1.

0 ABSTRACT/SUMMARY

The purpose of this experiment was to determine the acid dissociation constant, Ka of an
unknown weak acid solution and identify the weak acid using two methods. First, we titrated the
unknown acid solution with a standard sodium hydroxide solution until it is fully neutralised.
Second, we took samples of the unknown acid solution and directly measured its pH using a pH
meter. Finally we calculated the Ka of the unknown acid from the two methods. We found that
the Ka of the unknown acid solution matches that of Pyridine acid, and the value of Ka = 9.18 x
10-6 calculated from the titration method is closer to the theoretical value of Ka of Pyridine acid
(Ka = 5.90 x 10-6).
2.0 INTRODUCTION

Acids are substances that dissociate into Hydronium ions, H3O+ when dissolved in water.
This definition is based on the Arrhenius definition of acids. Generally, there are two types of
acids, strong acids and weak acids. Strong acids are acids that dissociate completely into H3O+ in
water, while weak acids are acids that dissociate partially into H3O+ in water. So, weak acids will
dissociate into H3O+ and coexist with it in dynamic equilibrium, as shown in equation 2.1.

HA(aq) + H2O(l) H3O+ (aq) + A- (aq) Equation 2.1

In weak acids, the acid dissociation constant, Ka value represents the strength of an acid.
The higher the value of Ka, the stronger the acid. The Ka of an acid can be calculated by using
equation 2.2, where all the concentrations are the concentrations of each species at equilibrium.
[3 + ][ ]
= []
Equation 2.2

In this experiment, an unknown weak acid with known molarity (0.1 M) is provided and
its Ka is to be found along with the identity of the acid. This was done by using two methods,
namely the titration method and the direct method. In the titration method, the weak acid acted
as the analyte while a standard 0.1 M NaOH was used as a titrant. The acid was titrated gradually
while making sure to keep track of the pH of the solution using a pH meter. The pH values were
used to plot the titration curve of pH vs volume of NaOH added. This curve was analysed to find
the Ka of the acid.

In the direct method, a known volume and known concentration of the weak acid solution
is transferred into a beaker and the pH electrode was dipped into the unknown acid solution after
homogeneity is reached within the solution to find its pH. The pH obtained from the solution was
used to calculate the Ka of the acid using equation 2.2 and by applying the knowledge of
dynamic equilibriums in reactions.

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3.0 AIMS AND OBJECTIVES

To:

(a) Determine the Acid dissociation constant, Ka of an unknown 0.1 M acid and what type of
that acid using titration method.
(b) Determine the Acid dissociation constant, Ka of an unknown 0.1 M acid and what type of
that acid using direct method.
(c) Determine which method is better suited to be used in finding the Ka of the acid.

2
4.0 THEORY

Acids are solutions that produces Hydronium ions when dissolved in water, according to
Arrhenius theory. Acids are generally divided into two categories, strong acids and weak acids.
Strong acids are acids that dissociates into Hydronium ions completely in water, while weak
acids only dissociate partially into Hydronium ions when dissolved in water. The acid
dissociation constant, Ka of an acid is a constant that measures the strength of a weak acid. The
higher the Ka value of an acid, the stronger it is. Generally, for a weak acid HA, the equilibrium
equation for it is shown in equation 2.1.

HA is the general way of denoting the formula for a weak acid, H3O+ is the Hydronium
ions and A- is the conjugate base to the acid. At dynamic equilibrium, the concentrations of HA,
H3O+ and A- remains constant. The concentrations of each of them are taken to calculate the
value of Ka as depicted in equation 2.2.

Where [H3O+] is the concentration of H3O+ ions, [A-] is the concentration of A- ions and
[HA] is the concentration of HA ions at equilibrium. In the equation shown, HA acts as an acid,
while A- acts as its conjugate base. H2O on the other hand acts as the base, and H3O+ is its
conjugate acid. This is consistent with Bronsted-Lowry theory about acids which states that in an
acid-base reaction, the acid will donate its proton to become a conjugate base, and the base will
accept a proton to become the conjugate acid. This dissociation reaction of weak acids will
proceed forward until equilibrium is achieved between the products and the reactants.

The value of Ka is unique to every weak acid. This means that the Ka of an acid can be
used to identify an unknown weak acid. Since the values of Ka is always inconvenient to be
written repeatedly, Ka of an acid is also commonly used to calculate the pKa of an acid, which is
analogous to calculating the pH of a solution by using the [H3O+]. The pKa of a weak acid can be
calculated with equation 4.1.

pKa = -log Ka Equation 4.1

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 In this experiment, the Ka of an unknown acid is to be determined, and from the Ka of the
acid, the type of acid can be determined since the value of Ka is unique toward each weak acid.
Two methods are used to find the Ka of the unknown acid. The first method is by potentiometric
titration, while the second method is the direct method.

Titration is a quantitative analysis of chemistry in which a burette is used to dispense a

standard solution of known solution called the titrant, gradually into a beaker containing the
solution to be analysed called the analyte. In this experiment, the titrant is a standard 0.1 M
NaOH solution, and the analyte is the 0.1M of unknown acid. The acid is measured with a
known volume and diluted with water in a beaker. A few drops of phenolphthalein is added as an
indicator. Phenolphthalein is a complex chemical which acts as an indicator for acid-base
titrations. Phenolphthalein is colourless in acidic solutions, and pink in basic solutions. The acid
is then titrated with NaOH.

The titration is started by inserting the pH electrode into the beaker containing the acid.
As the titration goes on, the hydronium ion concentration decreases and hence the pH of the
solution will slowly increase. When the equivalence point is almost reached, the next drops of
NaOH added to the beaker will cause a drastic sudden increase in pH. The volume of base
needed to completely neutralise the acid is determined at the equivalence point. At the
equivalence point, all of the moles of the base has reacted with all of the moles of the acid.
Equation 4.4 shows the equation for this chemical reaction

NaOH (aq) + HA (aq) NaA (aq) + H2O (l) Equation 4.2

The volume of NaOH added is taken at the equivalence point, and is divided by two to
find the half equivalence point. At this point, half of the moles of the acid has reacted. So, when
the solution reaches equilibrium [HA] = [H3O+] = [A-]. From Equation 4.2 the [HA] and [A-]
terms cancel each other out to give Ka = [H3O+]. Using the pH at the half equivalence point, the

4
the concentration of hydronium ions can be calculated using equation 4.5

pH = -log [H3O+] Equation 4.3

So, from the pH, the concentration of H3O+ can be found, and hence the Ka of the acid
can be found. The half equivalence point is located in the region called the buffer region on a
Strong base-Weak acid titration curve. Equations 2.2, 4.1 and 4.2 are combined to derive what is
called the Hasselbach-Henderson equation. This equation is as shown in Equation 4.4.

pH = pKa + log ( ) Equation 4.4

Once again, as the concentration of base = concentration of acid at the half equivalence
point, the logarithmic expression would equate to 0, giving pH = pKa. This equation is used for
simplification of calculation of Ka.

In method 2, the direct method is used. This basically revolves around measuring the pH
of the solution. Just like in method 1, the solution of unknown acid is prepared in a beaker. The
beaker is then stirred thoroughly to achieve homogeneity. The pH of the solution is then
measured. The pH of this solution is used to find the concentration of hydronium ions using
equation 4.3. Since the initial concentration of HA is known to be 0.1 M, and the concentration
of hydronium ions at equilibrium is known from the pH, the Ka of the solution can be calculated
using equation 2.2.

The values of Ka calculated from both methods are used to find the type of acid from the
table of weak acids along with their Ka values. By theory, the 1st method should give a more
accurate value, as taking the concentration of hydronium ions at the half equivalence point
automatically eliminates the need of finding the concentration of [HA] and [A-] at equilibrium.

5
6
5.0 APPARATUS AND MATERIALS

5.1 APPARATUS

1. Magnetic Stirrer 8. Burette

2. Magnetic Stirring Bar 9. 250-mL Volumetric flask
3. 250 mL Beakers 10. Retort Stand and Clamp
4. 500 mL Beaker 11. pH meter
5. 50-mL Graduated Measuring Cylinder 12. Mass Balance
6. 100-mL Graduated Measuring Cylinder 13. Pipette
7. Dropper

5.2 MATERIALS

1. 0.1 M Sodium hydroxide solution 4. Distilled water.

2. 0.1 M unknown weak acid solution
3. Phenolphthalein indicator

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6.0 PROCEDURE/METHODOLOGY

6.1 Determination of Ka of Unknown Acid by Titration Method

1. 150 mL of NaOH solution is pipetted into a 250 mL Beaker.

2. 90 mL of distilled water is measured using a graduated measuring cylinder. The distilled
water is then poured into a 250-mL beaker.
3. 10 mL of unknown acid is measured using a graduated measuring cylinder. The acid is
added to the beaker containing the water.
4. A few drops of phenolphthalein indicator is added to the acid solution in the beaker.
5. 50 mL of NaOH from the beaker is added to a burette.
6. The apparatus is set up for potentiometric titration.
7. The pH of the unknown acid solution in the beaker is measured using the pH meter. The
measurement is recorded. The unknown acid solution is then titrated with 1 mL additions
of NaOH solution. Between every interval, the pH electrode is rinsed with water, the
solution in the beaker is mixed with the magnetic stirrer and the pH is measured and
recorded. The colour of the solution is also observed between every interval.
8. The titration is continued for a few more gradual additions of NaOH even after the colour
of the solution has changed from colourless to pink completely.
9. Steps 2-8 are repeated for two more trials.
10. A graph of pH vs volume of NaOH added was plotted for each titration. The equivalence
point of each titration is determined. From there, the volume used is divided by two to
find the half equivalence point.
11. The Ka of the acid is determined from the half equivalence point for each titration. The
average value of Ka is calculated.

6.2 Determination of Ka of Unknown Acid by Direct Method

1. 90 mL of distilled water is measured using a graduated measuring cylinder and is poured

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 into a beaker.
2. 10 mL of unknown acid is measured using a graduated measuring cylinder. The acid is
then poured into the beaker with distilled water.
3. The solution is mixed thoroughly to achieve homogeneity.
4. The pH of the solution is measured using a pH meter by dipping the pH electrode into the
solution. The measurement of the pH is recorded.
5. Steps 1 to 4 are repeated for two more trials.
6. The acid dissociation constant, Ka is calculated from the pH of the solution, and an
average was calculated from the three Ka values calculated.

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7.0 RESULTS (CALCULATIONS)

7.1 Determination of Ka of Unknown Acid by Titration Method

1. Figures 7.1, 7.2 and 7.3 shows Weak Acid-NaOH Titration curves for Titration 1, 2 and 3
respectively.

Figure 7.1: Titration Curve for Titration 1 of Unknown acid by NaOH

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 Figure 7.2: Titration Curve for Titration 2 of Unknown acid by NaOH

Figure 7.3: Titration curve for Titration 3 Unknown acid by NaOH

2. Tabulation of the volume of NaOH required to neutralise 0.1 M unknown acid.

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 Titration 1 Titration 2 Titration 3

Volume of
NaOH to
neutralise the 9.30 9.5 9.5
unknown acid
solution (mL)

Volume of
NaOH to
neutralise half 4.65 4.75 4.75
of the unknown
acid solution
(mL)

pH of solution
at half 5.40 5.34 5.20
equivalence
point
Table 7.1: Table of volume of NaOH used for equivalence point, half equivalence point and pH
of solution at half equivalence point.

3. Calculate the acid dissociation constant, Ka of unknown acid for each titration..
Using Equation 4.4,

pH = pKa + log ( )

pH = pKa + log (1)

pH = pKa

In titration 1, pH at half-equivalence point = 5.40 (based on the titration curve)

pKa = 5.40

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 Subbing Equation 4.1 for pKa,

pKa = -log Ka

-log Ka = 5.40
Ka = 10-5.40
Ka in titration 1 = 3.98 x 10-6

From Calculations made in appendices,

Ka in titration 2 = 4.57 x 10-6

Ka in titration 3 = 6.31 x 10-6

4. Calculate the average acid dissociation constant, Ka of unknown acid from all three Ka
calculated.
Average Ka
=
1 + 2 + 3
3
Equation 7.1

3.98 106 + 4.57 106 + 6.31 106

Average Ka =
3

Average Ka = 4.95 x 10-6

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7.2 Determination of Ka of Unknown Acid by Direct Method

1. Tabulation of the pH and [H3O+] of 0.1 M unknown acid measured by pH meter..

Trial 1 Trial 2 Trial 3

pH of unknown 4.05 3.98 4.01

acid
Table 7.2: Table of volume of pH of unknown acid in all three trials of dipping.

2. Calculate the acid dissociation constant, Ka of the acid for each trial.
Using Equation 4.3

pH = -log [H3O+]
In titration 1, pH = 4.05
-log [H3O+] = 4.05
[H3O+] = 8.91 x 10-5

10 mL of 0.1 M of unknown acid was diluted with 90 mL of water, to produce 100 mL of

the acid.

M1V1 = M2V2 Equation 7.2

(0.1)(10) = M2(100)
M2 = 0.01 M

Based on Equation 2.1, [H3O+] = [A-] at equilibrium. Using equation 2.2.

[3 + ][ ]
Ka =
[]

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 (8.91 105 )2
Ka =
0.01

Ka = 7.94 x 10-7

From Calculations made in appendices,

Ka in trial 2 = 1.10 x 10-6
Ka in trial 3 = 9.55 x 10-7

3. Calculate the average acid dissociation constant, Ka of unknown acid from all three Ka
calculated.
1 + 2 + 3
Average Ka =
3
Equation 7.3

7.94 107 + 1.10 106 + 9.55 107

Average Ka =
3

Average Ka= 9.5 x 10-7

8.0 DISCUSSION

In this experiment, the objective was to determine the Ka of an unknown acid, and hence

15
identifying the weak acid. Two methods were used, the first being titration method and the
second is the direct method. For the titration method, the apparatus was set up for titration. The
titrant used was a standard 0.1 M NaOH solution. Between these two methods, we are required
to determine which method is better for determining the Ka of the acid.

The point of the titration in this experiment is to find the pH of the solution in the beaker
when half of the acid sample is neutralised (known as the half equivalence point). This is done
by first determining the volume of NaOH required to completely neutralise the weak acid
(known as the equivalence point). This was done by titrating the solution as usual until the
equivalence point is reached. The graph of pH of solution in the beaker against volume of NaOH
is plotted. From there, the equivalence point of the titration is determined. The volume of the
NaOH required is then divided by two. The pH of the solution at that point of the titration is the
pH at half equivalence point.

The significance of the half equivalence point is that at that point, half of the acid is
neutralised. Based on equation 4.2, the expression for Ka will be equivalent to only [H2O+] as the
[A-] and [HA] will cancel each other out in the expression. This makes it much easier to find the
Ka value. Since the pH is known at the half equivalence point, the [HaO+] can easily be
determined by using equation 4.3. So in the titration method, Ka = [H3O+] at half equivalence
point. The titration was repeated two more times, in order to get a more accurate value of Ka.
The average Ka value calculated from the 3 titrations is 9.18 x 10-6. Based on the table of Ka
values of common weak acids, this is approximately equal to Pyridine acid (Ka = 5.90 x 10-6).

As for the direct method, the pH of the weak acid is simply measured using the pH meter
and is recorded. From this pH, using the values of [H3O+], [A-] and [HA] at equilibrium, the Ka
can be calculated using equation 4.2. This method is very direct as it only requires the
measurement of the pH of the acid solution without any titration. This was repeated two more

16
times in order to get a more accurate value of Ka using this method. The average Ka value
calculated from the 3 titrations is 9.5 x 10-7. Based on the table of Ka values of common weak
acids, this is approximately equal to the Ka of Carbonic acid (Ka = 4.45 x 10-7).

It can be concluded that the titration method gives a much more accurate value of Ka as
opposed to the direct method. This is heavily attributed by a few reasons. Firstly, the titration
method makes use of the half equivalence point, at which the expression for the Ka of the acid is
simplified to Ka = [H3O+] based on equation 4.3. This means that the only variable that matters in
the calculation is the [H3O+]. The direct method on the other hand, requires the values of [H3O+],
[A-] and [HA]. This surely leads to more inaccuracies as compared to the titration method, as
three varying variables are being taken into the calculation.

Secondly, the direct method requires assumptions . In the direct method, the [H 3O+] , [A-
] and the [HA] of the solution must be at equilibrium. Sometimes, it requires some time for the
sample to completely reach its equilibrium after the solution just got diluted. This leads to the
varying concentrations of the substances and hence inaccuracies in the measurement. On top of
that, from the pH, only the [H3O+] is known with certainty. The [A-] and [HA] is assumed to
have similar change in concentration. This again, causes inaccuracies in the calculation of K a. As
opposed to the direct method, the titration method relies on the measurement of the pH for every
1 mL interval, to create a titration curve. The titration curve is then analysed to get the half
equivalence point. This is more accurate as at the region where the half equivalence point is
(called the buffer region), the pH of the solution barely changes. So, even if the half equivalence
point has slight deviations, it would not lead to a significant deviation in the calculation of Ka.

Thirdly, as seen in the calculations in section 7.0, the values of Ka calculated in method 2
deviates from each other by a huge amount. Even though the reading of pH measured does not
deviate that far from each other, a small deviation causes a big deviation in the calculation of Ka.
In the titration method on the other hand, the values of Ka does not deviate that much from each
other except for the value in the first titration, which will be discussed later in this section. This
is because even a slight deviation in the titration would not cause that much of a difference. This

17
means that the Ka value calculated will be more accurate compared to using the direct method.

Although the titration method is considered to be more accurate than the direct method,
it does have a few weaknesses of its own. Firstly, it relies on the concentration of two different
solutions. This means that there could be inconsistencies between the two solutions in between
each titration trial, which would yield an inaccurate value of pH. Secondly, as seen in the results,
the half equivalence point of titration 3 is deviates far away from the half equivalence points in
titrations 1 and 2. This in turn led to varying values of Ka that is calculated. This is obviously due
to many factors such as inconsistent gradual intervals of dispensing NaOH, the different amount
of phenolphthalein indicator being added to the analyte which are both attributed to human error.

Phenolphthalein indicator is slightly acidic, hence altering the value of the pH when quite
a lot is added. In the third trial, the phenolphthalein indicator added was slightly more than the
first two titrations by accident. This may very well likely be the cause to the deviation of the half
equivalence point. Nevertheless, the calculated value still must be taken into account, as it does
not deviate that far and may very well likely produce a more accurate experimental result.

There is another method other than the titration method and the direct method that can be
used to determine the Ka of the acid solution. That method is called the half volume method. The
half volume method involves preparing the acid solution, separating half of the volume of the
acid solution into another beaker, and titrating the other half of the solution until it reaches its
equivalence point. The titrated solution is then mixed with the other half of the acid, so that
exactly half of the acid in the new solution is neutralised, which automatically places the
solution at its half equivalence point.

Although the half volume method uses the same concept as the titration method, it gives a

18
more accurate reading of Ka as opposed to titration method because the pH of the solution
measured is more accurately placed at the half equivalence point, as opposed to the graph
analysis for the titration method. In the titration method, analysing the equivalence point might
be inaccurate, and so further analysis on the graph to find the half equivalence point would lead
to more inaccurate results. So, the half volume method is actually the most prefered method in
determining the Ka of the weak acid.

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9.0 CONCLUSION

In conclusion, the objectives of this experiment which are to determine the acid
dissociation constant, Ka of an unknown acid by using the titration method and the direct
method, determining what type of acid the unknown acid is, and comparing which method used
is more suitable for this experiment were achieved.

It was found that using the titration method is more suitable, the Ka of the acid calculated
in titration method is 9.17 x 10-6, and in the direct method the Ka is 9.5 x 10-7. By considering the
fact that the titration method produces a more accurate result, based on the Ka calculated from
the titration method, the unknown acid was identified as Pyridine acid (Ka = 5.90 x 10-6).

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10.0 RECOMMENDATIONS

Here are recommendations which will produce better results and observations for the
experiment. Firstly, every apparatus including the beakers, the burettes, and the graduated
cylinders should be washed with distilled water and wiped dry before filling it with any solution.
This is to maintain the molarity of solutions used.

Secondly, the apparatus used such as measuring cylinder and burette should be calibrated first to
make sure the the quantity of the material is measured correctly.

Thirdly, the solution being titrated in the beaker should be mixed for a longer time with the
stirrer. This is to get a more homogeneous mixture and hence, a consistent pH all throughout the
solution..

Fourth , beaker should be placed on a light coloured surface such as white paper for all titration
trial to make sure the colour of the phenolphthalein indicator can be detected even if the colour
change slightly.

Finally, before conducting the experiment, all the apparatus to be used must be checked in order
to check the condition of the apparatus, such as the pH meter and the mass balance.

11.0 REFERENCE

21
1. Kerber, R. C., Kinard, W. F., & Harris, D. C. (1998). Determination of the Identity of an
Unknown Weak Acid. Quantitative Chemical Analysis, 5.
2. Retrieved March 31, 2017, http://apbrwww5.apsu.edu/robertsonr/chem1110-
20/044%20Unknown%20Acid%20Ka%20MM.pdf
3. Skoog, D. A., West, D. M., Holler, J. F., & Crouch, S. R. (2000). Analytical Chemistry :
An Introduction, 7, A-3. Retrieved April 7, 2017, from
http://www2.chemistry.msu.edu/courses/cem262/aciddissconst.html
4. Khaira, G., & Kot, A. (2017, March 23). Henderson-Hasselbach Approximation.
Retrieved April 5, 2017, from
https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Acids_and_Bases/
Buffers/Henderson-Hasselbalch_Approximation

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12.0 APPENDICES

12.1 Sample Calculations

Figure 12.1: Sample Calculation for Section 6.1 of the Experiment (Part 1)

23
Figure 12.2: Sample Calculation for Section 6.1 of the Experiment (Part 2)

24
Figure 12.3: Sample Calculation for Section 6.1 of the Experiment (Part 3)

25
Figure 12.4: Sample Calculation for Section 6.2 of the Experiment (Part 1)

26
Figure 12.5: Sample Calculation for Section 6.2 of the Experiment (Part 2)

27
 Figure 12.6: Sample Calculation for Section 6.2 of the Experiment (Part 3)

12.2 Raw Data

28
 Figure 12.7: Raw data of pH and volume of NaOH added for titration of weak acid by NaOH
and pH of acid measured in direct method.
12.3 Images of Experiment

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 Figure 12.8: NaOH solution in beaker to be used in titration.

Figure 12.9: Unknown acid being measured in measuring cylinder to be diluted with water.

30
Figure 12.10: Measuring the pH of the analyte before titration is started.

Figure 12.11: The colour of the analyte starts turning purple slightly.

31
 Figure 12.12: Measuring the pH of the analyte after the equivalence point has been reached.

Figure 12.13: The analyte has been completely titrated.

The link below leads to a youtube video for the addition of NaOH at equivalence point of the

32
titration.
Video Link: https://youtu.be/Ckd8PVuF2C4

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