Expt 116

Soap From Nutmeg

Adapted by Keith Reber (PSU 04) from a procedure given by Marcio de Mattos and David Nicodem
(J. Chem. Ed. 2002, 79, 94-95)
Revised By Timothy Nowak (PSU 07)
Introduction:
For thousands of years, people have produced soap from fats through a process known as
saponification. Fats and oils are generally triesters consisting of three long fatty acid chains bonded
to a molecule of glycerol to form a triglyceride. When a strong base such as sodium hydroxide is
added to a fat or oil and heated, the ester bonds of the triglycerides are hydrolyzed, and fatty acid
salts are produced:
O O
CH
3
O O
O O
CH
3
C H
3 C
13
H
27
C
13
H
27
H
27
C
13
O
O
-
C H
3 H
27
C
13
Na
+
3
OH
O H OH
Trimyristin
(a fat)
723.14 g/mol
mp 56-57C
EtOH, H
2
O
Reflux 15 min.
NaOH
Sodium myristate
(a soap)
228.36 g/mol
mp 58C
+
Glycerol
These fatty acid salts have a polar end and a nonpolar end, giving the soap its unique emulsifying
properties. The long hydrocarbon tail is nonpolar and hydrophobic, and therefore dissolves well in
nonpolar environments, such as grease. The charged head of each fatty acid salt is polar and
water-soluble (hydrophilic):
Micelle formed from fat in water
(ex: washing grease from hands with soap)
Since the soap is somewhat miscible in both fat and water, it effectively produces emulsions. This is
accomplished by the formation of a micelle in which the fatty acid salts completely surround a
droplet of oil, oriented so that the nonpolar hydrocarbon chains are dissolved in the fat and the polar
carboxylate groups are dissolved in water. The micelle can then be easily washed away with water,
carrying the grease with it.
In this experiment, the fat trimyristin will be extracted from ground nutmeg and saponified to
produce sodium myristate, a carboxylate salt that functions as a soap. The properties of this soap will
be determined through a series of qualitative tests. Finally, an aqueous solution of sodium myristate
will be acidified to produce myristic acid, which will be characterized using IR and
1
H-NMR.
Prelaboratory Exercise:
1. Suppose that 2.5 g of trimyristin has been extracted from nutmeg. If the trimyristin is
saponified using excess NaOH, what is the theoretical yield of sodium myristate? If all of
this sodium myristate is then acidified (with excess acid), what is the theoretical yield of
myristic acid?
2. Write a step-by-step mechanism for the saponification of trimyristin with NaOH.
Cautions:
Ether is very flammable and should only be heated with a heating mantle. After the extraction step,
do not remove the ether through distillation as potentially explosive peroxides could be formed.
Sodium hydroxide is a strong base and concentrated HCl is a strong acid; both are extremely
corrosive, and gloves should be worn while handling them. If either should come into contact with
your skin, wash the area immediately with lots of cold running water.
Isolation and purification of trimyristin:
To a 100 mL round-bottom flask, add 20 g of ground nutmeg, 50 mL diethyl ether, and a magnetic
stir bar. Place small amounts of stopcock grease to connector end of the round bottom flask.Place the
flask in a heating mantle (no sand!) over a stir plate, and attach a reflux condenser. Turn on the
water so that it flows through the condenser, begin stirring the solution, and heat the flask on a
varistat setting of 40. When the ether begins to boil, allow the mixture to reflux for 30 minutes. Let
the solution cool to room temperature, and decant the ether into a large beaker. Wash the residual
nutmeg with two 10 mL portions of ether, and combine these with the decanted ether. Try not to
allow any brown solid to go into the beaker when decanting as nutmeg solids could cause impurities.
Allow the ether to evaporate under a stream of N
2
(or until the next lab period), leaving a yellow
solid. Break up the solid, and recrystallize in warm 95% ethanol (try adding about 12-15 mL); this
can be a challenge, as trimyristin melts at ~57
o
C! Heat the solution until it becomes translucent.
Cool the solution very slowly it is more likely that a slush will result instead of nicely formed
crystals, but this is fine. Vacuum filter the solution to collect the solid and wash liberally with
chilled ethanol until all traces of color are removed from the solid (the filtrate should be a transparent
yellow solution). Transfer the white solid to a tared watch glass, and allow it to dry completely
before determining the mass of product collected (typically 1.5 - 2.5 g). Determine the melting point
of the purified trimyristin, and run an IR analysis.
Saponification of trimyristin:
To a 100 mL round-bottom flask, add 20 mL of 95% ethanol and 0.20 g NaOH pellets. Stir this
solution with a magnetic stir bar until the pellets dissolve. Then, add 1.0 g of trimyristin. Attach a
condenser as before, and reflux for 20 minutes. Cool the mixture to room temperature, and add 20
mL of distilled water and 20 mL of saturated NaCl solution. Vacuum filter to collect the solid and
wash with 25 mL of cold water. Transfer the sodium myristate to a tared watch glass, and allow it to
dry thoroughly, weigh and determine the percent yield.
Tests on sodium myristate and synthesis of myristic acid:
Dissolve 0.5 g of sodium myristate in 40 mL of distilled water, and add ~5 mL of this
solution to each of three test tubes. To the first tube, add 3 drops of corn oil, stopper, and shake
vigorously to test the emulsifying properties of the soap. To the second tube, add 10 drops of a 1%
aqueous FeCl
3
solution; a brown precipitate of iron (III) myristate should form. To the third tube,
add 10 drops of a 1% aqueous solution of CaCl
2
; a white precipitate of calcium myristate should
form.
Cool the remaining aqueous sodium myristate solution in an ice bath, and acidify it using
concentrated HCl solution. Use pH paper to determine when the pH is below 4; a white solid should
precipitate from solution. Collect this solid using vacuum filtration, and wash with 10 mL of chilled
water. Transfer the myristic acid to a tared watch glass, and allow it to dry completely before
determining a percent yield.
Clean-up:
All aqueous solutions can be washed down the drain with copious amounts of cold running water.
After analyses are complete, any remaining trimyristin and myristic acid can be disposed of in the
non-halogenated organic waste container, as can any remaining ether solutions.
Analysis:
Determine the melting points of both trimyristin and myristic acid, and compare these to literature
values. Obtain solid IR spectra of both products, and note the presence of characteristic peaks (the
carbonyl peaks should be very prominent).
Final Report:
Discuss any important observations, including the results of the qualitative tests on sodium myristate.
Determine yields and percent yields for each reaction step. Comment on the purity of the isolated
trimyristin and myristic acid based on melting point data. Finally, annotate the IR spectrum.
Post-lab questions:
1. So-called hard water, which contains dissolved metal ions such as calcium, does not form
suds very well when used with soap. Instead, it tends to form a soap scum that is difficult
to wash away from surfaces such as glass. Explain these observations. To counter this
problem, many people have water softeners in their homes that mix the hard water with
rock salt (NaCl). How does this help to eliminate the problems mentioned above?
2. Lipid oxidation occurs from the reaction of oxygen and radicals of unsaturated fats. Lipid
oxidation in foods leads to spoilage and browning. In the reaction of oxygen and unsaturated
fats, aldehydes are produced from the non-carboxylic acid end of the chain. Between
polyunsaturated fat and a saturated fat, which fat would oxidize more rapidly?