DETERMINATION OF PURITY AND ACID DISSOCIATION CONSTANT

OF POTASSIUM HYDROGEN PHTHALATE BY POTENTIOMETRIC

TITRATION
S.A.P. SAAVEDRA1, J. C. VILLASIS2
1NATIONAL INSTITUTE OF PHYSICS, COLLEGE OF SCIENCE
2DEPARTMENT OF FOOD SCIENCE AND NUTRITION, COLLEGE OF HOME ECONOMICS
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
DATE PERFORMED: JULY 5, 2016
INSTRUCTORS NAME: GARRERO, M.J.

1. What are the significant regions in the

titration
curve?
Relate
the
characteristics of each region to the pH
results obtained.
Normal Titration Curve
Pre-equivalence point is the area where
the plot is concave up. A series of weak acid
buffer system determines the pH of the
solution (HA H+ + A-).
Equivalence point is represented by the
inflection point of the plot. It indicates a rapid
change in pH in a small amount of volume.
Hydrolysis of the anion of the weak acid
determines the pH of the solution
(predominating species is A-).
Post-equivalence point is the area where
the plot is concave down. Excess strong base
determines the pH of the solution
(predominating species are A- and OH-).
First and Second Derivative Curve
Through extrapolation, the equivalence
point can be obtained from the first and

second derivative curve. Plotting the change

of pH with respect to volume forms the First
Derivative Curve. From the normal curve, the
equivalence point is when the slope is
maximum, thus, a spiked curve should
appear and its peak representing the
equivalence point. Uncertainty arises, but can
be avoided by plotting a Second Derivative
Curve 1. Mathematically, the second derivative
should pass through zero at the equivalence
point.
2. Why is continuous stirring important
in potentiometric titration?
Continuous stirring is important in order
to keep the solution homogeneous. It also
ensures that the change in pH detected by the
pH meter accounts the whole pH of the
solution and not just the part nearest the
electrode.
3. Why should the increments of addition
of titrant be narrowed down as the
titration approaches the equivalence
point?

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As the equivalence point is approached,

larger volumes of titrant could affect the
sharpness of the curve. With smaller volumes,
a better curve with more accurate data points
can be taken 2.
4. Why is potentiometry a suitable
method for determining pKa of weak
acids?
Noting that weak acids do not dissociate
completely, normal titrations involving
physical indicators are not as accurate as
when used with a strong acid-strong base
reaction. This is due to the formation of a
weak acid-strong base buffer that prevents
reaction to indicator and a change in color.
With potentiometric titrations, the
amount of volume of titrant used for weak
acids is the same as that of strong ones since
the number of titratable protons is taken into
account, and not the actual concentration.
Potentiometric titration deals with the
potential between the electrodes and relating
the volume of the titrant to the pH. It is also
more advantageous since it helps reduce
systematic error such as colorblindness.
5. Discuss possible reasons behind the
discrepancies
(if
any)
in
the
experimental and theoretical pKa
values?
Note that at half-equivalence point,
[]. Thus, using activites, Ka
becomes,
=

+ [ ]
3
[]

+
3

[1]

Since the glass electrode gives a good

estimate of 3 + , the difference between the
measured pKa and the theoretical pKa only

comes from the ratio of the activity coefficient

of A- to the activity coefficient of HA 3.
3 +

[2]

As electrolyte concentration increases,

the activity coefficient of HA does not change
significantly because HA is a neutral species.
However, the activity coefficient of A- does
decrease. This makes the 3 +
to increase

and the experimental pH to decrease. In effect

the experimental pKa is also lower than the
theoretical.
6. What are the possible sources of
errors and their effect on the
calculated parameters? Rationalize.
Some possible sources of error
throughout the experiment and their effect on
parameters are discussed in Table 1 below.
TABLE 1. Possible Sources of Errors and
its Effect on Calculated Parameters
Source of
Error
Dehydration of
electrode

Parameter and Error

Causes erratic electrode

performance and having
fluctuations in pH reading.
Inaccuracy of Inaccuracies
during
pH
of
the preparation,
changes
standard buffer during storage are some of
the cases that make the pH
of the buffer erroneous,
thus making the calibration
erroneous
as
well.
Subsequent
pH
measurements will also be
incorrect.
Alkaline error
Gives a higher pH reading
at pH > 9 if glass electrode
respond to alkali metal ions

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REFERENCES
[1]

Fattaleh,
N.
POTENTIOMETRIC
TITRATION OF A WEAK ACID, 2007.
http://web.clark.edu/nfattaleh/classes/1
35/sp07/pottitrsp07.pdf (accessed July 6,
2016).

[2]

Nunag, I. G. J. POTENTIOMETRIC
DETERMINATION OF THE PURITY AND
DISSOCIATION CONSTANT OF POTASSIUM
HYDROGEN PHTHALATE; ATQ; Quezon
City, 2015.

[3] Skoog, D. A. . W. D. M. . e. a. Potentiometric

Titrations. In Fundamentals of Analytical
Chemistry, 8th ed.; Brooks/Cole-Thomson
Learning: California, 2004; pp 623-627.
[4] Potentiometric Titration of an Unknown
Weak Monoprotic Acid, 2008. East
Stroudsburg
University.
http://www.asdlib.org/onlineArticles/ec
ourseware/Gross_Potentiometry/UnkAci
dLab.pdf (accessed July 6, 2016).

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