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Experiment 4:

pKa of an Unknown Acid-Base Indicator

Bryan Zheng

Lab Instructor: Michael Boucher

October 9, 2015

In this experiment, the pKa of an unknown indicator was measured both qualitatively and
quantitatively. A solution of citric acid was added to a solution of ammonia with the unknown
indicator until the color of the ammonia solution was midway between the color of the acid and
base solutions. The pH of that solution was the qualitative pKa. The quantitative pKa was
calculated by taking the absorbance of many different combinations of of acid and base solution
with different pH values. The pKa can be found using the formula shown below, as well as
finding the x-intercept of the graph log10[(A-AIn-)/(AHIn-A)] versus pH.

pKa=pH +lo g10

First, 25mL of unknown indicator C was added to about 500mL of distilled water in a
600mL beaker. Roughly half the indicator solution was placed in another, 400mL beaker. 25 mL
of .5M citric acid solution was added to one beaker and .5M ammonia solution was added to the
other. The citric acid solution was observed to be clear while the ammonia solution was bright
Using a Pasteur pipet, the acid solution was added to the base solution until the color was
qualitatively midway between the clear acid and bright pink base. The midway solution was light
pink and had a pH of 8.65. This was the qualitative pKa from the experiment.
To determine the quantitative value of the pKa, different amounts of the original acid and
base solution were added to the midway solution to create different pH values. The absorbance at
each of those pH values was measured using the spectrometer and shown in table 1. The
absorbance of the original acid solution (AHIn) and the absorbance of the original base solution
(AIn-) were also recorded in table 1 as standards.
Results and Calculations:
Algebraic method:
A In

pKa=pH +lo g10

pKa=9.19+lo g 10(
The rest of the pKa for the 4 other pH values are shown in table 2, along with the average
pKa of the 5 trials.

Graphical method:
The graph of log10[(A-AIn-)/(AHIn-A)] versus pH can be seen in Graph 1 of the appendix.
Finding the x-intercept of the graph of log10[(A-AIn-)/(AHIn-A)] versus pH, obtained from
linear regression, was another method for determining the quantitative pKa. The y-value from the
least squares regression line was set to zero, and x was solved for:
y=1.6391 x +14.723

0=1.6391 x+14.723
The slope of the regression line was -1.6291, while the expected value was -1. The
magnitude of the experimental slope was greater than the expected slope by 63.0%, the sign was
still negative, as expected.
The pKa obtained by the graphical method, 8.98, was very close to the pKa obtained by
the algebraic method, 9.21. The graphical method resulted in a pKa value -2.5% less than the
pKa from the algebraic method.
A possible source of error in the experiment was the magnitude of some of the
absorbance values taken from the computer. At pH 7.92, the absorbance was only .007, in the
order of magnitude of 10-3. Thus, small variation in the absorbance resulted in a large percent
increase. When the log of the absorbance was taken, any variation was amplified, resulting in
varied pKa values. Another possible source of error was highlighted by the two highest pH
values, which resulted in points the deviated the most from the regression line. At those pH
values, the pH meter reading fluctuated more than it did at lower pH values. Thus, the recorded
pH was likely not the exact pH at which the absorbance was measured for the two highest pH
Unknown indicator C was most likely phenolphthalein, which has an accepted pH of 9.3
and has a bright purple color, both of which were consistent with observations and calculations.
algebraic percent error =
100 =0.92
graphical percent error=
100 =3.4
qualitative percent error =
100 =7.0
Additional Questions:
3a) Unknown indicator C was most likely phenolphthalein, which was a weak acid. Thus,
equation (4a) can be used. If, however, unknown indicator C was a weak base, the following
equation is analogous to equation (4a) but for a weak base:

pOH= pKb+lo g 10
3b) Different indicators have different pKa values, and thus change colors at different pH values.
Indicators change color over a range because they gradually shift from their first color to their
second. Furthermore, the endpoint of the titration is slightly subjective, not absolute.
The qualitative pH of unknown indicator C was 8.65, with a percent error of -7.0%. The
quantitative pKa using algebra was 9.21, with a percent error -.92%. The quantitative pKa using
the graph of the least squared regression line of log10[(A-AIn-)/(AHIn-A)] versus pH was 8.98, with
a percent error of -3.4%.