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EXPERIMENT ONE
Determination of the dissociation constant of a weak acid from pH measurements
AIM/OBJECTIVE: To determine the pKa for benzoic acid using pH measurements
PRE-LAB QUESTIONS
i. What is a buffer solution?
A solution that can resist significant changes in pH level when an acid or base is added to
it.
pK a=−log K a
INTRODUCTION/THEORY
Acids and bases play a significant role in many areas of chemistry and biochemistry. We can
classify substances as acids and bases based on chemical behavior. The definition of an
Arrhenius acid is a substance the produces hydronium ions (H3O+) in aqueous solution, while an
Arrhenius base is a substance that produces hydroxide ions (OH-). A more useful definition of
acids and bases is based on the Brønsted-Lowry theory. A Brønsted-Lowry acid is defined as a
substance that acts as a proton donor, while a Brønsted-Lowry base acts as a proton acceptor.
The Swedish chemist Arrhenius suggested that solutions that conduct electricity, so called
electrolytes, do so because they dissociate into charged species called ions. Compounds of this
type: acids, bases and salts may be classified as strong electrolytes dissociate in solution almost
completely into ions, weak electrolytes dissociate only to a small extent in solution (only 10% or
less ions are present in solution).
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The pH of a solution can directly be calculated from the initial concentration of the strong acid
and base using the equation; pH = -log (H3O + ). However, the determination of pH in a weak
acid or base solution is much more complicated. In the solutions, the pH is a function of both the
initial concentration of the weak acid or base and the degree of dissociation of the H+ . To
determine the degree of dissociation of the acid, HA, we need to know the equilibrium constant
that governs the ratio between the reactants and products in the weak acid equilibrium. When the
equilibrium involves a weak acid, we refer to the equilibrium constant as an “acid dissociation
constant” and give it the symbol, Ka.
An alternative method of finding is by titrating the weak acid HA with a base, there will be
no point in the titration at which the number of moles of base added is just one half of the
number of moles of acid initially present. This is the point at which 50% of the acid has been
titrated to produce , and 50% remains as HA. At this point in titration that is at one half the
equivalence or neutralization point pH=
By titrating a weak acid with a strong base and recording the pH versus the volume of base
added, the titration curve can be plotted, from which the pH at half neutralization point is
determined and hence the of the weak acid
PROCEDURE
Benzoic acid
150ML of distilled was boiled in a 250ml beaker. Benzoic acid was weighed between 0.12g and
0.13g using the mass balance and the benzoic was weighed in the boat. The electronic mass
balance was used to weigh the mass of the benzoic salt. The value was recorded, then the
benzoic acid was transferred into a 250ml beaker and the mass of the boat was also measured
and recorded.40ml of boiled water was added to the beaker with the benzoic acid and stirred
until the acid dissolved. The solution was allowed to cool and it was covered with petri dish.
After cooling the solution was transferred quantitatively into 100ml volumetric flask and it was
filled to the mark using boiled distilled water.50ml of the benzoic acid solution was measured
using measuring cylinder and transferred into 100ml beaker and the solution was covered with
petri dish. The burette was washed and filled with sodium hydroxide. The pH meter was
calibrated. Distilled water was used to rinse the electrode and then the excess water was removed
and the electrode was immersed in a pH 4.0 buffer and the electrode was calibrated. Then the
electrode was rinsed once more with distilled water and the excess water was removed again
then it was immersed in pH 7.0 buffer. After washing the electrode with distilled water it was
later immersed in the benzoic acid solution. The reading was recorded. Then the pH was
measured and recorded together with the temperature. Adding 0.5 of sodium hydroxide was
added quantitatively and later the electrode was rinsed and stored in its storage container.
Potassium hydrogen phthalate
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Potassium hydrogen phthalate was weighed and a 100mL solution was prepared. The solution
was used to standardize a sodium hydroxide solution. The sodium was used to fill up a 50mL
burette. A 10mL pipette was used to measure out the potassium solution into a conical flask. 2
drops of phenolphthalein were added to the potassium solution. Titration was performed with the
two solution until a pink color change was observed. The volume of sodium hydroxide used was
then recorded and the titration was repeated twice
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X : 0.1
Molarity = 0.1017M
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3. Calculation of pKa
Volume of [HA] [ A−¿¿ [ H +¿¿ [ HA ] −¿ ¿] ¿ ¿] pK a
NaOH ( M × 10−3 ) −3
M × 10 )
−4
M × 10 ) M × 10 )
−3 −3
M × 10 )
added
(mL)
0.00 10.50 0.00 5.62 9.93 0.56 4.50
0.50 9.39 1.03 3.31 9.06 1.36 4.30
1.00 8.30 2.08 2.14 8.09 2.29 4.21
1.50 7.23 3.15 1.38 7.09 3.29 4.19
2.00 6.18 4.24 0.87 6.09 4.33 4.21
2.50 5.16 5.35 0.54 5.10 5.40 4.24
3.00 4.15 6.49 0.32 4.12 6.52 4.29
3.50 3.16 7.65 0.18 3.14 7.67 4.36
4.00 2.19 8.84 0.06 2.18 8.85 4.58
4.50 1.24 10.00 0.07 1.23 10.00 5.26
−¿¿
V NaOH x C NaOH
[A =
V HA−V NaOH
0.5 x 0.1017
= = 1.03 x 10−3 M
50+ 0.5
Calculation of ¿
At 0.00mL: 10−3.25 = 0.000562341
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Calculation of [ HA ] −¿ ¿]
At 0.00mL
[10.50 x10−3 ¿ – [5.62 x 10−4] = 9.93 x 10−3
Calculation of ¿ ¿]
At 0.00mL
[0.00 x 10−3 ] + [5.62 x 10−4 ¿=0.56
Calculation of pKa
+¿
H
pK a= pH + log [ HA ] − ¿
¿¿
At 0.00mL
SD=
√
Σ( X−x ) 2
n−1
=0.3241467 ≈ 0.32
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12 Buffered regions
10
“Midpoint”
8
Equivalence point
pH
0
0 2 4 6 8 10 12
Volume of NaOH added (mL)
DISCUSSION
In the initial phase of the experiment, upon the addition of base to the acid, the influence of the
conjugate base of the weak acid on the solution's pH was notable. The tendency for the conjugate
base to combine with a proton, regenerating the weak acid, introduced fluctuations in the
concentration of (H+). It was imperative to account for the stoichiometric relationship between
the acid and base, considering the equilibrium reactions of the remaining species. The complete
dissolution of the added strong base resulted in the generation of a balanced quantity of OH-(aq)
and the conjugate acid. The stoichiometrically equivalent OH-(aq) reacted entirely with the H+
ions released by the weak acid, leading to the neutralization of a stoichiometric amount of weak
acid and the concurrent production of a stoichiometric quantity of the conjugate base.
The determination of the acid dissociation and pKa was based on the utilization of the half-
equivalence point in the acid-base titration. This point, where the ratio between the acid and its
corresponding base is 1:1, was pivotal for assessing the acid dissociation and pKa (Hein, 2011).
Approaching the equivalence point, the diminishing concentration of [H+] made small
increments of base have a substantial relative impact on [H+]. Consequently, a significant pH
alteration was observed in close proximity to the equivalence point.
The computed average pKa was 4.41, exhibiting a 4.90% deviation from the literature value of
4.204. The minimal percentage difference between the experimental and literature pKa values
implies a relatively low margin of error in the conducted experiment.
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CONCLUSION (S)
The computed mean pKa was determined to be 4.41, exhibiting a certain degree of deviation
from the literature value of 4.204. This disparity suggests a level of inaccuracy in the obtained
results, warranting further scrutiny and refinement in the experimental methodology or data
analysis techniques employed in the study.
ANSWERS TO QUESTIONS
i. Why is it necessary to prepare the solutions in boiled water?
-Removal of dissolved gases
-Consistency of temperature
ii. Why is it necessary to try and keep the temperature constant during the experiment
- Reaction rate consistency: Keeping the temperature constant ensures that the rate of the reaction
remains consistent throughout the experiment. This is essential for obtaining reliable and
reproducible results.
REFERENCES
Biust, (2024). Introductory Physical Chemistry (CHEM 206) Laboratory Manual
10 | P a g e