Experiment # 4

DETERMINATION OF ASPIRIN BY INDIRECT TITRATION

De Jesus, Mirra P.
Group Mates:
Bautista, Angelic Russel
Macañas, Micah
September 24, 2014

Introduction

From the previous experiment we have
learned to determine the volumetric
identification of acetic acid in vinegar by using
the method of titration, in this experiment
indirect titration was the process used to
determine the aspirin in the sample. It is a
“backwards” method in which the experimenter
needs to find the concentration of the reactant
with an unknown concentration (the HCl
solution) by reacting it to an excess volume of
another reactant of a known concentration, in
this case which is the NaOH retrieved from the
previous experiment. Once these mixtures react
with each other, the resulting mixture or the
analyte solution is titrated back in the process
to show how much of the excess reactant was
used in the first titration and the original
concentration of the analyte can then be
calculated. Along the process, we were
expected to accomplish the objectives which is:
(1) to evaluate the purity of an aspirin sample;
(2) to develop techniques for the proper
dilution of a solution to a definite volume and
the use of a volumetric pipet; and (3) to learn
how to carry out calculations involving back-
titration.
Methodology
In accordance to this experiment we
had to use the following equipment and
instruments: 250 mL Erlenmeyer flask, 250
Volumetric flask, 100 mL Volumetric flask, 20.00
mL pipette, 50.00 mL pipette, 50.00 mL acid
burette, 50.00 mL base burette, 25.00 or 50.00
mL graduated cylinder, standard 0.1 N NaOH
solution from Experiment 3, concentrated HCl
solution, phenol red and phenolphthalein
indicator, clean reagent bottle, ordinary pan or
digital balance, analytical balance, hot plate and
aspirin sample.
For the preparation and standardization
of 0.1 N HCl solution, 11.6 N of HCl was
prepared and we had to equate it to obtain 0.1
N of HCl solution. 0.86 mL from the 11.6 N HCl
solution was pipet out and placed in a 100 mL
volumetric flask, it was then added with distilled
water up until it had reached its mark. After the
solution was prepared, 20.00 mL was
transferred to each of the three 250 mL
Erlenmeyer flasks using a pipette and 2 to 3
drops of phenolphthalein indicator was also
added to those three flasks containing 20 mL
diluted HCl solution. All of those were titrated
with the standard NaOH solution, which was
stored from the last experiment, until a
permanent pink colour was obtained.
Subsequent readings that were needed were
also recorded during the course of the
experimentation.
Aspirin Front
The next procedure is the analysis of View
aspirin. The aspirin tablet was crushed to form
powder and into a 250 mL Erlenmeyer flask, we
weighed out to the nearest tenth of a milligram
0.1 gram of the ground aspirin sample. 20.00
mL of the standard 0.1 N NaOH solution was
Heating of
added inside the Erlenmeyer flask to let the
Aspirin in
aspirin dissolve, because aspirin is a weak acid
Erlenmeyer
that undergoes slow hydrolysis it was simmered flask on a hot
on the hot plate for 10-15 minutes to hydrolyse plate
the aspirin. After simmering it, we had to let it
reach its ambient temperature before cooling it
in a container filled with ice cold water. The
solution was transferred into a 250 mL Hydrolysed
volumetric flask and from the Erlenmeyer flask, Aspirin in a
it was washed several times with distilled water 250 mL
and poured the washings obtained into the Erlenmeyer
volumetric flask until it had reached its flask
indicated mark. The solution was mixed well
and 50.00 mL aliquot portions was transferred
to each of the three Erlenmeyer flasks. Phenol Titrated
red was used as an indicator for the titration hydrolysed
and it was added up to 2-3 drops to the analyte. Aspirin with
The three samples were then titrated with the standardized
HCl solution
standardized HCl solution until it reached the
at equivalence
equivalence point and a change of colour was
point
observed.

Table 1: Analysis of Aspirin Over titrated

hydrolysed
Aspirin with
standardized
Aspirin Back HCl solution
View at endpoint
 Experimenter
holding
titrated
hydrolysed
Aspirin with
standardized
HCl and the
set-up is
displayed at
the
background

Results and Discussion

Table 3: Preparation of 0.1 N HCl

NConc HCl 11.6 N
VConc HCl 0.86 mL ± 0.02 mL

Table 4: Standardization of 0.1 N HCl

NNaOH (ave. fr. Expt. 3)
Trial 1
VNaOH 21.05 mL ± 0.05 mL
VHCl 20.00 mL ± 0.02 mL
NHCl 0.1084 N ± 0.03087
Ave. NHCl
0.1030 N ± 0.003168
Trial 2 Trial 3
21.12 mL ± 0.05 mL 21.09 mL ± 0.05 mL
20.00 mL ± 0.02 mL 20.00 mL ± 0.02 mL
0.1088 N ± 0.03086 0.1086 N ± 0.03086
0.1086 N ± 0.0002000

Table 5: Analysis of Aspirin (ASA)

Mass ASA Sample 0.1014 g ± 0.0001 g
Trial 1 Trial 2 Trial 3
Valiquot 50 mL ± 0.02 mL 50 mL ± 0.02 mL 50 mL ± 0.02 mL
VHCl 1.32 mL ± 0.05 mL 1.79 mL ± 0.05 mL 1.40 mL ±0.05 mL
MassASA 0.1210 g ± 0.04884 0.09802 g ± 0.04160 0.1171 g ± 0.04718
%ASA 119% ± 0.4036 97% ± 0.4244 115% ± 0.4029
Ave. ASA 110% ± 0.4103

Regarding the preparation of 0.1 N HCl ( X ) ( 11.6 N ) =( 100 mL ) ( 0 .1 N )

solution, we had to acquire the desired ( 100 mL ) ( 0. 1 N )
normality since the original that was given to us X=
was 11.6 N and taking into consideration that
( 11. 6 N )
there is 0.1 N in 100 mL of the solution, the X =0 .86 mL
values were then equated as to what is shown:
 0.86 mL were then taken from the their consequent uncertainty, the formula for
original sample using a pipette with 0.02 mL standard deviation was used, to recall it is:
uncertainty.
2

The data for the normality of sodium

hydroxide were taken from Experiment 3 and
the uncertainty based on its attained standard
S . D .=
√ ∑ ( Χ− Χ ) n−1

( 0. 1084−0. 1086 )2 +( 0 .1088−0. 1086 )2 + (0 . 1086−0 .1086 )2

deviation. While the formula used to find the
normality of HCl is:
S . D .=
3−1
=0 . 0002000
√
( N )(V )=( N
HCl HCl NaOH )(V NaOH )
After obtaining the results from the
standardization of 0.1 normality of HCl solution,
And the respective calculations are:
the next step is to proceed to the analysis of
( 0 . 1030N )( 21 . 05 mL ) aspirin (Acetylsalicylic acid or ASA) which was
N of T1= =0 . 1084 N derived from two acids namely acetic acid and
( 20 .00 mL )
salicylic acid. It involves alkaline hydrolysis of
( 0 . 1030N )( 21 .12 mL ) the reaction of the aspirin solution with a
N of T2= =0 .1088 N measured amount of sodium hydroxide which is
( 20. 00 mL )
20 mL. Sodium hydroxide is the amount that
( 0. 1030N ) ( 21. 09 mL ) exceeds the amount of aspirin present. Also, at
N of T3= =0 . 1086 N
( 20 .00 mL ) room temperature, the hydrolysis reaction or
splitting of water proceeds at a very slow rate,
thus, it was conventionally heated to increase
Each uncertainties were calculated the rate of the reaction. From the hydrolysis
using the values as well as the uncertainties of that occurred, we can infer that the equation is:
the normality of NaOH, volume of both NaOH CH 3 COOC 6 H 4 COOH+2 NaOH →
and HCl:
CH 3 COO .Na+HOC 6 H 4 COO. Na+H 2 O
2 2
0. 02 0 . 003168
Uncertainty =
√( 0. 05 2
V NaOH) + ( V HCl ) ( +
0 .1030 N ) Wherein,

2 2 2  CH3COOC6H4COOH is the Acetylsalicylic

T 1= √(0.2105.05 mL ) +(020.02. 00 mL ) +(00 ..1030003168N )
¿ 0 .03087 
acid
NaOH is the Sodium hydroxide
 CH3COONa is the Sodium acetate or
2 2 2
T 2= √(021.05.12 mL ) +(0.2002.00 mL ) +(00 .003168
¿ 0 .03086
.1030 N )

Sodium ethanoate
HOC6H4COONa is the Sodium-2-
hydroxybenzoate or Sodium salicylate
2 2 2  H20 is the water
T 3= √(021. 05. 09 mL ) +(020. 02. 00 mL ) +(00 .. 003168
¿ 0 .03086
1030 N )

The average had to be considered as And the succeeding process is where

representation of these three trials and to find back titration occurs wherein HCl is titrated
with the added NaOH in the aspirin solution.
 NaOH + HCl→ NaCl+ H 2 O Uncertainty=
2
0. 003168 0 . 0002000 2 0. 02 2 0. 05 2
In doing this, the amount
hydrochloric acid which was neutralized to
of
the √( 0. 1030 N NaOH
+
)(
0 . 1086 N HCl
+
)(
20 mL
+
V HCl )( )
unreactive sodium hydroxide present in the T 1=
2
solution was easily determined. In turn, the 0. 003168 0 . 0002000 2 0. 02 2 0. 05 2

amount of sodium hydroxide added to

amount of aspirin was also determined.
the √( 0. 1030 N NaOH
+
)(
0 . 1086 N HCl
+
)(
20 mL
+ )(
1 . 32mL )
=0. 04884

T 2=
2
0. 003168 0 . 0002000 2 0. 02 2 0. 05 2

Aspirin molecule reacts with two

hydroxide ions. To overcome this problem, a
√( 0. 1030 N NaOH
+
)(
0 . 1086 N HCl
+
)(
20 mL
+ )(
1 . 79mL )
=0. 04160
known excess amount of base is added to the
sample solution and an HCl titration is carried T3=
2
0. 003168 0 . 0002000 2 0. 02 2 0. 05 2
out to determine the amount of unreacted
base. This is subtracted from the initial amount √( 0. 1030 N NaOH
+
)(
0 . 1086 N HCl
+
)(
20 mL
+ )(
1 . 40 mL )
of base to find the amount of base that actually =0. 04718
reacted with the aspirin and hence the quantity
To compute for the percentage of ASA
of aspirin in the analyte. To simply put, the
(which illustrates the purity of ASA):
mass of sample of ASA in the solution is
illustrated by the formula below: Mass ASA
% ASA = ×100
0 .1014 g
[
Mass ASA= Equivalent Weight ASA ( NV NaOH ) −( NV HCl ) (250 mL
50 mL )]
0. 1210 g
mg 250mL T 1= ×100=119 %
T 1=90.085
meq [ ( 0.1030 N×20mL) −( 0 .1086 N ×1 .32mL ) ( 50 mL )] 0. 1014 g
=121.0mg/0 .1210 g
0.09802
mg 250mL T 2= ×100=97 %
T 2=90.085
meq [
( 0.1030 N×20mL) −( 0 .1086 N ×1.79mL)
50mL ( )] 0.1014 g
=98.02mg/0 .09802g 0 .1171
T 3= ×100=115%
mg 0 . 1014 g
T 3=90.085
meq [ ( 0.1030 N×20mL )−( 0 .1086 N×1.40mL) (25050mLmL )]
And for the uncertainty of the
=117 .1 mg/0.1171g
percentage, it is composed of the original mass
To compute the uncertainties of the of the powdered ASA with its uncertainty and
mass of the three trials, it involves the the computed mass of ASA with its uncertainty:
normality of both NaOH and HCl, the volume of 2 2
Uncertainty Mass of ASA
HCl in the standardization of HCl and in the
analysis of aspirin with its respective
uncertainties.
Uncertainty=
√(
Mass of ASA
0. 04884 2 0 . 0001g
+
0 . 0001g
0 . 1014g
2
)( )
T 1=
√(
=0. 4036
0. 1210 )(+
0 . 1014g )
 0 . 04160 2 0. 0001g 2  If the reaction between the titrant and
T2=
√(
=0. 4244
)(
0 . 09802
+
0. 1014g ) the analyst is extremely slow which is
exemplified by the aspirin
 The sample consists of certain
2 2 impurities which are bound to interfere
T3= (√ 00 .04718
.1171 ) +(
0.0001g
0.1014g ) with a regular forward titration
 Used in the analysis of solids, which are
=0. 4029
insoluble or partially soluble in water
 The endpoint of a reverse titration is
1. If for instance, the NaOH used is more simpler to identify than the endpoint of
diluted during the titration, then larger a normal titration
amount of HCl solution is also needed.  If one of the reactants is volatile, for
It is because there are more moles in example ammonia
the content of a larger amount of
Some errors were also inevitable during
solution and since the equivalence
the experimentation, some may have faulty
point in titration means that the moles
weighing, titration, some of the aspirin were
of acid is equal to the moles of the base
not completely dissolved during simmering and
then in effect to increase the moles of
etc. Conversely, the objectives that were stated
HCl, the volume must also increase.
were met and well performed, and as a result
2. What volume of 1.0 N NaOH is used in
we were able to quantitatively determine the
the hydrolysis of four 250mg tablets of
amount of acetylsalicylic acid in aspirin (ASA) by
aspirin (90%pure acetylsalicylic acid) if
back-titration, analyse the purity of aspirin and
10.00mL of 0.05 N HCl is consumed in
to apply the concept of back-titration in the
the back titration?
determination of its purity.
From the given:
NNaOH – 1.0 N References
NHCl – 0.05 N
VHCl – 10.00mL
"Quantitative Inorganic Chemistry: The Final
( 0 .05 N ) ( 10 .00mL )
V NaOH = Wave". Web. 24 September 2014.
1. 0 N <http://austriajamesonphysics102lab.w
¿ 0 .5 mL ordpress.com/>.
From the computation above, we can
presume that 0.5 mL of 1.0 N NaOH is needed
to hydrolyse the aspirin. Rangwala, Fatima. "Back Titration". Web. 24
September 2014.
Conclusion <http://www.buzzle.com/articles/back-
titration.html>.
Although the indirect titration has a
difficult and complicated approach compared to
direct titration it elicits accuracy to certain
circumstances that direct titration cannot
achieve, such as:
Helmenstine, Anne Marie."Back Titration
Definition". Web. 24 September 2014.
<http://chemistry.about.com/od/organi
cchemistryglossary/fl/Back-Titration-
Definition.htm>.

Tharian, Abey. "RET Lab Lesson Plan

, Topic: Determination of aspirin in
tablets using back titration
". Web. 24 September 2014.
<http://www.njit.edu/precollege/docs/
RET_2010_Aspirin_in_Tablets_Lesson.p
df>.

"Chemistry Tutorial: Back (Indirect) Titration

Calculations". Web. 24 September
2014.
<http://www.ausetute.com.au/backtitr
ation.html>.