Chemistry 227

Steam Distillation
Isolation of Limonene from Citrus Fruits

The purpose of this experiment is to apply steam distillation to isolate limonene from the peel
of citrus fruits. This experiment will also introduce students to terpenes and chirality in natural
products. Refractive index will be used to assess identity and purity. IR will be used to identify
functional group.
Each research team will provide a very fresh citrus fruit to conduct this experiment. The goal is
to isolate the oil from a natural mixture and confirm its identity based upon chemical tests and
refractive index.
Introduction
Terpenes are a class of compounds isolated from essential oils of plants, which include a wide
variety of fragrances and flavors. Terpenes are composed of two or more five-carbon units
based on isoprene. Compounds with two isoprene units are called monoterpenes, for instance.
Limonene is a monoterpene oil that is commonly found in citrus fruits, dill, and caraway. It has
many industrial applications, from uses in the fragrance and flavor chemistry sectors, to
utilization as a solvent. In addition limonene is the cheapest chiral starting material for organic
synthesis.
The R (+) enantiomer of limonene is isolated from the zest peelings of citrus fruits, while the
S (-) enantiomer is found in pinecones. In a steam distillation, as the water-peel mixture is
heated to high temperatures, the limonene will covaporize with water at a much lower
temperature than its boiling point, condense and then collect in the receiving flask as a
different phase than water.
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Experimental Procedure
For this experiment bring in the assigned citrus fruit (posted on Canvas, the fresher the better.
Distillation
Prepare the distillation setup with an empty fractional column and a 25 mL round bottom flask
cylinder containing 5 mL of aqueous saturated NaCl to serve as the receiving vessel. See
figure 3-18, page 151. Modification: Replace the 4-place receiver with the 25-mL singleround-bottomed flask.
Using the fine grating side of a citrus zester, grate the peelings from the citrus. Try to avoid
getting the white pulp and be careful with your fingers. Transfer the gratings with 50 mL
distilled water in a blender and blend over high speed for few minutes. Pour the liquid in a 125
mL round bottom flask, rinse the blender with additional 25 mL of distilled water and add to the
round bottom flask. Add boiling chips and heat using a heating mantle. Continue distilling until
only water (clear liquid) comes over in the graduated cylinder.

Work-up
Remove the organic layer with a Pasteur pipet and place in a vial. Remove any water from the
vial with a pipet. Dry over anhydrous Na 2SO4 and transfer in a tared vial. Weigh the vial to
determine percent recovery.
Characterize with refractive index and / or IR per your instructor. Other characterizations will
include Unsaturation and Baeyer tests per your instructor.

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