QUANTITATIVE ANALYSIS OF ACETYLSALICYLIC ACID IN ASPIRIN

TABLETS BY BACK-TITRATION

G.M.L. CHUNGUNCO1 AND J.R.N. GENTOLEA2

1
DEPARTMENT OF MINING, METALLURGICAL, AND MATERIALS ENGINEERING, COLLEGE OF ENGINEERING
2
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
DATE PERFORMED: SEPTEMBER 19, 2017
INSTRUCTOR’S NAME: MELLA, L.

1. Discuss the use of a more dilute NaOH serve as representative samples of the aspirin
solution for the standardization of NaOH. sample.
3. Discuss the principles behind the use of
A dilute solution has less moles per mL than a back titration in the analysis of aspirin
more concentrated one. This decreases the tablet.
number of NaOH moles per drop. Since one
drop cannot be further divided during The reaction is as follows:
titration, a more dilute NaOH solution
prevents sudden overtitration and permits
greater accuracy in determining the endpoint.
Using a more concentrated solution runs the
risk of making the indicator change color
drastically after the addition of just one drop. Figure 1. Hydrolysis of ASA3
From this, a much more accurate
concentration of NaOH can be computed. The hydrolysis of ASA is incredibly slow
because it is an ester2. The hydrolysis of an
2. Explain the rationale behind the ester has slow rate-determining steps.
dilution and aliquoting of the aspirin
sample.

Dilution lessens the number of moles of ASA

per unit volume. This in turn lessens the local
concentration of each unit volume that comes
into contact with the titrant. As in the
previous number, a dilute sample produces a
sharper endpoint and prevents overtitration.
Since a diluted sample produces better
results, aliquots, having the same
concentration and equally divided mass of
ASA, were taken for practical reasons. Since
less moles of ASA are in an aliquot, less HCl
would be needed to reach endpoint, thus
conserving reagents and time. It is also easier
to manage a smaller sample when titrating
due to constant swirling; a larger sample does
not move as much when the same swirling
Figure 2. Hydrolysis of an ester2
Because of this, back titration is employed.
Excess NaOH is added to shift the equilibrium
towards complete hydrolysis1. Temperature
is increased to shift the endothermic reaction
forward. The excess base is then titrated with
HCl.
mO H −¿
excess =mHCl ¿
mO H −¿ −¿
T =mO H reac + mHCl ¿ ¿

force is applied. Aliquots lessen error and

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mASA= O H −¿
reac ¿
2
REFERENCES
From this, the moles, mass, and concentration
of ASA can be determined1. [1] Skoog, D.A.; West, D.M.; Holler, F.J.;
Crouch, S.R. Fundamentals of Analytical
4. What is the importance of simmering Chemistry, 9th ed.; Brooks/Cole: USA,
the tablet in the NaOH solution for 20 2014; pp 303
minutes?
From figure 1, ASA decomposes into salicylic [2] University of Victoria. Chem 463 Organic.
acid and acetate in the presence of OH-. Catalysis: The pH-Rate Dependence of the
Excess OH- increases the concentration of Hydrolysis of Aspirin.
OH- and shifts the reaction forward toward http://web.uvic.ca/~pmarrs/chem463/4
formation of salicylic acid and acetate. 63e35aspirinhydrolysis.pdf (accessed
Simmering, i.e. heating below the boiling Sep 21, 2017).
point, increases temperature. Bond breaking
is endothermic, thus the equilibrium shifts [3] ASELL Chemistry. Experiments Database.
forward, without too much evaporation of Kinetics of Hydrolysis of Acetylsalicylic
water, which is needed to contain NaOH and Acid, Aspirin.
ASA in solution. All this forces the reaction to http://www.asell.org/chemistry/experi
go towards completion faster. ments/experiments-database/kinetics-
of-hydrolysis-of-acetylsalicylic-acid--
5. Discuss the possible sources of errors aspirin#top (accessed Sep 16, 2017).
and their effect on calculated parameters.
[4] Utah State University. Department of
Moisture left in the burette or not rinsing it Chemistry and Biochemistry. Chemistry
with HCl results in diluted titrant in the 3600 Second Examination.
burette. A greater volume of HCl is needed to http://ion.chem.usu.edu/~sbialkow/Clas
titrate NaOH, creating positive error in the ses/3600/Exam2-1999/Exam2-key.html
concentration of excess NaOH and (accessed Sep 16, 2017).
consequently, ASA. Simmering NaOH for too
short a time may result in negative error as
the reaction did not go to completion,
meaning less moles of reacted hydroxide.
Using too concentrated NaOH for
standardization risks overtitration and thus
higher computed molarity of NaOH.
Carbonate error from CO2 in distilled water
that is not boiled (or mixing boiled distilled
water with normal distilled water from
previous washings) decreases pH, as NaOH
reacts with CO2 to form bicarbonates and
carbonates4. This increases the volume
needed for titrating the KHP standard or
decreases the volume of HCl titrant needed
for ASA analysis, thereby decreasing
calculated values for NaOH concentration or
increasing calculated moles of reacted
hydroxide, respectively.

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