QUANTITATIVE DETERMINATION OF THE PURITY

AND DISSOCIATION CONSTANT OF POTASSIUM

HYDROGEN PHTHALATE BY POTENTIOMETRIC
TITRATION

J. Tan1
1`Collegeof Education
University of the Philippines, Diliman, Quezon City 1101, Philippines.
Date submitted: November 15, 2019
Date Performed: November 6, 2019

ANSWERS TO QUESTIONS

1. What is potentiometry? Instrumentation wise what are the common features of

potentiometric instruments?

One of the methods of electroanalytical chemistry, that is usually used to find the concentration of a
solute in a solution, is potentiometry. Potentiometry is based on the measurement of the potential of
an electrochemical cell under static conditions or in what we call, equilibrium. Since current flow is
negligible or considered none, its composition remains unchanged. Because of this, potentiometry is
a prevalent and widely used quantitative method. In the1889, the Nernst equation was formulated;
this equation explains or relates an electrochemical cell’s potential to the concentration of
electroactive species in the cell. Instrumentation wise, the common features of potentiometric
instruments include the base electrode, an indicator electrode, and an instrument for measuring
potential. The base electrode with a known potential that is constant over time and independent of
the composition of the solution which contains the analyte of which it is immersed in, the indicator
electrode that depends on the concentration of the analyte and the measuring potential instrument
that will determine the potential of the indicator electrode.

2. What are the advantages of potentiometric techniques?

One of the advantages of using potentiometric techniques in titration is that is it requires no indicator
which is far more accurate and precise in determining the equivalence point than manual titration
that relies on color indicators. It is particularly useful with colored or turbid solutions as well as for
detecting presence of unsuspected species. Potentiometric titration is considered to be the most
consistent and robust technique among the non-NMR methods.[4] As mentioned, it is also conducted
under static conditions as current flow is negligible, the composition remains unchanged or constant.

3. What are the significant regions in the titration curve? What are the characteristics of
each region in the titration curve? What are the species present for each region?
Relate the occurrence of these species to the pH results obtained.

The significant regions in the titration curve is the steady curve defined by the subtle increments of
change in pH. This indicates where the equivalence point lies as of the steep curve. At this region, the
solution can still act as a buffer.

● Initial point: The analyte, KHP, has a pH value equivalent to the concentration of hydrogen
atoms from hydrolysis (determined through Ka)
 ● Pre-equivalence point: A slow increase in pH was observed upon the addition of sodium
hydroxide titrant. This is because the region is within the buffer capacity of the solution;
KHP was dominant, therefore making the pH acidic.
● Equivalence point: In this region, the basic titrant and the acidic analyte are the same
amount. This is evident as there is a sudden rise of the slope of the curve that shows the
change in pH.
● Post-equivalence point: the low /shallow slope is observed signifies the moderate increase
in pH. The pH value is high as the NaOH (titrant) is dominant.

4. Why is continuous stirring important in potentiometric titration?

Continuous stirring is important in potentiometric titration to ensure the solution in the beaker will
not accumulate in a certain area upon addition of titrant. This is important in preventing any delay
in the change of pH upon addition of titrant. This also ensures the complete reaction of the titrant in
the solution which gives a stable pH reading. The equilibrium is also attained faster.

5. Why should the increments of addition of titrant be narrowed down as the titration
approaches the equivalence point?

The narrowed increments of addition of titrant evenly to the solution, with the KHP analyte, as the
titration approaches the equivalence point ensures that the actual equivalence point is determined,
hence, limiting the amount of error.

6. Why is the potentiometry a suitable method in determining pKa of weak acids?

Potentiometry is a suitable method in determining the pKa of weak acids as it is more convenient than
other titration methods as pH meters are used to determine the pH of the solution as a specific amount
of titrant is added, It also limits the room for error, as usual titration methods are subjective due to
the reliance on visual indicators and other errors in the measurement of equivalence point. Visual
indicators give the endpoint (color change is observed) even if the amount of analyte and titrant are
not in equilibrium. Potentiometry is also able to measure the activity of Hydrogen ions through highly
sensitive glass electrode, despite a low concentration of solution.

7. Discuss possible reasons behind the discrepancies (if any) in the experimental and
theoretical pKa values.

A possible reason behind the discrepancies in the values would be the calibration of the pH meter. If
it were not calibrated carefully or if it were not calibrated, then inaccurate pH values will be attained.
Theoretical Ka values are assumed in 250C, which is not the definite or constant temperature in the
laboratory. An inaccurate increment of titrant may also lead to a discrepancy in the pKa value. This
may be reduced by narrowing down the increments of addition of titrant.

8. What are the possible sources of errors and their effect on the calculated parameters?
Rationalize.

The first possible source of error will be in the measurements of reagents as it may give inaccurate
values, hence obtaining unideal experimental data. In the standardization, errors in value reading in
the burette may lead to calculation errors. Overtitration may also occur and this will cause problems
in the experimental data. Inaccurate pH readings may also be caused by unwashed or not properly
washed glass electrode.
REFERENCES

[1] Bissonnette, C., Herring, F.G., Madura, J.D. and Petrucci, R.H., 2011. General Chemistry: Principles
and Modern Applications. 10th Edition. Toronto: Pearson Canada, Inc.

[2]Skoog, West, Holler, Crouch. Fundamentals of Analytical Chemistry 8th Edition. 2004. Belmont:
Thomson Learning Inc.

[3] Whitney K. (2011). Winkler titrations – measuring dissolved oxygen. Colby at Sea.

[4] Chemistry LibreTexts. (2016). LibreTexts Libraries. Retrieved from https://goo.gl/R5p8SZ.