Determination of Aspirin by Indirect Titration

J. Elijah1, J. Paderes2, S. Nota3

1
Department of Physical Sciences, College of Science, UP Baguio, Baguio City 2600
Performed 18 February 2020; Submitted 26 February 2020

ABSTRACT

Titration is a quantitative chemical analysis that determines the concentration of an identified

analyte. There are two different methods of titration. Direct titration is a method in which the
titrant is directly added to the analyte to an end point. Indirect titration or back titration involves
the addition of a quantity of a reagent to a solution which is in excess. The amount of excess
reagent is shown after a subsequent titration is performed. In this experiment, the percent
acetylsalicylic acid content of aspirin was determined through volumetric analysis. 0.1 N
hydrochloric acid (HCl) solution was standardized and used as titrant and phenol red was used
as indicator for the analysis. The end point, the experimental point at which the completion of
the reaction is marked, was detected by a color change to yellow upon the addition of the titrant
to the solution. Four trials were performed for the analysis of aspirin. The computed mean
normality of HCl, 0.08431 N ±0.1 mL, was computed to determine how likely it is for a random
variable underlying the data set to be normally distributed. The relative standard deviation,
2.07567311%, was also determined to see how the mean is related to the standard deviation to
know how close the gathered data are to each other. The results gathered were precise
however, the resulting concentration of aspirin was lower than the theoretical which may be
caused by certain errors while performing the experiment.

Introduction
Volumetric method of analysis is a
technique which compares an unknown with
a standard through titration. When a titrant
reacts directly with an analyte the procedure
is termed as direct titration. Direct titration
methods are those in which the analyte is
directly titrated to an end point by a solution
of known concentration (Shiundu, n.s.). In
cases where the titration reaction is slow, a
suitable indicator is not available, or there is
no useful direct titration reaction, an indirect
titration may be utilized. Indirect titration
methods refers to the reverse process of
performing titration. Generally, a quantity of
a reagent is added to a solution known to be
in excess with respect to a specific reaction
(Harvey, 2000). This technique is known as
back titration. Back titration involves an
intermediate reactant which is added in
excess amounts to exhaust the analyte,
then the degree of excess is determined by
a subsequent titration of the unreacted
intermediate with the titrant (Harvey, 2000).
The subsequent titration shows the amount
of the excess reagent used in the first
titration, thus allowing the original
concentration of the analyte to be
calculated. Regardless of the type of
titration, an indicator is always used to
detect the end point, the experimental point
at which the completion of the reaction is
marked.
Acetylsalicylic acid (aspirin) is a weak acid
therefore the end point would be difficult to
identify using direct titration since the
reaction may proceed at a slower pace.
However, using back titration the end point
is more easily detected. This type of
reaction occurs at a high rate and thus
produces an end point that is abrupt and
easily identified. Through back titration the
amount of hydrochloric acid (HCl) needed to
neutralize the unreacted sodium hydroxide
(NaOH) in the solution can be determined.
Knowing this along with the amount of
NaOH that was added, the amount of
aspirin that reacted with the NaOH can also
be determined.
The experiment aimed to evaluate the purity
of an aspirin sample through titration
methods. Specifically, the experiment
focused on the necessary calculations
involved in back titrations. Furthermore, it
aimed to develop the techniques for proper
dilution of a solution to a definite volume
and the use of a volumetric pipette.
Methodology
A. Preparation and Standardization of
0.1 N HCl Solution
Figure 1. Diagram of the preparation and
standardization of 0.1 N HCl solution.
Firstly, 250 mL 0.1 N HCl solution was
prepared in a volumetric flask by computing
the volume using equation 1 of the
appendix. 2.083 ml of HCl was placed in a
volumetric flask which contained a small
amount of water and was then diluted up to
the mark then set aside for later use.Qq
1 Standardization of NaOH Solution
Lastly, 20.00 mL of the prepared acid
solution was pipetted out into four 250 mL
Erlenmeyer flasks for four trials. Two to
three drops of phenolphthalein were then
added. The previously prepared and
standardized 0.1 N Sodium hydroxide
solution from experiment 3 were used in this
experiment to titrate the HCl solution until a
permanent faint pink color is obtained.
B. Analysis of Aspirin
Figure 2. Diagram of the analysis of aspirin.
Using a mortar and pestle, the aspirin was
first ground and then weighted to the
nearest tenth of a milligram and placed into
a 250 mL Erlenmeyer flask. 50.00 mL of the
standardized NaOH solution was then
added to the flask then simmered for 10 to
15 minutes using a hot plate in order to
hydrolyze the aspirin sample. The mixture
was then left to cool down.
The cooled reaction mixture was
then transferred into a 250 ml volumetric
flask. The flask was washed several times
with distilled water and the washings were
transferred into the volumetric flask.
Afterwards, it was diluted with distilled water
and mixed well by several inversions of the
flask.
The 50.00 mL aliquot of the hydrolyzed
aspirin was then titrated with the
standardized HCl solution. Two to three
drops of phenol red were used as an
indicator until yellow end point is obtained.
Four trials of the experiment were
performed.
Results
Mean Normality of HCl 0.08431 N ± 0.1 mL
Relative Standard
Deviation 2.07567311%
Table 4. Statistical Analysis of Preparation and
Since the preparation and standardization of
NaOH solution in Part A involves only a
small sample or set of data (2 trials), the
equivalent concentration or the normality of
HCl was computed to determine how likely it
is for a random variable underlying the data
set to be normally distributed. The relative
standard deviation was also determined to
see how the mean is related to the standard
deviation to know how close the gathered
data are to each other.
In this experiment, it is seen in table 4 that
the HCl sample has a low normality,
meaning there is no random variable
underlying that data, which is then
supported by its low standard deviation
indicating precision among the recorded
data in the two trials. In the case of the
relative standard deviation, it has a low
value in relation to the mean which also
implies the closeness of the gathered data
with each other and thus, making the results
more reliable as evidenced by the endpoint
showing a faint pink color which persisted
for a minute or more.
For Part B, titration is marked done if the
color of the analyte solution becomes yellow
in color. Results of the experiment shows
that the normality of HCl was short from the
standard 0.1 N to 0.08431 N. Using
equation 2 of the appendix, the actual value
gave a mean % ASA of 17. 18385 % which
is lower compared to the theoretical % ASA
which is 39.70%, calculated using equation
3 of the appendix. This just shows that the
results are varying due to some errors in
performing the experiment which may
include some interferences in the solution,
binders used in making the aspirin or can be
because of the faulty burette used. On the
other hand, it can also be the company's
error in weighing and declaring a different
mass of the aspirin product.
Discussion
Back titration involves determining the
concentration of an analyte by reacting it
with an unknown number of moles of
excess reagent. In this experiment, aspirin
is determined in the solution since it is a
compound derived from two acids, acetic
acid and salicylic acid. With that, it can then
be hydrolyzed by alkali and the two
components neutralized simultaneously.
The procedure given is an indirect one since
it degrades the aspirin. It is quite important
to distinguish between intact aspirin and its
degraded form in assessing the potency of
the drug.
For the first part of the experiment which
includes preparation and standardization of
0.1 N HCl solution, a standard NaOH
solution was titrated until a faint pink color
was achieved. Results on this part shows
low mean normality which means that there
has been no random interruption in terms of
the data gathered and that the sample
results were close to each other. Also, the
low relative standard deviation implies the
precision between the results gathered and
the relationship between the standard
deviation and the mean. This part of the
experiment indicates precise measurements
as evidenced on the faint pink color
endpoint of the two trials made.
For Part B which involves the analysis of
aspirin, a stock solution of hydrolyzed
aspirin with the standardized HCl solution
was titrated until a yellow endpoint
appeared. The results for this part show low
% ASA compared to the computed
theoretical concentration. Although the
results gathered were titrated to the
endpoint and were precise, the resulting
concentration of aspirin was lower than the
theoretical which may be caused by certain
errors while performing the experiment. This
may include some interferences in the
solution, the exposure of aspirin to the
environment and its concentration on the
solution and may also be because of the
faulty burette used. This may also be a
result of the company's error in declaring
the exact mass of the aspirin product.
Overall, using back titration, the end-point is
more easily recognised in this reaction, as it
is a reaction between a strong base and a
strong acid. This type of reaction occurs at a
high rate and thus produces an end-point
which is abrupt and easily seen which is
seen on the faint pink and yellow endpoints.
The results gathered were precise and
accurate, except the relation between the
actual % ASA and the theoretical
concentration which are caused by some
operative and random errors.
References
[1] Harvey, D. (2000). Modern Analtical
Chemistry. USA: The McGraw-Hill
Companies, Inc.
[2] Shiundu, P.M. (n.s.). Volumetric
Chemical Analysis. African Virtual
University.
[3]
Appendix

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