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Organic Chemistry I Lab

Extraction of Caffeine from Tea


Frequently, organic chemists must separate an organic compound froma mixture of compounds,
often derived from natural sources or as products of synthetic reactions. One technique used to
separate the mixture compounds is called extraction. Extraction is a process that selectively
dissolves one or more of the mixture compounds into an appropriate solvent. The solution of
these dissolved compounds is often referred to as the extract. (See Figure 1 below and read
Operation 16 in the lab text).

Extraction processes include removal of soluble compounds from a solid matrix, such as occurs
in brewing coffee or tea or in decaffeinating coffee with liquid carbon dioxide. In the organic
chemistry laboratory, however, extraction almost always refers to the transfer of compounds
from one liquid solvent to another liquid solvent.

Washing is the reverse process, in which the impurities are removed to the second solvent,
leaving the desired compound in the original solvent, as shown in Figure 2.

Extraction is a particularly effective means of separating organic compounds if one compound in


the mixture can be chemically converted to an ionic form. The ionic form is soluble in an
aqueous layer and can be extracted into it. Other non-ionized organic compounds in the mixture
will remain dissolved in the nonpolar solvent layer. Separation of the two layers results in the
separation of the dissolved compounds.

Ionic forms of some organic compounds can be produced by reacting them with aqueous acids or
bases. Reacting organic acids with bases such as sodium hydroxide (NaOH) converts these acids
to water-soluble anions (see structure below). Reacting basic amines with dilute aqueous acid
solutions such as hydrochloric acid (HCI) converts the amines to water-soluble cations.
COOH COO Na
NaOH(aq)

The extent to which an acid-base reaction proceeds to completion depends upon the relative
acidity and basicity of the reactants and products. Reactions occur so that stronger acids and
bases react to produce weaker conjugate bases and acids. Recall that the pKa is a measure of the
acidity of an acid, as shown in Eq. 1.

pKa = -log Ka (Eq.1)

Stronger acids have smaller pKs and their conjugate bases are inherently weaker. The position of
an acid-base equilibrium can then be predicted from a knowledge of the pKs of the acids
involved. Stronger acids, those with a smaller pK, will react with the conjugate bases of weaker
acids, those with a larger pK.

Once an organic acid (or base) has been converted to an ionic form, like the carboxylate salt of a
carboxylic acid, its solubility in in water is greatly increased and its solubility in a hydrocarbon
solvent is decreased. For this reason, acids can often be separated from hydrocarbon
contaminates by dissolving the mixture in a hydrocarbon solvent such as cyclohexane and
extracting the acid component into an aqueous layer of dilute sodium hydroxide. The hydroxide
converts the acid to its carboxylate salt which is more soluble in the aqueous layer than the
cyclohexane layer. The dissolved hydrocarbon is unaffected by the hydroxide and remains in the
cyclohexane layer. This is the mechanism by which you will separate two compounds in the lab
today.

Although the conversion of an acid to its salt greatly increases its solubility in the aqueous layer,
this does not mean that no acid can remain dissolved in the organic solvent layer. To quantify the
extent to which a solute has differential solubility in various immiscible solvents we calculate
something called the partition coefficient, k (also called the distribution coefficient). This is
simply the ratio of the solubilities of a single solute in two immiscible solvents. Imagine a solute
that has a solubility of 8g /100mL of ether, and 2g /100mL of water. The partition coefficient
would be

8g
100 mL ether 4
k 4
2g 1
100 mL water

This value can be used to calculate the effectiveness of an extraction by calculating the amounts
that remain dissolved in each layer following an extraction. For example, if 6g was dissolved in
100mL of ether and then extracted with 200mL of water, the water layer would contain 2g of the
solute and the ether layer would contain 4g of the solute.
6 x
4 100 mL ether
x
200 mL water

x 2g in water layer (and 4g in ether layer)

Such an extraction would not be very useful in moving the solute from one layer to another. For
effective extraction we need large values for k, typically greater than 5/1. For the experiment
today the value for the distribution coefficient is sufficiently large to achieve effective separation
of the components in the mixture you will be given. You should be able to do these types of
calculations!

Background
Tea and coffee have been popular beverages for centuries, primarily because they contain the
stimulant caffeine. It stimulates respiration, the heart, and the central nervous system and is a
diuretic (promotes urination). It can cause nervousness and insomnia and, like many drugs, can
be addicting, making it difficult to reduce the daily dose. A regular coffee drinker who consumes
as little as four cups per day can experience headache, insomnia, and even nausea upon with-
drawal of the drug.

Caffeine may be the most widely abused drug in the United States. During the course of a day,
an average person may unwittingly consume up to a gram of this substance. The caffeine content
of some common foods and drugs is given in the table below.

Coffee 80 to 125 mg per cup


Coffee, decaffeinated 2 to 4 mg per cup
Tea 30 to 75 mg per cup
Cocoa 5 to 40 mg per cup
Milk chocolate 6 mg per oz
Baking chocolate 35 mg per oz
Coca-Cola 46 mg per 12 oz
Anacin, Bromo-Seltzer, Midol 32 mg per tablet
Excedrin, extra strength 65 mg per tablet
Dexatrim, Dietac, Vivarin 200 mg per tablet
Dristan 16 mg per tablet
No-Doz 100 mg per tablet

Caffeine belongs to a large class of compounds known as alkaloids. These are of plant origin,
contain basic nitrogen, often have a bitter taste and complex structure, and usually have
physiological activity. Their names usually end in -ine, many are quite familiar by name if not
chemical structure-nicotine, cocaine, morphine, strychnine. In general, their function within the
plant is obscure. Tea leaves contain tannins, which are acidic, as well as a number of colored
compounds and a small amount of un-decomposed chlorophyll (soluble in dichloromethane). In
order to ensure that the acidic substances remain water soluble and that the caffeine will be
present as the free base, sodium carbonate is added to the extraction medium.
The solubility of caffeine in water is 2.2 mg/mL at 25°C, 180 mg/mL at 80°C, and 670 mg/mL at
100°C. It is quite soluble in dichloromethane, the solvent used in this experiment to extract the
caffeine from water.

Caffeine can be extracted easily from tea bags. The procedure one would use to make a cup of
tea, simply "steeping" the tea with very hot water for about 7 min, extracts most of the caffeine.
There is no advantage to boiling the tea leaves with water for 20 min. Since caffeine is a white,
slightly bitter, odorless, crystalline solid, it is obvious that water extracts more than just caffeine.
When the brown aqueous solution is subsequently extracted with dichloromethane, primarily
caffeine dissolves in the organic solvent, leaving the other substrates in the aqueous layer.
Evaporation of the solvent leaves crude caffeine, which on sublimation yields a relatively pure
product. When the concentrated tea solution is extracted with dichloromethane, emulsions can
form very easily. There are substances in tea that cause small droplets of the organic layer to
remain suspended in the aqueous layer. This emulsion formation results from vigorous shaking.
To avoid this problem, it might seem that one could boil the tea leaves with dichloromethane
first and then extract the caffeine from the dichloromethane solution with water. In fact, this does
not work. Boiling 25 g of tea leaves with 50 mL of dichloromethane gives only 0.05 g of residue
after evaporation of the solvent. Subsequent extractions give less material. Hot water causes the
tea leaves to swell and is obviously a much more efficient extraction solvent. An attempt to
sublime caffeine directly from tea leaves also was unsuccessful.

Procedure
In a 50-mL beaker place 20 mL of water, 2 g of sodium carbonate, and a wooden boiling stick.
Bring the water to a boil on the hotplate, remove the boiling stick, and brew a very concentrated
tea solution by immersing a tea bag (2.4 g tea) in the very hot water for 5 min. While wearing
latex gloves, squeeze as much tea from the bag as possible after it cools enough to handle. Be
careful not to break the bag. Again bring the liquid to a boil, and add a new tea bag to the hot
solution. After 5 min, remove the tea bag and squeeze out as much water as possible. This can be
done easily on the Hirsch funnel. Rinse the bag with a few milliliters of very hot water, but be
sure the total volume of aqueous extract does not exceed 12mL. Pour the extract into a 15-mL
centrifuge tube, and cool the solution in ice to below 40°C (the boiling point of
dichloromethane).

Using three 2-mL portions of dichloromethane, extract the caffeine from the tea. Cap the tube
and use a gentle rocking motion to carry out the extraction. Vigorous shaking will produce an
intractable emulsion, while extremely gentle mixing will fail to extract the caffeine. If you have
ready access to a centrifuge, the shaking can be very vigorous because any emulsions formed can
be broken fairly well by centrifugation for about 90 sec. After each extraction, remove the lower
organic layer into a reaction tube, leaving any emulsion layer behind. Dry the combined extracts
over anhydrous sodium sulfate for 5 or 10 min in an Erlenmeyer flask. Add the drying agent in
portions with shaking until it no longer clumps together. Transfer the dry solution to a weighed
25-mL filter flask containing a boiling chip, wash the drying agent twice with 2-mL portions of
dichloromethane, and add the washes to the test tube or filter flask. Evaporate the
dichloromethane to dryness by carefully placing the tube/flask into a hot water bath (NOT ON A
HOTPLATE) and allowing the ether to boil away. You can facilitate the removal of the vapors
by holding a Pasteur pipette connected to a water aspirator just above the surface of the boiling
liquid. Be careful not to touch the liquid or your product will be drawn into the pipet and lost
down the drain. Continue the evaporation until no trace of the smell of dichloromethane can be
detected. The residue remaining in the filter flask will be crude caffeine (determine its weight)
that is to be purified by sublimation.

Assemble the apparatus shown below making sure the system is sealed. Use a Pluro stopper that
has been cut off to facilitate the positioning of the centrifuge tube tip close to the bottom of the
flask. Make sure the centrifuge tube is completely dry on the outside before assembly.

Clamp the flask with a large three-prong clamp. After the apparatus is assembled, fill the
centrifuge tube with cool water, and heat the flask on a hot sand bath. Caffeine is reported to
sublime at about 170°C. Tilt the tube/filter flask and rotate it in the hot sand bath to drive more
caffeine onto the centrifuge tube. Use a heat gun to heat the upper walls of the test tube or filter
flask. Keep the water in the centrifuge cold by occasionally adding small pieces of ice. Make
sure no water runs down the outside of the tube when adding the ice. When sublimation ceases,
raise the flask from the sand, remove the water, and allow the apparatus to cool somewhat before
removing the inner tube. Scrape the caffeine onto a tared piece of weighing paper, weigh, and
transfer it to a small vial. Commonly, most of the caffeine will collect on the inner surfaces of
the flask. Carefully scrape off any caffeine that collects on the flask, but be careful not to scrape
impurities from the flask. At the discretion of the instructor, determine the melting point using a
sealed capillary. The melting point of caffeine is 238°C. Using the centrifugation technique to
separate the extracts, about 30 mg of crude caffeine can be obtained for each two tea bags used.
This will give you 10 to 15 mg of sublimed material, depending on the caffeine content of the
particular tea being used.

Cleaning Up

Discard the tea bags in the nonhazardous solid waste container. Allow the solvent to evaporate
from the drying agent, and discard in the same container. Place any unused and
unrecovered dichloromethane in the chlorinated waste bottle.
Complete the data sheet for this lab and turn in the following:

The data sheet for this lab and any spectra you obtain. Be sure to identify any important
peaks directly on your spectrum.

Be prepared to answer questions regarding the theory and practice of extraction on a quiz
next week.

The IR Spectrum of Caffeine in a Nujol Mull

REVISION 07/30/2004
Organic Laboratory Data Sheet
Name _____________________________________________ Partner ______________________

Experiment: EXTRACTION OF CAFFEINE

I. Structure of Caffeine:

II. Literature melting point:

Literature MP: Reference:

III. Data:

Extraction of Caffeine:

Mass of Tea Used __________________________

Mass of Crude Caffeine Recovered _______________________________________________

Mass of Purified Caffeine (from sublimation) ____________________

IV. Spectra or chromatographic analysis (Attach labeled spectra and/or chromatogram to report):

Discuss spectrum here. Include a comparison to the given spectrum of caffeine:

V. Perform the following calculation

The partition coefficient K for a compound between dichloromethane and water is determined to be 56 : 1 (K=56).
If 10.0 mg of the compound is dissolved in 50.0 mL of water and this solution extracted with 25.0 mL of
dichloromethane, how many mg of the compound will remain in the water layer following the extraction
procedure? _____________ mg

VI. Technique – Provide a self-evaluation and grade yourself on your technique (percentage out of 100%):

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