CHAPTER 17 USING

ELECTRODE
POTENTIAL
APRIL ALCANTARA, RMT
OBJECTIVES
Learn how to:
1. Calculate thermodynamic cell potentials
2. Calculate equilibrium constants for redox reactions
3. Derive redox titration curves
Calculating Potentials Of
Electrochemical Cells
We can use standard electrode potential and the Nerst equation to
calculate the potential obtainable from a galvanic cell or the potential
required to operate an electrolytic cell.

Thermodynamic potential of an electrochemical cell is the difference

between the electrode potential of the right hand electrode and the
left hand electrode
-
EXAMPLE 17-1
Calculate the thermodynamic potential of the following cell and the
free energy change associated with the cell reaction.
SOLUTION
GENERAL FORMULA: = - 0.0592 log

GENERAL FORMULA THERMODYNAMIC POTENTIAL:

SOLUTION
GENERAL FORMULA FOR FREE ENERGY:

divide the energy value by 4184

EXAMPLE 17-2
Calculate the potential of the following cell and indicate the reaction
that would occur spontaneously if the cell is short-circuited
Pt | (0.2M), (0.0150M), (0.03M) (0.01M), (0.0250M) | Pt
Two half reactions are:
+ E= +0.771V
+ 4+ 2  + E= +0.334V
SOLUTION
GENERAL FORMULA: = - 0.0592 log
= – 0.0592 log = - log = 0.79461V
= - log = - log = 0.1204V
-
-
Positive sign means that it is a spontaneous reaction.
EXAMPLE 17-3
Calculate the cell potential for

Note that this cell does not require two compartments (nor a salt bridge) because
molecular H2 has little tendency to react directly with the low concentration of Ag
in the electrolyte solution
SOLUTION
GENERAL FORMULA: = - 0.0592 log
= - log = - log =
= -0.0977V
SOLUTION
The negative sign indicates that the cell reaction as considered, is
nonspontaneous.

To get this reaction, we would have to apply an external voltage and construct
an electrolytic cell.
Calculating Redox
Equilibrium Constants
Consider the equilibrium that is established when a piece of copper is immersed
in a solution of dilute silver nitrate:

The equilibrium constant for this reaction is:

At chemical equilibrium, we may write:

 We can generalize that at equilibrium, the electrode potentials for all half-reactions
in an oxidation/reduction systems are equal.
SOLUTION
2  Ag(s)
 +  Cu(s)

Rearrangement of Equation gives:

SOLUTION
Calculate the equilibrium constant for the reaction:
EXAMPLE
CALCULATE THE EQUILIBRIUM CONSTANT FOR THE REACTION:

+ 2  E = +0.771 V
+  E = +0.536 V
EXAMPLE
CALCULATE THE EQUILIBRIUM CONSTANT FOR THE REACTION:
2+ 5
2+ +  2 E = +1.695 V
3+ +  + E = +1.23 V
CONSTRUCTING REDOX
TITRATION CURVES
Because most redox indicators respond to changes in electrode potential, the
vertical axis in oxidation/reduction titration curve is an electrode potential
instead of the logarithmic p-function.
Electrode Potentials during
Redox Titrations
Let us now consider the redox titration of iron(II) with a standard solution of
cerium(IV).

This reaction is rapid and reversible so that the system is at equilibrium at all
times throughout the titration

If a redox indicator has been added to this solution, the ratio of the
concentrations of its oxidized and reduced forms must adjust so that the
electrode potential for the indicator, EIn, is also equal to the system potential.
Electrode Potentials during
Redox Titrations
The electrode potential is readily derived from standard potential data.
S , , , | Pt
NOTE: Titration reaction is at equilibrium but overall cell reaction (including SHE) is not. The
potential of the platinum electrode with respect to the SHE is determined by the tendency of
iron and cesium to accept electron
+ 
+ 
Because data for a titration curve can be obtained by applying the Nernst
equation for either the cerium(IV) half-reaction or the iron(III) half-reaction.
Equivalence-Point Potentials
At the equivalence point in the titration of iron(II) with cerium(IV), the potential
of the system Eeq is controlled by both half reactions:

Adding this two expressions:

Equivalence-Point Potentials
The definition of equivalence point requires that:
EXAMPLE
Obtain an expression for the equivalence-point potential in the
titration of 0.0500 M U⁴⁺ with 0.1000 M Ce⁴⁺. Assume that both
solutions are 1.0 M in H₂SO₄ .
SOLUTION

To combine the log terms, we must multiply the first equation by 2 to give:
SOLUTION
At equivalence:

The equivalence-point potential for this titration is pH-dependent.

Effect of Variables on Redox
Titration Curves
Reactant Concentration
- titration curves for oxidation/reduction reactions are usually independent of
analyte and reagent concentrations.
Completeness of the Reaction
- The change in the equivalence-point region of an oxidation/reduction titration
becomes larger as the reaction becomes more complete.
General Redox Indicators
Substances that change color upon being oxidized or reduced. In contrast to
specific indicators, the color change of true redox are independent of the nature
of the analyte and the titrant and dependent instead of in the electrode
potential of the system that occurs as titration progresses
General oxidation/reduction indicators are substances that change color upon
being oxidized or reduced.
General Redox Indicators
Change from the color of the oxidized form of the indicator of the reduced form requires a
change of about 100 in the ratio of reactant concentration, thus a color change is seen at:

The potential change required to produce the full color change of a typical general indicator

A typical general indicator exhibits a detectable color change when a titrant causes the system
potential to shift from to or about (0.118/n) V.
For many indicators, n=2 and a change of 0.059 V is sufficient.
SELECTED
OXIDATION/REDUCTION
INDICATORS
INDICATOR OXIDIZED REDUCED
5-Nitro-1,10-phenanthroline iron(II) complex Pale-blue Red-violet
2,3’-Diphenylamine dicarboxylic acid Blue-violet Colorless
1,10-Phenanthroline iron(II) complex Pale blue Red
5-Methyl-1,10-phenanthroline iron(II) complex Pale blue Red
Erioglaucin A Blue-red Yellow-green
Diphenylamine sulfonic acid Red-violet Colorless
Diphenylamine-p-Ethoxychrysoidine Yellow Red
Methylene blue Blue Colorless
Indigo tetrasulfonate Blue Colorless
Phenosafranine Red Colorless
Starch/Iodine Solutions
Starch, which forms a blue complex with triiodide ion, is widely used specific
indicator in redox reaction involving iodine as an oxidant or iodide ion as
reductant.
In the presence of excess oxidizing agent, concentration ratio of iodine to iodide
is high giving a blue color to the solution.
With excess reducing agent, iodide ion predominates and color blue is absent.
Thus, the indicator system changes from colorless to blue in titration of many
reducing agents with various oxidizing agents. (functions as true redox indicator)
 Starch/Iodine Solutions

(a) Acidifying the sample and adding KI forms a brown solution of I3–.
(b) Titrating with Na2S2O3 converts I3– to I– with the solution fading to a pale yellow color
(c) Adding starch forms the deep purple starch–I3– complex.
(d) As the titration continues, the end point is a sharp transition from a purple to a colorless solution. The change in color from (c) to (d)
typically takes 1–2 drops of titrant.
Specific Indicators
Best-known specific indicator is starch, which forms a dark blue complex with
triiodide ion as discussed. This complex signals the end point in titrations in
which iodine is either produced or consumed.
Potassium thiocyante: used for titration of iron (III) with solution of titanium (III)
sulfate. The endpoint involves the disappearance of the red color of the
iron(III)/thiocyanate complex as a result of the mark decrease in the iron (III)
concentration at the equivalence point.
Potentiometric End Points
End points for many oxidiation/reduction titrations are readily
observed by making the solution of the analyte part of the cell