1

INTRODUCTION
Acid and bases can be classified into two types of categories which are weak and
strong. The relative acidity of a substance or a system is important in many situations, such
as quality of drinking water, food preservation, soil conditions for agriculture and
physiological functions.
The strength of an acid is measured based on its ability to donate protons to base.
The acid ionization constant, K
a
, is a quantitative measure of the strength of an acid. The
ionization of an acid is shown by following equation:
HA
(aq)
H
+
(aq)
+ A
-
(aq)
(Equation 1)
The K
a
value is a characteristic of an acid and can be used to identify an unknown acid.
Since the equilibrium exists, K
a
can be written:
Ka = [H
+
][A
-
] (Equation 2)
[HA]
The K
a
value indicates the relative strength of an acid. The larger the K
a
value, the stronger
the acid and vice versa. A similar system for base is also exists (K
b
). [H
+
] can be calculated
using the following equation:
pH = -log [H
+
] (Equation 3)
By using equation 3 [H
+
] can be determine using the pH value. Therefore [H
+
] = 10
-pH
.
Two methods can be used to determine the K
a
value. Both methods require the use
of a pH meter. For the first method, acid-base titration is used. Using the unknown acid as
sample and the acid is titrated with NaOH solution. With the data recorded, plot pH values
versus volume of NaOH titrated. Using the graph, equivalence point can be determined. In
the graph, halfway point to the equivalence, [H
+
] = [HA] = [A
-
] for monoprotic acid. Cancelling
[A
-
] and [HA] in equation 2 gives K
a
= [H
+
].
Second method is by using half volume. A three separate beaker is prepared and
each of the beakers is filled with small amount of the unknown monoprotic acid. The amount
must be equal and enough to let the tip pH electrode immersed to obtain the pH values each
of the three beakers. Since half of the acid has been titrated, [H
+
] = [HA] = [A
-
]. Therefore, K
a

= [H
+
], and H
+
can be find using pH = -log [H
+
].

2

OBJECTIVES
To determine the acid ionization constant, K
a
of a weak acid by titration with sodium
hydroxide and by measuring the pH of the weak acid.
To determined the best method to find the Ka value of the weak acids.
To determined the molarity of the unknown acid.
To determined the relationship between the pH value and the Ka value.

THEORY
K
a
of a weak acid refers to the acid dissociation constant which is a quantitive measure of
the strength of an acid. There are a few methods in determining the value of a weak acid,
which are:
Titration of a weak acid with sodium hydroxide
Measure the pH of the weak acid solution.
By titrating a weak acid with sodium hydroxide solution, NaOH every increment in pH will
be recorded for every 1 mL additions. Then, a graph of pH of the solution versus volume of
NaOH added is plotted. From the titration curve, the equivalent point in which all the weak
acid (HA) is completely reacted with sodium hydroxide. The equivalence point is read at the
center of the region where the pH spike sharply. The half-equivalence point occurs when
exactly one half of the base required to completely neutralized an acid has been added. At
this point, the concentration of the acid in the solution, [HA] is equal to the concentration of
the conjugate base [

].
The equation of ionization of weak acid in water is :
HA(aq) H
+
(aq) + A
-
(aq)
Since [HA] is equal to concentration of conjugate base, therefore:
[HA] = [

]
This equation can be simplified into :
K
a
= [H
+
(aq)]
Then, take a negative of the algorithm to bothe side of the equation:
-log K
a
= -log [H
+
(aq)]
3

So, pK
a
=pH
The pK
a
of the acid is equal to the pH of the solution as indicated in the above equation at
the equivalence point. The K
a
of the acid is determine from pK
a,.
Once the value of K
a
is
determined, the unknown acid is figured out based on the ionisation constant table.


K
a
=

MATERIAL AND APPARATUS
250mL beaker
Burette
Distilled water
Sodium hydroxide(NaOH) solution
Measuring cylinder
An unknown acid solution
pH electrode
Magnetic flea

PROCEDURES
A. Acid - Base Titration Method
1. Sodium hydroxide, NaOH solution was placed in a beaker before filled in the burette.
2. Burette was cleaned with distilled water, rinsed and filled with NaOH solution.
3. 10 ml of unknown monoprotic acid was prepared and then transferred into a small
beaker.
4. Beaker was placed on a stir plate & a magnetic stirrer was inserted into the beaker to
stir the solution during titration.
5. pH electrode was cleaned and rinsed using distilled water. Before using the pH
meter, the electrode must be dry first
6. pH electrode was inserted into the beaker and pH of the unknown acid the recorded
after each 1ml of NaOH was titrated into the beaker.
7. The titration must was continued until reach pH 12.
4

8. The whole titration was repeated for the second time.
9. Data of pH reading and volume of NaOH solution added was added and tabulated.
10. By using the titration data recorded, titration curve of pH versus volume of NaOH
solution titrated was plotted. Based on curve, pKa value of acid was calculated and
the unknown acid can be identified.
B. Measuring pH of the weak acid
1. After the second titration completed, second part of the experiment called half volume
was conducted.
2. Three beakers were used and each of the beakers was filled with small amount of the
unknown acid.
3. Using the pH meter, pH values of each of the unknown acid in the beakers was
recorded.

RESULTS AND CALCULATIONS
Results
Experiment A
Volume of unknown acid: 10 mL
Volume of NaOH
added (mL)
Titration 1 Titration 2
pH readings
0 3.72 3.63
1 3.90 4.02
2 4.38 4.38
3 4.46 4.53
4 4.71 4.67
5 4.89 4.94
6 5.12 5.12
7 5.35 5.24
8 5.72 5.79
9 5.98 6.50
10 11.91 11.48
11 12.25 12.07
12 12.34 12.27
5

13 12.44 12.35
14 12.45 12.41
15 12.56 12.51
16 12.62 12.56
17 12.62 12.61
18 12.62 12.63
19 - 12.65
20 - 12.65



Figure 1: Titration curve of unknown acid with NaOH for Titration 1.
0
2
4
6
8
10
12
14
0 5 10 15 20
p
H

Volume NaOH added (mL)
Trial 1
pH versus Volume NaOH added
Titration curve
6


Figure 2: Titration curve of unknown acid with NaOH for Titration 2.

Experiment B
Unknown acid 1 2 3
Initial pH 3.51 3.51 3.44

Calculations
Experiment A
Trial 1
Volume of NaOH used at equivalence point = 9.5 mL x


= 0.0095 L
Volume of NaOH used at half equivalence point =

= 0.00475 L
pH at half equivalence point = 4.8
pH = pKa = - log Ka
Ka = 10
-pKa

Ka = 10
-4.8

0
2
4
6
8
10
12
14
0 5 10 15 20 25
p
H

Volume NaOH added (mL)
Trial 2
pH versus Volume NaOH added
Titration curve
7

Ka = 1.58 x 10
-5

Trial 2
Volume of NaOH used at equivalence point = 9.4 mL x


= 0.0094 L
Volume of NaOH used at half equivalence point =

= 0.0047 L
pH at half equivalence point = 4.8
pH = pKa = - log Ka
Ka = 10
-pKa

Ka = 10
-4.8

Ka = 1.58 x 10
-5

Average Ka =
(

= 1.58 x 10
-5

Therefore the value of Ka of acid is 1.58 x 10
-5
which is nearest to Ka of acetic acid with Ka
value 1.8 x 10
-5
.
Calculations for finding the molarity of acetic acid for each titration.

Trial 1

o The moles of NaOH reacted.

9.5 mL NaOH x


= 0.0095 L NaOH

0.0095 L NaOH x


= 0.00095 mol NaOH

o The moles of CH
3
COOH neutralized the moles of NaOH.

0.00095 mol NaOH x


= 0.00095 mol CH
3
COOH

o The molarity of the CH
3
COOH solution.

10 mL CH
3
COOH x


= 0.010 L CH
3
COOH solution

Molarity (M) =


= 0.095 M CH
3
COOH





8

Trial 2

o The moles of NaOH reacted.

9.4 mL NaOH x


= 0.0094 L NaOH

0.0094 L NaOH x


= 0.00094 mol NaOH

o The moles of CH
3
COOH neutralized the moles of NaOH.

0.00094 mol NaOH x


= 0.00094 mol CH
3
COOH

o The molarity of the CH
3
COOH solution.

10 mL CH
3
COOH x


= 0.010 L CH
3
COOH solution

Molarity (M) =


= 0.094 M CH
3
COOH
The average molarity of CH
3
COOH.

Average molarity =

= 0.0945 M CH
3
COOH
Experiment B
Assume initial molarity of unknown acid = 0.1 M for all trials.
Trial 1
Initial pH = 3.51
[H
+
] = 10
-pH
= 10
-3.51
= 3.09 x 10
-4

Molarity
HA
H
3
O
+
A
-

Initial (M) 0.1 0 0
Change (M) - 3.09 x 10
-4
+ 3.09 x 10
-4
+ 3.09 x 10
-4

Equilibrium (M) 0.09969 + 3.09 x 10
-4
+ 3.09 x 10
-4


Ka =

Ka =
(

= 9.58 x 10
-7

9

Trial 2
Initial pH = 3.51
[H
+
] = 10
-pH
= 10
-3.51
= 3.09 x 10
-4

Molarity
HA
H
3
O
+
A
-

Initial (M) 0.1 0 0
Change (M) - 3.09 x 10
-4
+ 3.09 x 10
-4
+ 3.09 x 10
-4

Equilibrium (M) 0.09969 + 3.09 x 10
-4
+ 3.09 x 10
-4


Ka =

Ka =
(

= 9.58 x 10
-7


Trial 3
Initial pH = 3.44
[H
+
] = 10
-pH
= 10
-3.44
= 3.63 x 10
-4

Molarity
HA
H
3
O
+
A
-

Initial (M) 0.1 0 0
Change (M) - 3.63 x 10
-4
+ 3.63 x 10
-4
+ 3.63 x 10
-4

Equilibrium (M) 0.09964 + 3.63 x 10
-4
+ 3.63 x 10
-4


Ka =

Ka =
(

= 1.32 x 10
-6
Average Ka =

= 1.08 x 10
-6


Therefore the value of Ka of acid is 1.08 x 10
-6
which is nearest to Ka of Hydroxyl ammonium
ion acid with Ka value 1.1 x 10
-6
.

10

DISCUSSION
The objective of experiment A was to determine the value of acid ionization constant
of a weak acid. From the result, Figure 1 and 2 shows the titration curve of unknown weak
acid with sodium hydroxide, NaOH for titration 1 and 2 respectively. Before the addition of
NaOH, the pH of the unknown acid is 3.72 and 3.63 respectively. The pH for both solutions
increase slowly at first when NaOH is added. This is because the some of the hydrogen ions
were neutralized. As the hydrogen ion decreases, the pH of the solution gradually increased.
The next drop of NaOH added caused a sudden sharp increase in pH for both solutions. The
sudden change in the solution pH shows that the titration has reached equivalence point. In
Figure 1 and 2, the pH of the solution sudden increase sharply from 5.98 to 11.91 and 6.50
to 11.48 respectively.
At the equivalence point that is the point at which equimolar amounts of unknown
weak acid and NaOH have reacted completely. In Figure 1 and 2, the pH at equivalence
point was 9.1 and 8.9 respectively. Therefore, at equivalence point, the pH was greater than
7 as a result of the excess hydroxide ions formed in a weak acid-strong base titration.
Beyond the equivalence point when NaOH was continuously added, the pH again increases
slowly until the pH of the solution became constant. This is because the hydrogen ions were
consumed and the solution contains only excess hydroxide ions. In the Figure 1 and 2, the
pHs of the solution starts to constant were at 12.62 and 12.65 respectively.
The volume of NaOH needed to neutralize the unknown weak acid was determined
from the titration curve. In the titration 1 and 2, the volumes of NaOH needed to neutralize
the unknown weak acid were 9.5 mL and 9.4 mL respectively. Therefore, the volumes of
NaOH at half equivalence point were 4.75 mL and 4.7 mL respectively. At this point, the pH
values obtained at half equivalence was 4.8 for both titrations. Then, the Ka values were
determined from the pH values at the half equivalence point which was 1.58 x 10
-5
for both
titrations that is nearest to Ka of acetic acid with Ka value 1.8 x 10
-5
. Lastly, the molarity of
the unknown acid was also calculated for each titration and the average was 0.0945M.
Experiment B was aimed to find the value of Ka for the unknown weak acids. The Ka
value was determined by recording the initial pH of the unknown acid in three trials. The
initial pH readings for the three trials were 3.51, 3.51 and 3.44 thus this shows that there was
not much difference in term of the initial pH of unknown acid at each trial. In this experiment,
the concentration of the generic acid present HA reacts with water molecules to produce
hydronium ion H
3
O
+
and the conjugate base of the weak acid, A
-
. Therefore the average Ka
calculated was 1.08 10
-6
which was relatively close to the Ka of Hydroxyl ammonium acid,
1.1 10
-6
.
11

There were no clear explanations to describe which method gives more accurate
value in determining the acid ionization constant and the type of acid used in the
experiments. However, the titration method seems to give accurate value of Ka. This is
because the strength of the acid which relatively related to the Ka can be achieved by
reactions with NaOH solution.

Many factors were needed to take into considerations when running the experiment to
avoid the disturbance to get the accurate Ka value. First of all, the drop speed of the sodium
hydroxide from the burette must be control to avoid the uncontrolled rate drop from
happened. The uncontrolled rate drop of the sodium hydroxide will make the readings of the
pH meter will be disturbed. Only 1 ml sodium hydroxide was allowed to drop and mixed with
the unknown acid in the experiment. During the experiment, the changes of pH value need to
be monitored by using the pH meter as well as the position of the eyes when reading the
volume of the sodium hydroxide to avoid parallax errors. Besides that, the inaccuracy result
might cause by the long time used and maintenance of the pH meter. On the other hand, the
beaker should be rinsed with unknown weak acid solution in preparing the unknown weak
acid solution. This is because rinsing the beaker with unknown weak acid solution would
increases the number of unknown weak acid molecules in the flask and thus compromises
the method. In addition, alkaline solutions absorb carbon dioxide from the atmosphere. The
NaOH should not be prepared for use until it is needed, and fresh NaOH should be added if it
has stood in the buret for more than about 20 minutes.

CONCLUSION
In the nutshell, the acid ionization constant (Ka) value of the unknown weak acid solution can
be obtained through two methods which were through titration of weak acid solution with
sodium hydroxide and by measuring the pH of the weak acids. The average Ka value from
the two trials of the titration was determined in order to identify the type of acid used in the
experiment. The average Ka value obtained in the Experiment A was 1.58 x 10
-5
which was
nearest to Ka of acetic acid with Ka value 1.8 x 10
-5
while in the Experiment B, the Ka value
obtained was 1.08 10
-6
which was relatively close to the Ka of Hydroxyl ammonium acid,
1.1 10
-6
. Between both of the two methods, the titration method was found to be most
accurate method to determine the Ka value of the unknown weak acid.


12

RECOMMENDATION
For this experiment, there are few recommendation can used to minimize errors during the
experiment to avoid getting inaccurate values.
First, the apparatus used must be cleaned with distilled water to avoid any
disturbance during the mixture of the solution in the beaker during titration.
Second, bubbles must be removed in the burette before filling the NaOH solution. By
using distilled water, inserted small amount of distilled water into the burette and open the tip
of the burette to let some of the distilled water flows.
Third, make sure the pH meter device is working in good condition. The pH meter
used must be clean first with distilled water to avoid errors. For every 1 ml of NaOH titrated;
the pH electrode must be clean with distilled water before taking a reading in the solution.
Final recommendation is to get a good average between the titration. At least three
times titration is needed to be done so that the result will receive a good average.

REFERENCE
1. Laboratory manual CHE 485, Faculty of Chemical Engineering, UiTM Shah Alam, 2013.
2. Chng, R., Chemistry, 10th edition, New York: McGraw-Hill, 2010.
3.http://apbrwww5.apsu.edu/robertsonr/chem111020/044%20Unknown%20Acid%20Ka%20
MM.pdf
4. http://www.scribd.com/doc/39166239/Identifying-an-Unknown-Weak-Acids-Experiment
5. http://www2.chemistry.msu.edu/courses/cem262/AcidDissConst.html