1.

0 Abstract/ Summary
The purpose of conducting this experiment is to determine the acid ionizations constant, K
a
,
of a weak acid. There are two methods to determine the K
a
of the weak acid which are; first
by titration of theunknown acid with sodium hydroxide (NaOH) solution and by measuring
the pH of unknown acid. An unknown acid was given to be identified. In first method, three
titrations were conducted. The volume of NaOHsolution and the pH of the mixture were
taken. Then, a graph of pH versus volume of NaOH solution was plotted and from the graph
obtained, the equivalence point was determined.

2.0 Introduction
The relative acidity of a substance or a system is of importance in many situations, such as
the quality of drinking water, food preservation, soil conditions for agriculture and
physiological functions.Acids and bases are often described as being weak or strong. One
measure of the strength of an acid is its ability to donate protons to a base. For acids, K
a
values are commonly used. The acid ionization constant, K
a
is a quantitative measure of the
strength of an acid. The ionization of generic acid HA can be represented by the following
equation:
( ) ( ) ( ) ( )
2 3 aq l aq aq
HA + H O H O + A
+
(Equation 4-1)
In which the weak acid donates a proton, H
+
to a water molecules, to form the hydronium ion,
H
3
O
+
and the conjugate base of the weak acid, A
-
. The corresponding acid ionization constant
expression, K
a
can be written as:

( ) ( )
( )
3 aq aq
a
aq
H O A
K =
HA
+
( (

(

(Equation 4-2)
The K
a
value is characteristic of an acid and can be used to identify an unknown acid. The K
a

indicates the relative strength of an acid. The larger the K
a
value, the stronger the acid. The
smaller the K
a
value, the weaker the acid.

3.0 Aims/ Objectives
The objective of this experiment is 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.


4.0 Theory
These are two general methods used to determine the K
a
value of a weak acid:
- titrating the weak acid with sodium hydroxide
- measuring the pH of the weak acid solution
Weak acid titrated with sodium hydroxide (NaOH)
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 half-equivalence 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 4-3)
Equation 4-2 can be simplified to yield Equation 4-4.

( )
a 3 aq
K = H O
+
(

(Equation 4-4)
Taking the negative of the algorithm of each side of Equation 4-4, Equation 4-5 can be
deriving.

( )
a 3 aq
log K = log H O
pKa = pH
+
(


(Equation 4-5)
Equation 4-5 indicates that the pK
a
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 pK
a
value as follow.

a
pK
a
K = 10

(Equation 4-6)
Sample calculation using the 1
st
method.
A weak acid is titrated with 0.10 M NaOH. The titration curve is shown in Figure 4-1
Determine the K
a
of the weak acid.





Figure 4-1: Titration curve for weak acid titrated with NaOH
Equivalence point = 11.62 mL; determined from the titration curve.
Half equivalence point = 11.62/2 = 5.81 mL
The pH value corresponding to 5.81 mL is 4.2; determined from the titration curve.
pK
a
= pH = 4.2 at the half equivalence point.
a
-pK 4.2 5
a
K = 10 = 10 = 6.310



1.1.1 Knowing the pH of the weak acid and initial weak acid concentration.
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 4-7
+ -pH
3
H O = 10 (

(Equation4-7)
By substituting [HA], [H
3
O
+
] and [A
-
] at equilibrium in to Equation 4-2 the value of K
a
can
be calculated.
Sample calculation using the 2
nd
method
The pH of a 0.10 M weak acid solution is 2.52 at 25
o
C. Calculate the K
a
of the weak acid at
25
o
C.
Initially, only the weak acid HA is present in the solution. At equilibrium, a fraction of HA
molecules ionize, forming H
3
O
+
and A
-
. The initial HA concentration decreases while the
concentrations of H
3
O
+
and A
-
increase until equilibrium is attained. The equilibrium
concentrations of HA, H
3
0
+
and A
-
are calculated as follows:

The calculated K
a
value of the unknown acid is closest to that of benzoic acid, 6.3 10
-5
.








Table 4-1: Ionization constant (K
a
) for some weak acids at 25
o
C


5.0 Apparatus
Equipments
- Beaker (250mL)
- Measuring cylinder
- Burette
- pH electrode
Reagents
- Sodium hydroxide (NaOH) solution
- Unknown acid
- Distilled water







6.0 Experimental Procedure
6.1 Determination of the K
a
value of a weak acid by titration with NaOH
1. Approximately 40mL of an unknown acid solution was obtained.
2. 10.0mL of the unknown acid solution was added to a dry 250mL beaker.
3. The solution was titrated with NaOH.
4. The reaction mixture as poured into the lab sinks and washed away with copious
amounts of water.
5. Steps 2-4 were repeated twice more.
6. The titration curve was drawn using Excel.
7. From the titration curve, the volume of NaOH required to neutralize the weak acid
solution in each titration was determined. The data was recorded.
8. The volume of NaOH added at the half-equivalence point in each titration was
calculated. At the graph determine the weak acid solution, the data was recorded.
9. The K
a
value for each titration was calculated.
10. The average K
a
value for the weak acid was calculated.
11. Using the average Ka value calculated in Step 10; the unknown weak acid from
Table 1 was identified.
12. The molarity of the unknown acid solution for each titration was calculated.
13. The average molarity of the unknown acid solution was calculated.

6.2 Determination of the Ka from the initial concentration and pH of a weak acid
solution
1. 20mL of the unknown weak acid solution (same unknown used in Part 6.1) was
added to a dry beaker.
2. The pH electrode was removed from the buffer solution. The electrode was rinsed
with distilled water and the tip of the probe was dried.
3. The electrode was inserted into the beaker containing the acid solution from Step 1.
The solution was stirred. After the pH reading stabilized, the pH of the solution was
recorded.
4. The weak acid solution was decanted into the designated waste container.
5. Steps 1-4 were repeated twice more.
6. The pH probe was rinsed with distilled water.
7. Using the initial concentration (molarity calculated in step 12, Part 6.1) and the pH
of the unknown acid solution, K
a
for each trial was calculated.
8. The average K
a
for the weak acid was calculated.
9. Using the average Ka value calculated in Step 8, the weak acid was identified from
Table 1.

RESULTS
Method 1:
Initial burette reading: 15 mL
Titration 1 Titration 2
Volume at equivalence point
(mL)
9.20 8.90
Volume at half equivalence
point (mL)
4.60 4.45
pH at half equivalence point 4.80 5.20

Trial 1:
Volume NaOH (mL) pH
0 3.89
1 4.22
2 4.52
3 4.79
4 4.94
5 5.12
6 5.33
7 5.54
8 5.83
9 6.51
10 11.13
11 11.50
12 11.69
13 11.79
14 11.89
15 11.98





Trial 2:
Volume NaOH(mL) pH
0 3.16
1 4.17
2 4.53
3 4.76
4 4.98
5 5.17
6 5.37
7 5.59
8 5.68
9 6.57
10 11.24
11 11.64
12 11.81
13 12.02
14 12.10
15 12.18

Method 2:
1 2 3
pH 2.91 2.94 2.98

CALCULATIONS


Figure 2: graph of pH vs volume NaOH added for titration 1


Figure 3: graph of pH vs volume NaOH added for titration 2

0
2
4
6
8
10
12
14
0 2 4 6 8 10 12 14 16
p
H

volume NaOH (mL)
graph of pH vs volume of NaOH
0
2
4
6
8
10
12
14
0 2 4 6 8 10 12 14 16
p
H

volume NaOH (mL)
graph of pH vs volume NaOH

METHOD 1
Titration 1
Volume at equivalence point = 9.20 mL (determined from the titration curve).
Volume at half equivalence point = 4.60 mL
The pH value corresponding to 4.60 mL is 4.8, determined from the titration curve.
pKa = pH = 4.8 at the half equivalence point.
Ka =

Titration 2
Volume at equivalence point = 8.90 mL (determined from the titration curve).
Volume at half equivalence point = 4.45 mL
The pH value corresponding to 4.45 mL is 4.7, determined from the titration curve.
pKa = pH = 5.2 at the half equivalence point.
Ka =

The average Ka =

= 1.79

The closest Ka value is 1.8 10
-5
(Acetic Acid)

The molarity of the unknown acid
Titration 1
MV = MV
(0.1 M) (9.20 X 10
-3
L) = M (0.01L)
M = 0.092 M




Titration 2
MV = MV
(0.1 M) (8.90 10
-3
L) = M (0.01 L)
M = 0.089 M
The average molarity =

= 0.091 M

Method 2
Titration 1
pKa = pH = 2.91
Ka =

= 1.23

Titration 2
pKa = pH = 2.94
Ka =

= 1.15

Titration 3
pKa = pH = 2.98
Ka =

= 1.05

The average Ka =

= 1.14

- pH = 2.91
[HO] =

=1.23

M
HA HO HO + A
Initial (M) 0.091 - 0 0
Change (M) -1.23

- 1.23

1.23

Equilibrium(M) 0.091 - 1.23

- 1.23

1.23

][

]
[]


[

][

]
[

]

= 1.69

- pH = 2.94
[HO] =

=1.15

M

HA HO HO + A
Initial (M) 0.091 - 0 0
Change (M) -1.15

- 1.15

1.15

Equilibrium(M) 0.091 - 1.15

- 1.15

1.15

][

]
[]


[

][

]
[

]

= 1.47

- pH = 2.98
[HO] =

=1.05

M
HA HO HO + A
Initial (M) 0.091 - 0 0
Change (M) -1.05

- 1.05

1.05

Equilibrium(M) 0.091 1.05

- 1.05

1.05

][

]
[]


[

][

]
[

]

= 1.23

The average Ka =

= 1.46

The closest Ka value is 1.8 10
-5
(Acetic acid)





DISCUSSION
First method used to determine the K
a
value of a weak acid is by titrating the weak acid by
sodium hydroxide solution .
The pH of the unknown acid was recorded with every 1 mL titration of NaOH, in two
replicates. As for the graph, when there is a sudden change in the pH value, it shows the
equivalence point of the titration has reached.Thats mean,at the time the solutions have been
mixed in exactly the right proportions according to the equation and the colour change would
happen . The titration curves were then plotted to obtain the equivalence and half-
equivalence points, as shown in Figure 1 2.
In Figure 1, the equivalence point is observed at 9.20 mL addition of NaOH to the unknown
acid. While the half-equivalence point is observed at 4.60mL. The pH of half-equivalence
point at 4.96 mL is 4.80.The Ka value for trial 1 in first method is

and the
molarity of unknown acid is 10.87 M .
In Figure 2, the equivalence point is observed at 8.90 mL addition of NaOH to the
unknown acid. While the half-equivalence point is observed at 4.45mL. The pH of half-
equivalence point at 4.45 mL is 4.70. The Ka value for trial 2 in first method is

and the molarity of unknown acid is 11.24M .The average molarity and the average Ka
value for trial 1 & 2 are 11.06 M and1.79

respectively.
Second method used to determine the K
a
value of a weak acid is by measure the pH of the
weak acid solution. The pH of the unknown acid was recorded in three replicates.
For trial 1, the pH recorded is 2.91. The molarity of unknown acid when the pH 2.91 is
1.23

M by using the equation pH = -log [H

3
O
+
]. While the Ka value is 1.69

calculated by using ICE Table .
For trial 2, the pH recorded is 2.94. The molarity of unknown acid when the pH 2.94
is1.15

M by using the equation pH = -log [H

3
O
+
]. While the Ka value is 1.47

calculated by using ICE Table .

For trial 3, the pH recorded is 2.98. The molarity of unknown acid when the pH 2.98 is
1.05

Mby using the equation pH = -log [H

3
O
+
]. While the Ka value is 1.23

calculated by using ICE Table. The average Ka value for trial 1,2&3 is .1.46

From average Ka value that are recorded in method 1&2,there are the same which is 1.8
10
-5
. Therefore,they are the same acid use in method 1&2,which is acetic acid .
It is not necessary to know the exact mass of the acid to determine the Ka because to find the
end point only the concentrations are relevant. and not necessary to know the exact
concentration of the NaOH solution used because the only thing that must be known about
the concentrations is that they reach the endpoint, where the OH
-
and H
+
concentrations are
equal.
Buffer solution is water mixed with a chemical to give it special properties in regards to pH
(acidity). The chemical, known as a buffer agent, resists pH changes when exposed to acids
and bases when properly mixed in a solution. This property makes a buffersolution extremely
useful in protecting sensitive equipment, dealing with chemical accidents, and even in
balancing the internal processes of living things.
Brnsted and Lowry independently came up with the idea that an acid is an acid because it
provides or donates a protonto something else. When an acid reacts, the proton is
transferred from one chemical to another. Bases are the opposite of acids. Bases are basic
because they take or accept protons. Hydroxide ion, for example can accept a proton to form
water. Brnsted and Lowry realized that not all bases had to have a hydroxide ion. As long as
something can accept a proton it is a base.
Through Henderson-Hasselbalch Equation pH = pKa + log (A
-
/ HA) , when the
concentration of the conjugate base and weak acid are equal , the log of 1is zero. So the pH
and pKa are equal.




CONCLUSION
From the findings of this experiment, it can be concluded that when determining the Ka of a
substance when using equal concentrations of a weak acid and conjugate base that the pH and
pKa are the same number. And by using the function Ka= 10
-pH
an acids Ka is rather simple
to find. The unknown acid that we get from method 1&2 is acetic acid .
Due to several factors and errors, a miscalculation might occur. One of the factor is the
apparatus is not cleaned enough and not rinsed with distilled water that can cause the
impurities such as dust and other chemicals to present. Secondly, the NaOH solution is not
use immediately after it is standardized. The impurity of the sodium hydroxide can be
affected with the present of the sunknown acid. This is because sodium hydroxide is one of
the unstable solutions that can easily absorb carbon dioxide from the air. To overcome this
problem, the standardized NaOH solution should be used immediately after standardization.








RECOMMENDATIONS
- Rinse the burette with tap water then distilled water. If the burette drains without
leaving drops of water behind, it is clean. Also make sure there is no air bubbles
inside the burette, if there is, rinse the burette with NaOH solution to make sure all the
air bubbles are gone. This is to make sure we got the accurate reading of volume of
NaOH solution used to titrate the unknown acid solution.
- In order to get the accurate pH reading of the unknown acid solution, we must
immerse the pH meter into the solution for a while, and then take the reading, to make
sure that the solution is completely stabilized when the pH reading is recorded.
- We also can add a smaller portions of NaOH when the pH of the solution begin to rise
after certain titration. Rinse the sides of the beaker occasionally with distilled water
from the wash bottle and continue the titration until the pH of the solution is about
11.5-12.0. In case, when the reading of the pH meter already rise in between 11-12,
theres no need to add anything.

REFERENCES
http://faculty.kutztown.edu/vitz/limsport/LabManual/KAWeb/KA_DET.htm
http://spot.pcc.edu/~gbackes/CH223/Labs.Ch223/Exp.25.Ka.Titration.htm
http://www.uvm.edu/~jcmorris/Lab%20experiment%203%20Ka%20determination%2
0through%20pH%20titration.pdf


APPENDIX
1.2 Ka of Weak Acids
Name Formula K
a
pK
a

Acetic HC
2
H
3
O
2
1.8 x 10
-5
4.7
ascorbic (I) H
2
C
6
H
6
O
6
7.9 x 10
-5
4.1
ascorbic (II) HC
6
H
6
O
6
-
1.6 x 10
-12
11.8
Benzoic HC
7
H
5
O
2
6.4 x 10
-5
4.2
boric (I) H
3
BO
3
5.4 x 10
-10
9.3
boric (II) H
2
BO
3
-
1.8 x 10
-13
12.7
boric (III) HBO
3
2-
1.6 x 10
-14
13.8
carbonic (I) H
2
CO
3
4.5 x 10
-7
6.3
carbonic (II) HCO
3
-
4.7 x 10
-11
10.3
citric (I) H
3
C
6
H
5
O
7
3.2 x 10
-7
6.5
citric (II) H
2
C
6
H
5
O
7
-
1.7 x 10
5
4.8
citric (III) HC
6
H
5
O
7
2-
4.1 x 10
-7
6.4
Formic HCHO
2
1.8 x 10
-4
3.7
Hydrazidic HN
3
1.9 x 10
-5
4.7
Hydrocyanic HCN 6.2 x 10
-10
9.2
Hydrofluoric HF 6.3 x 10
-4
3.2
hydrogen peroxide H
2
O
2
2.4 x 10
-12
11.6
hydrogen sulfate ion HSO
4
-
1.2 x 10
-2
1.9
Hypochlorous HOCl 3.5 x 10
-8
7.5
Lactic HC
3
H
5
O
3
8.3 x 10
-4
3.1
Nitrous HNO
2
4.0 x 10
-4
3.4
oxalic (I) H
2
C
2
O
4
5.8 x 10
-2
1.2
oxalic (II) HC
2
O
4
-
6.5 x 10
-5
4.2
Phenol HOC
6
H
5
1.6 x 10
-10
9.8
Propanic HC
3
H
5
O
2
1.3 x 10
-5
4.9
sulfurous (I) H
2
SO
3
1.4 x 10
-2
1.85
sulfurous (II) HSO
3
-
6.3 x 10
-8
7.2
Uric HC
5
H
3
N
4
O
3
1.3 x 10
-4
3.9