SCES3163: Physical Chemistry

Topic 2: Electrochemistry

2.1 Constructing redox equations

At the end of this section, students are able to:
• Explain the concept of oxidation and reduction
• Construct redox equations using
• The oxidation number method
• The ion-electrons method

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(A) Oxidation number
1. An atom or molecule of an element in their respective
elemental state are assigned oxidation numbers of zero.
Example: Formula Oxidation number
H2 0
O2 0
S 0
Fe 0
Cu 0

The oxidation number of an element in a compound is the charge

obtained when the element exists as ions in the compound, with the
assumption that all the bonds in the compound, whether ionic or
covalent compound, are ionic bonds.
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2. In monoatomic ions, the oxidation number is
the same as the charge on the ion.
Example: Ion Oxidation number
Na+ +1
Cu2+ +2
Fe3+ +3
F- -1
O2- -2
N3- -3

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3. For polyatomic ions, the sum of all the
oxidation numbers of the elements in the ion
is equal to the nett charge on the ion.
Example: SO4 2-
↙ ↓
(+6)+4(-2)=-2
MnO4-
↙ ↓
(+7)+4(-2)=-1

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4.For ionic compounds or covalent compounds,
the total oxidation number of all atoms
present in the formula of the compound is
zero.
Example: CaCO3
↙ ↓↘
(+2)+(+4)+3(-2)=0

CO2
↙ ↓
(+4)+2(-2)=0 5
5. For a neutral covalent molecule, the more
electronegative element would be assigned a
negative oxidation number, while the less
electronegative element will have a positive
oxidation number. The sum of the oxidation
numbers of all the atoms in the molecule is
zero.
Example:
F2O HClO
↙ ↓ ↙↓ ↘
2(-1) (+2) (+1) (+1) (-2)
I, Br, Cl, N, O, F
Increasing electronegativity 6
(B) Oxidation:
• In terms of electron transfer, oxidation refers to
the loss of electrons from a substance (atom, ion
or molecule).
• In terms of oxidation numbers, oxidation is
defined as an increase in oxidation number.

Example: Mg → Mg2+ + 2e-

Fe2+ → Fe3+ + e-

2I- → I2 + 2e-

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(C) Reduction:
• In terms of electron transfer, reduction refers
to the gain of electrons by a substance (atom,
ion or molecule).
• In terms of oxidation numbers, reduction is
defined as a decrease in oxidation number.
Example: Cl2 + 2e- → 2 Cl-
MnO4- + 8H+ + 5e- → Mn2+ + 4H2O
Fe3+ + e- → Fe2+

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(D) Balancing a redox reaction :
• Oxidation and reduction always occur together. Processes that involve
oxidation and reduction are called redox reactions.
• A redox reaction can be constructed by combining oxidation and
reduction half-equations.
• One or both of the half-equations are multiplied by some integer to
make the number of electrons gained equal the number of electrons
lost.
• Hence, the overall equation will have the electrons on both sides of the
equation cancelled.

Example:

Fe2+ → Fe3+ + e- Oxidation (half-equation)

MnO4- + 8H+ + 5e- → Mn2+ + 4H2O Reduction (half-equation)
________________________________________________________
5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 4H2O Redox (overall equation)
________________________________________________________

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Note: When balancing the equation, ensure that the
number of electrons in both oxidation and reduction are
the same before combining the two half-equations.
With reference to the example from the previous slide,

Fe2+ → Fe3+ + e- Oxidation (half-equation)

MnO4- + 8H+ + 5e- → Mn2+ + 4H2O Reduction (half-equation)
_____________________________________________________
5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 4H2O Redox (overall equation)

_____________________________________________________

To make the number of electrons gained equal the number of electrons lost, the first
equation is multiplied by 5.
5Fe2+ → 5Fe3+ + 5e- Oxidation (half-equation)
MnO4- + 8H+ + 5e- → Mn2+ + 4H2O Reduction (half-equation)
___________________________________
5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 4H2O Redox (overall equation)
___________________________________ 10
Activity
Write the overall equation for the oxidation and
reduction half-equations below:

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(E) Oxidising agent and reducing agent
Oxidising agent:
A substance that gains electrons and causes the
oxidation of some other substance. This
substance itself is reduced.
Reducing agent:
A substance that loses electrons and causes the
reduction of some other substance. This
substance itself is oxidised.

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Example:
Fe2+ → Fe3+ + e- Oxidation

Reducing agent

MnO4- + 8H+ + 5e- → Mn2+ + 4H2O Reduction

Oxidising agent
_________________________________________________________

5Fe2+ + MnO4- + 8H+ → 5Fe3+ + Mn2+ + 4H2O Redox

_________________________________________________________

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Balancing a redox equation using the ion-electron method

• When using the ion-electron method, divide the redox

equation into two half-equations, one for oxidation and
one for reduction.
• Balance each of the half-equations by following the steps
below:
– Balance all the other elements except hydrogen and oxygen
– Balance oxygen by adding H2O to the appropriate side of the
equation
– Balance hydrogen by adding H+ to the appropriate side of the
equation.
– Balance the charge by adding electrons to the appropriate side
– Finally combine the two half-equations such that the electrons
cancel one another.

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Balancing a redox equation using the ion-electron method
Example: Balance the following equation
Cr2O72- + Fe2+  Cr3+ + Fe3+
Steps:
• Divide the equation into two half-equations
Fe2+  Fe3+
Cr2O72-  Cr3+

• Balance the first half-equation by adding 1 electron to the right-hand side.

Fe2+  Fe3+ + e

• For the second half-equation, balance Cr first.

Cr2O72-  2Cr3+

• Then add 7H2O to the right-hand side to balance the oxygen atoms
Cr2O72-  2Cr3+ + 7H2O

• Then add 14H+ to the left-hand side to balance the hydrogen atoms
Cr2O72- + 14H+  2Cr3+ + 7H2O

• Finally, add 6 electrons to the left-hand side to balance the charge:

Cr2O72- + 14H+ + 6e  2Cr3+ + 7H2O

• Multiply the first half-equation by 6, then add to the second half-equation:

6Fe2+  6Fe3+ + 6e
Cr2O72- + 14H+ + 6e  2Cr3+ + 7H2O

Cr2O72- + 14H+ + 6Fe2+  6Fe3+ + 2Cr3+ + 7H2O

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 Balancing a redox equation using the oxidation number method

• Redox reactions involve transfer of electrons from one chemical

species to the other
• The same number of electrons that is released by a reducing agent
must be accepted by an oxidising agent.
• The total increase in the oxidation number of one species
= the total decrease in the oxidation numbers of the other species
• The nett change in the oxidation numbers of all the species in a
balanced redox equation is zero.
• In places where there is not enough oxygen atoms, it is balanced by
adding ‘H2O’.
• To balance hydrogen atoms, add ‘H+’ to the appropriate side of the
equation.
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Balancing a redox equation using the oxidation number method

• Consider a general redox reaction:

aA + bB  Products
Let the change in the oxidation number of A in the
reaction be +x unit, and the change in the oxidation
number of B be –y unit, then,
a(+x) + b(-y) = 0 The total increase in the
oxidation number of one
species
= the total decrease in the
oxidation numbers of the
other species

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Balancing a redox equation using the oxidation number method
Example:
Balance the following equation using the oxidation number method.
H2O2 + Fe2+  Fe3+ + H2O
(a) Let the equation be:
aH2O2 + bFe2+  cFe3+ + dH2O
Oxidation number: -1 +2 +3 -2
(b) The change in the oxidation number of oxygen is -2 – (-1) =-1
The change in the oxidation number of iron is +3 – (+2) = +1.
(c) The total change in the oxidation number of oxygen is 2a(-1), since there are 2a
atoms of oxygen.
The total change in the oxidation number of iron is b(+1)
(d) Hence, 2a(-1) + b(+1) = 0 The total increase in the oxidation
b – 2a = 0 number of one species
If, a = 1, = the total decrease in the oxidation
numbers of the other species
Then, b = 2
(e) Substitute into the equation, we get: H2O2 + 2Fe2+  cFe3+ + dH2O
(f) Balancing both sides: c = 2 and d = 2
H2O2 + 2Fe2+  2Fe3+ + 2H2O
(g) The left-hand side of the equation is short of 2 hydrogen atoms.
This is balanced by adding 2H+ to the left-hand side of the equation.
(h) The balanced equation is: H2O2 + 2H+ + 2Fe2+  2Fe3+ + 2H2O 18
Activity
Balance the following equation using the oxidation number
method.
KIO3 + Na2SO3  KIO + Na2SO4

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Balance the following equation using the oxidation number method.
KIO3 + Na2SO3  KIO + Na2SO4

(a) Let the above equation be:

aKIO3 + bNa2SO3  cKIO + dNa2SO4
Oxidation number: +5 +4 +1 +6

(b) The change in the oxidation number of iodine = +1- (+5) = -4

The change in the oxidation number of sulphur = +6 – (+4) = +2.
(c) The total change in the oxidation number of iodine = a(-4)
The total change in the oxidation number of iron = b(+2)
(d) Hence, a(-4) + b(+2) = 0
2b – 4a = 0
If, a = 1,
Then, b = 2
(e) Substitute a and b in the equation:
KIO3 + 2Na2SO3  cKIO + dNa2SO4
(f) Balance both sides of the equation: c = 1 dan d = 2
KIO3 + 2Na2SO3  KIO + 2Na2SO4 20
Activity:
Use the oxidation number method to balance the following
equation:

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 THE END

11/2/2011 YEW LH 22