Analysis of Aspirin1

Frederick R. Wight
Manatee Community College

Introduction
Acetylsalicyclic acid, aspirin, was synthesized from salicylic acid in CHM2045L
by the reaction in Figure 1:
Figure 1 Aspirin synthesis:
O

O
O

OH

O
O

CH3

CH3

Acetic Anhydride

+ HC
3

O
OH

O
O

Salicylic Acid

CH3

Aspirin

Acetic Acid

Aspirin is not stable indefinitely and can, over time, react with moisture to revert back to
salicylic acid by a process known as hydrolysis, Figure 2.
Figure 2: Aspirin Hydrolysis
O

O
OH

O
O

Aspirin

H2O

O
OH

+ HC
3

OH

OH
CH3

Salicylic Acid

Acetic Acid

In this laboratory we will analyze lab synthesized and commercial aspirin for purity by
both qualitative and quantitative methods.
Qualitatively, the purity of an aspirin sample can be determined from its melting point.
Qualitative chemical analysis is concerned with identifying the elements and compounds
present in a sample of matter. The melting point of a substance is essentially independent
of atmospheric pressure, but it is always lowered by the presence of impurities (recall
colligative properties: freezing point depression and boiling point elevation). The degree
of lowering of the melting point depends on the nature and concentration of the
impurities. The term melting point is somewhat of a misnomer since substances rarely
melt at a single temperature. Rather they melt over a range of temperatures and the
smaller the temperature range the purer the substance. Note also that even though
1

Partly adapted from a procedure by Kerber, Akhtar & Schneider, SUNY Stony Brook. Parts of this lab
have been taken from Laboratory Manual for Principles of General Chemistry, J.A. Beran

Aspirin Synthesis

salicylic acid has a higher melting point than aspirin, if the aspirin has a trace amount of
salicylic acid the melting point of the mixture will be lower than pure aspirin.
Qualitatively, it is also possible to detect the presence of salicylic acid using ferric
chloride. Salicylic acid forms a colored complex with acidified iron (III) ion which is
readily visible at low concentrations. Figure 3.

Figure 3:
The addition of acidified iron (III) ion produces the violet tetraaquosalicylatroiron (III) complex.
+

O-

O
+3

- + [Fe(H2O)6 ]
C O

Fe(H2O)4
O

+ H 2O + H 3O

Aspirin does not form this complex. This forms the basis for a simple qualitative test for
the presence of unreacted salicylic acid in your aspirin.
Quantitatively, the purity of an aspirin sample can be determined by a simple acid-base
titration. Both aspirin and salicylic acid are weak organic acids but with different
properties, Table 1.
Table 1
Compound:
Formula:
Molar Mass:
Melting point:
Ka
pKa
Solubility (g/100mL)

Salicylic Acid
C7H6O3
138.12
158-160C
1.08 x 10-3
2.99
0.18

Aspirin
C9H8O4
180.15
140-142C
2.72 x 10-5
4.57
0.25

A standardized NaOH solution titrates the acid to the phenolphthalein endpoint,

where
(1) Volume NaOH, L x Molarity of NaOH, mol/L = mol NaOH = moles acid
Note that salicylic acid has a lower molar mass. This means if we titrate the same
weight of each substance it will take more NaOH to reach the endpoint with salicylic
acid. Thus if our aspirin is contaminated with salicylic acid it will require more NaOH to
reach the endpoint than if our sample were 100% pure aspirin. In fact, by titrating a
known weight of our sample with a standard NaOH solution we can determine the
effective molar mass (EMM).
EMM = grams of sample/moles acid from titration

Aspirin Synthesis

If the sample consists of ONLY salicylic acid and aspirin, then the percent composition
can be derived from the EMM according to the relationship:
% Aspirin = 100(EMM-138.12)/(180.15-138.12) = 2.379(EMM-138.12)
If the EMM is greater than 180.15 or less than 138.12 then the formula does not apply.
Procedure
Part I
1. Place a few crystals of pure aspirin, salicylic acid and the lab synthesized aspirin
in 3 separate test tubes.
2. Add approximately 3-5 drops of 95% ethanol to dissolve the aspirin. Then add 1-2
ml of water to each sample.
3. Add 2 drops of Iron (III) Chloride solution to each and observe the color of each
sample. Record the observations in your notebook.
Part IIa
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Part IIb

Calculate the mass of pure aspirin that requires 20 mL of a 0.1 M NaOH to

reach the stoichiometric equivalence point. Show your instructor to verify
Weigh out this mass of pure aspirin and place it into a 250 mL Erlenmeyer
flask.
Add 10 mL of 95% ethanol (Make sure you add this before the water!!)
Add 50 mL of DI water
Add 2 drops of phenolphthalein indicator and swirl to dissolve the aspirin
Fill a clean 50 mL buret with standardized 0.1 M NaOH
Read the initial volume
Slowly add the NaOH solution to the flask with the aspirin in it until the
endpoint is reached (very light pink color)
Record the final buret reading along with the exact molarity of the base
Repeat the titration.

1. Repeat the procedure above using the aspirin synthesized in CHM2045L.

Aspirin Synthesis

Data Sheet
Part I Observations on addition of Iron(III)chloride
Salicylic acid:____________________________________________________________
Pure aspirin:_____________________________________________________________
Lab synthesized aspirin:____________________________________________________
Part IIa (Pure Aspirin)
Calculate the mass of aspirin needed to reach the stoichiometric equivalence point
with 20 mL of a 0.1 M NaOH solution. (Show calculation below)
.
Trial 1

Trial 2

____________

____________

Mass of aspirin sample (g)

Molarity of NaOH (mol/L)
Initial buret reading (mL)
Final buret reading (mL)
Volume of NaOH used (mL)
Moles of NaOH used
Effective Molar Mass (g/mol)
Percent purity of aspirin (%)
(Show calculations below for 1st run)
Average % purity of aspirin (%)

Aspirin Synthesis

Part IIb (Lab Synthesized Aspirin)

Calculate the mass of aspirin needed to reach the stoichiometric equivalence point
with 20 mL of a 0.1 M NaOH solution. (Show calculation below)

Trial 1

Trial 2

____________

____________

Mass of aspirin sample (g)

Molarity of NaOH (mol/L)
Initial buret reading (mL)
Final buret reading (mL)
Volume of NaOH used (mL)
Moles of NaOH used
Effective Molar Mass (g/mol)
Percent purity of aspirin (%)
(Show calculations below for 1st run)
Average % purity of aspirin (%)

Aspirin Synthesis

Pre-Lab Questions
1.

A 0.536 g sample of aspirin prepared in the laboratory is dissolved in 95%

ethanol, diluted with water, and titrated to the phenolphthalein endpoint with 18.5
mL of a 0.135 M NaOH
a) How many moles of acetylsalicyclic acid are present in the sample?

b) Calculate the % purity of acetylsalicyclic acid in the aspirin sample

c) Determine the number of grams of acetylsalicyclic acid that will react with
25.00 mL of a 0.100 M NaOH solution

d) In the experiment 3.00 g of salicyclic acid reacts with an excess amount of

acetic anhydride. Calculate the theoretical yield of acetylsalicyclic acid for
this synthesis

2. Looking at the reaction used to prepare aspirin, can you suggest a reason why it might
be possible to obtain an EMM of less than 138.12?

Aspirin Synthesis