Astrero, Fatima; Marcos, Junica; Martin, King Dave; Navarro, Diana Rachelle

March 01, 2016

Chem 26.1 gh
Experiment # 4
DETERMINATION OF ASPIRIN BY INDIRECT TITRATION
INTRODUCTION
In direct titrations, a titrant of standard concentration is directly added to an
analyte of unknown concentration (Harris,2010). Indirect methods of titration is
carried out by adding a quantity of the excess reagent to a specific reaction and the
unconsumed excess reagent is determined via titration (Harris, 2010). Back titration
is a process where an excess which is used to consume an analyte is determined by
titration with a second titrant. It is useful when its endpoint is clearer than the
endpoint of the direct titration, or when an excess of the first reagent is required for
complete reaction with analyte (Harris, 2010)
Acetyl salicylic acid (C9H8O4), more commonly known as aspirin, is one of the
most widely used over-the-counter drugs. It is often taken to relieve pain such as
toothache, headache and may even lower fever. As its name suggests, acetyl
salicylic acid is a mixture of two acidsacetic acid and salicylic acid which may be
hyrdolized by an alkali to simultaneously neutralize the two acids. The weak acid
salts of these acids at equivalence point will result to a pH which lies within the
range of the indicator which is phenol red, giving an evident change in color from
pink to faint yellow.
The objectives of this experiment were to evaluate the purity of an aspirin
sample, to practice proper dilution of a solution and the use of a volumetric pipette
and to learn how to calculate and evaluate results in a back titration.
MATERIALS AND METHODS
In the preparation and standardization of 0.1 N HCl solution, 0.9 mL

0.05 mL

of 12N concentrated HCl was diluted in a 100-mL volumetric flask. In 3

separate Erlenmeyer flasks, 20.00 mL of the HCl solution was added and 2-3 drops
phenolphthalein as indicator was also added. It was then titrated with the standard
NaOH solution previously prepared in experiment 3 until a permanent faint pink
color was achieved. Titration was performed three times.
After successful standardization of the HCl solution, the aspirin sample was
analyzed. In a small beaker, 0.1 gram of aspirin was measured and 50.00 mL of
standard NaOH solution was added to the aspirin, which was simmered for about
10-15 minutes. The aspirin solution was the cooled and tansferred to a 250-mL
volumetric flask and was diluted to mark with distilled water. 50.0 mL aliquot of
stock solution of the hydrolyzed aspirin was then titrated with the standard HCl
solution using 2-3 drops phenol red to indicate a faint yellow endpoint. Titration was
also performed thrice.
Page 1 of 10

RESULTS
In this experiment, the determination of aspirin by indirect titration was done.
The experiment was divided into two parts; the preparation and standardization of
sodium hydroxide (NaOH) solution and the analysis of acetylsalicylic acid (ASA) or
aspirin. For the results, the tables for the different data are shown below.
DATA
A. Preparation and Standardization of NaOH solution
Normality of concentrated HCl
Volume of HCL used to prepare
0.1 N
Normality of Standard NaOH
Volume of HCL titrated ( 0.05
ml)
Volume of NaOH used ( 0.05
ml)
Normality of HCl

12 N
2.08 mL 0.0008 mL
0.1030 N
Trial 1
20.00 ml

Trial 2
20.00 ml

Trial 3
20.00ml

15.20 ml

15.40 mL

15.40 ml

0.07828 N
0.0004 N

0.07931 N
0.07931 N
0.0004 N
0.0004 N
Mean Normality of HCl
0.07897 0.0004
RSD
0.75%
Table 1. Standardization of NaOH solution using HCl
For the table 1, the normality of the concentrated hydrochloric acid (HCl) solution is
12 N. The volume of hydrochloric (HCl) acid solution used to prepare 0.1 N sodium
hydroxide (NaOH) is 0.90 ml with the uncertainty of 0.05 ml while the normality of
the standard sodium hydroxide (NaOH) solution which was used from the previous
experiment is 0.1030 N.
For the standardization of NaOH solution, 20.00 ml hydrochloric (HCl) acid solution
was used for the three trials. The volume of sodium hydroxide (NaOH) solution
however varied for the three trials. The volume of NaOH used for the first trial is
15.20 ml while 15.40 ml NaOH was used for the second and third trial. The
normality of HCl was computed for every trial using this equation:
NHCl x VHCl = NNaOH x VNaOH
The normality of HCl computed for the first trial was 0.07828 N. The normality of the
second and third trial was the same which was 0.07931 N since the volume of NaOH
Page 2 of 10

used in standardization was also the same. The mean normality of HCl for the three
trials was 0.07897 N while the relative standard deviation was 0.75%. For the
calculations of these results, the solutions are shown below.
Volume of HCl Used to Prepare 0 .1 N HCl

V HCl =

N NaOH x V NaOH
N HCl

0;1 N x 0.250 L
12 N

= 2.08 ml

Uncertainty of the Volume of HCl Used to Prepare 0.1N HCl

combined uncertainties
=
computed vol
combined uncertainties
=
2.08 ml HCl
c.u. =

(( ) )
0.10
250

(
(

uncertainty of vol . flask

volume
0.10
250

x 2.08 ml

c.u. = 2.08 0.0008 ml

Normality of Standard NaOH
Trial 1
NHCl x VHCl = NNaOH x VNaOH
NHCl x 0.02000 L = 0.1030 N x 0.01520 L
NHCl =

1.5656 x 103
0.02000

NHCl = 0.07828 N
NHCl x VHCl = NNaOH x VNaOH
NHCl x 0.02000 L = 0.1030 N x 0.01540 L

Trial 2

NHCl =

1.5862 x 103
0.02000

NHCl = 0.07931 N
NHCl x VHCl = NNaOH x VNaOH
NHCl x 0.02000 L = 0.1030 N x 0.01540 L

Trial 3

NHCl =

1.5862 x 10
0.02000

NHCl = 0.07931 N
Uncertainties in the Normality of HCl
Trial 1

c.u.
=
computed N

unc .of burette 2 unc . of pipette 2 meanunc . of N NaOH

+
+
vol
volume
mean N NaOH

)(

) (

Trial 1

Page 3 of 10

c.u.
=
computed N
c .u .
=
0.07828
c.u. =

unc .of burette 2 unc . of pipette 2 meanunc . of N NaOH

+
+
vol
volume
mean N NaOH

) (

)(

0.05 2 0.07 2 0.0004

+
+
15.20
50.00
0.1030

)(

)(

(( ) ( ) (

0.05 2 0.07 2 0.0004

+
+
15.20
50.00
0.1030

))
2

x 0.07828

c.u. = 0.07828 0.0004 N

Trial 2

c.u.
=
computed N

c .u .
=
0.07828
c.u. =

2
2
mean unc . of N NaOH
unc .of burette
unc . of pipette
+
+
vol
volume
mean N NaOH

) (

)(

0.05 2 0.07 2 0.0004

+
+
15.40
50.00
0.1030

)(

)(

(( ) ( ) (

0.05 2 0.07 2 0.0004

+
+
15.40
50.00
0.1030

))
2

x 0.07931

c.u. = 0.07931 0.0004 N

Trial 3

c.u.
=
computed N
c .u .
=
0.07828
c.u. =

unc .of burette 2 unc . of pipette 2 meanunc . of N NaOH

+
+
vol
volume
mean N NaOH

) (

)(

0.05 2 0.07 2 0.0004

+
+
15.40
50.00
0.1030

)(

)(

(( ) ( ) (

0.05 2 0.07 2 0.0004

+
+
15.40
50.00
0.1030

))
2

x 0.07931

c.u. = 0.07931 0.0004 N

Mean Uncertainty in the Normalities of HCl
Mean =
N
Mean
of HCl

( 0.07828 0.0004 )+ ( 0.07931 0.0004 ) + ( 0.07931 0.0004 )

3
Normality

x
n

0.07828+ 0.07931+ 0.07931

3

Page 4 of 10

= 0.7897 0.0004

Relative Standard
Deviation

x =

0.2369
3

= 0.07897 N

Standard Deviation
s=

( x ix )2
n1

s=

( 0.07828 0 07897 ) + ( 0.07931 0 07897 ) + ( 0.07931 0 07897 )

31

s=

s=

s=
s=

4 2

4 2

4 2

(6.9 x 10 ) +(3.4 x 10 ) +(3.4 x 10 )

2

(4.761 x 107 )+(1.156 x 107 )+(1.156 x 107)

2
7.073 x 107
2

3.5365 x 107

s = 5.9468 x 10
RSD =

s
x 100
x

5.9468 x 104
0.07897

x 100%

= (7.5305 x 10 3) x 100% = 0.75305% or 0.75%

Table 2. Calculations on the Preparation and Standardization of NaOH Solution
B. Analysis of Sample
Mass of ASA sample ( 0.0001 g)

0.0986 g
Trial 2
50.00ml

Trial 1
Trial 3
Volume aliquot ( 0.03
50.00 ml
50.00 ml
ml)
Volume of HCl used (
11.40 ml
11.20 ml
11.20 ml
0.05 ml)
Mass
ASA
in
sample
0.05843 g
0.06555 g
0.06555 g
(grams)
0.0005 g
0.0005 g
0.0005 g
% ASA
58.43%
65.55%
65.55%
Mean mass ASA
0.06318 0.0005 g
RSD
6.51%
Mean % ASA
63.18%
Table 3. Calculated Results on Analysis of Acetylsalicylic Acid (ASA)

Page 5 of 10

For the part of analysis of sample, 0.0986 g of aspirin was weighed. 50.00 ml of
volume aliquot was measured for every trial. For the first titration, 11.40 ml of HCl
was used while for the second and third titration, the volume of hydrochloric acid
(HCl) used was 11.20 ml. In the first trial, 0.05843 g of aspirin was used in the 11.40
ml of HCl solution while same mass of aspirin which was 0.06555 g was used in the
same volume also of the 11.20 ml HCl solution. The mean mass was computed
which was 0.06318 with 0.0005 g uncertainty. The relative standard deviation was
6.51%. The percent mass was also computed. 58.43% for the first trial and 65.55%
for second and third trial. The percent mass of aspirin was 63.18% which means it
has impurities. For the sample calculations regarding analysis of sample, the
solutions are tabulated below.
Mass of ASA in sample (grams)

g ASA= ( N NaOH x V NaOH ) N HCl x V HCl x

)]

vol. stock
x EW ASA
vol . aliquot

Trial 1

)]

250 ml
180.159 mg ASA
x
50 ml
2 meq ASA

250 ml
180.159 mg ASA
x
50 ml
2 meq ASA

250 ml
180.159 mg ASA
x
50 ml
2 meq ASA

g ASA= ( 0.1030 N NaOH x 50.00 ml NaOH ) 0.07897 N HCl x 11.40 ml HCl x

g ASA = 58.43 mg = 0.05843 g
Trial 2

g ASA= ( 0.1030 N NaOH x 50.00 ml NaOH ) 0.07897 N HCl x 11.20 ml HCl x

)]

g ASA = 65.55 mg = 0.06555 g

Trial 3

g ASA= ( 0.1030 N NaOH x 50.00 ml NaOH ) 0.07897 N HCl x 11.20 ml HCl x

)]

g ASA = 65.55 mg = 0.06555 g

Uncertainties in the mass of ASA in sample

c.u.
=
computed mass

meanunc . of N NaOH 2 unc . of pipette 2 meanunc .of N HCl 2 unc . of burette

+
+
+
mean N NaOH
volume
mean N HCl
volume

)(

) (

)(

Trial 1

c .u .
=
0.05843 g ASA
c .u .=

((

2
2
0.0004 N
0.07 2
0.0004 N
0.05
+
+
+
0.1030 N NaOH
50.00 ml
0.07897 N HCl
11.40 ml HCl

)(

) (

) (

2
2
0.0004 N
0.07 2
0.0004 N
0.05
+
+
+
0.1030 N NaOH
50.00 ml
0.07897 N HCl
11.40 ml HCl

)(

)(

c.u. = 0.05843 0.0005 g

Trial 2
Page 6 of 10

) (

) ) x 0.05843 g ASA
2

c .u .
=
0.06555 g ASA
c .u .=

((

2
2
0.0004 N
0.07 2
0.0004 N
0.05
+
+
+
0.1030 N NaOH
50.00 ml
0.07897 N HCl
11.20 ml HCl

)(

) (

) (

2
2
0.0004 N
0.07 2
0.0004 N
0.05
+
+
+
0.1030 N NaOH
50.00 ml
0.07897 N HCl
11.20 ml HCl

)(

)(

) (

) ) x 0.06555 g ASA
2

c.u. = 0.06555 0.0005 g

Trial 3

c .u .
=
0.06555 g ASA
c .u .=

((

2
2
0.0004 N
0.07 2
0.0004 N
0.05
+
+
+
0.1030 N NaOH
50.00 ml
0.07897 N HCl
11.20 ml HCl

)(

) (

) (

2
2
0.0004 N
0.07 2
0.0004 N
0.05
+
+
+
0.1030 N NaOH
50.00 ml
0.07897 N HCl
11.20 ml HCl

)(

)(

) (

) ) x 0.06555 g ASA
2

c.u. = 0.06555 0.0005 g

Mean Uncertainty of the Mass of ASA in Sample
Mean

( 0.05843 0.0005 g ) + ( 0.06555 0.0005 g ) + ( 0.06555 0.0005 g )

3

0.0005 g
Relative Standard Deviation of ASA Mass
RSD =

S
x 100

RSD =

(0.058430.06318)2+(0.065550.06318)2+(0.065550.06318)2
31
x 100

0.06318

RSD = 6.51%
% ASA
% ASA =

g ASA
x 100
0.1

Trial 1:
% ASA =

g ASA
x 100
0.1

0.05843
x 100
0.1

= 58.43%

g ASA
x 100
0.1

0.06555
x 100
0.1

= 65.55%

g ASA
x 100
0.1

0.06555
x 100
0.1

= 65.55%

Trial 2:
% ASA =
Trial 3:
% ASA =

Page 7 of 10

0.06318

Mean % ASA
Mean % =

58.43 +65.55 +65.55

=63.18
3

Table 4. Calculations On Analysis of Acetylsalicylic Acid

DISCUSSION
Aspirin, a drug widely known for its analgesic, antipyretic, and antiinflammatory properties, is a compound derived from two acids namely acetic acid
and salicylic acid.
This experiment, sought to quantitatively determine the amount of
acetylsalicylic acid in aspirin (ASA) by back-titration to analyze the purity of aspirin
and to apply the concept or back-titration in the determination of its purity. This
activity consisted of two parts. First is the preparation and standardization of 0.1N
sodium hydroxide (NaOH) solution and the analysis of aspirin.
Many carboxylic acids in this case, aspirin is not sufficiently soluble in water
to perform direct titration in aqueous solution. The acid can be titrated with
aqueous base when this problem exists. Alternatively, the acid can be dissolved in
an excess of standard base followed by back-titration with standard acid which was
hydrochloric acid in this case. But before using sodium hydroxide (NaOH) to titrate
Aspirin, it must be standardized first in order to get knowledge of its accurate
concentration.
Even so, to be able to analyze the composition of an aspirin sample or the
amount of acetylsalicylic acid, the hydrolysis of the sample by alkali into neutrality
is required. Neutralization titrations are often used to determine the equivalent
masses of purified organic acids. Equivalent masses serve as an aid in the
qualitative identification of organic acids. (Skoog, et. al, 2014)
The hydrolysis of the aspirin often uses large amounts or excess NaOH for
such reaction is slow and sufficient amount of NaOH reacting with acetylsalicylic
acid would just yield water as product and since solid sodium hydroxide cannot be
massed accurately because it absorbs water and carbon dioxide from the air, it is
not possible to make an aqueous solution to a very specific and accurate
concentration. This process is called back-titration. It is a process in which the
excess of standard solution used to consume an analyte is determined by titration
with a second standard solution. Back-titrations are often required when the rate of
reaction between the analyte and reagent is slow or when the standard solution
lacks stability.
Back titration rather than direct titration was used because there was no
suitable indicator for acetylsalicylic acid and sodium hydroxide solution. Therefore,
excess amount of NaOH was used to react with acetylsalicylic acid. The number of
moles of unreacted NaOH was determined from titration with hydrochloric acid.
Eventually the number of moles of acetylsalicylic acid and its percentage in the
commercial aspirin tablet were deduced.

Page 8 of 10

To evaluate for the purity of the acetylsalicylic acid, it is a vital factor to

establish a step by-step equation. The number of moles of the total NaOH that was
applied is equal to the number of moles of NaOH that reacted or that was consumed
in the chemical reaction plus the number of excess NaOH in the back-titration
process and in the hydrolysis of the acetylsalicylic acid. The computed value for the
total number of Na however, 2 moles of OH reacted with only one mole of
acetylsalicylic acid so the number of moles of the NaOH which reacted is just equal
to one-half of the mole of acetylsalicylic acid (Austria, 2013). This can be used in
the computation of the % ASA in the sample.
Based from the results, the commercial aspirin utilized has 63.18% purity
only. This showed that there were other chemicals affecting its purity like the
presence of binder. In addition, the tablet might not be stored in dry condition
permitting the acetylsalicylic acid to be hydrolyzed by moisture in the air.
However, there are still some possibility that errors was done during the
experiment. Possible causes of error in the experiment include the faulty titration
and standardization of solutions, faulty weighing of samples that can lead to wrong
calculations of data and incomplete hydrolysis of sample (Austria, 2013).

SUMMARY AND CONCLUSION

ANSWERS TO POSTLAB QUESTIONS
1. What would be the effect of a more dilute solution of NaOH on the titration?
More dilute NaOH would lead to unreliable and less accurate results because
as more water is added, the solution becomes comparable to the naturally
deprotonized H2O which is OH- in distilled water.
2. What volume of 1.0 N NaOH is used in the hydrolysis of four 250 mg tablets of
aspirin (90% pure acetylsalicylic acid) if 10.00 mL of 0.05 N HCl is consumed in the
back titration?

mg ASA
=[ ( V NaOH ) ( N NaOH ) ] [ (V HCl)(N HCl) ]
EW ASA

( 250 mg ASA ) ( 0.90 )=225mg ASA

Page 9 of 10

225 mg ASA
=[ (1 N NaOH )( X mL NaOH ) ] [ (0.05 N HCl)(10.00 mL HCl)]
mg
180.159
ASA
mmol
meq
2
mmol

225 mg ASA
+ [ (0.05 N HCl)(10.00 mL HCl) ]
mg
180.159
ASA
mmol
meq
2
mmol
=x mL NaOH
1 N NaOH

x mL NaOH =2.997793616 mL NaOH=3.0 mL NaOH

REFERENCES
Austria, J. (2013). Quantitative Inorganic Chemistry: The Final Wave. Retrieved
March 27, 2016 from: https://austriajamesonphysics102lab.wordpress.com/
Back Titration. n.d. Retrieved 28 February 2016 from
www.ibchem.com/IB16/03.55.htm#back
BR. Standard Solution of Hydrochloric Acid. (936.15) Official Methods of Analysis.
1990. Association of Official Analytical Chemists. 15th Edition.
Denby, D. (1997). Chemistry Review, Volume 6, Number 3, pp. 18-19. Philip Allan
Updates.
Harris, D.C. (2010). Quantitative Chemical Analysis (8th ed.) New York: W.H.
Freeman & Co.
Skoog, D., West, D., Holler, F., and Crouch S. (2014). Fundamentals of Analytical
Chemistry, 9th ed. Belmont, CA: Brooks/Cole, Cencage Learning
Stapel, E. (2014). Mean, Median, Mode, and Range. Accessed 02 February 2016
from: http://www.purplemath.com/modules/meanmode.htm.

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