Experiment 1

Potentiometric Titration of an HCl-H3PO4 Mixture

BRACERO, JESTONI L.
BSCHEM2

Group Members:

Jerom Alry Librea

Verenice Dianne Fuentes
John Mark Revilla

CHY56
Analytical Chemistry I, Laboratory
TTH (1:00 PM – 4:00 PM)

A Formal Laboratory Report

Presented to:

Aileen May G. Ang RCh, M.Sc.

Instructor

October, 2019
I. INTRODUCTION

Aspirin is one of the oldest and generally the most useful drugs known. Pure aspirin,
chemically called acetylsalicylic acid (ASA) or 2-acetoxybenzoic acid is both an organic ester and an
organic acid. It is both an analgesic (painkiller) and an antipyretic (reduces pain). Most aspirin tablets
contain a small amount of “binder,” which helps prevent the tablets crumbling. Even though the
binder is chemically inert and was deliberately added by the manufacturer, its presence means that
aspirin tablets are not 100% acetylsalicylic acid. Moreover, moisture can hydrolyze aspirin; thus
aspirin that is not kept dry can decompose.
This experiment utilized back titration (also called indirect titration) which is one of
analytical technique wherein a primary reactant of unknown concentration is to be reacted in excess
with another reactant. The solution is then directly titrated to determine the amount of the second
reactant in excess (Skoog, West, Holler & Crouch, 2004). The main principle is to add an excess of
the standard titrant and then determine the excess amount by back titration with a second standard
titrant. Indirect method 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. According to 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.
Further, this method was performed in order to determine the amount of ASA due to the fact
that aspirin hydrolyzes at a slow rate, which makes it difficult to determine the endpoint during
titration. Hence, adding a base in excess, ensuring complete hydrolysis and then determining the
unreacted base by titration with HCl would assure that the reaction proceeds to completion.
In this experiment, an aspirin tablet with a known concentration of NaOH solution was
titrated. The end point will be determined with phenolphthalein indicator. Thus, the ASA content in
aspirin tablet can be determined by hydrolysis using strong base, NaOH, followed by back titration
with HCl. NOTE: Two moles of NaOH is required to completely hydrolyze one mole of aspirin:

Figure 1. Aspirin (ASA) is a weak acid made by combining two acids, salicylic acid and acetic acid
and therefore it has two acid portions, each of which can be neutralized by base
In the sense of considering the above-mentioned concepts, an investigation was then carried
out through a laboratory experiment. The objectives of this experiment are as follows: (a) illustrate
techniques used in a typical indirect or back titration; (b) determine the difference between a direct
and a back titration and know all relevant reactions; (c) describe the physical that will occur when the
endpoint of the titration is reached; (d) explain clearly why back titration is used for this aspirin
analysis; and (e) determine the weight of aspirin and its percentage composition from the sample
tablet.

II. METHODOLOGY

A. CHEMICALS AND APPARATUS

Prior in performing this experiment, the chemicals/substances used were sodium hydroxide
(NaOH, with concentration 0.0972 M) standard solution, hydrochloric acid and phosphoric acid (HCl-
H3PO4 with unknown concentration), and KHP.

This experiment utilized as well the following apparatuses and equipment: (a) volumetric
flask; (b) wash bottle; (c) 50-mL burette with holder and brush; (d) burette clamp; (e) iron stand; (f)
funnel; (g) 20-mL graduated cylinder; (h) dropper; (i) stirring rod; (j) beaker; (k) pH meter (brand);
(l) analytical balance (ShimadzuTM ATX224); and (m) hot plate (Corning PC-420D); (n) magnetic stir
bar.

B. PROCEDURE

This experiment was divided into three parts: (1) preparation and standardization of 0.1 M
NaOH; (2) calibration of pH meter; and (3) titration of mixture of hydrochloric acid and phosphoric
acid.

B.1. Preparation and Standardization of 0.1 N NaOH

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B.2. Calibration of the pH meter

In calibrating ….

B.3. Titration of Mixture of Hydrochloric Acid and Phosphoric Acid

Using a 25-mL volumetric pipette, a 25-mL of the unknown HCl-H3PO4 solution was
transferred into a clean, dry 100-mL beaker and the sample was diluted with 40-mL distilled water.
After some time, the pH electrode was rinse with distilled water into an empty beaker and the
electrode was positioned and 50-mL burette filled with sodium hydroxide (NaOH) as indicated in
Figure. (Be sure that the pH electrode is not in a position to be damaged by magnetic stir bar. No air
bubbles should be trapped under the polyethylene shield of the electrode. Also, make sure that no air
bubble is trapped in the tip of the burette. Insulate the beaker from the magnetic stirrer with a layer of
folded paper towel to prevent warming of the solution by the magnetic stirrer.)

With continuous stirring, small increments (0.2-mL) of the standardized NaOH solution were
added from the burette. Thereafter, letting the solution and pH meter to equilibrate was an essential
method in this experiment before reading and recording the pH of the solution after addition of each
portion of the NaOH solution. Initially, the change of pH upon the addition of titrant will be minimal.
However, as the first equivalence point is approached, pH increments will increase more rapidly, and
only dropwise increments of NaOH should be added until it is apparent that the first equivalence point
has been passed. Periodically, the inside of the beaker may be washed down with distilled water from
wash bottle. (Be sure no drops are left on the tip of the buret when you are reading the pH). The drop
was part of the measured volume. Remember not to take pH reading above 11.5, because high pH
damages the glass electrode.

After potentiometric titration, the electrode was removed from the solution, and was washed
with distilled water and the electrode was allowed to stand in a beaker of distilled water for at least
15 minutes before turning of the equipment. Using the MS EXCEL software, the data was plotted.
Thus three graphs will be formed; potentiometric curve, first derivative curve and second derivative
curve.

C. MATHEMATICAL EQUATIONS

This experiment utilized the following formulas:

III. DATA/RESULTS/CALCULATIONS
 The results of this experiment were recapitulated in tables below (all tables presented display
all the data taken in different stages of the experiment).

Table 1. Blank Determination

TRIALS
Trial 1 Trial 2 Trial 3
Volume of Base added, mL 0.05 0.05 0.05
Mean Volume added, mL 0.05

Table 2. Determination of Percent Aspirin present in Aspirin tablet-Scheeprin 80 mg (Analysis)

TRIALS
Trial 1 Trial 2 Trial 3
Weight of sample, g 0.3024 0.3026 0.3001
Total weight of sample used, g 0.9051
Volume of base added to reach endpoint, mL 7.35 7.20 7.40
Volume of additional base added (excess 17.35 17.20 17.40
included), mL
Total Volume of the base added, mL 24.70 24.40 24.80
Corrected Volume of base added, mL 24.65 24.35 24.75
Total moles of base added (base on corrected 2.322×10-3 2.294×10-3 2.337×10-3
volume), mol
Mean Total moles of base added (base on 2.318×10-3
corrected volume), mol
Volume of acid used for back titration, mL 8.15 8.15 7.50
-4 -4
Total moles of acid added, mol 7.906×10 7.906×10 7.275×10-4
Mean Total moles of acid added, mol 7.796×10-3
-3
Moles of Base reacted with aspirin, mol 1.532×10 1.503×10-3 1.605×10-3
Mean moles of Base reacted with aspirin, mol 1.547×10-3
-4
Moles of Aspirin, mol 7.658×10 7.515×10-4 8.025×10-4
Weight of Aspirin, g 0.1380 0.1354 0.1446
Mean weight of Aspirin, g 0.1393
Percent Aspirin, % (w/w) 45.63 44.75 48.18
Mean Percent Aspirin, % (w/w) 46.19
Standard Deviation of percent Aspirin, % 1.7815
*The concentration of the base NaOH and the acid HCl was known as 0.0942 M and 0.0970 M
respectively. This is useful in the process of calculating weight of aspirin from the weight of the
sample tablet.

SAMPLE CALCULATIONS

0.05+0.05+0.05
Mean Volume of base added in blank determination = 3
= 0.05 mL
 Volume of additional excess base added = 7.35 mL + 10 = 17.35 mL

Total volume of the base added = 7.35 mL+ 17.35 mL = 24.70 mL

Corrected Volume of the Base added = 24.70 mL ̶ 0.05 mL = 24.65 mL

1𝐿 𝑚𝑜𝑙
Total moles of base added = (24.65 mL × 1000 𝑚𝐿) × (0.0942 𝐿
NaOH)

= 2.322×10-3 mol. NaOH

1𝐿 𝑚𝑜𝑙
Total moles of acid added = (8.15 mL× 1000 𝑚𝐿
) × (0.0970 𝐿
HCl)

= 7.906×10-4 mol. HCl

Moles of base reacted with aspirin = [2.322×10-3 mol. NaOH ̶ 7.906×10-4 mol. HCl]

= 1.532×10-3 mol. NaOH reacted with aspirin

1 mole aspirin
Moles of aspirin = 1.532×10-3 mol. NaOH × 2 mole NaOH
= 7.658×10-4 mol. Aspirin
𝑔
Weight of aspirin = [(7.658×10-4 mol. Aspirin) × (180.158 𝑚𝑜𝑙 aspirin)]

= 0.1380 g. Aspirin

Calculations for percent aspirin in three trials:

0.1380 g Aspirin
Percent aspirin (T1) = 0.3024 g sample
× 100% = 45.63% Aspirin

0.1354 g Aspirin
Percent aspirin (T2) = × 100% = 44.75% Aspirin
0.3024 g sample

0.1446g Aspirin
Percent aspirin (T3) = 0.3024 g sample
× 100% = 48.18% Aspirin

45.63% + 44.75% + 48.18%

Mean percent aspirin = = 46.19% Aspirin
3

IV. DISCUSSION AND INTERPRETATION OF RESULTS

The experiment indispensably revolves around the concept of titration and back titration
which is imperative in explaining the determination of aspirin and thereby laying down the idea of
hydrolysis and neutralization. The purity of aspirin was expected to be determined by the end of the
experiment using the aforementioned concepts and the reasons and errors behind the obtained results
will be further discussed as below.

The aim of the experiment was to investigate the purity of the aspirin in sample tablet
(Scheeprin with 80 mg dosage strength). The techniques used to determine the purity of the sample
tablet were titration and back titration. As what was stated, back titration uses an excess amount of
base with known concentration where in the case is therefore the NaOH solution. This was added to
the ASA sample, so its actual mass can be determined. Afterwards, this solution was titrated with HCl
to determine the amount of unreacted NaOH. This amount is the subtracted from the initial amount of
NaOH to find the actual quantity of NaOH base that reacted with the aspirin. This also yields to the
actual quantity of aspirin in the aliquot. Thus, the purpose of doing titration is to neutralize all acid
present in the sample and the back titration is used to determine the moles of acetylsalicylic acid
present in the sample.

In this experiment, blank determination was made using 20 mL absolute ethanol. According
to Markings (2019), a blank determination is carried out by titrating a fixed and known concentration
of titrant into a solvent with zero analyte. The only difference from the regular titration is the absence
of analyte. This allows the amount of reactive substance within the plain solvent to be determined and
hence allows a determination of the error in future titration experiments using this solvent. Results
showed that in each trial, 0.05 mL sodium hydroxide with 0.0942M concentration was used as
reflected in Table 1. Next section of the experiment, the concept of hydrolysis was introduced. It
proliferates the idea that 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. Hydrolysis of the drug can be a major reason for the instability of drug
solutions. Thus, the degradation products are salicylic acid and acetic acid. As shown in Figure 4B,
the aspirin sample was titrated with the said base to the first permanent cloudy pink color.

(A) (B) (C) (D)

Figure 4: (A) Before titration: solution is colorless; (B) After titration colorless to light pink: (C)
Before back titration: 2 drops of phenolphthalein were added to increase the intensity of
pink):and (D) After back titration: Solution turns from pink to colorless

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)

Back titration rather than direct titration was used in this experiment 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.

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 as shown in Equation 4.1C below, 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.

(A)

(B)

(C)

Equation 4.1 Step-by-step Reaction made in the analysis

At low temperature, aspirin can be neutralized with base as shown in Equation 4.1A. If no
impurities are found in the compound, a normal acid-base titration can be used to determine the purity
of the aspirin. However, if impurities are present, the base will neutralize both the acid present in the
acetylsalicylic acid and the acid present in the impurities. Thus, the volume of the base required to
neutralize the solution can be used to determine the number of moles present in the acid. And at high
temperature, aspirin can be neutralized with the excess base as reflected in Equation 4.1B.
 The back titration technique used in this experiment involves the titration of excess base with
acid. Base used was sodium hydroxide (NaOH) and the acid used was hydrochloric acid (HCl) with
known concentration. The amount of moles reacted from the hydrolyzed excess base with the acid
will give the number of moles of acetylsalicylic acid present in the solution.

To determine the amount of acid present in the aspirin prepared, excess base is added to the
titrated solution and placed in hot water bath to speed up the reaction. This process is known as
saponification of esters. In high temperature and with the presence of excess base, the ester will
undergo hydrolysis forming alcohol and carboxylic acid. The excess base not reacted in the hydrolysis
will be determined by a back titration with acid, HCl. With all the data collected, the mass of the
aspirin can be calculated and determined. This experiment also investigated the reaction of aspirin to
heat. It was hypothesized that the heat would cause the aspirin hydrolyzed and subsequently increase
the concentration of salicylic acid present. Techniques of titration and back titration were used to
quantitatively calculate results. The hypothesis was supported by all results.

As reflected in Table 2, the total moles of base used (base on corrected volume) in the
hydrolysis process were 2.322×10-3 moles, 2.294×10-3 moles, and 2.337×10-3 moles whereas the total
moles of acid used in back titration were 7.906×10-4 moles, 7.906×10-4 moles and 7.275×10-4 moles
and the moles of base reacted with aspirin were 1.532×10-3 moles, 1.503×10-3 moles and 1.605×10-3
moles for Trial 1, Trial 2 and Trial 3 respectively. By the end of the titration and back titration, the
solution should experience a color change of from pale pink to colorless.

Considering the EQ5, the moles of NaOH used during titration can be calculated and the
computed moles per trial were 2.322×10-3 moles, 2.294×10-3 moles, 2.337×10-3 moles of NaOH
respectively. Furthermore, the mole of excess NaOH was computed using EQ6. The molarity of HCl
was known as 0.0970 M and the volume for every trial was given which can be used to determine the
total moles of acid added in the reaction. The calculated results were 7.906×10-4 moles, 7.906×10-4
moles, 7.275×10-4 moles for first, second and third trial respectively. And then the mole of aspirin
was calculated by dividing the mole of base reacted with aspirin to two moles of
hydroxide ions. The computed number of moles of aspirin were 7.658×10-4 moles,
7.515×10-4 moles, 8.025×10-4 moles for first, second and third trial respectively.

Moreover, weight of aspirin was computed by multiplying the number of moles of aspirin to
its molecular weight (180.158 g/mol) which is useful to determine the percent aspirin present in the
sample tablet which is the main focus of this experiment. The calculated results of weight of aspirin
were 0.1380 g, .1354 g, and 0.1446 g for first, second, and third trial respectively. Now, the percent
aspirin for the three trials can be determined using EQ10. The computed results were given as
45.63%, 44.75%, and 48.18% for first, second and third trial respectively.
 Also in Table 2, the data gathered in the titration of ASA indicates that 0.9051 grams of
ground commercial acetylsalicylic acid was used and analysed. Volume of acid used indicated in the
table shows the amount that was used before the solution reached the endpoint. From these data, the
actual mass and the percent aspirin can be calculated. The table showed the percent purity of ASA in
every sample taken during the activity and the mass of ASA in every sample. The percent of ASA
shows that most values range from 44% to 49%. On the other hand, the mass of the ASA in sample
also ranged from 0.1350 g to 0.1450 g, which is also related to the percent purity as it is one of the
variables that must be considered in getting the percent purity.

Aspirin tablets are mainly composed of acetylsalicylic acid or ASA. Getting the percent
weight by weight of ASA in an aspirin tablet will determine its percent purity. According to Medrano,
Pasco, Lubrin & Marinque (2014), it is important to determine the percent aspirin of the sample tablet
since it presents the aspirin’s potency as a drug. Table 2 showed the percent weight per weight of
acetylsalicylic acid in each trial. On average, the aspirin (Scheeprin) sample has 46.19% (w/w) of
acetylsalicylic acid (ASA) with a standard deviation of approximately 1.7815. This suggests that the
aspirin tablet sample, on average, is 46.19 percent pure. The data disagrees with the data of Asjali
(2015) where approximately 51.53% to 75.97% purity of aspirin sample of the same brand was
recorded. The findings further suggest that Asjali (2015) recorded around 51.53 mg to 75.97 mg of a
100 mg sample of the said brand of aspirin, and the computed values were larger than the data
recorded of this experiment and far beyond.

The results of this analysis suggest that the recorded data is precise, which only have a
standard deviation of approximately 1.7815. The deviation can have been caused by some random
errors in the duration of the experiment. These errors are unavoidable types of error; however, it can
be resolved through estimating and getting the average of the recorded measurements. Thus, it can be
deduced that the measurements were precise and reliable. However, the accuracy of the data recorded
has a great issue. The theoretical ASA (acetylsalicylic acid) or aspirin content of a low dose aspirin
tablet of the same brand used in the experiment is around 80 mg, or 80% aspirin content per 100 mg
sample. However, this experiment only recorded about 46.19 mg of aspirin content per 100 mg
sample, which is smaller than the expected aspirin content of a low dose aspirin tablet. The cause of
this inaccuracy might be traced as to how the experimenters did the experiment. It is possible that
there were some steps or some proper laboratory techniques that were neglected that altered the data.

Moreover, the aspirin tablet sample in the activity has a lower percent purity than the low
dose aspirin tablets of aspirin content. This idea implies that the aspirin tablet sample is much weaker
than the very low dose aspirin tablets which further suggest its effectivity (Nordqvist, 2017).

However, there are still some possibilities that errors was done during the experiment.
Possible causes of error in the experiment include the faulty titration and improper reading of volume
added to the solution and faulty weighing of samples that can lead to wrong calculations of data and
incomplete hydrolysis of sample (Austria, 2013). Source of personal error is over titration during
back titration, which would result to using a greater volume of hydrochloric acid - lower calculated
percentage of acetylsalicylic acid. Incomplete hydrolysis could also be a source of error as alkaline
solutions have tendencies to absorb carbon dioxide from the atmosphere. Other possible errors may
include that of the uncertainties of the analytical balance, burette, and pipettes used throughout the
experiment.

V. CONCLUSIONS AND RECOMMENDATION

With the aim of verifying the concepts, principles and theories governing back titration of
aspirin, the overall experiment conducted positively supplemented and effectively facilitated the
understanding to these aforementioned concepts. Such concepts tailored in the experiments which are
hydrolysis of aspirin, neutralization, acid-base titration that is useful in the analysis had been
productively established and was clearly emphasized.

The back titration process was properly executed and introduced. Consider using titration to
measure the amount of aspirin in a solution would be difficult to identify the end point because aspirin
is a weak acid and reactions may proceed slowly. 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.
Moreover, the objectives of the experiment were successfully met. It was also observed that the
volume of NaOH used to titrate HCl along with the volume of HCl used to titrate aspirin does not
have a significant difference. The end-point will be seen when the pink solution produced by the
adding of phenolphthalein fades to colourless.

Furthermore, the data of the experiment which is reflected in Section III validated further the
ideas behind as data recorded coincide with principles involved in the analysis of aspirin. The %
acetylsalicylic acid (ASA), which also suggests the percent purity of the aspirin tablet sample, is
approximately 46.19%. The result also corresponds around 46.19 mg of ASA in a 100 mg sample of
the aspirin tablet, which is smaller than the expected weight, 80 mg of ASA in the sample as claimed
by the manufacturer. The experiment recorded 1.7815 mg standard deviation, which suggests that the
data recorded were precise and reliable.

Thus, the inaccuracy may have been possibly caused by the negligence of some laboratory
techniques such as an improper reading of the volume in the burette, negligence of air bubbles in the
burette used, or carelessness in the contamination of the chemicals and reagents used in the activity.
Furthermore, it is recommended to always check if proper laboratory techniques are followed and
determine the theoretical yield that can be used to calculate the percentage error. Also, more trials
must be done to truly determine the % ASA or % purity of the aspirin tablet since the more trials are
made, higher chances of getting and achieving the true value. It may also be possible for future
experiments to analyze another type of acid using the back titration method.

VI. REFERENCES

Austria, J. (2013). Quantitative Inorganic Chemistry: The Final Wave. Retrieved on October 25, 2019
from: https://austriajamesonphysics102lab.wordpress.com

Harris, D.C. (2010). Quantitative Chemical Analysis (8th ed.) New York: W.H. Freeman & Co.

Markings S. (2019, May 9). Why is Back Titration is Needed?. Retrieved on October 25, 2019 from
https://education.seattlepi/com/blank-tritration-needed-4452

Medrano E.M.M., Pasco J.M., Lubrin M.E., Marinque M., (2014). Quantitative Determination of
Acetylsalicylic Acid by Back-titration. Retrieved on October 28, 2019 from
https://www.academia.edu/12405205

San K. T. (2016, October 17). Analysis of Aspirin. Retrieved on October 29, 2019 from
https://www.scribd.com/document/360173569/Analysis-of-Aspirin-Lab-Report

Scheele Laboratories Phils., Inc. (2019). Retrieved on October 29, 2019 from
http://scheelelab.com/web/products

Skoog, D., West, D., Holler, F., and Crouch S. (2014). Fundamentals of Analytical Chemistry, 9 th ed.
Belmont, CA: Brooks/Cole, Cencage Learning

University of Texas (2008). Determination of Aspirin Using Back Titration.

http:// mccord.cm.utexas.edu/courses/fall2004/ch455/aspirin.pdf