QUANTITATIVE DETERMINATION OF THE PURITY AND DISSOCIATION CONSTANT OF

POTASSIUM HYDROGEN PHTHALATE BY POTENTIOMETRIC TITRATION

P.G. BUGAYONG1
1Department of Mining Metallurgical and Materials Engineering, College of

Engineering
University of the Philippines, Diliman, Quezon City1101,
Philippines
V. Go2
2Department of Mining Metallurgical and Materials Engineering, College of

Engineering
University of the Philippines, Diliman, Quezon City1101,
Philippines

Date submitted: April 04, 2019

Date Performed: April 11, 2019

1. What is potentiometry? Instrumentation wise what are the common features of

potentiometric instruments?

Potentiometry is one of the methods of electroanalytical chemistry. It is usually

employed to find the concentration of a solute in solution. In potentiometric instruments, the
potential between two electrodes is measured using a high impedance voltmeter. A
potentiometric instrument usually consists of electrodes, one of which is filled with a solution of
known/standard concentration and pH level which is then used to measure the pH of the
solution with unknown pH an/or concentration by their difference in H+ ions.

2. What are the advantages of using potentiomeric techniques?

The advantage of using potentiometric techniques is that they are highly pH sensitive.
This provides a more accurate way to determine the equivalence point in the titration than with
the use of an indicator.

3. What are the significant regions in the titration curve? What are the species present on each?
Relate the occurrence of this species to the pH results obtained.

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.
Mathematically, the second derivative should pass through zero at the equivalence point.
4. 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.

5. Why should the increments of addition of titrant be narrowed down as the titration
approaches the equivalence point?

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.

6. Why is potentiometry a suitable method in 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 error such as
colorblindness.

7. Discuss possible reasons behind the discrepancies (if any) in the experimental and
theoretical pKavalues.

Note that at half-equivalence point, [HA] ≈ [A- ] . Thus, using activites, Ka becomes

Since the glass electrode gives a good estimate of aH30+, 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
HA3.

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 aH30+ exp to
increase and the experimental pH to decrease. In effect, the experimental pKa is also lower than the
theoretical.
REFERENCES:

[1] Fattaleh, N. POTENTIOMETRIC TITRATION OF A WEAK ACID, 2007.

http://web.clark.edu/nfattaleh/classes/1 35/sp07/pottitrsp07.pdf.

[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
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