1.1 Abstract.

The purposes of this experiment is to determinate the Ka value for a week acid by
two method. First method is potentiometric titration. A titration in which the endpoint is indicated by a change in potential at an electrode immersed in the solution.
This change in potential occurs as the solution changes from having excess
substance to be determined to having excess titration. Second method is half
volume method. A solution of the acid is prepared and divided in half as
accurately as possible. One portion is titrated to its endpoint with
phenolphathalein. The two portions are then recombined, and the pH of the
resulting solution is measured. For the first method, graph of pH against volume of
NaOH as a base was constructed. From the graph we will get the pH
corresponding to half equivalence point for titration 1 is 4.3 whereas other titration
is 4.1. By the formula, Ka value was calculated and we got 5.01210 -5 for titration
1 and 7.94310-5 for titration 2. So the average Ka value of unknown acid is
6.47810-5. The calculated Ka value of the unknown acid is closest to the value of
benzoic acid, 6.310-5. Volume of NaOH at equivalent point was used to calculate
the molarity of the acid. So the average molarity of unknown acid is 0.033 M. For
the second experiment, the value of pH was used to determine the Ka value. For
trial 1, the value of Ka is 4.808 10-8 while 5.268 10-10 for trial 2. So the average
Ka value of unknown acid is 2.43 10-8. The calculated Ka value of the unknown
acid is closest to the value of Hypochlorous acid, 3.510 -8.

1.2 Introduction.
[2] Acids and bases are classified as being weak or strong. A quantitative
measure of the strength of an acid is known as the ionization constant (or Ka) which
describes how well the acid ionizes in solution. The ionization of an acid can be shown
by the following equation:
HA (aq) H3O+ (aq) + A- (aq)

(Equation 1)

Since an equilibrium to exists, an equilibrium constant, Ka can be written

Ka =

+
H 3 O

(Equation 2)

Rearrange equation 2 and take log on both sides,

pH = pKa log ([HA]/[A -])

(Equation 3)

The value of Ka can be determined experimentally by measuring the

concentrations of H3O+, A-, and HA at equilibrium. The Ka value is an indication of
acid strength. The larger value of the Ka, the stronger the acid. This value is
characteristic of the acid and can be used to help identify an unknown acid. A similar
system exists for bases (Kb).
In this experiment two methods will be used to determination the Ka value. Both
of the methods required the use of a pH meter. In the first method is potentiometric
titration. Firstly, a sample acid is titrated with a NaOH (base). The pH values are
plotted against the volume of base added. The equivalence point is determined from
the graph. Next, the volume of base halfway to the equivalence point is found and the
pH at this volume is noted. The [H+] corresponding to this pH is equal to the Ka for the
acid. At a point halfway to the equivalence point, [H +] = [HA] = [A-] for a monoprotic
acid. Cancelling out [A-] and [HA] in equation 2 gives Ka = [H+].
The second method, we will be using the half volume method for determining
Ka values of unknown acids. A solution of the acid is prepared and divided in half as
accurately as possible. One portion is titrated to its endpoint with phenolphthalein.
After that, this reaction goes to completion. Therefore all of the weak acid has been
converted to its conjugate base, A-. The two separated aqueous portions (the half that
was set aside and the half that was titrated) are then recombined, and the pH of the
resulting solution is measured. The combined solution will now contain a mixture
where [HA] = [A-]. Using equation 2, we can see that when [A-] = [HA], they will cancel
out of the equation and Ka = [H+]. The pH value of the combined solutions can be
converted to [H+] to give a Ka value.

1.3

1.3 Objective
a) To determinate of the Ka of a weak acid by two methods which are by titration
with NaOH solution and by measuring the pH of the weak acid.
b) To identify the unknown weak acid solutions from the calculated K a values
obtained during experiment.
1.4 Theory
There are two general methods used to determine the Ka value of a weak acid
which is titration the weak acid with sodium hydroxide (potentiometric titration) and
other method is measuring the pH of the weak acid solution (half volume methods).
For this experiment the base is NaOH. The weak acid will titrate with the sodium
hydroxide solution for both of the methods.
When a weak acid, HA, is dissolved in water, only some of the molecules
dissociate to yield H3O+ and A- ions. At this point, a dynamic equilibrium is established:
HA (aq) + H2O (l)

H3O+ (aq) + A- (aq)

Under these equilibrium conditions, the total concentration of each species

remains constant, even though the species in solution are constantly dissociating and
recombining. The degree of dissociation of the weak acid is used to characterize the
acid, and is calculated according to the equation:

Ka =

A titration curve is produce by plotting the pH of the acid solution versus the volume
or NaOH added. The equivalence point of the titration is reached when all of the weak
acid (HA) has completely reacted with NaOH. On the titration curve, the equivalence
point is read at the center of the region where pH increases sharply. The halfequivalence point for the titration is reached when exactly one half of the base
required to completely neutralize the acid has been added. At this point of
concentration of the acid in the solution, [HA] is equal to the concentration of its
conjugate base, [A-].
[HA] = [A-]
Equation 2 can be simplified to yield equation 5.

(Equation 4)

K a = H 3Oaq

(Equation 5)

Take log on both sides of equation 5. Equation 6 can be derived

- log Ka = - log [ H3O+]

(Equation 6)

pKa = pH
pKa for the acid is equal to the pH of the solution at the half-equivalence point. The K a
of the acid is determined from the pKa value as follow.

K a = 10 pKa
(Equation 7)
From the pH of the acid solution (HA), we can determine the H + and A- ion
concentration, which is related to the pH of a solution by equation 8
H 3O + = 10-pH

(Equation8)

By substituting [HA], [H3O+] and [A-] at equilibrium into equation 2 the value of K a can
be calculated.
Table 1: Ionization constant (Ka) for some weak acids at 25oC

1.5 Apparatus
0.10 M sodium hydroxide solution, Phenolphthalein, distilled water and unknown acid
sample.
250 beaker, pipette, 50mL burette, pH electrodes, glass rod, magnetic stirrer, magnetic
stirring motor, 10mL measuring cylinder, retort stand and Erlenmeyer flask.

1.5.1 Titration 10 mL of unknown acid with sodium hydroxide solution.

Figure 1 set up apparatus fot titration unknown acid with NaOH solution.

1.5.2 From initial concentration and measuring the pH of the weak acid.

Figure 2 set up apparatus for method 2 by measuring the pH of the weak acid.

1.6 Procedure
1.6.1 Titration 10 mL of unknown acid with sodium hydroxide solution.
Firstly, a burette was rinsing with tap water and with distilled water. Next, some
of the sodium hydroxide solution was poured into beaker. Burette was filled with
sodium hydroxide solution and the tip of the burette had been completely filled. The
sodium hydroxide solution was drain to 0.00 mL line or below. Then, 10 mL of the
unknown acid was pipette in a beaker and enough water was adding. So, the end of
the pH electrode has been covered. Titration was done in flask. Initial reading of the
sodium hydroxide solution was recorded. The pH electrode was rinsing with distilled
water and placed it in beaker with the acid. The magnetic stirrer and stirring bar was
used and the pH electrode was above the stirring bar. After that, the solution was
titrated with NaOH solution and the pH with 1 mL of NaOH solution was recorded.
When pH begins rise rapidly, smaller portions of NaOH solution was adding. The sides
of the beaker occasionally was rinsing with distilled water. Continued, the NaOH
solution was adding until the pH was in basic region and has been levelled off. Steps
above were repeated to perform second trial. At the same time, the titration was
repeated with another unknown acid. For each trial, the graph pH against volume of
base added had been plotted. The equivalence point was determined on each graph.
The volume of NaOH corresponds to the equivalence point had been determined. This
value was divided by two and the amount of base needed to reach half way to
equivalence point was determined. The pH at this volume of base was converted to
[H+] to give Ka of the acid.

1.6.2 From initial concentration and measuring the pH of the weak acid.
It was assumed that the pH meter and burette were ready for used. A sample of
the unknown acid was obtained. A 100 mL of distilled water was measured out with the
cylinder and poured into 250 mL flask. After that, the sample of acid was dissolved in
the water and the solution was stirred to mix thoroughly. The solution was divided into
two equal portions by cylinder and so as accurately as possible. The portions were
titrated to a phenolphthalein endpoint with NaOH solution. NaOH solution was adding
slowly while swirling the flask. When the endpoint approaches, NaOH solution was
adding drop by drop until the solution has a permanent pink colour. Next, the titrated
was mixing with the other half of the acid solution and the pH of the resulting solution
was determined. Again, half of the acid has been titrated, [H +] = [HA] = [A-] . Using
equation 2, the values for [HA] and [A-] had been cancelling out and Ka value was
once again determined from [H+] value. From the observed pH, Ka of the unknown acid
has been calculated. Steps above were repeated to perform second trial. At the same
time, the titration was repeated with another unknown acid.

1.7 Result.
Part 1 : Titration 10 mL of unknown acid with sodium hydroxide solution.
Titration 1
Volume NaOH added (mL)

pH

0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
14.00
15.00
16.00
17.00
18.00
19.00
20.00
21.00
22.00
23.00
24.00
25.00
26.00
27.00
28.00
29.00
30.00
31.00
32.00
33.00
34.00
35.00
36.00
37.00
38.00
39.00
40.00

4.01
4.32
5.55
9.93
10.49
10.58
10.68
10.78
10.89
10.96
11.01
11.06
11.11
11.12
11.19
11.23
11.25
11.29
11.31
11.33
11.35
11.37
11.39
11.42
11.43
11.45
11.47
11.48
11.49
11.50
11.52
11.53
11.54
11.55
11.56
11.57
11.58
11.59
11.60
11.60
11.61

41.00
42.00
43.00
44.00
45.00
46.00
47.00
48.00
49.00
50.00

11.62
11.63
11.63
11.64
11.65
11.66
11.66
11.67
11.67
11.67

Table 2 : volume of NaOH added ( mL ) for titration 1

pH against volume of NaOH ( mL )

14
12
10
8
pH

6
4
2
0

Volume of NaOH ( mL )

Graph 1 : pH against volume of NaOH ( mL ) for titration1

Titration 2
Volume NaOH added (mL)

pH

0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
9.00
10.00
11.00
12.00
13.00
14.00
15.00
16.00
17.00
18.00
19.00
20.00
21.00
22.00
23.00
24.00
25.00
26.00
27.00
28.00
29.00
30.00
31.00
32.00
33.00
34.00
35.00
36.00
37.00
38.00
39.00
40.00
41.00
42.00
43.00
44.00

3.40
3.99
4.16
6.38
8.69
10.00
10.48
10.59
10.74
10.86
10.93
10.98
11.01
11.06
11.09
11.11
11.14
11.16
11.19
11.22
11.24
11.26
11.28
11.30
11.32
11.34
11.35
11.36
11.37
11.38
11.39
11.40
11.41
11.42
11.43
11.44
11.46
11.47
11.48
11.49
11.50
11.51
11.51
11.52
11.53

45.00
46.00
47.00
48.00
49.00
50.00

11.53
11.54
11.55
11.55
11.56
11.56

Table 3 : volume of NaOH added ( mL ) for titration 2

pH against Volume of NaOH ( mL )

14
12
10
8
pH

6
4
2
0

Volume of NaOH ( mL )

Graph 2 : pH against volume of NaOH ( mL ) for titration 2

Part 2: From initial concentration and measuring the pH of the weak acid.
Trial 1
Unknown acid 1:
pH of combined solutions: 4.40
Unknown acid 2:
pH of combined solutions: 5.38

1.8 Calculations
1.8.1 Titration 10 mL of unknown acid with sodium hydroxide solution.
Titration 1
Equivalence point

3.0 mL

Half equivalence point

1.5 mL

pH corresponding to half equivalence point

4.3

pKa = pH = 4.3
Ka = 10-pKa = 10-4.3 = 5.012 10-5

Molarity of unknown acid

(

M1

)(

V1

M2

( 0.1 )( 3.0 ) = (
M2

=(

M2

)(

V2

)( 10.0 )

= 0.03 M

Titration 2
Equivalence point

3.5 mL

Half equivalence point

1.75 mL

pH corresponding to half equivalence point

4.1

pKa = pH = 4.1
Ka = 10-pKa = 10-4.1 = 7.943 10-5

Molarity of unknown acid

(

M1

)(

V1

=(

M2

)(

V2

M2

= 0.035 M

Average Ka value of unknown acid :

( 5.012 10-5 ) +( 7.943 10-5 )

2

6.478 10

Average molarity of unknown acid :

( 0.03 M ) +(0.035 M )
2

= 0.033 M

Error calculation of Ka value of unknown acid :

( 1.8 105 )(6.478 105 )

( 1.8 105 )

Unknown acid : Benzoic acid.

100 = - 259.89 %

1.8.2 From initial concentration and measuring the pH of the weak acid.
First trial
pH of unknown acid : 4.40
[H3O+] = 10-pH = 10-4.40 = 3.981 10-5
HA (aq)
Initial
Change

H2O (l)

0.033 M

H3O+ (aq)

A- (aq)

- 3.981 10-5 M

+ 3.981 10-5 M

Equilibrium ( 0.033 - 3.981 10-5 M )

10-5 M

+ 3.981 10-5 M

3.981 10-5 M

Ka =

+ (aq)
(aq)
A

Ka =

[3.98110 ][3.981 10 ]
5
[ 0.0333.981 10 ]

3.981

Ka = 4.808 10 -8
Second trial
pH of unknown acid : 5.38
[H3O+] = 10-pH = 10-5.38 = 4.169 10-6
HA (aq)
Initial
Change

0.033 M
- 4.169 10-6 M

H2O (l)

H3O+ (aq)
0
+ 4.169 10-6 M

A- (aq)
0
+ 4.169 10-6 M

Equilibrium ( 0.033 - 4.169 10-6 M )

10-6 M

Ka =

+ (aq)
(aq)
A

Ka =

[4.169 106 ][4.169 106 ]

6
[ 0.0334.169 10 ]

Ka = 5.268 10 -10

Average Ka of unknown acid :

( 4.808 108 ) +(5.268 1010)

2

= 2.43 10-8

Error calculation of Ka value of the unknown acid:

( 1.8 105 )(2.43 108 )

( 1.8 105 )

4.169 10-6 M

100 = 99.87 %

Unknown acid : Hypochlorous acid.

4.169

1.9 Discussion
Objective for this experiment is to determine of the Ka of a weak acid by two
methods which are by titration 10 mL of unknown acid with sodium hydroxide and from
initial concentration and measuring the pH of the weak acid. Two unknown acid was
given to find the value of the Ka. Based on theory, the larger Ka value, the stronger the
acid. At the same time, we need to determine the average molarity of unknown acid
and find equivalence point. From equivalence point we will get half equivalence point
and find pH of that.
For the first experiment, graph of pH against volume of NaOH as a base was
constructed. The graph showed that in every titration, the pH of unknown acid was
increased when the volume of NaOH added increased. For titration 1, the volume of
NaOH required to neutralize the solution is 3.0 mL while 3.5 mL for titration 2. For this
experiment, the half equivalence point ( mL ) was measured from the graph. The
values of the half equivalence point 1.5 mL for titration 1 and 1.75 mL for titration 2.
The pH corresponding to half equivalence point for titration 1 is 4.3 whereas other
titration is 4.1.
By the formula, Ka value was calculated and we got 5.01210 -5 for titration 1
and 7.94310-5 for titration 2. So the average Ka value of unknown acid is 6.47810 -5.
The calculated Ka value of the unknown acid is closest to the value of benzoic acid,
6.310-5. Volume of NaOH at equivalent point was used to calculate the molarity of the
acid. So the average molarity of unknown acid is 0.033 M.
For the second experiment, the value of pH was used to determine the Ka
value. For trial 1, the value of Ka is 4.808 10-8 while 5.268 10-10 for trial 2. So the
average Ka value of unknown acid is 2.43 10 -8. The calculated Ka value of the
unknown acid is closest to the value of Hypochlorous acid, 3.510 -8.
Thus, the first method is more accurate to determine the Ka values. This is
because by using titration method, we can find the equivalent point of that acid, the
point where the amount of acid and base present exactly neutralize one another.
Therefore we can conclude that unknown acid for first experiment is Benzoic acid and
unknown acid for second experiment is Hypochlorous acid.

2.0 Conclusion
This experiment that determined the acid ionization constants, Ka of weak acid
solutions been done by titration process. To make sure the experiment has less error
or no error, the titration process must be done repeatedly. From the experiment
conducted above, we can conclude that the graphs increase rapidly after the
equivalence point.
For the first method, graph of pH against volume of NaOH as a base was
constructed. From the graph we will get the pH corresponding to half equivalence
point for titration 1 is 4.3 whereas other titration is 4.1. By the formula, Ka value was
calculated and we got 5.01210-5 for titration 1 and 7.94310-5 for titration 2. So the
average Ka value of unknown acid is 6.47810 -5. The calculated Ka value of the
unknown acid is closest to the value of benzoic acid, 6.310 -5. Volume of NaOH at
equivalent point was used to calculate the molarity of the acid. So the average
molarity of unknown acid is 0.033 M. Percentage error of Ka value of unknown acid is
259.89%. There are many error and experiment unsuccessful.
For the second experiment, the value of pH was used to determine the Ka
value. For trial 1, the value of Ka is 4.808 10-8 while 5.268 10-10 for trial 2. So the
average Ka value of unknown acid is 2.43 10 -8. The calculated Ka value of the
unknown acid is closest to the value of Hypochlorous acid, 3.510 -8. Percentage error
of Ka value of unknown acid is 99.87%.

2.1 Recommendation
There are several errors during experiments. Firstly, the eyes are not
perpendicular to reading a scale cause a parallax error. Next, there is zero error
because air bubbles at the burette while filling the NaOH solution and has effect initial
reading. The apparatus such as beakers are not being rinsed with distilled water
before use and some of apparatus such as beaker not completely dry and clean and
give effect to solution. Titration had been faster during portions were titrated to a
phenolphthalein endpoint with NaOH solution.
Precaution steps that we must take are the eyes must perpendicular to reading a
scale to avoid parallax error. Next, make sure air bubble doesnt present in the nozzle
of the burette. Besides, the beaker, pipette, burette and the flask should be washed
properly with distilled water. At the same time, make sure the apparatus such as
beaker is completely dry and clean. Repeat the experiment a few times to get more
accurate result. Titration must be slow during titration of solution with phenolphthalein
endpoint with NaOH solution.

2.2 References
1) Laboratory manual CHE 485, fakulti kejuruteraan kimia, Universiti Teknologi
Mara.
2) http://www.lisgar.net/magwood/Determination%20of%20the%20Ka%20of%20a
%20Weak%20Acid.pdf [ retrieved : 21/10/2014 ]
3) http://thesciencedictionary.org/potentiometric-titration/ [ retrieved : 21/10/2014 ]
4) Martin S. Silberberg, 2009, Chemistry The molecular Nature of Matter and
Change, 5th edition, McGraw Hill Higher Education, New York, page 789.
5) https://www.scribd.com/doc/3744536/Precautions-of-experiment-of-physics
[retrieved : 25/10/2014].