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Experiment 2: Synthesis of Aspirin

Data and Results


I.

Synthesis of Aspirin

Table 1. Obtained Values for Synthesis of Aspirin


Amount/Mass
2.1020 g
0.7301 g
3 ml
2.4145 g

Salicylic acid
Filter Paper
Acetic anhydride
Crude aspirin generated + Filter Paper
Table 2. Physical Observations
Compound

Observations
White fine powder with few bulk
particles
White crystals

Salicylic acid
Crude aspirin generated
II.

Purifying the aspirin by recrystallization

Table 3. Obtained Values for Recrystallization


Amount/ Mass
Crude Aspirin used

1.4383 g

Filter paper

0.6539 g

Recrystallized Aspirin + Filter paper

1.7687 g

Recrystallized Aspirin

1.1148 g
100 =77.51
1.4383 g

% Recovery

Table 4. Physical Observation


Compound
Purified Aspirin Product
III.

1.7687 g 0.6539 g = 1.1148 g

Observations
White fine crystals

Melting Point Determination

Table 5. Melting Point Values


Compound
Salicylic acid
Crude Aspirin
Purified Aspirin

Melting Point (C)


Melting starts
Melting complete
159
161
128
136
137.2
140

Percentage Yield

Yield
100 %
( Experimental
Theoretical Yield )

Yield=

Theoretical Yield

2.1020 g

1 mol Salicylic acid


=0.0152 Salicylic acid
138.12 g Salicylic acid

3.0 ml Acetic anhydride

1.08 g Acetic anhydride


1 mol Acetic anhydride

=0.0317 mol Acetic Anhydrid e


1 ml Acetic anhydride 102.09 g Acetic anhydride

Since mol Salicylic acid < mol Acetic anhydride, Salicylic acid is the limiting reagent.
Balanced Reaction:
C7H6O3 + C4H6O3

C9H8O4 + C2H4O2

Salicylic
Acid

Aspirin

Therefore, the mole ratio between Salicylic acid and Aspirin is 1:1.

0.0512 mol Salicylic acid

1 mol Aspirin
180.17 g Aspirin

=2.7286 g Aspirin
1mol Salicylic acid
1 mol Aspirin

Experimental Yield of Crude Aspirin


(Crude aspirin generated + Filter Paper)
of crude aspirin

mass

(Filter Paper)

2.4145 g0.7301 g=1.6844 g


% Yield of Crude Aspirin

100 % = 61.51%
(1.6844g
2.7386g )

% Yield of Purified Aspirin

recrystallied Aspirin
( mass ofTheoretecal
) 100
yield

%Yield=

mass

= Experimental Yield

1.1148 g
100 =40.8 6
( 2.7286
g)

%Yield=

Discussion
Synthesis of Aspirin
Acetylsalicylic acid or aspirin was obtained by a modified esterification
reaction. Esterification reaction is the reaction between a carboxylic acid and
an alcohol to prepare a compound containing an ester functional group and
water as a by-product. In synthesizing aspirin, an acid anhydride, acetic
anhydride, was used instead of carboxylic acid (e.g. acetic acid). This is
because esterification with acetic acid is unfavourable.

As mentioned, alcohols react with carboxylic acid to form ester and


water. Water causes the reaction to be reversible thus, causing a decrease in
yield. This is also the reason why it is important for the flask (to be used in
the catering the reaction) to be dry leaving no traces of water. Acetic
anhydride, on the other hand, lacks water as it is anhydride and therefore,
would make the reaction more favourable. Instead of water as the byproduct, acetic anhydride generates carboxylic acid. Esterification is an acidcatalysed reaction. Both the addition of concentrated Sulfuric acid and the
presence of heat act as catalyst in the reaction. Sulfuric acid acts as a proton
donor increasing the rate of the reaction. The presence of heat drives the
reaction into completion.
Figure 2 shows the mechanism for the reaction of salicylic acid and acetic
anhydride. In the reaction, the OH group in the salicylic acid is being
replaced by an ester group from the acetic anhydride. Salicylic acid acting as
an alcohol attacks the acetic anhydride on its carbon double bonded on
oxygen. The H bonded on the positively charged oxygen is deprotonated and
the negatively charged oxygen donates electrons to the electrophilic carbon
to form a double bond. The carboxylate leaves forming the aspirin. The
carboxylate is protonated to form carboxylic acid.
After heating, that is when almost all the solid had dissolved, the flask
is cooled down by gradually adding increments of distilled H 2O.This is also
done to treat the remaining acetic anhydride. Salicylic acid in the reaction is

the limiting reagent and therefore, the acetic anhydride is added in excess.
After heating, there might still be unreacted acetic anhydride. Water will
react with the excess acetic anhydride to form acetic acid. 10 grams of
crushed ice is then added to the flask. This is crucial to separate aspirin from
other by-products of the reaction. Aspirin is slightly soluble in cold water
causing it to precipitate in cold environment. The precipitated aspirin was
collected by vacuum filtration. Acetic acid, Sulfuric acid and all other soluble
materials were passed though the filter paper.
The aspirin generated was weighed. The numerical data is summarized
on table 1. On table 2, physical differences are cited between salicylic acid
and the crude aspirin. Percentage yield for the crude aspirin was calculated:
61.51%. This percentage suggests a lower yield for pure aspirin. However, it
is still reasonable noting the flaws of the procedure itself. It is possible that
some of the yield didnt precipitated and were washed through the filtration
process. Other errors must be of mishandling and of personal errors.
Recrystallization
The aspirin collected from the first part of the experiment still needs
further purifying. The aspirin obtained might still contain contaminations
such as unreacted starting materials and unwanted products from sidereactions. The main impurity in the crude aspirin is salicylic acid which may
be the product of the hydrolysis of the product during isolation steps.
Recrystallization was the technique used in the experiment. A large fraction
of the crude aspirin was used in recrystallization. The small fraction was
saved for melting point determination in part 3. Recrystallization involves the
dissolution of a solid in a pre-selected solvent at an elevated temperature
thereby re-forming crystals upon cooling, leaving the impurities to
remain in solution to be filtered. The solvent used to dissolve the crude
aspirin was ethanol. Ethanol dissolves the aspirin and the impurities as
ethanol and all the compounds are polar (like dissolve like). 10 ml of water
was added, again, to react with the unreacted acetic anhydride and to
gradually cool down the solution. It is then heated to assure the dissolution
of the solid. After, it was cooled in an ice bath until crystals are formed.
Cooling will precipitate the pure aspirin and leave the soluble impurities to be
passed through the filter paper. The recrystallized aspirin is separated from
its impurities by suction filtration.
The data obtained in recrystallization is summarized on table 3. The
percentage recovery was 77.51% which is considered as an accepted

percentage recovery for recrystallization. The technique of recrystallization


induces errors. However, appropriate selection of solvent and careful
handling lessens these errors.
The mass of the purified aspirin is then used as an experimental value
to calculate for the percentage yield: 40.86%. As expected, it was a bit lower
than it should be. This low value can be justified by the small fraction of the
crude aspirin taken for the melting point determination and thus, was not
included in the recrystallization process. Too much washing might be done
that some of the yield were dissolved and filtered out. Another cause of error
is not completely cooling down the flask into room temperature and was put
immediately in cold water bath. This would yield smaller crystals with lower
impurity.

Melting Point Determination


Melting point is index of purity used to test the effectivity of
recrystallization. The melting point of a solid is defined as the
temperature at which the solid and liquid phases are in equilibrium. It is
usually the melting point range (from the first sign of melting to the
complete melting of the solid) of the substance that is obtained rather the
exact time consumed to acquire the said equilibrium.
The melting points of salicylic acid, crude aspirin and purified aspirin
were obtained using the melting point apparatus. The data is summarized at
table 5. A narrow melting point range would indicate high purity compare to
that of a broader range. As seen in table 5 for the crude aspirin, the melting
point range took 8 units while the purified aspirin took 2.8 units. This narrow
range indicates high purity. Noting the salicylic acids melting point range
which was only 2 units gives us the idea that the purity of the experimentally
purified aspirin is comparable to that of the manufactured compounds such
as salicylic acid.
Conclusion
Aspirin was synthesized by reacting salicylic acid with acetic acid. This reaction is an
esterification reaction which used anhydride to produce the ester group to replace
the hydroxyl group of salicylic acid. The reaction proceeded in the presence of heat
and the addition of strong acid as catalysts. The mixture was cooled to allow

crystallization to take place. Crystallization was done to separate impurities such as


unreacted starting materials from the aspirin. Aspirin has a low solubility in cold
environment and therefore subjecting the mixture on a cold water bath precipitates
the aspirin out leaving the impurities in liquid form to be separated via vacuum
filtration. The aspirin obtained was weighed and the percentage yield for crude
aspirin was 61.51%. The crystallized aspirin was recrystallized to completely isolate
aspirin from remaining impurities. In the recrystallization method, crude aspirin is
dissolved in ethanol. It was then cooled to form crystals of pure aspirin. The product
was weighed and the percentage recovery was 77. 51%. The percentage yield for
the recrystallized aspirin was only 40.86%. The obtained percentage yields were of
reasonable and satisfactory magnitude considering the error induced nature of the
techniques used.
To test the purity of the recrystallized aspirin, melting point determination was
done. The melting point range of the crude and the recrystallized aspirin was
compared. In theory, the narrow the melting point the pure the substance. The
obtained values coincide with the expected results. The melting point range of the
crude aspirin was broader than the recrystallized aspirin. This verifies the high
purity of the aspirin from recrystallization.

References

Zubrik, James W. 1997. The Organic Chem Lab Survival Manual: A Student's Guide to
Techniques. 4th ed. John Wiley & Sons.
McMurry, R.S. 2008. 7TH Ed. Organic Chemistry. USA: Prentice Hall, 332-345.
Pavia, Donald L. 2005. Introduction to Organic Laboratory Techniques: A Small Scale
Approach. USA: Brooks/Cole, 55-57.