order to find the maximum brightness, the observer (person or instrument) will accept to rotate the axis of the analyzer back, either clockwise or counterclockwise direction depending on the nature of the chemical compound. For clockwise direction, the rotation (in degrees) is defined every bit positive ("+") and chosen dextrorotatory (from the Latin: dexter=right). In contrast, the counterclockwise direction is defined as negative ("-") and called levorotatory (from the Latin laevus=left). Unfortunately, in that location is no direct correlation between the configuration [(D/L) in Rosanoff, (R/S) in Cahn-Ingold-Prelog classification] of an enantiomer and the direction [(+) or (-)] in which they rotate plane-polarized light. This means that the R-enantiomer tin showroom a positive or negative value for the optical rotation depending on the compound. In some cases, the solvent has an impact on the magnitude and the sign too i.east.,(S)-lactic acrid exhibits an optical rotation of [α]= +3.9o in water and [α]= +13.seveno using 2 M sodium hydroxide solution equally solvent considering the observer looks at a dissimilar species (lactate).The observed specific rotation [α] obs depends on the length of the tube, the wavelength that it is used for the acquisition, the concentration of the optical active compound (enantiomer), and to a sure degree on the temperature as well. However, the temperature effect is very difficult to specify since it differs for each compound. For instance, the [α]-value for α-pinene simply slightly increases in the range from 0 oC to 100 oC (at λ=589.three nm), while it is almost cut in half for ß-pinene. These two compounds merely differ by the position of the alkene part.

Generally the following equation is used to calculate the specific optical rotation from experimental data:

α obs = observed optical rotation
c = the concentration of the solution in grams per milliliter
fifty = the length of the tube in decimeters (1 dm=10 cm)

Example ane:

A educatee obtained the following specific optical rotation from his measurement.

This notation means that the measurement was conducted at 25 oC using the D-line of the sodium lamp (λ=589.three nm). A sample containing 1.00 thou/mL of the compound in a one dm tube exhibits an optical rotation of 3.vo in clockwise direction. Notation that the instrument used in Chem 30BL and Chem 30CL tin can provide the specific optical rotation, which already corrects the optical rotation for the cell dimensions and the concentration. The optical rotation is raw data, which does not include these corrections. It is very important to pay attention which fashion was used to larn the data!

Equally mentioned earlier, polarimetry can exist used to determine optical purity of enantiomers.

Example 2:

The observed specific optical rotation of a compound is

[α]= +7.00o. The specific optical rotation for the pure enantiomer is .

Per centum optical purity

The sample consists of 75 % of the racemic grade (=equimolar mixture of both enantiomers, α=0o) and an excess of 25 % of the enantiomer in question (62.5 % and 37.5 %).

The instrument used below allows y'all to calculate the specific rotation, if you know the concentration of the solution. The jail cell used for the measurement has a pathlength of 10.0 cm.

Actual polarimeter used in the lab (Autopol Four) located in YH 6104

Polarimetry cell (5 cm stainless steel cell shown here)

Practical Aspects The cell has to be handled carefully since it costs more than $k to manufacture. It has to be cleaned thoroughly after the measurement was performed and is returned to the teaching assistant or instructor. Special attending should be given to the inlets that have been cleaved off several times already due to negligence on the student'due south office!

one. The musical instrument has to warm up for at least 10-15 minutes, if information technology is not already turned on. The switch is located in the dorsum of the instrument. The proper wavelength is called.

ii. A solution with a known concentration (~0.5-3 %) of the compound in the proper solvent is prepared.

three. The polarimetry cell is filled with the solvent. After filling the prison cell, the path through the prison cell should be clear (If the path is non clear, the air bubbling in the path accept to be removed prior to the measurement). The cell is placed on the rails inside the instrument, all the way on either the right or the left side.

4. The "Zero push button" is pressed to nothing the instrument. The screen should show 0.000 and non fluctuate as well much. If this is not the instance, make sure that the calorie-free can pass through. If this does not solve the trouble, inform the teaching assistant or teacher about this problem immediately.

5. And so, the solvent is removed and the prison cell is dried. The solution of the compound is filled into the dry polarimeter cell making certain that the unabridged inner part is filled without whatsoever air bubbling or particulate matter.

vi. The "I" push button on the keypad is pressed and specific rotation is selected.

vii. The proper prison cell dimension is selected: 100 mm (the prison cell provided is 100.0 mm=one dm long)

8. Side by side, the proper concentration in % is entered (=the actual concentration of your solution and not the 1 recommended since they will most likely differ slightly!)

9. The reading on the display (=specific optical rotation) is recorded including the sign. (The experimenter has to enquiry the literature data before performing the measurement in order to see if he is in the correct ballpark!).

10. The cell is taken out, cleaned thoroughly with the solvent used for the measurement and returned it to your educational activity banana or instructor. If the pupil is the last i to perform a measurement for the twenty-four hour period, the musical instrument has to be turned off also.

11. The sample from the optical rotation measurement tin be recovered after the measurement if needed past removing the solvent i.e., Jacobsen ligand.

12. It is entirely unacceptable that the student locks upwards the cells somewhere, where they are not available to others because all the students in the form use the polarimetry cells. Doing and so volition result is a significant penalty for the student at error.

jacobsonafor1997.blogspot.com

Source: https://www.chem.ucla.edu/~bacher/General/30BL/tips/Polarimetry.html

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