IV.

DATA

Table 1. Sample description of salicylic acid, acetic anhydride and phosphoric acid
SAMPLE

OBSERVATIONS

salicylic acid

white crystalline powder

acetic anhydride

solid white powder-like granules

phosphoric acid

clear colorless liquid with pungent odor

Table 2. Observations on the synthesis of Aspirin form Salicylic Acid.

Observations
After addition of acetic anhydride

White solution with white solids

After addition of phosphoric acid

White solution with white solids

After swirling and hot water bath

Colorless solution with white solids

After addition of three 1mL water

Cloudy solution (white)

Addition of 40mL cold water

Formation of white solids and clear solution

After placing on ice bath

Formation of white solids and clear solution

Crystals of filtration

White crystals

Filtrate of filtration

Clear solution

After washing with water

White crystals residue with clear filtrate

Table 3. Calculation of Percentage Yield

Parameters
weight of salicylic acid (g)

1.00

volume of acetic anhydride (mL)

6.00

volume of phosphoric acid (mL)

3 drops

weight of watch glass + weight of filter paper +

product (g)

45.14

weight of empty watch glass (g)

43.64

weight of dry filter paper (g)

0.24

weight of crude product (g)

1.26

% yield of crude product:

Table 4. Observations of recrystallization of crude aspirin

SAMPLE

OBSERVATIONS

Mixture of crude sample and solvent

clear solution

Suction filtration

a.) Filtrate

clear solution

b.) residue

white powder-like solid

Air-dried crystals

white long crystals

Table 5. Recovery data on recrystallization of aspirin

Parameter
Weight of container + sample
(g)

Crude sample

Recrystallized sample

45.14

44.68

Weight of container (g)

43.64

43.64

Weight of filter paper (g)

0.24

0.24

Weight of sample (g)

% recovery (B/A x 100):

1.26

(A)

0.80

(B)

Table 6. Melting point data on aspirin

Parameter

Crude sample

Purified sample

Temp. when melting starts (C)

124 C

125 C

Temp. when melting complete (C)

127 C

126 C

Melting point range

130 C

127 C

Melting point of pure sample (literature value):

Table 7. Solubility of starting materials and products in water

SUBSTANCES

OBSERVATIONS

+/-

acetic anhydride

soluble

salicylic acid

insoluble

synthesized aspirin

insoluble

commercial aspirin

insoluble

Table 7. Ferric chloride test

Description of ferric chloride: yellow-orange liquid solution
SUBSTANCES
acetic anhydride

OBSERVATIONS

+/-

underwent a vigorous reaction; hot; yellow-

orange liquid

salicylic acid

formation of black-violet complex

aspirin

formation of black-violet complex

Table 8. Acidic potassium permanganate test

Description of potassium permanganate: deep purple-colored solution
SUBSTANCES

OBSERVATIONS

+/-

acetic anhydride

Purple solution

Dark orange to black liquid with solid substance

salicylic acid

on the upper part

aspirin

Black solution

OBSERVATIONS

+/-

yellow-orange liquid with white precipitate at the

Table 9. Starch test

Description of I2/KI: brown-black solution
SUBSTANCES
synthesized aspirin

commercial aspirin

bottom
yellow-orange liquid with black precipitate at the
bottom

VI. Results and Discussion

Aspirin can be made by using a process called esterification. Esterification occurs when a
carboxylic acid and an alcohol combine in a reaction to produce an ester. This reaction can be
used to synthesize aspirin from salicylic acid. In the lab, the carboxylic acid alcohol mixture is
heated in the presence of a catalyst. During the reaction process, a molecule of water splits off
and the remaining carboxylic acid and alcohol fragments become attached producing an ester.
The reaction that is used for the synthesis is shown below. In this reaction, an excess of acetic
anhydride (C4H6O3) is added to a measured mass of salicylic acid (C7H6O3). The mixture is
heated to form the acetylsalicylic acid (C9H8O4) and acetic acid (C2H4O2).

Based on Table 2, salicylic acid, a white crystalline powder, was used to synthesize aspirin.
Phosphoric acid, a clear colorless liquid with pungent odor, was used as a catalyst or the
substance which makes the reaction rate faster. Acetic anhydride was used as a solvent rather
than the acetic acid because it contains a better leaving group, the acetoxy group (-O2CCH3),
than the hydroxyl group (OH-) of the latter. Upon the addition of acetic anhydride and 85% of
phosphoric acid in the salicylic acid, there was a formation of white solids in the cloudy solution.
Aside from being a catalyst, phosphoric acid also donates H which binds to the reaction
complex. H is generated by the end of the reaction. The following reaction shows the
nucleophilic acyl substitution in the esterification of aspirin in which an acid-base reaction takes
place. This allows the resulting intermediate product to be susceptible to nucleophilic attacks.

Salicylic attacks the carbon where positively charged oxygen is attached to via the oxygen from
its hydroxyl group.

Rearrangement of positive charge occurs since the intermediate formed is not stable.

A reaction via elimination proceeds due to further rearrangement that leads the acetic acid to
leave the intermediate.

Lastly, the resulting reaction intermediate donates a proton to dihydrogen phosphate hence,
forming acetylsalicylic acid or aspirin.

The solution was then subjected to hot water bath to maximize solubility. Furthermore, heat
enhances the reaction since it is an exothermic reaction, which ultimately favors the formation of
products. As the reaction proceeds, the solid salicylic acid disappears and the acetylsalicylic
acid product remains dissolved in the hot solution. Once the entire solid has disappeared, the
reaction is complete.
At this point, the excess acetic anhydride must be hydrolyzed to acetic acid. Acetic anhydride is
very reactive toward water, so the hydrolysis has been done slowly water was added dropwise. The excess acetic acid will be quenched with the addition of water. The aspirin product is
not very soluble in water so the aspirin product will precipitate when water is added.

Ice cold water is then added and the flask is placed in an ice bath to lower the solubility and
precipitate the acetylsalicylic acid product.

The aspirin crystals are collected on a Buchner funnel and washed with additional ice cold
distilled water. Ice cold distilled water was used instead of room temperature distilled water
because aspirin is insoluble in cold water and to avoid dissolving any of the aspirin products.
The acetic acid and phosphoric acid are water soluble, in any temperature water, and can be
removed by washing the aspirin with the chilled water. Salicylic acid is only slightly soluble in
water and any unreacted salicylic acid cannot be removed completely in the washing process.
The first set of crystals will be considered as the crude product. Using this, percentage yield was
determined 96.92%. The computed crude product yield is 1.26 g which is lower than the
theoretical yield, 1.30 g. This error could be due to weighing of product when it is still wet.
However, instead of having a higher yield due to presence of water, the crude is actually lower
which means there were already errors from the start of the experiment. This incident might be
a result of presence of impurities in the compound used, improper conducting of techniques and
human errors being reckless or not cautious.
Once the final product (aspirin crystals) is purified it was allowed to dry. It was then weighed and
tested for purity. Final purification is accomplished through recrystallization. The crude product
was dissolved in water and subjected to heat; obtaining a supersaturated solution. Then, the
solution was left to cool at room temperature before putting in a cold bath. Finally, unwanted
substances mainly impurities were eliminated using cold water via suction filtration. Hot gravity
filtration is not recommended since esters hydrolyze in boiling water under acidic conditions.
And if we use hot water, no crystal/s will be extracted since high temperature will inhibit the
crystals to form.
Afterwards, final product was weighed and percent recovery was also computed 63.49%. The
mass of the recrystallized sample (0.8 g) is relatively higher than the crude product (1.26 g). The
following factors may have influenced the result product: (a) amount of water used to dissolve
the crude product, (b) failure to eliminate impurities/unwanted substances; and (c) weighing of
wet recrystallized sample. These factors all contribute to low purity of the product.
Melting point is a physical property inherent to a substances identity. The purer the substance,
the smaller the melting range is. The broader range of an impure sample results from the
creation of a solution upon melting. A mixtures melting point is a colligative property which
means it is dependent on the ratio of the chemicals present. For this experiment, we can
assume that the acetylsalicylic acid is the solvent and the impurities as the solute. The more
impurities present, the lower the melting point.
The melting point range of pure aspirin is 138-140 C and the melting point range of the salicylic
acid starting material is 158-161 C. Based on table 6, the melting point range of crude sample
is 150-157 degrees Celsius while the recrystallized sample ranges from 151 to 154 degrees
Celsius. If the product is not pure, it will acquire lower melting point relative to the literature
value. The melting point range of the recrystallized sample that we have obtained is much
higher than the literature value thus; the final product is not aspirin. If we compare the melting
point ranges, we can say that the product is salicylic acid.
Characterization tests such as solubility in water, FeCl3 test, KMnO4 test and Iodine test were
conducted to differentiate the product form the starting materials. Due to the presence of large

non-polar group, the starting materials and the synthesized product as well as the commercial
are all insoluble. However, acetic anhydride must give a positive result and react with water as
shown in the reaction below.

When FeCl3 was used to test the recrystallized products purity, the product formed a purple
complex which means it is not pure since Iron (III) ion reacts with phenols. Salicylic acid
contains phenols while acetylsalicylic acid does not.
.

FeCl3

Cl-

Fe

2H+

2Cl-

A test using Potassium permanganate will give a brown precipitate as a positive result. It is used
to detect the presence of salicylic acid since it reacts with the former to produce a quinone and
MnO2 (brown precipitate). As observed in table 8, final product gave a positive result hence, it is
not a pure aspirin and it contains salicylic acid.

Lastly, commercial aspirin and synthesized aspirin were differentiated using I2/KI test which
detects the presence of starch in the sample. Commercial aspirin reacts with the reagent since
starch serves as binder for its tablet. Positive reaction will form a blue intense complex as
shown below. Based on table 9, the synthesized aspirin gave a negative result.
I- + I2 + starch

(starch, I-, I2)

VII. SUMMARY AND CONCLUSION

Organic synthesis is a process of converting a starting material to a certain product through
various reactions and observations. To understand this, an experiment was conducted
synthesis of Aspirin. Synthesis of aspirin was produced using esterification of salicylic acid in

acetic anhydride in the presence of an acid catalyst, which is 85% phosphoric acid and heat by
means of nucleophilic acyl substitution. After heating, water was added to hydrolyze excess
acetic anhydride into acetic acid. Cold bath and suction filtration proceeded to extract crystals
that will serve as crude product. Percentage yield was determined and the value computed was
96.92%. This means that the mass of crude product (1.26 g) is lower than the theoretical yield
(1.30 g). The crude product was used to synthesize aspirin through the use of the same
procedure and set up. The recrystallized sample has relatively lower weight (0.8 g) than the
crude sample giving a 63.49 % recovery.
Melting point of both samples was determined to identify them and to classify their purity.
Results showed that the crude sample has 150-157 degrees Celsius range of melting point
while the recrystallized sample has 151-154 degrees Celsius range. The literature value of a
pure aspirin is 135 degree Celsius and if the sample has lower melting point, then it contains
impurities. However, our samples have relatively higher ranges thus; the final product was not
aspirin and identified to be salicylic acid. It is so since the melting point of salicylic acid ranges
from 158-161 degrees Celsius. This proves that certain errors were committed during the
experiment.
To characterize the products, different tests were also conducted. When solubility in water was
conducted, result showed that the starting materials and the products were insoluble however
acetic anhydride gave a positive result. Ferric chloride test which gives a positive result of
forming purple complex was also done. Since Iron (III) reacts with phenols which can be found
in salicylic acid, the recrystallized product gave a positive result. Potassium permanganate test
was also used for the presence of salicylic acid. The product showed a positive result which is
forming a brown precipitate and a quinone. The last test is for the commercial aspirin and the
synthesized aspirin. Iodoform test was used to detect the presence of starch which gives a blue
intense complex as a positive result. Since starch is used as a binder for a tablet, the
commercial aspirin reacted.
Based on the result, we can conclude that we fail to synthesize aspirin. This is mainly due to
weighing method, time of drying and uncompleted filtration.

VIII. REFERENCES

Baum S., Bowen W., Poulter S., Laboratory Exercises in Organic & Biological
Chemistry, 2nd Ed. Esterification. Macmillan Publishing Co.:New York
[2] Bettelheim F., Brown W., March L., Introduction to Organic and Biochemmistry.
5th Ed. From Willow Bark to Aspirin-And Beyond. pg 214. Thomson Brooks/Cole:
Singapore
th
[3] Beran J., Lab Manual for Principles of General Chemistry, 7 Ed. Experiment 28,
pg 323.
th
[4] McMurry, J., Organic Chemistry, 7 Ed. Esterification. pg 317-318, 323.
[1]

[5]

Rowland et al., Organic Chemistry Laboratory Manual: Susquehanna University.

Thomson Learning: Ohio

IX. RECOMMENDATIONS
Future experimenters could take steps to better the yield by running the reaction for longer than
15 minutes to encourage more product formation, or by more carefully rinsing the flask when
transferring crystals. Also, some product may have been lost when transferring thus; Id suggest
being more cautious since the sample was transferred to different medium many times.
Cleanliness of the glass wares must also be enhanced to avoid impurities and unwanted
substances. We should add a lot more time on the experiment especially on the drying and
filtration part. The drying of the filter paper and the melting point determination is not done
properly because of the insufficient time allotted.