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DETERMINATION OF PURITY AND ACID DISSOCIATION

CONSTANT OF POTASSIUM HYDROGEN PHTHALATE BY

POTENTIOMETRIC TITRATION
S.A.P. SAAVEDRA1, J. C. VILLASIS2
1
NATIONAL INSTITUTE OF PHYSICS, COLLEGE OF SCIENCE
2
DEPARTMENT 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

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meter accounts the whole pH of the

solution and not just the part nearest
the electrode.
3. Why should the increments of
down
as
the
titration
approaches the equivalence
point?

5. Discuss
possible
reasons
behind the discrepancies (if
any) in the experimental and
theoretical pKa values?
Note that at half-equivalence point,

A
. Thus, using activites, Ka
[ HA ]
becomes,

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.

H 3 O+

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
systematic
error
such
as
colorblindness.

a
A
H 3 O +
a
K a =

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.

A
HA

[1]

good

estimate

of

H 3 O+
,
a

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.

exp
A

a K a HA

[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.

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exp
a

metal ions

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

Inaccuracy
of pH of the
standard
buffer

Inaccuracies
during
preparation, changes
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

REFERENCES
[1]

Fattaleh, N. POTENTIOMETRIC
TITRATION OF A WEAK ACID, 2007.
http://web.clark.edu/nfattaleh/class
es/135/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/ColeThomson
Learning:
California,
2004; pp 623-627.
[4]

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Potentiometric Titration of an
Unknown Weak Monoprotic Acid,
2008. East Stroudsburg University.
http://www.asdlib.org/onlineArticles
/ecourseware/Gross_Potentiometry/
UnkAcidLab.pdf (accessed July 6,
2016).

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