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The three main objectives of the experiment are to (1) apply the principles of
potentiometry in the determinatitaon of the equivalence point in a titration, (2)
determine the purity of KHP using potentiometric titration, and (3) derive the acid
dissociation constant of KHP from the potentiometric data.
Aside from the commonly used volumetric analysis, another method used for
determining the concentration of a substance is the potentiometry. This is used
when visual indicators are unavailable and when one is aiming to get more accurate
results. There are two types of potentiometry: direct and indirect. In direct
potentiometry, the potentials of a cell with the indicator electrode at different
analyte concentrations and a constant potential at reference electrode are
Acompared. While in indirect potentiometry, the pH is measured at each addition of
titrant.
Because the endpoint is indicated at the largest potential break, the exact
potential is unnecessary and only the change in cell potential is needed. Also, the
glass electrode does not need to be calibrated with a standard buffer nor does the
pH meter need to be a high-end model since potential need not be read closely.
However, in order to anticipate the endpoint, so that one will add smaller
increments as it begins to neutralize, the approximate equivalence point may be
predetermined using calculations, volumetric titrations or a run of potentiometric
titration.
1
Aside from the concentration of the sample, its acid-dissociation constant
(Ka) and percent purity was also determined. Three trials were done using a pH
meter set-up as described in Figure 1.
The data gathered was then plotted so that one can clearly see the
equivalence point. The first plotted graph was the normal titration curve. Shown in
Figure 2 is the normal titration curve for trial 2.
2
For this graph, the equivalence point can be seen at the corresponding
volume of the curve’s inflection point where the pH change is highest. The
preceding points are the pre-equivalence points where the pH values are acidic
while the points following the inflection point are the post-equivalence points where
the pH of the analyte is towards basic.
Another graph used was the First Derivative plot where dpH/dV is a function
of the average volume. Figure 3 shows the First derivative plot of trial 2.
This graph gives a clearer image for determining the equivalence point.
Because the change in potential with respect to the added volume is highest at
equivalence point, the graph will have a “spiked” curve and will peak at the
corresponding volume. The pre- and post-equivalence points have almost equal
changes in potential as certain volumes of titrant are added.
KHP↔KP-+H+
Ka=KP-[H+][KHP]
At ½ equivalence point,
KP-=[KHP]
Ka=KP-[H+][KHP]
Ka=[H+]→pKa=pH
The percent purity, on the other hand was calculated by using the formula:
3
%KHP=MNaOH×VNaOH×1 mol KHP1 mol NaOH×204.2 gmol KHPg KHP
sample×100%
It was found out that the sample’s percent purity is 69.24% with a confidence
interval of + 0.3 and a pKa of 4.87 with a confidence interval of 4.87 + 0.01. When
compared to the book value of KHP’s pKa which is 5.51 at room temperature, the
calculated percent error was 11.62%.
The two trials yielded slightly different endpoints, hence, also different half-
equivalence points and volume used in calculating the acid-dissociation constant.
Also, because several very small increments of titrant were added at each point,
there were errors due to volume measurements.
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