Experiment 2b

Determination of the aspirin content of Macs aspirin

Lab session: Monday 8-11am
Group Members: Laurenjay Henry 1001735
Camelia Samuels 0803467
Searena Treasure 0800417
Aim: To determine the amount of aspirin (acetylsalicylic acid) present in commercially available
aspirin tablets using a back titration method.
Abstract
A weighing dish was obtained and measured. Two aspirin tablets were weighed separately to
obtain the mass of the each tablet. The tablets were crushed in a mortar and pestle, and then three
0.5g samples were weighed. The weighing was transferred to a flask and 25ml of cooled
(15celcius) 95% ethanol was added to the flask and swirled to dissolve the aspirin. Two drops of
phenolphthalein was added and the sample was rapidly titrated with standard 0.1M NAOH to a
faint pink end point. The volume of NAOH used was recorded. The aspirin was hydrolyze by
adding additional NAOH from the burette. An extra 15ml more than what was required to reach
the initial endpoint was added. This volume of NAOH was added from the burette then the
burette reading was recorded again. The aspirin was hydrolyze by heating the mixture for about
15 minutes in a bath of boiling water in a 600ml.The flask was swirled occasionally. The flask
was cooled to room temperature with cooled tap water. The initial volume of standard HCL was
recorded and the excess base was back-titrated with HCL until the pink colour disappears. The
procedure was repeated with two samples.
The mass of aspirin was found to be 437.5mg and the average percentage of aspirin in sample
was found to be 85.11%.
Introduction
Aspirin is slightly acidic and reacts with bases in neutralization reactions. If the reaction is
followed with an indicator, a color change will occur when the acid is completely neutralized and
one drop of excess base has been added. The number of moles of base consumed and the
number of moles of acid in the sample can be calculated from the volume of the base needed to
obtain the color change. The relationship between these two mole values is determined form the
balanced chemical equation for the reaction.
In this experiment, an aspirin tablet with a known concentration of sodium hydroxide solution
was titrated. The end point will be determined with phenolphthalein indicator. The following
equation describes the neutralization reaction that will be observed in this experiment.
NaOH
(aq)
+ C
6
H
4
OCOCH
3
COOH
9(aq)
C
6
H
4
OCOCH
3
COONa
(aq)
+ H2O
(aq)

The mole ratio is 1:1, the number of moles of the base will equal the number of moles of acid at
the equivalence point of the titration. The molar mass of the solid aspirin can be approximated by
dividing the mass of the aspirin in the tablet by the moles of aspirin present. The mass of the
aspirin inside the tablet is usually near 325 mg. Inactive ingredients, such as binders, are added
to the aspirin during the manufacturing process. Therefore, the actual mass of the tablet exceeds
325 mg because it is not 100% pure aspirin.
Aspirin (acetylsalicylic acid, ASA) is a drug that hydrolyzes according to the chemical equation:

This hydrolysis is evident by the smell of acetic acid detected when a bottle of aspirin is opened.
The rate of hydrolysis is dependent on the temperature, pH and amount of moisture present. The
efficiency of any drug depends on its chemical stability. Hydrolysis of the drug can be a major
reason for the instability of drug solutions. Thus, when Aspirin undergoes hydrolysis, the
degradation products are salicylic acid and acetic acid.













Results:

Table 1: Values Obtained in Determining the Mass of KHP


Sample 1 Sample 2 Sample 3



Weight of beaker + KHP 34.073 34.116 34.360
Weight of beaker + Residue 33.495 33.608 33.845
Weight of KHP 0.578 0.508 0.521


Table 2: Titration Values Obtained in the Standardization of
Sodium Hydroxide (NaOH)and KHP


Sample 1 Sample 2 Sample 3
Mass of KHP 0.578 0.508 0.521

Final Volume (ml) 32.20 27.65 28.10
Initial Volume (ml) 1.70 0.40 1.30
Volume Used (ml) 30.5 27.25 26.80

Table 3: Values obtained for two (2) aspirin 325mg tablet
Weight of weighing dish 26.0252g
Aspirin tablets Weight of weighing
dish + aspirin tablet
(g)
Weight of weighing
dish + aspirin tablet
(g)
Actual mass (g)
Tablet 1 26.3646 --------- 0.3394
Tablet 2 ------------ 26.3532 0.3280

Average mass of aspirin tablets = 0.3394 + 0.3280
2
= 0.3337g


Table 4: Values Obtained in Determining the Mass of Aspirin tablet powder

Samples Weighing dish +
tablet powder (g)
Weight + Residue (g) Actual Mass (g)
1 33.4864 32.9831 0.5033
2 33.9656 33.4677 0.4979
3 33.7502 33.2240 0.5262

Table 5: Titration Values Obtained in the Standardization of Hydrochloric acid (HCL)

Table 6: Titration Values obtained in Acetylsalicyclic acid content of Aspirin with NaOH using
Phenolphthalein as an Indicator







Table 7: Back Titration with HCL of the ASA sample with Excess NaOH


Sample 1 Sample 2 Sample 3
Initial Volume (ml) 0.3200 0.1800 3.870
Final Volume (ml) 24.18 24.04 28.26
Volume used (ml) 23.86 23.90 24.39
Sample 1 Sample 2 Sample 3
Initial Volume
(ml)
0.9800 0.5400 1.120
Final Volume
(ml)
28.32 29.08 28.23
Volume used
(ml)
27.34 28.58 27.11
Excess volume
of Naoh used
(ml)
44.48 44.08 42.37
Sample 1 Sample 2 Sample 3
Initial Volume (ml) 13.29 0.2800 0.9300
Final Volume (ml) 27.97 13.29 13.72
Volume used (ml) 14.68 13.01 12.79
Pre-Lab Calculations
Calculate the volume of 50% (by weight) of NaOH solution necessary to prepare one litre of
0.1M NaOH. (The density of the 50% NaOH solution is 1.53 0.01 g/ml)

Molecular Mass of NaOH = 39.9972 = 39.9972g/mol
Diluting 50% to 0.1 M NaOH:

Therefore 19.13 mol/L is contained in a 50% solution of NaOH
Using C
1
V
1
= C
2
V
2
19.13M x V
1
= 0.1M x 1000ml
Therefore volume of solution V
1
needed to make a 0.1 mol/L NaOH

= 0.00523 L or 5.23 ml
This 5.23ml of NaOH was added to approximately 1L of previously boiled and cooled water.

To determine actual molar concentration of sodium hydroxide used (Standardization of
Sodium Hydroxide)
KH
5
C
8
O
4(aq)
+ NaOH
(aq)
KH
4
C
8
O
4
Na
(aq)
+ H2O
(l )
(Equation 1)
Molar mass of KHP = (39.098 + (5 X 1.008) + (8 X 12.011) + (4 X 15.999) gmol
-1

Molar mass of KHP = 204.22gmol
-1


Sample 1:

x10
-3
mol
From result Table 2, volume of NaOH used is 30.5 ml, thereforex 10
-3
mol is contained in
30.5 ml of NaOH, therefore 1000 ml contain


= 0.09279 mol/L
Sample 2:

From result Table 2, volume of NaOH used is 27.25 ml, therefore mol is
contained in 27.25ml of NaOH, therefore 1000 ml contain


=
0.09130mol/L
Sample 3:

From result Table 2, volume of NaOH used is 26.8ml, therefore is
contained in 26.8 ml of NaOH, therefore 1000 ml contain


=
0.09519mol/L
Averaging all three (3) Molarities obtained =

= 0.09309 mol/L
From equation 1 NaOH and KHP reacted in a 1:1 mole ratio
# of moles of NaOH reacted = # of moles of KHP reacted
Therefore the molar concentration of sodium hydroxide used in the experiment was
0.09309mol/L
Finding the molar concentration of HCl solution
Determination of the actual molar concentration of HCl used (Standardization of Hydrochloric
acid):
Reaction that occurred between NaOH and HCl:
HCl
(aq)
+ NaOH
(aq)
NaCl
(aq)
+ H2O
(l)
(Equation 2)
From titration: Avg volume of NaOH used to neutralize HCl: (23.86+ 23.90+ 24.39) ml
3
= 24.05ml or 0.02405L
From equation 2 NaOH and HCl reacted in a 1:1 mole ratio
Moles = Avg Volume of HCl used x Molarity of NaOH
= 0.02405L X 0.09309 mol/L
= 2.240 X 10
-3
mol NaOH
Since 1 mole NaOH reacts with 1 mole of HCl (see equation 2) then the number of moles of
NaOH reacted with 2.240 X 10
-3
mol so therefore the number of HCl reacted = 2.240 X 10
-3
moles
Molar concentration of HCl: 2.240 X 10
-3
mol
0.02500L
= 0.08960M of HCl
To determine the amount of ASA
NaOH
(aq)
+ C
6
H
4
OCOCH
3
COOH
9(aq)
C
6
H
4
OCOCH
3
COONa
(aq)
+ H2O
(aq)
(Equation 3)
Molar mass of ASA is 180.1g
Sample 1: From table 4: - 0.5033g of aspirin tablet powder
From table 6: - 27.34ml of 0. 0.09309 mol/L NaOH used for neutralization and excess
NaOH was back titrated with 17.14ml of 0.08960M of HCl.
27.34ml NaOH was used to neutralize all the material of an acidic nature. However for
hydrolysis additional 44.48ml was added.
# of moles NaOH used for hydrolysis is: 44.48ml x 0.08960M = 3.985 X 10
-3
moles
1000ml
Moles of HCl is equal to moles of excess NaOH
therefore = 0.08960M X 17.14ml = 1.536 X 10
-3
moles
1000ml
The difference between the moles of NaOH added for hydrolysis and that consumed by
hydrolysis equals the moles of NaOH used for hydrolysis.
3.985 X 10
-3
moles - 1.536 X 10
-3
moles = 2.449 x 10
-3
moles
Since the mole ratio of NaOH and ASA is 1:1 (see equation 3) then there were 2.449 x 10
-3
moles
of ASA in the sample.
2.449 x 10
-3
moles x 180.1g of ASA = 0.4412g or 441.2mg of ASA
Sample 2: From table 4: - 0.4979g of aspirin
From table 6: - 28.58ml of 0. 0.09309 mol/L NaOH used for neutralization and excess
NaOH was back titrated with 16.50ml of 0.08960M of HCl.
28.58ml NaOH was used to neutralize all the material of an acidic nature. However for
hydrolysis additional 44.08ml was added.
# of moles NaOH used for hydrolysis is: 44.08ml x 0.08960M = 3.950 X 10
-3
moles
1000ml
Moles of HCl is equal to moles of excess NaOH
therefore = 0.08960M X 16.50ml = 1.478 X 10
-3
moles
1000ml
The difference between the moles of NaOH added for hydrolysis and that consumed by
hydrolysis equals the moles of NaOH used for hydrolysis.
3.950 X 10
-3
moles - 1.478 X 10
-3
moles = 2.472x 10
-3
moles
Since the mole ratio of NaOH and ASA is 1:1 (see equation 3) then there were 2.472 x 10
-3
moles
of ASA in the sample.
2.472 x 10
-3
moles x 180.1g of ASA = 0.4452g or 445.2mg of ASA

Sample 3: From table 4: - 0.5262g of aspirin
From table 6: - 27.11ml of 0. 0.09309 mol/L NaOH used for neutralization and excess
NaOH was back titrated with 15.26ml of 0.08960M of HCl.
27.11ml NaOH was used to neutralize all the material of an acidic nature. However for
hydrolysis additional 42.37ml was added.
# of moles NaOH used for hydrolysis is: 42.37ml x 0.08960M = 3.796 X 10
-3
moles
1000ml
Moles of HCl is equal to moles of excess NaOH
therefore = 0.08960M X 15.26ml = 1.367 X 10
-3
moles
1000ml
The difference between the moles of NaOH added for hydrolysis and that consumed by
hydrolysis equals the moles of NaOH used for hydrolysis.
3.796 X 10
-3
moles - 1.367 X 10
-3
moles = 2.429 x 10
-3
moles
Since the mole ratio of NaOH and ASA is 1:1 (see equation 3) then there were 2.429 x 10
-3
moles
of ASA in the sample.
2.429 x 10
-3
moles x 180.1g of ASA = 0.4375g or 437.5mg of ASA

Percentage weight of ASA in the sample = mass of ASA X 100
Weight of sample

% weight of ASA in the sample 1 = 0.4412g x 100 = 82.78%
0.5033g

% weight of ASA in the sample 2= 0.4452g x 100 = 89.42%
0.4979g

% weight of ASA in the sample 3 = 0.4375g x 100 = 83.14%
0.5262g

Average weight of ASA in tablet = (82.78+ 89.42+ 83.14)% = 85.11%
3





Discussion
Sodium hydroxide was standardized using KHP and the molarity was found to be 0.09309M.
The average volume of NaOH from table 2 used in the neutralization of the KHP was 28.18ml.
This process was done as NaOH is not a highly pure solid and so was titrated against KPH which
was the primary standard. The hydrochloric acid used in the back-titration was also standardized
against the 0.09309M NaOH solution. The average volume of NaOH used in the standardization
of HCl was 24.05ml and the molarity was calculated to be 0.0896M.
Back titration was the method used in the determining the amount of aspirin (macs) in the
sample. The indicator of choice was phenolthalein as the pH at the equivalence point of this
titration is basic and the end point would therefore be observable, which is pink/ fuchsia. The
reverse of this would be seen since the solution was pink with the excess NaOH. At the end point
of the back titration the solution became colourless. From table 6, the volumes used to achieve
the end point of the reaction were 27.34ml, 28.54ml, 27.11ml, ie the amount of base needed to
neutralize all the material of acidic nature. The aspirin content in the flask was hydrolyzed with
addition NaOH of 44.48ml, 44.08ml, and 42,37ml respectively. This was done to obtain acetic
acid and salicylic acid, to have complete reaction of all the acidic content present.
The amount of excess NaOH that was present in the sample was reacted with the standard
solution of 0.0896M HCl. This was done as the analyte may be speed up in the presence of
excess NaOH. From this reaction, the amount of mole of the sample that the HCL reacted with
can be determined. The average amount of mole of NaOH used/ added for the Hydrolysis was
found to be 4.059x10
-3
mole and that which was consumed in the hydrolysis process was
1.209x10
-3
mole, the difference of both values was the number of moles of aspirin present/reacted
in the sample. The average mass of aspirin present in the sample was found to be 0.4413g.
Post Lab Question
1. What would be the average mass of aspirin in a tablet if the results from the direct
titration was used?
Average: From table 4: -average mass of aspirin tablet powder is 0.5091g
From table 6: -average volume 27.66ml of 0. 0.09309 mol/L NaOH used for
neutralization of ASA using direct titration.
Number of moles of NaOH used in the neutralization= molarity * volume
=

* 27.66ml
= 2.575x10
-3
moles
Since Sodium hydroxide and aspirin is a 1: 1 ratio, ASA= 2.575x10
-3
moles
Mass of ASA= # of moles * molecular mass = 2.575x10
-3
moles * 180.1g= 0.4637g

Average weight of one tablet=0.3337g
If 0.4637g of ASA is contained in 0.5091g of sample aspirin tablet powder
Then x is contained in 0.3337; x= 0.3039g
Therefore 0.3039g/303.9mg of aspirin is present in one tablet of Macs aspirin.