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4.

0 THEORY
There are two methods used to determine the Ka value for an acid which are:
1) Acid-Base Titration,
2) Measuring the pH of the Acid Solution.

1)Acid-Base Titration
A titration curve is produced by plotting the graph of the pH of the solution versus the volume
of sodium hydroxide solution used. The equivalence point of the titration is reached when all
of the hydrogen (H+) ion in the acid [HA] completely reacted with the hydroxide (OH-) ion in
the base solution. 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, the concentration of the acid [HA] in the solution is identical with the concentration of
its conjugate base [A].

[𝐇𝐀] = [𝐀] (Equation 1)

Equation 1 can be simplified to yield equation 2,

𝐊 𝐚 = [𝐇𝟑 𝐎 + (𝐚𝐪) ] (Equation 2)

Taking the negative logarithm of each side of Equation 2, Equation 3 can be derived

− 𝐥𝐨𝐠 𝐊 𝐚 = − 𝐥𝐨𝐠 [𝐇𝟑 𝐎 + (𝐚𝐪) ] (Equation 3)

𝐩𝐊 𝒂 = 𝐩𝐇

Equation 3 indicates that the pKa for the acid is equal to the pH of the solution at the half
equivalence point. The Ka of the acid is determined from the pKa value as follows,

𝐊 𝒂 = 𝟏𝟎−𝐩𝐊𝒂 (Equation 4)
Sample Calculation Using Method 1
A weak acid is titrated with 0.1M sodium hydroxide, NaOH solution. The titration curve is
shown in Figure 1. Determine the Ka of the weak acid,

Half-equivalence
point, 5.81mL

Figure 1 - Titration Curve For Weak Acid Titrated With NaOH

The pH at half-equivalence point of the graph is the value for pKa. Half equivalence point on
the graph is at 5.81 mL with the corresponding pH of 4.2.
pKa = pH = 4.2 (at the half-equivalence point)

Ka = 10-pKa = 10-4.2 = 6.3096 x 10-5

2) Measuring the pH of the Acid Solution


From the pH of the acid solution (HA), we can determined the H+ and A- ion concentration,
which is related to the pH of solution by Equation 5,

[𝐇𝟑 𝐎+] = 𝟏𝟎−𝐩𝐇 (Equation 5)

By substituting [HA], [H3O+] and [A-] at equilibrium in to Equation 6 the value of Ka can be
calculated.

[𝐇𝟑𝐎+(𝐚𝐪)]
𝐊𝐚 = (Equation 6)
[𝐇𝐀]
Sample Calculation Using Method 2

The pH of a 0.10M weak acid solution is 2.52 at 25⁰C. Calculate the Ka of the weak acid at
25⁰C. Initially, only the weak acid (HA) is present in the solution,. At equilibrium, a fraction
of weak acid (HA) molecules ionize, forming H3O+ and A-. The [HA] decreases while the
[H3O+] and [A-] increases until equilibrium is attained. The equilibrium [HA], [H3O+] and [A-
] are calculated as follows,

pH = 2.52

[H3O+] = 10-pH = 10-2.52 = 3.020 x 10-3 M

HA + H2O → H3O+ + A-
Initial 0.10M 0 0
Change -3.02 x 10-3 M -3.02 x 10-3 M -3.02 x 10-3 M
Equilibrium (0.10 – 3.02x10-3)M -3.02 x 10-3 M -3.02 x 10-3 M

[𝐇𝟑 𝐎+(𝐚𝐪)][𝐀− ] [−𝟑.𝟎𝟐 𝐱 𝟏𝟎−𝟑 ][−𝟑.𝟎𝟐 𝐱 𝟏𝟎−𝟑 ]


𝐊 𝒂 = = = 𝟗. 𝟒𝟎𝟒𝟒 𝐱 𝟏𝟎−𝟓
[𝐇𝐀] [𝟎.𝟏𝟎−𝟑.𝟎𝟐 𝐱 𝟏𝟎−𝟑 ]

The calculated Ka value of the unknown acid is closest to that of benzoic acid, 6.28 x 10-5 (refer
Appendix).
11.0 RECOMMENDATIONS

There are a few recommendations and precautions that need to be re-evaluated throughout this
experiment.

Students should research more about the experiment before conducting the experiment.
This is to ensure the procedures are followed properly and within the time limit without
confusion. Data table should be prepared before the experiment so all the data is recorded.

The students who is responsible for taking the burette reading should be aware to
measure the reading with eyes parallel to the meniscus of the sodium hydroxide, NaOH in
order to avoid reading error from occurring. This is to ensure all the data measured is accurate.

The pH meter should also be cleaned with distilled water before after each reading so
that the data is as accurate as possible.

Students should always wear complete PPE in the lab such as gloves, covered shoes,
protective glasses and lab coat throughout the experiment. Unwanted accidents is usual in the
lab so safety should be a priority to everyone in the lab.
12.0 REFERENCES

Determination of Ka Value of a weak acid.


from Analytical Sciences Digital Library (ASDL):
http://www/asdlib.org/onlineArticles/ecourseware/Text_Files-files/Appendix.pdf

Harvey, D. (2008). Modern Analytical Chemistry. McGraw-Hill.

Determination of Ka of Weak Acids Lab Report.


Retrieved from Scribd: http://www.scribd.com/doc/87709893

Martell, A. S. (1976). Critical Stability Constants. New York: Plenum Press.