An Old Undergraduate Experiment Revisited
Scott D. Murray and Peter J. an sen'
Northwestern College, Orange City, IA 51041
For a t least three decades a common undergraduate or-
-ofeanic chemistm.exneriment
. has consisted of the extraction
caffeine from tea leaves. The caffeine is extracted from
the tea leaves using hot or boiling water, extracted from
this aqueous solution using a n immiscible organic solvent,
isolated in crude form bv e v a ~ o r a t i n eoff the organic sol-
vent, and purlfied by rccl~staliwatlon'oriuhllma;mn Dur-
ing the 60's and 70's the oraanlc solvent of choice was chlo-
roform (131, while more recent organic laboratory
manuals have specified the use of diebloromethane (4-7).
Both chloroform and dichloromethane generally are recog-
nized a s having significant toxicity. Chloroform is a "con-
firmed carcinogen" and dichloromethane is a "suspected bu-
man carcinogen" (8).A recent article reported increasing
concerns about "chlorinated organics a s a class and human
health" (9).These potential hazards prompted the authors to
seek a more suitable organic solvent for use in this experi-
ment.
The initial set of criteria used in selecting a n alternative
organic solvent included:
1. immiscibility with water;
2. low toxicity;
3. low cost;
4. high stability (especially with respect to peroxide forma-
tion); and
5. appreciable caffeine solubility.
The reasons for the first four are apparent, while the last
is necessary for a favorable caffeine partition coefficient
between the organic solvent and water. Unfortunately, we
were unable to identify a common organic solvent that met
all five of these criteria. Leggett, e t al., however, reported
that the salting-out effect can be employed to reduce dra-
matically the solubility in water of some normally water-
' Author to whom correspondence should be addressed,
miscible organic solvents (10). This suggested to us that
the first criterion above could be relaxed.
Employing the salting-out effect, a number of wmmon or-
ganic solvents were tested and of these l-propanol appeared
to be the most suitable. In comparison to either chloroform or
dichloromethane, l-propanol is less toxic (8) and less expen-
sive (by a factor of two). In addition, it is stable under normal
storage wnditions and readily dissolves caffeine.
Experimental
Pour 200 mL of boiling water into a beaker containing
10-12 tea bags and allow the beaker to stand for 10 min.
Decant the "tea" from the tea bags and compress the tea
bags to maximize solvent recovery. Return the tea bags to
the original beaker, and repeat this extraction twice using
50-mL portions of boiling water. Combine the aqueous ex-
tracts, cool, add sodium chloride (26 g1100 mL of "tea") and
calcium hydroxide (-1 g), the latter to precipitate tannins.
Filter this solution using Celite, fast filter paper, and vac-
uum filtration. (This filtration may be omitted without se-
riously affecting one's results, but the unfiltered extract is
prone to emulsion formation during the next step.)
Transfer the filtrate to a separatory funnel and extract
with three successive portions of l-propanol(45,35, and 35
mL). Combine the l-propanol extracts in a flask and
evaporate off the solvent (-80% l-propanol and -20%
water) using rotary evaporr~tionor distillation.
Rmsc the reeldue in tht: flask (mostly sodlurn chloride, with
two successive 10-mL portions of acetone to extract the crude
caffeine. Filter this acetone extract and carefully boil off the
acetone. The crude caffeine obtained can be purified by re
nystallization (dissolvein 23 mL toluene and add hexane to
effect crystallization) or by sublimation (5-7).
Volume 72 Number 9 September 1995 851
Discussion
The ~urifiedcaffeine obtained in this ex~erimentwas
identified using IR spectroscopy.
The sodium chloride concentration specified above is sig-
nificantly less than that required to saturate the aqueous
solution. If the aaueous laver is saturated with sodium
chloride, crystallizkion of iportion of the sodium chloride
will occur upon addition of the l-propanol. Analysis of the
two layers of a waterll-propanollsodium chloride ternary
system with a composition similar to that used in this ex-
periment yielded the results given in the table.
Composition of the Waterll-PropanollSodium Chloride
Ternary System
Aqueous Layer (%) 1-PropanolLayer (%)
water 74 19
1-propano1 6 80
sodium chloride 20 1 whistell, R. K.; O'Connor. R. Eds.; Freeman: San Francisco, 1971; Vol.2.
The partition coefficient of caffeine between the l-propanol
and aqueous phases was determined to be approximately
3.7-probably lower than the corresponding values for the
chlorofodwater and dichloromethanelwater systems. (Using
the reported solubilities of caffeine in chloroform and in water
(11),a rough estimate of 8.3 was calculated for the partition
wefficient of caffeine between these two solvents. For the di-
chloromethane/water system a value was not established, but
one might expect a value similar to that for the chloro-
fondwater system.) Nonetheless, given the wnditions of this
852 Journal of Chemical Education
experiment it is estimated that approximately 80% of the
caffeine in the tea leaves is recovered as crude caffeine.
Using a larger quantity of l-propanol or a smaller quantity
of water would obviously increase the percentage of caf-
feine extracted from the aqueous layer, but the latter
would reduce the percentage of caffeine extracted from the
tea leaves by the water since the tea leaves retain a signifi-
cant quantity of water.
The procedures employed in this experiment do not re-
quire dry l-propanol. The l-propanollwater solvent mix-
ture that is recovered by rotary evaporation or distillation
can be saved and used repeatedly. This recycling reduces
both waste generation and cost. If recycled l-propanol is
used in the procedure described above, the amounts should
be increased by about 25% to account for the dissolved
water present in this solvent.
Literature Cited
1. Helmkamp, G.K; Johnson. H. W. Sdeead Experiments in O ~ e n i Chemistry,
c 2nd
ed.; Freeman: Ssn Francisco, 1968; pp 157-158.
2. O'Connor, R. In The Fmman Library ofLahrofory Separates in Chpmuiv; B i d
3. Pavia, D. L.:Lmpman, G. M.; Kriz. G.S. lntmduction to O~ganieLabornfo~ rich.
niquas; Saunders:Philadelphia, 1976: pp 5&62.
4. Williamson, K L. Macrnscokand Micrnscok OlgonicErpprimnls; Heath: Tomno,
1989 .PP 130-133.
~
5. Mayo, D. W; Pike, R. M.: Butcher, S. S. Microsmle 01gonic Lobornmy, 2nd ed.:
. ...
Wile": New York. 1989: oo 162-164.
6. Nimitz, J. S. Erpen'ments in Organic Chmzisfv: PrenticrHall: Englewood Cliffs,
NJ. 1991: pp 61-62.
7. Landgrebe, J. A. Theory and Proelice in iha Organic Laboratory. 4th ed.:
BmokYCole: Pacific Grove, CA. 1993; pp 381383.
8. Lewis, R. J.Hazardous ChemicalzDesk Refeenee, 2nd ed.:Ven Noatrand Reinhold:
NewYork. 1991.