Oxidation Reduction

Equilibria and Titrations

1
Introduction

1.) Redox Titration

Ø Based on an oxidation-reduction reaction between analyte and titrant
Ø Many common analytes in chemistry, biology, environmental and materials science
can be measured by redox titrations

Electron path in multi-heme active site of P460

Measurement of redox
potentials permit detailed

analysis of complex
enzyme mechanism

Biochemistry 2005, 44, 1856-1863

Oxidation - Reduction reactions (Redox rxns) involve
the transfer of electrons from one species of the
reactants to another. This results in an increase in
oxidation number (O.N.) of a specific species and a
complementary decrease in oxidation number of
another species. Example:

Ce4+ + Fe2+ D Ce3+ + Fe3+

The O.N. of cerium was decreased while that of iron was

increased. Cerium is reduced while iron is oxidized. A
process that involves an increase in O.N. is an oxidation
process and vice versa

3
Usually, a Redox reaction can be
separated into two halves.

Ce4+ + e D Ce3+ Reduction

Fe2+ D Fe3+ + e Oxidation

Electrons appear in each half reaction

while they do not show up in the overall
equations.

4
Identification of a Redox Reaction
It is a good practice to indicate the O.N. of each
species in a chemical reaction in order to check
if it is a Redox reaction or not. If the O.N. of any
species changes, then it is a definite indication
of a Redox reaction. Example,
2 KMnO4 + 5 H2C2O4 + 6 HCl D 2 MnCl2 + 2KCl + 10 CO2 + 8 H2O

It is observed that in the left-hand part of the

equation, manganese has an O.N. equals 7 and
carbon has an O.N. equals 3. In the right-hand
part, the O.N. of manganese is 2 and that of
carbon is 4. Therefore, permanganate is
reduced while oxalic acid is oxidized.
5
An example of a non-Redox reaction can
be written where no change in O.N.
occurs,

Na2CO3 + 2 HCl = 2 NaCl + CO2 + H2O

+1 +4 -2 +1 -1 +1 -1 +4 -2 +1 -2

There is no change in O.N. of any species

involved in the reaction, which
indicates that this is not a Redox
reaction.
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Balancing Redox Reactions
Balanced chemical equations are the basis of
any reasonable quantitative calculations.
Therefore, it is very important to learn
balancing chemical equations, especially
Redox equations that can be manipulated
through definite steps. For example,
dichromate reacts with iron yielding Fe3+
and Cr3+
Cr2O72- + Fe2+ D Cr3+ + Fe3+

To balance this equation, the following steps

should be followed:
7
1. Split the equation into two half reactions
Fe2+ D Fe3+
Cr2 O72- D Cr3+

2. Balance elements other than O and H

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3. Add H2O to balance oxygen.

4. Add H+ to balance hydrogen.

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5. Balance the charge with e-

6. Balance the number of e-

7. Add together the half equations

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Example (Balance the equation in Basic Medium)
C2O42- + MnO4- D Mn4+ + CO2

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12
13
Redox Titrations
The idea of redox titrations is that the potential of a
redox reaction will change as the concentration
changes. Therefore, consider the following
redox reaction,
Fe2+ + Ce4+ D Fe3+ + Ce3+

If we titrate Fe2+ with Ce4+, the concentration of Fe2+ will

decrease upon addition of Ce4+ and thus the potential
of an electrode immersed in a Fe2+ solution will start
to change. This means that the potential of the cell will
be a function of Fe2+ concentration. Thus, if the
volume of Ce4+ added is plotted against the electrode
potential, a titration curve will be obtained.
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 Redox Titrations
Shape of a Redox Titration Curve

1.) Voltage Change as a Function of Added Titrant

Ø Consider the Titration Reaction (essentially goes to completion):

K ≈ 1016

Ø Ce4+ is added with a buret to a solution of Fe2+

Ø Pt electrode responds to relative concentration

of Fe3+/Fe2+ & Ce4+/Ce3+
Ø Calomel electrode used as reference

Indicator half-reactions at Pt electrode:

Eo = 0.767 V

Eo = 1.70 V
 Redox Titrations
Shape of a Redox Titration Curve

2.) Titration Curve has Three Regions

Ø Before the Equivalence Point
Ø At the Equivalence Point
Ø After the Equivalence Point
Titration Curves
Oxidation-reduction titrations and
titration curves can be followed by
measuring the potential of an indicator
electrode (e.g. platinum) as compared
to a reference electrode (has a fixed
constant potential, like Saturated
Calomel Electrode, SCE).
The potential of the cell measured is:

Ecell = Esolution – Ereference electrode

17
Ecell = Esolution – Ereference electrode
This means that:
Esolution = Ecell + Ereference electrode
Assume the process of titration of Fe2+
with Ce4+, we have

Fe2+ + Ce4+ D Fe3+ + Ce3+

Fe3+ + e D Fe2+ Eo = 0.771 V
Ce4+ + e D Ce3+ Eo = 1.70 V

We have three cases to consider:

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1. Before equivalence point we have
Fe2+/Fe3+ couple and we can use the
Nernst equation to calculate the
electrode potential where:

EFe = EFeo – (0.0592/nFe) log [Fe2+]/[Fe3+]

Therefore, we calculate the concentration

of Fe2+ and Fe3+ and insert the values
in the Nernst equation to find the
resulting potential of the electrode .
19
We can use the other half reaction to
calculate the potential of the cell but it
is easier to use the Fe2+/Fe3+ couple
since the concentration of Ce4+ is
difficult to calculate at this stage. The
Nernst equation for such potential
calculation is:

ECe = ECeo – (0.0592/nCe) log [Ce3+]/[Ce4+]

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2. At the equivalence point, we may combine
the two Nernst equations for the two half
reactions by adding them up. We get:

nFe EFe + nCe ECe = nFe EFeo + nCe ECeo – (0.0592)

{log [Fe2+]/[Fe3+] + log [Ce3+]/[Ce4+]}

nFe EFe + nCe ECe = nFe EFeo + nCe ECeo – (0.0592)

{log [Fe2+] [Ce3+]/[Fe3+] [Ce4+]}

But [Fe3+] = [Ce3+] and

[Fe2+] = [Ce4+] at equivalence point.
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Therefore, the equation simplifies to:
nFe EFe + nCe ECe = nFe EFeo + nCe ECeo

Also, at equivalence point we have

EFe = ECe = Eeq pt, therefore:

(nFe + nCe) Eeq pt = nFe EFeo + nCe ECeo

The final equation can be written as:

Eeq pt = (nFe EFeo + nCe ECeo)/ (nFe + nCe)

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3. After equivalence point, it is easier to
calculate the cell potential from the
cerium half-cell using the equation:

ECe = ECeo – (0.0592/nCe) log [Ce3+]/[Ce4+]

It is easier to calculate the Ce3+ and Ce4+

concentrations and it will be difficult to
calculate the Fe2+ concentration since it
is totally consumed, except for an
equilibrium concentration.
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Example
Find the potential of a 50 mL solution of a 0.10
M Fe2+ after addition of 0, 25, 40, 50, and 75
mL of 0.1 M Ce4+.
Fe3+ + e D Fe2+ Eo = 0.771 V
Ce4+ + e D Ce3+ Eo = 1.70 V
Solution
1. After addition of 0 mL Ce4+
The solution contains Fe2+ only and attempts to
apply Nernst equation will not be possible
since assumably no Fe3+ will be present.
EFe = EFeo – (0.0592/nFe) log [Fe2+]/[Fe3+]
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EFe = EFeo – (0.0592/nFe) log [Fe2+]/[Fe3+]
EFe = EFeo – (0.0592/nFe)log 0.1/0

This means that as Fe3+ approaches zero, the

electrode potential approaches negative infinity.
This, in fact, is not practically true since it
suggests that a Fe2+ solution will have
unbelievably high reducing power. The way out
of this problem is to always assume the
presence of very small Fe3+ concentration in
equilibrium with Fe2+, even in very pure Fe2+
solutions. The conclusion with regards to
calculation of electrode potential after addition
of 0 mL Ce4+ is that we can not calculate it using
direct Nernst equation. 25
2. After addition of 25 mL Ce4+
Initial mmol Fe2+ = 0.10 x 50 = 5.0
mmol Ce4+ added = 0.10 x 25 = 2.5
mmol Fe2+ left = 5.0 – 2.5 = 2.5
[Fe2+] = 2.5/75 M
mmol Fe3+ formed = 2.5
[Fe3+] = 2.5/75 M
Application of Nernst equation gives:
EFe = EFeo – (0.0592/nFe)log {(2.5/75)/(2.5/75)}
EFe =0.771 V

Therefore, the standard electrode potential for Fe2+/Fe3+

couple can be calculated at half the way to the
equivalence point.
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3. After addition of 40 mL Ce4+
Initial mmol Fe2+ = 0.10 x 50 = 5.0
mmol Ce4+ added = 0.10 x 40 = 4.0
mmol Fe2+ left = 5.0 – 4.0 = 1.0
[Fe2+] = 1.0/90 M
mmol Fe3+ formed = 4
[Fe3+] = 4.0/90 M
Application of Nernst equation gives:
EFe = EFeo – (0.0592/nFe) log {(1.0/90)/(4.0/90)}
EFe = 0.771 – 0.0592 log 1.0/4.0
EFe = 0.807 V

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4. After addition of 50 mL Ce4+
Initial mmol Fe2+ = 0.10 x 50 = 5.0
mmol Ce4+ added = 0.10 x 50 = 5.0
mmol Fe2+ left = 5.0 – 5.0 = ??
This is the equivalence point
mmol Fe3+ formed = 5.0
[Fe3+] =5.0/100 = 0.05 M, [Ce3+] = 0.05 M
At equivalence point, we have from the above
discussion:
Eeq pt = (nFe EFeo + nCe ECeo)/ (nFe + nCe)
Eeq pt = (1 * 0.771 + 1 * 1.70)/(1 + 1)
Eeq pt =1.24 V

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3. After addition of 75 mL Ce4+
Initial mmol Fe2+ = 0.10 x 50 = 5.0
mmol Ce4+ added = 0.10 x 75 = 7.5
mmol Ce4+ excess = 7.5 – 5.0 = 2.5
[Ce4+] = 2.5/125 M
mmol Ce3+ formed = 5.0
[Ce3+] = 5.0/125 M
Application of Nernst equation gives:
ECe = ECeo – (0.0592/nCe) log [Ce3+]/[Ce4+]
ECe =1.70 – (0.0592/1)log {(5.0/125)/(2.5/125)}
ECe = 1.68 V
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 Redox Titrations
Finding the End Point

1.) Indicators or Electrodes

Ø Similar to Acid-Base Titrations

Ø Electrochemical measurements (current or potential) can be used to determine

the endpoint of a redox titration

Ø Redox Indicator is a chemical compound that undergoes a color change as it

goes from its oxidized form to its reduced form
- Similar to acid-base indicators that change color with a change in protonation
state
 Redox Titrations
Finding the End Point

2.) Redox Indicators

Ø Color Change for a Redox Indicator occurs mostly over the range:

æ 0.05916 ö
E = ç Eo ± ÷volts
è n ø

where Eo is the standard reduction potential for the indicator

and n is the number of electrons involved in the reduction
 Redox Titrations
Finding the End Point

2.) Redox Indicators

Ø Color Change for a Redox Indicator occurs over a potential range

Ø Illustration:
For Ferroin with Eo = 1.147V, the range of color change relative to SHE:

æ 0.05916 ö
E = ç 1.147 ± ÷volts = 1.088 to 1.206 V
è 1 ø

Relative to SCE is:

æ 0.05916 ö
E = ç 1.147 ± ÷ - E ( calomel ) = (1.088 to 1.206 V ) - ( 0.241 ) = 0.847 to 0.965V
è 1 ø
 Redox Titrations
Finding the End Point

2.) Redox Indicators

Ø In order to be useful in endpoint detection, a redox indicator’s range of color
change should match the potential range expected at the end of the titration.

Relative to calomel electrode (-0.241V)

 Redox Titrations
Common Redox Reagents

1.) Starch
Ø Commonly used as an indicator in redox titrations involving iodine

Ø Reacts with iodine to form an intensely blue colored complex

Ø Starch is not a redox indicator

- Does not undergo a change in redox potential

I6 bound in center of starch helix

Repeating unit
 Redox Titrations
Common Redox Reagents

2.) Adjustment of Analyte Oxidation State

Ø Before many compounds can be determined by Redox Titrations, must be
converted into a known oxidation state
- This step in the procedure is known as prereduction or preoxidation

Ø Reagents for prereduction or preoxidation must:

- Totally convert analyte into desired form
- Be easy to remove from the reaction mixture
- Avoid interfering in the titration

Ø Examples:
- Preoxidation:
a) Peroxydisulfate or persulfate (S2O82-) with Ag+ catalyst

Powerful oxidants

Oxidizes Mn2+, Ce3+, Cr3+, VO2+

excess S2O82- and Ag+ removed by boiling the solution
 Redox Titrations
Common Redox Reagents

2.) Adjustment of Analyte Oxidation State

Ø Examples:
- Preoxidation:
b) Silver(II) oxide (AgO) in concentrated mineral acids also yields Ag2+
excess removed by boiling

c) Hydrogen peroxide (H2O2) is a good oxidant to use in basic solutions

Oxidizes Co2+, Fe2+, Mn2+
Reduces Cr2O72-, MnO4-
excess removed by boiling

- Prereduction:
a) Stannous chloride (SnCl2) in hot HCl
Reduce Fe3+ to Fe2+
excess removed by adding HgCl2

b) Jones reductor (Zn + Zn amalgam – anything in mercury)

 Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions

Ø Potassium Permanganate (KMnO4)
- Strong oxidant
- Own indicator

pH ≤ 1
Titration of VO2+ with KMnO4
Eo = 1.507 V
Violet colorless

pH neutral or alkaline
Eo = 1.692 V
Violet brown
Before Near After pH strolngly alkaline
Equivalence point
Eo = 0.56 V
Violet green
 Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions

Ø Potassium Permanganate (KMnO4)
- Application of KMnO4 in Redox Titrations
 Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions

Ø Cerium (IV) (Ce4+)
- Commonly used in place of KMnO4
- Works best in acidic solution
- Can be used in most applications in previous table
- Used to analyze some organic compounds
- Color change not distinct to be its own indicator

Yellow colorless

Ce4+ binds anions very strongly results in variation of formal potential

1.70V in 1 F HClO4
Formal potential 1.61V in 1 F HNO3 Measure activity
1.47V in 1 F HCl not concentration
1.44V in 1 F H2SO4
 Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions

Ø Potassium Dichromate (K2Cr2O7)
- Powerful oxidant in strong acid
- Not as Strong as KMnO4 or Ce4+
- Primarily used for the determination of Fe2+
- Not an oxidant in basic solution
- Color change not distinct to be its own indicator

Eo = 1.36 V
orange green to violet
 Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions

Ø Iodine (Solution of I2 + I-)
- I3- is actual species used in titrations with iodine

K = 7 x 102

- Either starch of Sodium Thiosulfate (Na2S2O3) are used as indicator

I3- + Starch
I3- I3- + S2O32-

Before Before At
endpoint endpoint endpoint
 Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions

Ø Iodine (Solution of I2 + I-)
- Application of Iodine in Redox Titrations
 Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions

Ø Iodine (Solution of I2 + I-)
- Application for Redox Titrations that Produce I3-
 Redox Titrations
Common Redox Reagents

3.) Common Titrants for Oxidation Reactions

Ø Periodic Acid (HIO4)
- Commonly used in titration of organic compounds (especially carbohydrates)

4.) Titrations with Reducing Agents

Ø Not as common as titrations using oxidizing agents
- Available titrants are not very stable in the presence of atmospheric O2

Ø Reagents can be generated directly in solution by means of chemical or

electrochemical reactions
 Redox Titrations
Common Redox Reagents

5.) Example
A 50.00 mL sample containing La3+ was titrated with sodium oxalate to
precipitate La2(C2O4)3, which was washed, dissolved in acid, and titrated
with 18.0 mL of 0.006363 M KMnO4.

Calculate the molarity of La3+ in the unknown.