Lec 1 (Redox)

Lecture 1
Analytical Chemistry-II
(Clinical)
Redox Titration
BY
Shimaa S. Soliman
Lecturer of Analytical Chemistry
Faculty of pharmacy – October 6 University
Redox Reaction
Oxidation – Reduction Reactions
 They occur together

Oxidation Reduction
Reaction of compounds Reaction of compounds
with oxygen. with hydrogen
 No oxygen is involved in the oxidation of ferrous by

chlorine gas
 For Fe2+ iron to be oxidized to Fe3+  one electron must be lost.
Fe2+ Fe3+ + e
 Electrons can not exist free in solution  the oxidation

reaction proceeds only in presence of substance capable of
accepting electrons i.e. reduced.
Cl2 + 2e 2Cl-
Such reactions are therefore oxidation-reduction reactions

termed simply " Redox " reactions.
Oxidation Reduction
1- Loss of one or more electrons by 1- Gain of one or more electrons by
atoms or ions. atoms or ions.
2- Increase of Oxidation No. 2- Decrease of Oxidation No.
Example Example
2 Mg 2Mg2+ + 4e O2 + 4e 2O2-
Oxidizing agent Reducing agent

(Oxidant) is one that gains (Reductant) is one that loses
electrons and is reduced. electrons and is oxidized.
Examples of oxidizing agents or Oxidants:
• potassium permanganate
• potassium dichromate
• ceric sulphate
• iodine
• potassium bromate
• potassium iodate
Examples of reducing agents or Reductants:

• Ferrous sulphate
• metallic iron
• sodium thiosulphate
• sodium arsenite
• oxalic acid and oxalates
How to calculate the equivalent weight??
1- Hypothetical equation method
2- Ion-electron equations method
3- The oxidation number method

1- Hypothetical equation method
 The equivalent - weight of an oxidant or reductant: is that weight of

the substance that reacts with or contains 1 .008 g of available hydrogen
or 8.000 g of available oxygen.
 By "available" is meant capable of being used in oxidation or reduction.

2 KMnO4 give up 5 atoms of available oxygen;
2KMnO4 = 5 X 16 gm oxygen
???? = 8 gm oxygen
Equivalent weight = molecular weight/5.
equivalent weight =molecular weight/3.
equivalent weight = molecular weight/6

2- Ion-electron equations method
 Redox equation is divided into two half equations:
1- Reduction half equation. 2- Oxidation half equation.
 Redox equation must be balanced:
1- Ionically. 2- Electronically (Electrically).
 e.g. Oxidation of ferrous ions by potassium permanganate in acid medium.
1- The reaction equation is first divided into 2 balanced half equations representing:
A- The reduction of permanganate B- The oxidation of ferrous ions

2- The reaction equation is balanced ionically & electronically:
Reduction half equation Oxidation half equation
 Ionically:  Ionically:
MnO4- Mn2+ Fe2+ Fe3+
MnO4- + 8 H+ Mn2+ + 4H2O

 Electronically (Electrically):  Electronically (Electrically):
MnO4- + 8 H+ Mn2+ + 4H2O Fe2+ Fe3+

(-1) + (+8) (+2) + (Zero) (+2) (+3)
(+7) (+2) Fe2+ Fe3+ + 1 e- -------- > x 5
MnO4- + 8 H+ + 5 e- Mn2+ + 4H2O 5Fe2+ 5 Fe3++ 5 e-
MnO4- + 8 H+ + 5 e- Mn2+ + 4H2O
5Fe2+ 5 Fe3+ + 5 e-
Final Equation: MnO4- + 8 H+ + 5Fe2+ Mn2+ + 5 Fe3+ + 4H2O

 The equivalent - weight of an oxidant or reductant: is the molecular
weight divided by the number of electrons that one molecule gains or
loses in the reaction.
Thus equivalent weight of Permanganate:
MnO4- = Mol. weight/5.
Thus equivalent weight of Ferrous:
Fe2+ = Mol. weight/1.

3- The oxidation number method
 The equivalent - weight of an oxidant or reductant: = Molecular
weight/change in the oxidation number of the element suffering oxidation or
reduction.
 The change in the oxidation number of the manganese is from +7 to +2.

 The equivalent weight of KMnO4 = Molecular weight/5
 Equivalent weight of KMnO4 = Molecular weight/3

Electrical properties of redox systems
 Electrochemistry: is a relationship between chemical reactions and
electricity.
 Certain chemical reactions can create electricity.
• e.g. Galvanic cell (or voltaic cell) contains chemicals which react together giving
electricity.
 Electricity can make certain chemical reactions happens that wouldn’t
happen otherwise (e.g. Battery).
Redox
reactions
Movement
of electrons
Movement of electrons
Through wire, light bulb, battery
Electricity
 Electrode Potential:
Suppose a metal rod dipped
into a solution of one of its
salts, there is a tendency for
the metal to dissolve, this
tendency is termed electrolytic
solution pressure.
The reverse tendency, namely,

passage of metal cations from
the solution to be deposited on
the metal is also possible and
is called ionic pressure.
Zn/Zn2+ system Cu/Cu2+ system
• ionic pressure > solution

• Solution pressure > ionic pressure.
pressure. • Cu2+ ions leave the solution to
• Zinc metal tends to dissolve be deposited on the copper rod.
forming Zn2+ in solution • The solution acquires a
negative charge (owing to the
• the solution acquires an
excess of anions in the vicinity of
excess of positive charges
the metal) and the copper rod, a
and of negative ones on the
positive one (double electric
metal rod (double electric
layer).
layer).
• A certain potential difference
• A certain potential difference appears between the metal and
appears between the metal and the solution
the solution.
 The potential difference between the metal rod (electrode) and the
solution is known as "electrode potential" abbreviated E.
 The potential difference between a metal and its ions is actually a
measure of the tendency of the metal to be oxidized to metal ions or
the tendency of the ions to be reduced to metal atoms.
Zn(s) Zn2+ (aq) + 2 e- Cu2+ (aq) + 2 e- Cu (s)

Metal atoms Metal ions Metal ions Metal atoms
(Solid) (Aqueous) (Aqueous) (Solid)
 The prevailing tendency whether oxidation or reduction depends upon :

1- The chemical nature of the system
2- The concentration of the solute present .
Nernest Equation for electrode potential
 It is an equation relating the potential difference-observed when an electrode

is immersed in a solution of its own ions - to the concentration of the ions
Where :
Et = Electrode potential at temperature (t)
E0 = A constant dependent upon the system termed standard electrode 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.
n = Valency of the ions.
[Mn+] = Molar concentration of metal ions.
 Nernest equation can be simplified by introducing the known values of R
and F, and converting the natural logarithms to base 10 .
 For a temperature of 25°C it becomes:
 If [Mn+] equals one molar, then:
E = E0 = Standard electrode potential.

Standard Electrode Potential
In order to measure the potential of an electrode it must be connected to

another electrode (reference one); an electric current will then flow from
that having a higher potential to the other one.
E cell = E cathode – E anode

The standard electrode potential (E0): is electrode potential in volts (V)
measured under standard conditions relative to the standard hydrogen
electrode (SHE).
 OR defined as the electromagnetic force (e.m.f.) produced when a half-

cell consisting of the element immersed in a molar solution of its ions is
coupled with a standard hydrogen electrode.
Normal hydrogen electrode
The standard (fixed) conditions:
• 1 atmospheric pressure.
• 1 normal concentration of H+ ions.
• Temperature of 298 K.
At these conditions  SHE
possesses (assigned) a definite
potential which is assumed to be
zero volt.
 By connecting the normal hydrogen
electrode with a metal electrode (a metal
in contact with a molar solution of its ions)
by means of a salt bridge (allows ion 2 H+ + 2e H2
diffusion) the standard electrode potential
can be determined. H2 (Pt) / H+
Example
Example
Electrochemical series
 Metals are arranged in the order of their standard electrode potential
Standard electrode potentials at 25oC

Eo Eo
System System
Volts Volts
Li/Li+ -2.96 Sn/Sn2+ -0.13
Increasing reducing
K/K+ -2.92 H2(pt)/H+ 0.00

properties
AL/AL3+ -1.33 Cu/Cu2+ +0.34
Increasing
oxidizing
properties
Zn/Zn2+ -0.76 Hg/Hg2+ +0.79
Fe/Fe2+ -0.44 Ag/Ag+ +0.79
The sign of the potential is similar to the charge on the metal electrode.
Standard electrode potential is a quantitative measure of the readiness

of the element to lose electrons (oxidized) giving its ions.
The greater the negative value of the potential, the greater is the
tendency of the metal to pass into the ionic state.
A metal with a more negative potential will displace any other metal
below it in the series from its salt solution. e.g. iron and zinc will
displace copper or mercury from their salt solutions.
Zno + CuSO4 ZnSO4 + Cuo

26

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Lecture 1

Oxidation – Reduction Reactions

 They occur together

 No oxygen is involved in the oxidation of ferrous by

 Electrons can not exist free in solution  the oxidation

Such reactions are therefore oxidation-reduction reactions

2- Increase of Oxidation No. 2- Decrease of Oxidation No.

Oxidizing agent Reducing agent

Examples of reducing agents or Reductants:

1- Hypothetical equation method

2- Ion-electron equations method

3- The oxidation number method

 The equivalent - weight of an oxidant or reductant: is that weight of

 By "available" is meant capable of being used in oxidation or reduction.

Equivalent weight = molecular weight/5.

equivalent weight =molecular weight/3.

equivalent weight = molecular weight/6

1- Reduction half equation. 2- Oxidation half equation.

 Redox equation must be balanced:

1- Ionically. 2- Electronically (Electrically).

 e.g. Oxidation of ferrous ions by potassium permanganate in acid medium.

A- The reduction of permanganate B- The oxidation of ferrous ions

MnO4- + 8 H+ Mn2+ + 4H2O

MnO4- + 8 H+ Mn2+ + 4H2O Fe2+ Fe3+

Final Equation: MnO4- + 8 H+ + 5Fe2+ Mn2+ + 5 Fe3+ + 4H2O

Thus equivalent weight of Permanganate:

MnO4- = Mol. weight/5.

Thus equivalent weight of Ferrous:

Fe2+ = Mol. weight/1.

 The change in the oxidation number of the manganese is from +7 to +2.

 Equivalent weight of KMnO4 = Molecular weight/3

The reverse tendency, namely,

• ionic pressure > solution

Zn(s) Zn2+ (aq) + 2 e- Cu2+ (aq) + 2 e- Cu (s)

 The prevailing tendency whether oxidation or reduction depends upon :

 It is an equation relating the potential difference-observed when an electrode

 For a temperature of 25°C it becomes:

 If [Mn+] equals one molar, then:

E = E0 = Standard electrode potential.

In order to measure the potential of an electrode it must be connected to

E cell = E cathode – E anode

 OR defined as the electromagnetic force (e.m.f.) produced when a half-

Standard electrode potentials at 25oC

K/K+ -2.92 H2(pt)/H+ 0.00

AL/AL3+ -1.33 Cu/Cu2+ +0.34

Standard electrode potential is a quantitative measure of the readiness

Zno + CuSO4 ZnSO4 + Cuo

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