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Redox Reactions

Oxidation number
Balancing redox equation
Voltaic cells
Standard voltages
Oxidation number
1.The concept of Oxidation number
It is used to refer to the charge an
atom would have if the bonding electrons
were assigned arbitrarily to the more
electronegative element.
For example: HCl H : Cl
Oxidation number of Cl is -1,
Oxidation number of H is +1,
The Oxidation number of an atom in a
molecule is an artificial concept, unlike the
charge of an ion, Oxidation number can not
be determined experimentally.
For ionic compounds, the oxidation
number is the charge of ion.
For example: NaCl (Na:+1, Cl:-1)
How to determine the oxidation number of elements?

2. Rules for Assigning oxidation numbers

a. The oxidation number of an element in an
elementary substance is 0.
e.g. O2, H2, N2,P4
b. The oxidation number of an element in a
monatomic ion is equal to the charge of
that ion.
e.g. Na+, Cl-, Fe3+ , O2- , Mg2+
c. Certain elements have the same oxidation
number in all or almost all their compounds.
e.g. Group 1 metals always exist as +1 ions
in their compounds, so the oxidation number is
+1. Group 2 : +2.
Fluorine, the most electronegative of all
elements, has an oxidation number of -1 in all
of its compounds.
O: -2, but, in H2O2 O: -1
H have different oxidation number in different
compounds in H2O (H:+1), in NaH (H:-1)

d. The sum of the oxidation numbers of all

the atoms in a neutral species is 0; in an
ion, it is equal to the charge of that ion.
e.g. NaCl, Fe2O3, Mg(OH)2, KCl,

OH-, CN-, NH4+

3. Oxidation and Reduction
Oxidation is defined as an increase in
oxidation number,
Reduction is defined as a decrease in
oxidation number.
e.g. 2Na + Cl2 = 2NaCl Na oxidized(0--+1)
Cl reduced(0---1)
4Fe + 3O2 = 2Fe2O3 Fe oxidized(0--+3)
O reduced(0---2)
An element which loses electrons must
increase in oxidation number, the gain of
electrons always results in a decrease in
oxidation number.
4. Oxidizing and Reducing Agents
In a redox reaction, we usually have at
lease two reactants, one of these is referred
to as the oxidizing agent, another as the
reducing agent.
An oxidizing agent brings about the
oxidation of another species. To do this , it
must take electrons away from that species
and the oxidation number decrease, hence
the oxidizing agent is itself reduced in the
An reducing agent brings about the
reduction of another species. To do this , it
must give up electrons to that species and
the oxidation number increase, hence the
reducing agent is itself oxidized in the
Na + Cl = NaCl
Here Na is oxidized, Na is reducing agent.
Cl is reduced, Cl is oxidizing agent.
4Fe + 3O2 = 2Fe2O3

Here Fe is oxidized, Fe is reducing agent.

O2 is reduced, O2 is oxidizing agent.

Balancing redox equation
The half-equation method

The steps:
1) Breaking the overall equation down into two
half-equations, one is oxidation, the other is a
2) Balancing the two half-equations separately;
3) Combining them in such a way so as to
obtain an overall equation.
e.g. Reaction between MnO4- and Cl- (acidic
MnO4- + Cl- + H+ = Mn2+ + Cl2 +H2O
1)Recognize which species undergo oxidation
and reduction;
Oxidation: Cl- -- Cl2 (a)
Reduction: MnO4- + H+ -- Mn2+ +H2O (b)
2)Balance the two half-equations with respect
to mass;
2Cl- -- Cl2 +2e
MnO4- + 8H+ +5e -- Mn2+ + 4H2O
3)the two half-equations are combined so as to
eliminate electrons from the final equation.
To do this, a least common multiple of 10
electrons is used, thus a is multiplied by 5
and b by 2, producing 10e on each side:
5× a: 10Cl- -- 5Cl2 +10e
2× b: 2MnO4- + 16H+ +10e -- 2Mn2+ + 8H2O
2MnO4- + 16H+ + 10Cl- = 2Mn2+ + 5Cl2 + 8H2O
e.g. Reaction between MnO4- and I- (basic solution)
MnO4- + I- -- MnO2 + l2
1) Oxidation: l- -- l2 (a)
Reduction: MnO4- -- MnO2 (b)
2) In basic solution: more OH-, H2O
2l- -- l2 +2e
MnO4- + 2H2O +3e -- MnO2 + 4OH-
3) 3a+2b
3a 6l- -- 3l2 +6e
2b 2MnO4- + 4H2O +6e -- 2MnO2 + 8OH-
2MnO - + 4H O + 6l- = 2MnO + 8OH- + 3l
Voltaic cells
Redox reactions:
Spontaneous 2Na + Cl2 = 2NaCl
Nonspontaneous 2NaCl = 2Na + Cl2
a Voltaic cells : a kind of electrical cell, a
spontaneous redox reaction takes place , and it
produces electrical energy.
Like dry cells used in flashlights and calculators
The lead storage battery in an automobile
the Zn electrode the Cu electrode

How a voltaic cell works?

The Zn-Cu cell

A piece of zinc is added to a Cu2+ solution,
the following redox reaction takes place:
Zn + Cu2+ = Zn2+ + Cu
We can see that electrons transfer from Zn
atom to Cu2+ ion.
To design an electrical cell
1)At the Zinc anode, electrons are produced by
the oxidation half-reaction. This electrode is
marked as the negative pole of the cell.
2)Electrons move through the external circuit,
this pat of the circuit may be a simple
resistance wire, a light bulb or some other
divice that consumes electrical energy.
3)Electrons pass from the external
circuit to the copper cathode where
they are used in the reduction of Cu2+
ions in the surrounding solution. The
copper electrode is considered to be
the positive pole of the cell.
4)To complete the circuit, ions must
move through the aqueous solutions in
the cell. Movement of ions occurs
through a salt bridge, which consist of
an inverted U-tube, the tube is filled
with a solution of salt which takes no
part in the electrode reactions.
In the notation
Left: the anode reaction (oxidation)
Zn -- Zn2+ + 2e
Middle: “II” the salt bridge the Zn
the Cu

Right: the cathode reaction


Cu2+ + 2e – Cu
So Zn-Cu cell can express the
(-)ZnIZn2+ IICu2+ ICu(+)
e.g.1 Ni + Cu2+ = Ni2+ + Cu
(-)NiINi2+ IICu2+ ICu(+)
e.g.2 Zn + 2H+ = Zn2+ + H2
Anode: Zn -- Zn2+ + 2e
Cathode: 2H++2e -- H2
(-)ZnIZn2+ IIPt(H+)IH2(+)(Pt: an inert platinum