Nathalie Dagmang Group 8

Co-workers: Annjaneth Briones and Date Performed: February 22, 2011

groups 5, 6, 7 and 9

Results and Discussion Report 11:

Potentiometric Determination of the Purity and Dissociation Constant of

Potassium Hydrogen Phthalate

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.

Potentiometric methods are very accurate compared to volumetric titrations

because of the high sensitivity of the pH meter as compared to visual indicators, the
possibility of human error in determining the endpoint by looking at the color
change of the analyte and the effect of the indicator on the pH of the analyte. Also,
indirect potentiometry use potential as the function of titrant volume, where it
follows the actual change in concentration at different amounts of titrant added.
Hence, one can see the pH values of the analyte at many different points, not just
the point at which it reaches the equivalence point. Thus, potentiometry is often
used for dilute solutions.

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.

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 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.

Figure 1. Set-up for Potentiometric Titration

The pH meter’s electrode is immersed in the beaker containing the analyte

while it is titrated with a NaOH solution. The magnetic stirrer was used so that the
solution is constantly mixed and the NaOH is equally distributed throughout the
analyte, Potassium Hydrogen Phthalate (KHP). At each addition of titrant, the pH
was recorded and was used to determine the equivalence point, acid-dissociation
constant and percent purity. For the first run, the solution was added 50 ml of
titrant. For each pH recording, 1 ml of titrant was added. The approximate endpoint
determined in the first run was used in the following runs so that the complete
neutralization can be anticipated and smaller increments can be added as it
reaches the endpoint. However, the volume increments should not be too small as
there may be two or more points of the straight line of the second derivative plot
that passes zero and it may become vulnerable to experimental errors due to more
volume measurements. Also, the volume increments should not be too large or
there would not be enough points to make accurate results and graphs.

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.

Figure 2. Normal Titration Curve

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 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.

Figure 3. First Derivative Plot

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.

Lastly, a Second Derivative Plot was graphed, which is showed in Figure 4.

For this graph, one can see the endpoint at which y is equal to zero.

Figure 4. Second Derivative Plot

The KHP analyzed in the experiment follows the dissociation reaction:

KHP↔KP-+H+

In order to calculate the acid-dissociation constant of KHP, the half-

equivalence point was determined. At half-equivalence point, where the volume of
titrant used is half of the volume used at equivalence point, the number of moles of
the KP- is equal to the number of moles of KHP left. Therefore, given the pH at half-
equivalence point and using the formula for the acid-dissociation constant, the Ka
can be calculated.

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:

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%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.

Sources:

Skoog, et al., Fundamentals of Analytical Chemistry, Eighth edition, 2004

Day, Underwood, et al. Quantitative Analysis, 1967

Christian, G.D. Analytical Chemistry, 1986