Experiment 7: Stereochemistry and Polarimetry

Hayley Williams, willi553@go.stockton.edu

CHEM 2125 007
April 24, 2018

Abstract

The objectives of this experiment were to study the optical rotation of enantiomers using polarimetry and
to understand how concentration, cell length, observed rotation (αobs), and specific rotation [α] are related.
Measurements of specific rotation and enantiomeric excess were calculated and chirality centers were
identified. Another objective was to learn and identify the relationship between stereoisomers. The
enantiomers used in this experiment were: (R)-(-)-Carvone, (S)-(+)-Carvone, (S)-(-)-Limonene, (R)-(+)-
Limonene, unknown substance A, and sucrose solution B. The unknown was identified ((S)-(-)-
Limonene) by comparing the observed rotations. Once all rotation values were calculated, % error was
found for R-(-)-carvone (4.26%) and R-(+)-limonene (28.27%) in part A, % ee was found for (S)-(+)-
Carvone (69.5%) and (S)-(-)-Limonene (56.4%) in part B, % difference for [α] of unknown A/(S)-(-)-
Limonene and known [α] (4.26%) was found in part C, and the concentration of the sucrose solution
(0.221 g/cm3) was calculated.
Purpose/Theory
The purpose of this experiment was to find the optical rotation of enantiomers using polarimetry,
while learning how concentration, cell length, observed rotation (αobs), and specific rotation [α] are all
related. Other values/aspects that were found consist of measurements of specific rotation, enantiomeric
excess (% ee), and chirality centers. Chirality centers follow three main rules, an atom (mainly carbon) is
bonded to 4 different groups of atoms, the atom is not identical to its mirror image, the atom is not
superimposable on its mirror image (mirror images cannot be placed on top each other and result in the
same molecule). Optical activity occurs when plane polarized light passes through a solution containing a
single chiral compound, and the chiral compound causes the plane of vibration to rotate. Optically active
compounds can easily be identified because chirality is what makes a compound optically active.
Enantiomers rotate the planes the same amount, only in different directions. Polarimetry is a laboratory
technique, using a polarimeter, that measures the interaction between a compound and plane polarized
light. Since enantiomers interact with plane polarized light differently, polarimetry can be used to
distinguish between enantiomers, which is how the unknown enantiomer was determined in this
experiment.
The angular rotation observed (αobs) in a polarimeter depends on the optical activity of the
compound, the concentration of the sample, and the path length of the sample cell. Once the αobs is
determined by the polarimeter, it is used to find the specific rotation [α]. Specific rotation is the angle of
rotation (in degrees) of the plane of polarization of a ray of monochromatic light that passes through a
tube 1 dm long containing the substance in a solution at a concentration of 1 g/mL. It can be used as a
characteristic physical property of a compound. Enantiomeric excess (% ee) is the ratio of the [α] of a
mixture to the [α] of a pure enantiomer, showing the optical purity of the mixture. Enantiomers are two
molecules that are mirror images but are not identical and are non-superimposable (chiral). Enantiomers
have the same melting point, density, solubility, and refractive index, but they have a different degree of
rotation of plane-polarized light. Each enantiomer rotates plane-polarized light in opposite directions.

Results and Discussion

A: Specific Rotation of R Carvone and R Limonene Sample Calculations:

Name of Sample R-(-)-carvone R-(+)-limonene
Length of Sample 5.28 cm/0.528 dm 4.90 cm/ 0.490 dm
Density of Sample 0.96 g/mL 0.841 g/mL
obs -29.6 +34.3
[] -58.40 +88.23
Known  value -61 +123
% error 4.26% 28.27%

B: Determine ee in Impure Samples

Name of Sample S-(+)-carvone S-(-)-limonene
Length of Sample 7.10 cm/ 0.710 dm 6.65 cm/ 0.665 dm
Density of Sample 0.96 g/mL 0.841 g/mL
obs +37.55 -53.0
[] +55.10 -94.77
Known  value +54 -94
% ee 69.5% 56.4%
 C: Identify Unknown
Unknown Sample A
Concentration 0.841 g/mL
Length 3.19 cm/0.319 dm
obs -22.7
[] -87.42
ID of Unknown S-(-)-Limonene
% Difference from Known 4.26%

D: Concentration of Sucrose Solution

Unknown Sample B
Length 6.64 cm/0.664 dm
obs +9.7
Known  +66.5
Determined Concentration 0.221 g/cm3

The goal of this experiment was accomplished. All obs values were measured using the polarimeter,
α
and then all specific rotation values were calculated using the equation, [α] = 𝑜𝑏𝑠 , where l is length of
𝑙∗𝑐
substance (dm) in the tube, and c is the concentration or density of the substance. Unknown A was
determined to be S-(-)-Limonene. The obs for Unknown A did not come close to any of the previously measured
obs, so it was unidentifiable from that factor. Fortunately, carvone and limonene each have very distinct aromas,
and the unknown smelled similar to the limonene. Based on whether the obs was positive or negative, it could be
distinguished as being either R-(+)-limonene or (S)-(-)-Limonene. The % error was found for R-(-)-carvone
(4.26%) and R-(+)-limonene (28.27%) in part A. The % ee was found for (S)-(+)-Carvone (69.5%) and
(S)-(-)-Limonene (56.4%) in part B. The % difference for [α] of unknown A/(S)-(-)-Limonene and known
[α] (4.26%) was found in part C. Lastly, the concentration of the sucrose solution (0.221 g/cm3) was
calculated in part D. (sample calculations shown above in the designated section) Enantiomeric excess (%
ee) was used to assess the purity of the S-(+)-carvone mixture (69.5%) and the S-(-)-limonene mixture (56.4%).
The higher the % ee, the more pure the mixture is. The % ee for both mixtures showed that they are moderately
pure. The concentration of sucrose solution B was determined by solving for c in the previously mentioned equation
for [], using the obs (+9.7), the length (0.664 dm), and the known [] for sucrose (+66.5).

Conclusions
All obs values were measured using the polarimeter, and then all specific rotation values were
α
calculated using the equation, [α] = 𝑜𝑏𝑠 . The % error was found for R-(-)-carvone (4.26%) and R-(+)-
𝑙∗𝑐
limonene (28.27%) in part A. The % ee was found for (S)-(+)-Carvone (69.5%) and (S)-(-)-Limonene
(56.4%) in part B. The % difference for [α] of unknown A/(S)-(-)-Limonene and known [α] (4.26%) was
found in part C, and the concentration of the sucrose solution (0.221 g/cm3) was calculated. Unknown A
was identified as (S)-(-)-Limonene. The concentration of sucrose solution B was 0.221 g/cm3. The
mixtures in part B were determined to be moderately pure, based on the mid-range % ee for both S-(+)-
carvone (69.5%) and (S)-(-)-Limonene (56.4%). The main source of error in this experiment was the quality of the
samples provided by the school. They weren’t completely pure, so it is expected that some of the values are
unusual.

References

Experiment #7: Stereochemistry and Polarimetry pre-lab notes, Dr. Aaron Wohlrab
https://blogs.stockton.edu/chem2/files/2015/07/Polarimetrylab_F15.pdf
Zubrick, James. The Organic Chem Lab Survival Manual, 9th ed.; Wiley: NJ, 2014.