QUANTITATIVE DETERMINATION OF THE PURITY AND

DISSOCIATION OF POTASSIUM HYDROGEN PHTHALATE BY

POTENTIOMETRIC TITRATION

ANSWERS TO QUESTIONS

1. What are the significant regions in the titration curve? Relate the characteristics of each
region to the pH results obtained.
The significant regions are: initial, pre-equivalence point, equivalence point and post-
equivalence point.
At the initial region, titration has not yet begun. The component of the solution is merely
the KHP solution. The pH of the KHP solution is equal to the amount of H+ ions from its
hydrolysis reaction, quantified by its acid dissociation constant.
At the pre-equivalence region, titration occurs. There is the presence of NaOH which
causes a rise in the pH of the solution. It can be divided into to two, the buffer region and half-
equivalence point. At the buffer region, the pH change resists increase per drop, shown in the
gradual rising of the graph. Another region under this part is the half-equivalence point wherein
the pKa of the weak acid is equal to the pH value.
The equivalence point is considered to be a crucial stage of titration because it is the point
wherein the amount of added titrant is chemically equivalent to the amount of analyte in the
sample. Using a graph, it can be shown as the region wherein adding a particular amount of the
titrant results in a large jump in pH level. Even though it implies that the solution is completely
neutralized, the solution is not necessarily at pH 7 (neutral pH level). In the given scenario, a
weak acid-strong base titration, the basic salt hydrolyzes and contributes to the slight increase in
pH of the solution.
At the post-equivalence region, the pH of the solution is solely determined by the reactant
in excess, the strong base. Even though salts produced by the neutralization reaction between
titrant and analyte at equivalence would hydrolyze and increase the pH, it would be insignificant
because it only raises it slightly and it would be overwhelmed by the pH contribution of the
strong base.

2. Why is continuous stirring important in potentiometric titration?

Just like in any titration, while adding the titrant, one rotates the Erlenmeyer flask. The
continuous stirring keeps the solution homogenous throughout the measurement. In this
experiment, to avoid damage to the glass electrode immersed in the beaker, it was stirred using a
spin bar and a hot plate that has a stirrer function.

3. Why should the increments of addition of titrant narrowed down as titration approaches
the equivalence point?
 The increments of addition of titrant should be narrowed down as the titration approaches
the equivalence point as to get the actual amount of titrant used to neutralize the analyte.
Accuracy plays a crucial role in getting the equivalence point.

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

The relationship being studied is between the potential of a suitable indicator electrode
and the volume of the titrant. Potentiometry also provides a sharper endpoint. The values are also
affected by the alkaline and acid errors. This means that at high pH, the pH meter provides a low
and inaccurate reading because the glass electrode reacts/responds to both the alkali metal ions
and the hydronium ions present in the solution. Whereas if there is very low pH, the results
obtained would be much higher than the expected. Potentiometric titration uses pH change as
indicator instead of color change, thus it eliminates the possibility for bias during the reading.

5. Discuss possible reasons behind the discrepancies (if any) in the experimental and
theoretical pKa values.
Determination of the half-equivalence point and pH corresponding to it was done only
through visual inspection and estimation. There was no mathematical attempt to obtain the pH
value at the said point. Because this experiment required derivatives of the initial graphs, a
compounded error could occur if ever data from the original observations were incorrect.

6. What are the possible sources of errors and their effect on the calculated parameters?
Rationalize.
One possible source of error is the incorrect process of standardization which could lead
to a very different concentration of NaOH from the actual. Another is inaccurate reading of the
volume of the titrant, and also the inaccurate determination of the endpoint during the titration
process. The concentrations may also not be consistent due to improper preparation of the
solutions. Dehydration of the electrode itself can also be a possible source of error.

REFERENCES

[1] Skoog, D.; West, D.; Holler F.J.; Crouch, S.R. Fundamentals of Analytical Chemistry 8th ed.
2004. Belmont, CA: Brooks/Cole, Thomson Learning. 338.
[2] Skoog, D.; West, D.; Holler F.J.; Crouch, S.R. Fundamentals of Analytical Chemistry 8th ed.
2004. Belmont, CA: Brooks/Cole, Thomson Learning. 235.
[3] Whitten, K.; Davis, R; Peck, M.; Stanley, G. Chemistry 8th ed. 2007. Belmont, CA:
Brooks/Cole, Cengage Learning.