Lecture 2

Analytical Chemistry-II
(Clinical)
Redox Titration
BY
Shimaa S. Soliman
Lecturer of Analytical Chemistry
Faculty of pharmacy – October 6 University
 Standard Oxidation Potential

 In a system containing an oxidant and its reduction product (conjugate reductant)

there will be an equilibrium represented as:

 The stronger the oxidant the weaker its conjugate reductant & vice versa

 Every system acquires a predominating character of either giving or collecting

electrons, becoming predominantly reducing or oxidizing to other systems.
 If an inert electrode such as platinum is placed in a redox system e.g. Fe3+/Fe2+ 
it will assume a definite potential indicative of the position of the equilibrium.

If the oxidation tendency predominates, the system will take electrons from the
platinum leaving it positively charged; if, however, the system has reducing
properties, electrons will be given up to platinum which will then acquire a
negative charge.

The magnitude of the potential is a measure of the oxidizing or reducing

properties of the system.

Standard oxidation potential is the e.m.f. produced when a half cell consisting of
an inert electrode, as platinum, is dipped in a solution of equal concentration of
both the oxidized and reduced form of a system (Fe3+/Fe2+) and connected to a
normal hydrogen electrode.
 Apparatus for determination of standard oxidation
potential of Fe3+/Fe2+

1) Salt bridge (allows ion diffusion).

2) Potentiometer.

3) Normal hydrogen electrode.

Fe3+/Fe2+ solution

NHE 1 N HCl solution

 Standard Oxidation Potentials at 25°C.
Increasing Oxidizing
properties
E.g.:
• Cl2/Cl- (Eo = + 1.36 V)
• Fe3+/Fe2+ (Eo = + 0.77 V)
• Cl2 + 2 Fe 2+ 2 Fe3+ + 2 Cl-
Strong + Strong weak + weak
Oxidant reductant oxidant reductant

N.B. :
1- The most powerful oxidizing agent are those at the top.

2- If any 2 redox systems are combined the stronger of the 2 oxidizing

agents will oxidize the other.
Their must be at least 0.4 volt between 2 systems.
If the difference is < 0.4 volt, the reaction will be reversible.
 Nernest Equation for oxidation potential

n = Number of electrons gained or lost

[Ox] = Concentration of the oxidized form
[Red] = concentration of the reduced form
Et = Oxidation potential of the electrode at temperature t
E0 = A constant characteristic for each system termed standard
oxidation potential.
R = Gas constant = 8.314.
T = Absolute temperature = (X°C + 273)
F = Faraday = 96500 coulombs
Loge = Natural log. i.e. to the base 2.718 and is converted to common log to
base 10 by multiplying by 2.303.
 Nernest Equation for oxidation potential

E25oC = Eo + 0.059/n log [Ox]/[Red]

Therefore, the oxidation potential of a redox system at constant

acidity and temperature varies with the ratio of [Ox] / [Red].

When [Ox] = [Red] then

Et = E0 = Standard Oxidation Potential
 Electrical properties of redox systems
 A metal rod dipped into a solution of one of its  An inert electrode such as platinum is placed
salts in a redox system
• electrolytic solution pressure.
• ionic pressure
“Electrode potential" E.  Standard oxidation potential is the e.m.f.
produced when a half cell consisting of an
• Standard electrode potential is defined as inert electrode, such as platinum, is dipped
e.m.f. produced when a half-cell consisting in a solution of equal concentration of both
of the element immersed in a molar solution the oxidized and reduced form of a system
of its ions is coupled with a standard (Fe3+/Fe2+) is connected with a normal
hydrogen electrode. hydrogen electrode.

E25oC = Eo + 0.059/n log [Ox]/[Red]

Electrochemical series
A metal with a more negative potential will  A system with higher positive potential can
displace any other metal below it in the series oxidize systems with lower potential
from its salt solution. e.g. iron will displace
copper or mercury from their salt solutions.
 Factors affecting oxidation potential

1. Common Ion Effect.

2. Effect of hydrogen ion concentration.

3. Effect of complexing agents.

4. Effect of precipitating agents.

 1- Common Ion Effect

E25oC = Eo + 0.059/n log [Ox]/[Red]

E.g.: MnO4-/Mn2+ system

• E25oC = Eo + 0.059/n log [MnO4-]/[Mn2+ ]

• The oxidation potential will decrease in presence of excess

manganous salt.
 1- Common Ion Effect
E25oC = Eo + 0.059/n log [MnO4-]/[Mn++ ]
Application:
• Titration of Fe2+ using KMnO4
• MnO4-/Mn2+ E = 1.52
• Cl2/Cl- E = 1.36
• Fe3+/Fe2+ E = 0.77

• If Fe2+ is titrated with potassium permanganate in presence of chloride ions; unless

the oxidation potential of MnO4-/Mn2+ system is reduced, Cl- will also be attacked by
potassium permanganate leading to higher results.

• In such case, manganous sulphate in the form of Zimmermanns' reagent is added to

the solution to be titrated; permanganate is thus unable to oxidize chloride ions.
 2- Effect of hydrogen ion concentration, [H+]
 [H+] conc. affects oxidation potential of some oxidizing agents.
The increase in H+ conc. will increase oxidation potential of oxygenated
systems & when H+ conc. decrease, the oxidation potential will decrease.
• Example 1 : In acid medium
MnO4- + 8 H+ + 5e Mn2+ + 4 H2O
E = Eo + 0.06 / 5 log [MnO4-][H+]8 / [ Mn+2]
• In alkaline medium
MnO4- + 4 H+ + 3e MnO2 + 2 H2O
E = Eo + 0.06 / 3 log [MnO4-][H+]4 / [MnO2]

Therefore E MnO4-/Mn+2 > E MnO4-/MnO2

 2- Effect of hydrogen ion concentration, [H+]
• On addition of MnO4- to mix. of Cl-, Br-, I-
• At pH = 5 , I- only is oxidized to I2
• At pH = 3 , both I- & Br- will be oxidized into I2, Br2.
• At pH < 3 , I-, Br-, Cl- are oxidized into I2, Br2, Cl2.

• Example 2:- AsO4-3 / AsO3-3 system # I2 / 2I- system.

E = 0.57 volt E = 0.54 volt
- It is reversible reaction as follows :
AsO4-3 + 2 I- + 2 H+ AsO3-3 + I2 + H2O

1- AsO4-3 will oxidize I- to I2 in presence of conc. acid due to increase H+ conc.

2- I2 can oxidize AsO3-3 by rendering medium alkaline by NaHCO3.
3- Therefore E [AsO4-3/AsO3-3] is increased in presence of increasing H+
• N.B. :
- Conc. acid is HCl but not H2SO4 or HNO3 as both of them can oxidize I- to I2.
 3- Effect of complexing agents
Example
I2 + 2 e 2 I-
• Addition of mercuric chloride solution to iodine/iodide system  removes
iodide ions as they form a complex with mercuric ions (HgI4)2- (low
dissociation)  thus the oxidation potential of iodine/iodide system is
increased.

Fe3+ + e Fe2+

• Addition of F- or PO43- to Fe3+/Fe2+ system removes Fe3+ ions due to the

formation of stable complexes [FeF6]3- or [Fe(PO4)2]3- and the oxidation
potential of the system is therefore reduced
 4- Effect of precipitating Agents
• Example: Ferricyanide/Ferrocyanide system

• E25oC = Eo + 0.059/n log [Ferri]/[Ferro]

The addition of zinc ions to Ferri/Ferro system  will precipitate

ferrocyanide  increasing therefore the ratio [Ox]/[Red].

The oxidation potential of the system will increase.

 i.e. The ppting agent & complexing agents will affect E of system according to
reaction with oxidized or reduced form.
 Example
“Zimmerman reagent [MnSO4 +H2SO4 + H3PO4]”

Used in determination of Fe2+ by MnO4- in presence of Cl-

• MnSO4: By common ion effect  will dec. the ratio MnO4-/Mn+2  So, decrease
the Eo of MnO4-/Mn+2  So that it cannot oxidize Cl-.

• H3PO4: Decrease the Eo of Fe+3/Fe+2 by formation of complex with Fe+3 to

increase the difference in oxidation potential between MnO4- & Mn+2 to enable
quantitative reaction.

• H2SO4: Improve end point  as MnO4- in acid medium will be reduced to Mn+2
(colorless) not Mn+4 (brown color)
e.p :pink colorless
 Formal Potential

Standard Potentials are ideal values rarely observed in practice.

Therefore, a sort of practical standard potential have been

proposed.
The formal potential: is the potential observed experimentally in a
solution containing equal formal concentrations of the oxidized
and reduced substances and other specified substances at
specified concentrations.

It was found that the formal potentials vary considerably, with the
nature and concentration of the acid present.
 Formal Potential
Example:
For the ferric /ferrous system:

• The standard oxidation potential is +0.77 volt

• However, the potential differ experimentally according to the media.

- Potential = +0.73 volt in 1M HCLO4,

- Potential = +0.70 Volt in 1M HCl,
- Potential = +0.68 volt in 1M H2SO4
- Potential = +0.61 volt in 0.5 M H3 PO4 + 1 M H2SO4.
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