Extraction of Caffeine from Tea Leaves

Introduction
The active ingredient that makes tea and coffee valuable to humans is caffeine. Caffeine is an
alkaloid, a class of naturally occurring compounds containing nitrogen and having the
properties of an organic amine base.
Caffeine is a naturally occurring alkaloid found in over 60 plant species. Caffeine belongs to a
family of naturally occurring compounds known as xanthines. The xanthines, which come
from plants, are possibly the oldest known stimulants. Caffeine is the most powerful xanthine
in its ability to increase alertness, put off sleep and to increase ones capacity for thinking.
Caffeine is a vasodilator (relaxes the blood vessels) as well as a diuretic (increases urination).
Caffeine does not exist alone in tealeaves; the leaves are mainly cellulose, pigments and
chlorophylls, and tannins. Tannins are phenolic compounds of high molecular weight that have
certain properties in common.
Some of the better-known plant sources are coffee and cocoa beans, tealeaves, and kola nuts.
While coffee and tea are both popular products containing caffeine, the amounts vary widely in
a single serving. To further confuse the matter, coffee beans contain less caffeine than tea
leaves when measured dry. However, a serving of coffee contains roughly twice the caffeine of
tea. Much of the flavor of coffee and tea comes from tannins and other flavoring agents.
Caffeine has a slightly bitter flavor. As a result, decaffeinating coffee beans and tea leaves will
leave the flavor slightly changed even if no other compounds are lost.

Beverage Caffeine (mg)/cup

Coffee 80 – 125
Coffee, decaffeinated 2-4
Tea 30 – 75
Chocolate milk/cocoa 3 – 30
Soft drink 20 – 50

Several health concerns have been raised over the consumption of caffeine. The Food and Drug
Administration (FDA) has extensively studied the consumption of caffeine and its health
effects. In 1987 the FDA concluded that normal caffeine consumption does not increase risk to
health. These studies included cancer risk, coronary heart disease, osteoporosis, reproductive
function, birth defects, and behavior of children.
Many consumers prefer to avoid caffeine partially or altogether due to its stimulant effects and
others still have health concerns. This makes decaffeinating coffee and tea an important
industrial process. Decaffeination is also significant for the world’s economy; approximately
eight billion pounds of coffee are grown a year making it second only to oil as an international
commodity. It should be noted that decaffeinated coffee and tea are not caffeine free. These
products can be labeled decaffeinated as long as 97% of the caffeine has been removed.

Greening the Chemistry

The industrial decaffeination process has evolved over the years. Initially direct contact
methods used chloroform (CHCl3), and more recently methylene chloride (CH2Cl2), as the
solvent to repeatedly rinse the green (unroasted) coffee beans that had been softened by steam.
Once sufficient caffeine had been removed, the beans would be roasted. Since these organic
solvents have a high vapor pressure and low boiling point, any solvent remaining in the beans is
removed during roasting. This method has several brown characteristics. Both of these solvents
are carcinogenic and have several human health concerns with methylene chloride having the
lesser overall hazard. Chlorinated hydrocarbon waste has significant environmental impacts and
is costly to dispose. Roasting also does not guarantee full removal of the solvent, although
solvent levels are rarely detectable. So why were these solvents used in the first place? Their
advantages are that they are not water-soluble, have a low boiling point, and remove caffeine
without removing significant amounts of other compounds, leaving the majority of the flavor
unaltered.
Recently the direct contact process has been greened significantly using supercritical CO2. The
green coffee beans are steam softened with water and then supercritical CO2 is used to extract
the caffeine. Once the system is returned to room temperature and pressure the coffee beans
and separated caffeine are now solvent free as CO2 returns to the gas phase. Then the CO2 can
be captured and reused. This method has all the advantages of the above technique without the
environmental and human health risks.
Indirect contact methods have also been developed to decaffeinate coffee. The green coffee
beans are soaked (steeped) in almost boiling water until the caffeine is removed from the bean.
The coffee solution is then treated with ethyl acetate (a natural ester), which has moderate
human health hazards but is not carcinogenic. Ethyl acetate solvates caffeine more effectively
than water and extracts the caffeine. The remaining ethyl acetate is removed from the coffee
solution by steaming. The coffee solution is then combined with the beans, which reabsorb the
coffee oils as they are dried.

Theory
Caffeine (C8H10N4O2) is an alkaloid with the structure given below.
O
N
N
(1)
O N N

Alkaloids are bitter tasting, natural nitrogen-containing compounds found in plants. The basic
property of alkaloids comes from the lone pair of electrons found on at least one nitrogen.
Alkaloids are often found to have potent physiological activity. Some better-known examples
are morphine, heroin, lysergic acid (LSD), cocaine, quinine, strychnine, and nicotine.
The basic N in caffeine can be used to increase or decrease its water solubility.
O O
N N
N N
+ H3O+
+
+ H2O (2)
O N N O N N
H
Acidic conditions will form the conjugate acid salt giving caffeine increased water solubility as
a cation. On the other hand if caffeine is in a basic environment it takes the neutral form and is
only somewhat polar.
In order to successfully extract any substance from one solvent into another, we must maximize
differences in solubility. By choosing a green process we have traded some efficiency for
human and environmental health. While 1-propanol is a less efficient extractor than CHCl3 and
CH2Cl2, we can maximize our efficiency by using a few simple techniques. Adding NaCl to the
water to increase the polarity of the water and Ca(OH)2 which makes the solution basic.
Caffeine is now in its least polar form and more readily solvated in 1-propanol than water.
The extraction is analyzed by determining the partition coefficient (KP)
solubility in extractant (3)
KP =
solubility in source solution
where solubility is usually given in g/mL. Partition functions with larger values result in more
efficient extractions. Our process has a KP of approximately 4, which makes for an effective
extraction. Extractions are most effective when repeated several times with small volumes of
solvent rather than once with a large volume.
Adding base to the solution has a second important effect. The water solution contains much
more than just caffeine, and some of these compounds are also soluble in 1-propanol. Making
the solution basic with Ca(OH)2 forms insoluble tannin salts which removes them from the
solution before the caffeine is extracted into 1-propanol. The 1-propanol extract will primarily
contain caffeine with small amounts of impurities. This solution is washed with 10% NaOH to
remove impurities. Caffeine is also water soluble, but by keeping the washing solution basic it
minimizes the caffeine lost, while maximizing the removal of impurities.

Procedure
Heat 20 mL of distilled water in a beaker to boiling. Turn off the heat and prepare your tea
solution by adding 2 pre-weighed tea bags*. Let the solution steep for 10 minutes. Decant the
tea solution and press out as much of the water in the tea bags as possible to maximize solvent
recovery. Set the extracted solution aside, allowing it to cool. Repeat this procedure twice with
4 mL of hot distilled water each, let stand for five minutes, decant and press out as much water
as possible. Combine the washings with the initially extracted solution.

Add sodium chloride (2.6g per 10 mL extracted tea) and about 0.1 gram of calcium hydroxide to
the combined extracts, the latter to precipitate tannins. Heat and stir the solution for 15 minutes
(near boiling). This process will dissolve the salt and digest the precipitate that forms. Decant
the solution using gravity filtration (flute the filter paper) and recover the remaining extract.

Transfer the combined extracts into a separatory funnel and extract with four successive 2.5 mL
portions of 1-propanol. Remember to mix the solutions gently to minimize emulsion formation
and vent the separatory funnel frequently, especially initially. Make sure the emulsion layer has
mostly disappeared before separating. Combine the 1-propanol extracts in a separatory funnel
and wash once with 2.5 mL of 10% aqueous NaOH solution. Dry the 1-propanol solution by
adding anhydrous magnesium sulfate until it no longer clumps and filter. Transfer the 1-
propanol solution into a round bottom flask and add a few boiling chips.

Prepare a simple distillation apparatus. Distill the 1-propanol from the caffeine extract.
Carefully monitor the sample so as not to overheat the caffeine product as the 1-propanol distills
away. The crude caffeine should be a light tan and only turns dark brown when degraded due to
high heat. Stop the distillation (remove the heating mantle) just before the flask is dry. Take
your distilled 1-propanol product, and add it to the recycled 1-propanol collection container
located in the hood. It will be used next year for this experiment.

Rinse the residue in the flask with two successive 1-mL portions of acetone to extract the crude
caffeine. Filter the acetone extract and carefully boil off the acetone. Take your crude caffeine
product and determine its mass.

* Alternatively, add 10 – 12 grams of ground coffee to the 200 mL of boiling water

The final washing of the coffee grounds may need to be filtered to recover all the extracts.
Purify your caffeine by sublimation, carefully
monitoring the heat so as to minimize the
decomposition of your caffeine. Determine
the mass of the pure product and the melting
point. Use the FT-IR to identify your product
as caffeine.

Questions
1. Explain why salt is added to the water before the caffeine is extracted with 1-propanol.
2. What two things does the addition of Ca(OH)2 do to aid the extraction of caffeine.

References
Murray, D.S.; Hansen, P.J., J. Chem. Educ., 1995 (72) 851.
Hampp, A., J. Chem. Educ., 1996 (73) 1172.

Notes
The partition coefficient of caffeine between the 1-propanol and aqueous phases was determined
to be approximately 3.7. This is probably lower than the corresponding values for the
CH2Cl2/water systems, which is about 8.
The experimental conditions using 1-propanol produce about 80% crude caffeine. Using a
larger quantity of 1-propanol or smaller quantity of water would obviously increase the
percentage of caffeine extracted.

Helpful websites:
http://swampfox.fmarion.edu/web/chem/aclabo/caffeine.PDF
http://www.sinc.sunysb.edu/Class/orgolab/newcaffeineexperiment.PDF

Go to
http://wwwchem.uwimona.edu.jm:1104/lectures/coffee.html or
http://www.sinc.sunysb.edu/Class/orgolab/Caffeine_New.PDF
to find some interesting facts about coffee!!!