REDOX INDICATORS

Shefali Ainkar
Assistant Professor
PG Department of Chemistry
Parvatibai Chowgule College of Arts & Science
Email: ssa019@chowgules.ac.in

1
Agenda
• Introduction
• Types of indicators
• General redox indicators
• Structural aspects of redox indicators
• Specific indicators
• Effect of variables of redox titration curves
• Review questions
• References

2
Introduction
• The most important class of redox indicators, however, are substances that do
not participate in the redox titration, but whose oxidized and reduced forms
differ in color. When added to a solution containing the analyte, the indicator
imparts a color that depends on the solution’s electrochemical potential. Since
the indicator changes color in response to the electrochemical potential, and not
to the presence or absence of a specific species, these compounds are called
general redox indicators. A visual indicator used to signal the end point in a
redox titration is called a redox indicator.

• Two types of indicators are used for obtaining end points for oxidation/reduction
titrations:
1. General redox indicators
2. Specific indicators
3
 General redox indicators
• The relationship between a redox indicator’s change in color and the
solution’s electrochemical potential is easily derived by considering
the half-reaction for the indicator:

where Inox and Inred are, respectively, the indicator’s oxidized and
reduced forms. The Nernst equation for this reaction is

• If we assume that the indicator’s color in solution changes from that

of Inox to that of Inred when the ratio [Inred]/[Inox] changes from 0.1 to
10, then the end point occurs when the solution’s electrochemical
potential is within the range:
4
• This equation shows that a typical general indicator exhibits a
detectable color change when a titrant causes the system potential to
shift from E°In + 0.05912/n to E°In - 0.05912/n or about (0.118/n) V.
• When n=2, a change of 0.059 V is enough.

Color changes for general redox indicators depend only on the potential
of the system.

5
1. Titrant as indicator
- When the titrant of intense color is used the end point can be detected by the
color imparted to the solution by the first excess of titrant.
- The agreement between the end point and the equivalence point will depend on
both the intensity of the titrant and masking effect introduced by the solution
titrated if it is colored or turbid.
- E.g. KMnO4
- If the titrant is highly colored, this color may be used to detect the end point. For
example, a 0.02 M solution of potassium permanganate is deep purple. A dilute
solution of potassium permanganate is pink. The product of its reduction, Mn2+,is
extremely faint pink, nearly colorless.
- During a titration with potassium permanganate, the purple color of the MnO4−
is removed as soon as it is added because it is reduced to Mn2+. As soon as the
titration is complete, a fraction of a drop of excess MnO4− solution imparts a
definite pink color to the solution, indicating that the reaction is complete.
Obviously, the end point does not occur at the equivalence point, but at a
fraction of a drop beyond. The titration error is small and can be corrected for by
running a blank titration, or it is accounted for in standardization. 6
2. External Indicators
- The best known example is the spot test method for the titration of
ferrous ion with standard K2Cr2O7 solution.
- Near the equivalence point, drops of the solution are removed and
brought into contact with dilute freshly prepared potassium
ferricyanide solution.
- The end point is reached when a drop of test solution first fails to give
blue coloration.
- External indicators have now been replaced by more better internal
redox indicators.

7
Structural aspects of redox indicators
• Redox indicators are organic molecules that undergo
structural changes upon being oxidized or reduced.

A) Iron(II) complexes of orthophenanthrolines

A class of orthophenanthrolines form stable
complexes with Fe (II) and certain other ions.
Three orthophenanthroline molecules combine with
each iron (II) ion to yield a complex which is called as
‘ferroin’ formulated as (phen)₃Fe²⁺.

+1.25V +1.02V
The color change occurs at +1.12V. It is obvious that
Figure 1: Structure of ferroins
ferroin will be suitable iron-cerium titrations. Source: F. Holler, S. C. (2014),
pp 504
8
B) Starch/Iodine solutions
This indicator is used for titrations involving iodine. Starch forms a
complex with triiodide ion or iodide ion that is a dark-blue color. The
color reaction is sensitive to very small amounts of iodine and is not
very reversible. In titrations of reducing agents with iodine, the solution
remains colorless up to the equivalence point. A fraction of a drop of
excess titrant turns the solution a definite blue.
In presence of excess oxidizing agents the concentration ratio of iodine
to iodide is high giving blue color.
With excess reducing agent, iodide ion predominates and the blue
color is absent.
This color change is dependent on the potential of the system at the
equivalence point.

9
C) Diphenylamine and its derivatives
Diphenylamine was the first redox indicator to be used.
For the titration of Fe(II) with K2Cr2O7 in the presence of a strong
oxidizing agent, Diphenylamine undergoes a series of reactions.

The reaction transforms Diphenylamine to Diphenyl benzidine which is

irreversible.
The indicator reactions is the transformation of Diphenyl benzidine to
Diphenyl benzidine violet. (transition potential = +0.76 V at 25°C)

Sodium Diphenyl benzidine sulfonate is used as Diphenyl benzidine is

insoluble is water. (transition potential = +0.85 V at 25°C)
Equivalence point potential comes around 1.14 V. (color change before
equivalence point)
10
Therefore medium used is 85% H3PO4. the presence of phosphate ions
results in the formation of stable ferric phosphate complex which
considerably decreases the reducing potential of iron.
So the equivalence point now coincides nearly with that of the
indicator potential.

11
Specific indicators
• A specific indicator is a substance which reacts in a specific manner
with one of the reagents in a titration to produce color change.
• Eg. Starch, thiocyanate ion ( forms red complex withFe(III) )
• Potassium thiocyanate is used for the titration of Fe(III) with solution
of titanium(III) sulfate.

12
13
Effect of variables on redox titration curves
I) Reactant concentration
Esystem for an oxidation/reduction reactions are usually independent of
dilution. Hence redox curves are independent of analyte and reagent
concentration.

14
II) Completeness of the reaction
The change in the potential in the
equivalence point region becomes larger
as the reaction becomes more complete.

Higher the equilibrium constant, more

complete is the reaction.

Figure 2: Effect of titrant electrode potential

on reaction completeness.
Source: F. Holler, S. C. (2014), pp 501

15
III) Standard potential
Standard potential reveals whether or not a reaction proceeds far
enough towards completeness but provides no information about the
rate at which the equilibrium is attained.
It means reaction which appears extremely thermodynamically stable
may be totally unacceptable from kinetic point of view.
Example:
Oxidation of Arsenic (III) with Ce(IV) where reduction potential of Ce
is already known. Reduction potential of Arsenic is 0.577V.
For this reaction, the equilibrium constant is very high (1029) yet the
reaction is very slow. Hence requires a catalyst.

16
Review questions
• Explain the structural aspect of diphenyl amine indicator.
• State the factors which affect redox titration curve.
• State any two examples of redox indicators.
• Define specific indicators.

17
References
• Christian, G. D. (2015). Acid-Base titrations. In Analytical Chemistry
(Sixth ed., pp. 437-464). Delhi: Wiley India Pvt. Ltd.
• F. Holler, S. C. (2014). Acid-Base Titrations. In Skoog and West`s
Fundamental of Analytical Chemistry (9th ed., pp. 473-508). Delhi:
Cengage Learning.

18