I.

Introduction
Potentiometry is a method used in electroanalytical, usually to find the
concentration of a solute in solution. In potentiometric measurements, the potential
between two electrodes is measured using a high impedance voltmeter. In the most
common forms of potentiometry, two different types of electrodes are used. The
potential of the indicator electrode varies, depending on the concentration of the
analyte, while the potential of the reference electrode is constant.
Potentiometry is probably the most frequent used electroanalytical method. It can
be divided into two categories on the basis of the nature of the indicator electrode. If the
electrode is a metal or other conductive material that is chemically and physically inert
when placed in the analyte, it reflects the potential of the bulk solution into which it is
dipped. Electrode materials that are commonly used for this type of potentiometry
include platinum, gold, silver, graphite, and glassy carbon.
Another method of potentiometry is potentiometric titration. Potentiometric
titration is a technique similar to direct titration of a redox reaction. It is a useful means
of characterizing an acid, no indicator is used; instead the potential is measured across
the analyte, typically an electrolyte solution. In this experiment, potentiometric titration
was used together with Silver Nitrate(AgNO 3) as a titrant.

II. Methodology
A.) Preparation of Reagents

A.)Dissolve 2.395g of
AgNO3 in distilled
water and dilute to 1L.

B.) Dissolve 4g NaOH

in 100mL distilled water.

B.) Titration Process

Dissolve 0.1-0.2g of
[Co(NH33)55]Cl33 in 10mL distilled
water.

Titrate with 0.0141M AgNO33

solution. Read the potential after
each addition of 1mL titrant.

Locate the endpoint and

determine the number of
chlorides that are not in the
coordination sphere.

Dissolve 0.1-0.2g of
[Co(NH33)55]Cl33 in 100mL distilled
water.

Dry the [Co(NH33)55]Cl33 by adding

7-8mL NaOH.

The number of chlorides that are

found in the primary coordination
sphere is the difference between
the number of chlorides in step 6
and 3.
III. Discussions

Repeat steps 1 -3.

Repeat steps 1 to 7 for

[Co(NH33)55Cl]Cl22.

Potentiometric titrations are preferred to manual titrations, since they are more
accurate and precise. There are several types of potentiometric titrations for the
determination of analytes in photoprocessing solutions include acid-base, redox,
precipitation and complexometric. Oxidation-Reduction titration involves the transfer of
electrons from the substance being oxidized to the substance being reduced. This kind
of titration involves insoluble salts of metals such as mercury, silver, lead and copper
and followed potentiometrically. This was the method used and AgNO 3 was used as
titrant. [Co(NH3)5]Cl3 and [Co(NH3)5Cl]Cl3 are titrated with 0.0141M Silver Nitrate,
AgNO3, in which electrode potential is determined versus the volume of the titrant
added.
In potentiometric titration, there are many ways in
locating the end point. One method, is to create a titration
curve. Titration curve is obtained by plotting the successive values of
the cell emf on ordinate and corresponding values of volume of titrant
added on the abscissa. This gives an S-shaped curve. The
central portion of this curve which shows the steeply rising
corresponds to the volume for the end point of the titration.
Another way to locate the end point is the derivative method.
method, the end point can be located precisely from the first
derivative and second derivative curves. The first derivative curve
involves the plot of slope of the titration curve, E/ V,
against the volume of the titrant added. Sometimes,

In

this

E/ V is

plotted against the average volume of the titrant added corresponding

to the values of emf taken. The volume on the x-axis corresponding to
the peak of the curve is the end point of the titration.
In the second derivative, on the other hand, the slope of the first
derivative curve ( 2E/ V), is determined by plotting it against

slope of the

volume. The point on volume axis where the curve cuts through
zero on the ordinate gives the end point. This point corresponds to
the largest steepest point on the titration curve and the maximum
E/ V curve.

The first two method on locating the end point was believed to be used only in
symmetric reaction. Another method wherein unsymmetrical reaction can be used in
locating the end point is with the use of Gran Plot method. Gran Plot Method or Gran
titration is developed by G. Gran in 1952. This method does the numerical manipulation
of titration curves into linear straight lines intersecting at the equivalence point.

V O+ V
VO

) 10-FEcell/2.30RT = 10-FEcell/2.30RT

C (V e V )
VO

Where: VO = initial volume of the solution

V = volume of the titrant added
Ve = volume of the titrant added
C = concentration of the titrant
F = Faradays Constant
R = Gas constant
T = Temperature
= Activity coefficient
V O+ V
) 10-FEcell/2.30RT is called as Grans function. A
VO

straight line will be obtained if it will be plotted against the volume

of the titrant. The end point from Gram plot can be obtained by
either taking the points before the end point or taking the points
after the end point. The results obtained from linear curves are more accurate than from
non-linear ones. Simplicity of measurement, simplicity of calculation, versatility and
precision are the advantages of using Gran Plot Method.

IV. References
ChemBuddy(2009).
Mohr
Method.
Retrieved
October
18,
2014
http://www.titrations.info/precipitation-titration-argentometry-chlorides-Mohr

from

Chemicool(2014). Definition of Potentiometry. Retrieved October 18, 2014 from

http://www.chemicool.com/definition/potentiometry.html
Determination of Chloride using Potentiometry. Retrieved October 18, 2014 from
www.asdlib.org/onlineArticles/...Potentiometry/SPECION%203%201.pdf
NepaChem. Potentiometry in Analytical Chemistry. Retrieved October 19, 2014 from
http://www.nepachemistry.com/2011/03/potentiometry-in-analytical-chemistry.html
UCDAVIS Chemwiki. Potentiometric Methods. Rerieved October 19, 2014 from
http://chemwiki.ucdavis.edu/Analytical_Chemistry/Analytical_Chemistry_2.0/11_Elec
trochemical_Methods/11B_Potentiometric_Methods
Wikipedia.
Argentometry.
Retrieved
http://en.wikipedia.org/wiki/Argentometry

October

18,

2014

from

Wikipedia.
Potentiometric
Titration.
Retrieved
http://en.wikipedia.org/wiki/Potentiometric_titration

October

Wikipedia. Standard Electrode Potential. Retrieved October

http://en.wikipedia.org/wiki/Standard_electrode_potential

18,
19,

2014
2014

from
from