POTENTIOMETRIC DETERMINATION OF THE PURITY AND DISSOCIATION CONSTANT

OF POTASSIUM HYDROGEN PHTHALATE

Submitted By: Frances Abegail G. Quezon

Potentiometry is a method that measures the electric potential difference in a cell. [1]
The objective of the experiment was to determine the purity and dissociation constant of
KHP. The type of electrode used in the experiment is a glass membrane electrode. A glass
membrane electrode is an ion selective electrode, or an electrode that is for specific ions
only.[3] The titrant used in this experiment is NaOH while the analyte and standard used is
KHP. The reaction for this system is:
NaOH + KHP  NaKP + H2O (1)
For the standardization of NaOH, normal acid-base titration was done, since
potentiometric titration is time-consuming.
A titration curve has 3 significant regions. These are pre-equivalence point,
equivalence point, and post-equivalence point. Pre-equivalence point is the region when the
titrant was just added. In acid-base reactions such as in the experiment, this region is a
slowly increasing curve because of the presence of a buffer. Equivalence point is when the
analyte and titrant were equal in the number of moles. This is the steep part of the graph in
a pH vs. V graph. The post-equivalence point is the last part of the graph. At this point, all of
the analyte are converted to another form. [3]

Figure 1. pH vs. V

Based from the titration curve above, at the pre-equivalence point, there was a slow
but steady increase in the pH. At the equivalence point, pH changes drastically over a small
volume interval. At the post equivalence point, the pH change returns to slow and steady
again. Below are the graphs for pH vs V’ and 2pH vs V”.
Figure 2. pH vs V’
 Figure 3. 2pH vs V”
The equivalence point from plot 1 is a middle point on the steep curve. On plot 2, it
is the peak, and on plot 3 it is the x-intercept of the graph. The volume of NaOH at
equivalence point for trial 1 is the same for all plots. On the second trial, volumes have a
difference of 0.05 per plot. And on trial 3, volumes from plot 1 and plot 2 are the same but
plot 3 has a difference of 0.01.
Potentiometric titration does not make use of any indicator, instead, it adds titrant
volume in increments of 1mL or less while the pH is continuously monitored. A large jump
in pH indicated the equivalence point. As the solution reaches its equivalence point, the
increments of titrant addition should be narrowed down in order to have better accuracy in
determining when the pH jump occurs, and consequently, better accuracy in determining
the equivalence point. Usage of a stirrer or a magnetic stir bar is important in order to mix
the reactants. The beaker cannot be swirled just like in normal titrations because of the pH
electrode dipped in the solution. The electrode is fragile and might break with manual
stirring.
Potentiometric titration allows the constant monitoring of pH changes, therefore the
volume at equivalence point could be determined more accurately than in normal titration.
There is also no risk of overtitration that could affect your results. Also, the data obtained
from this type of titration could be used to make a titration curve for the system. However,
potentiometric titration is tedious and time-consuming. It is also dependent on the pH
meter, and a faulty meter would cause the results to be incorrect. There is also the added
danger of the spin bar hitting the electrode of the pH meter as it spins inside the beaker.
Errors may arise from instrumental errors such as a faulty pH meter. This is an
indeterminate error and may cause inconsistencies in the results.
After processing the data obtained from the experiment, the average percent purity
of the sample was determined to be 34.8%. It has an RSD of 200ppt meaning that data were
imprecise. Average pKa is 5.14. This has a 152% error with the theoretical value of 5.51 [2].
The experimental Ka is 7.80x10-6. pKa values have an RSD of 700ppt meaning that the data
are not only inaccurate but also imprecise. The experiment and the laboratory techniques
involved were successfully executed, and the data, processed properly. Since the objective of
determining %purity and Ka is achieved, the experiment could be considered successful.

REFERENCES
[1]Harris, D. Quantitative Chemical Analysis 5th ed. W.H. Freeman and Company: New York,
2001.
[2]Institute of Chemistry. Quantitative Inorganic Analysis Laboratory Manual
[3] Skoog, D., et al. Fundamentals of Analytical Chemistry 8th ed. Thomson Learning Asia:
Singapore; 2004.