UNIVERSITY OF SOUTHERN MINDANAO

CHAPTER 19
POTENTIOMETRY
JOHN ERIC TANDOG MARIANO, RPH
FACULTY
DEPARTMENT OF PHARMACY
 Objectives
• Determine the standard electrode potential,
• Application of standard electrode potential values in
calculations involving the preparation of redox curves,
prediction of spontaneity of redox reaction, and
• Determination of chemical equilibrium constant.
 What is Potentiometry?
• Branch of electrochemistry which deals with the study and
measurement of electrode potentials.
 Standard Electrode Potentials
• Determining the relative tendencies
which different metals, ions, and
molecules have to gain or lose electrons
under controlled conditions.
• Arrange these chemical species in the
order of their affinity for electrons.
• Top: strongest reducing agents
• Bottom: strongest oxidizing agents
• The relative tendency of metals, ions, or molecules to gain
or lose electrons can be studied quantitatively:
• One approach is to determine the standard electrode
potential (Eº) of these species.
• This may be accomplished by:
1. Choosing an electrode used as a standard with which to
compare all other electrode measurements.
2. Choosing suitable single concentration for all solution
measured, and
3. Choosing suitable temperature.
To measure the potential of a copper electrode immersed in a
1 M solution of its ions relative to the SHE.
The potentiometer is adjusted until no current flow through
galvanometer
A (+) value is assigned to a electrode systems in which
electron flow from the hydrogen electrode to the test
electrode.
A (-) value to system in which electrons flow in the opposite
direction.
Given: Solution:
Eº cupper = +o.34 V Eº = El – Er
Eº zinc = -0.76 V Eº = o.34 – (-0.76 )
Eº = 1.10 V
Nernst Equation

0.0592 [𝑜𝑥]
𝐸 = 𝐸° + 𝑙𝑜𝑔
𝑛 [𝑟𝑒𝑑]

or

0.0592 𝑟𝑒𝑑
𝐸 = 𝐸° − 𝑙𝑜𝑔 @ 25℃
𝑛 𝑜𝑥
 Nernst Equation
• When calculating emf values from half-cell data it is
necessary to follow carefully a set of conventions or rules in
order to ensure accurate results.
1. When representing the cell, the electrode which has the
more positive 𝐸° is written on the left.
2. To determine the emf of the cell , the potential of the
right electrode is always subtracted from that of the left
electrode.
 Nernst Equation
3. To determine the chemical rxn which takes place
spontaneously in the half cells, the chemical species in the left
half cell appears in its higher valence state on the left side of
the chemical reaction.
4. A positive emf value for the cell as calculated using
convention 2 means that the electrons from R to L when the
cell is short-circuited, and the chemical reaction proceeds
spontaneously as written in convention 3.
5. Solid and pure liquids have values of unity
 REDOX Titration Curve
• Titration curve may be prepared from the emf data obtained
experimentally, or the data for the graph may be calculated.
 REDOX Indicator
• Titration curve may be prepared from the emf data obtained
experimentally, or the data for the graph may be calculated.