General Chemistry

Lecture 8 – Redox Reactions

CH1101 – General and Physical Chemistry

Dr Carl Poree
Room 3.1, Chemistry Building
poreec@tcd.ie

Wednesday 4th October 2017

Redox – reduction and oxidation
Redox reactions involve the transfer of electrons between different chemical
species.

Fe2O3 (l) + 3CO (g) → 2Fe (l) + 3CO2 (g)

Fe3+ → Fe0

 iron(III) is reduced to iron metal

 carbon monoxide is oxidised to
carbon dioxide

If a species is oxidised in a chemical reaction, it loses electrons, and we will

sometimes refer to it as a reducing agent or reductant.

If a species is reduced in a chemical reaction, it gains electrons, and we will

sometimes refer to it as an oxidising agent or oxidant.

Trinity College Dublin, The University of Dublin CH1101 General Chemistry

Oxidation numbers
Oxidation numbers allow us to keep track of how many electrons an atom has.

In ionic compounds, they are the charge on the ion.

In molecules, they represent the charge the atom would have if the electrons
were completely transferred, rather than shared.

 Free elements have oxidation numbers of zero.

Na, Mg, Hg, H2, O2, P4, S8 - all = 0

 In monoatomic ions, the oxidation number is equal to the charge on the

ion.
Fe2+ = +2, Li+ = +1, O2− = −2, N3− = −3

 The oxidation number of oxygen is usually −2. Exceptions include H2O2,

O22−, where the oxidation number is −1.

Trinity College Dublin, The University of Dublin CH1101 General Chemistry

Oxidation numbers

 The oxidation number of hydrogen is +1, except when bonded to metals in

binary compounds, when the oxidation number is −1 (e.g. NaH).

 Alkali metals (Li, Na, K, Rb, Cs) have oxidation states of +1. Alkaline earth
metals (Be, Mg, Ca, Sr, Ba) have oxidation states of +2.

 Fluorine always has an oxidation state of −1, except in its elemental form
(F2).

 The sum of oxidation numbers of all the atoms in a molecule or ion must
equal the charge on the molecule or ion.

Trinity College Dublin, The University of Dublin CH1101 General Chemistry

Oxidation numbers in combustion

CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g)

H: +1 O: 0 O: −2 O: −2
∴ C: −4 ∴ C: +4 H: +1

Oxidation number increases for carbon: C is oxidised

Oxidation number decreases for oxygen: O is reduced

Trinity College Dublin, The University of Dublin CH1101 General Chemistry

Working out oxidation numbers

Cr2O72− (aq) + 3Sn2+ (aq) + 14H3O+ (aq) →2Cr3+ (aq) +3Sn4+ (aq) + 21H2O (l)

Sn: +2 to +4 oxidised

Cr2O72−: O: −2
7 x O: −14
2 x Cr: +12
Cr: +6
Cr: +6 to +3 reduced

Trinity College Dublin, The University of Dublin CH1101 General Chemistry

Words to formulae in redox chemistry
Oxalic acid (C2H2O4) is oxidised by the permanganate ion (MnO4−) in acidic
solution. During the reaction, Mn2+ and CO2 are formed.

Write an (unbalanced) equation in ionic form:

MnO4− (aq) + C2H2O4 (aq)  Mn2+ (aq) + CO2 (g)

Calculate oxidation numbers:

MnO4− C2H2O4 CO2 Mn2+

O = −2 O = −2 O = −2 Mn = +2
4 x O = -8 H = +1 2O = −4
∴ Mn = –1 –(–8) 4O + 2H = −6 ∴ C = +4
=+7 ∴ C = +3

Trinity College Dublin, The University of Dublin CH1101 General Chemistry

Words to formulae in redox chemistry
Split into half-reactions, and balance atoms (except O, H):

MnO4− (aq)  Mn2+ (aq)

C2H2O4 (aq)  2CO2 (g)

Add electrons to one side of each half-reaction to account for redox:

+7 +2
MnO4 (aq) + 5e  Mn2+ (aq)
− −

+3 +4
C2H2O4 (aq)  2CO2 (g) + 2e−
Balance oxygen atoms with water:

MnO4− (aq) + 5e−  Mn2+ (aq) + 4H2O (l)

C2H2O4 (aq)  2CO2 (g) + 2e−

Trinity College Dublin, The University of Dublin CH1101 General Chemistry

Words to formulae in redox chemistry
Balance oxygen atoms with water:

MnO4− (aq) + 5e−  Mn2+ (aq) + 4H2O (l)

C2H2O4 (aq)  2CO2 (g) + 2e−

We’re in acid, so add H+ to balance hydrogens:

MnO4− (aq) + 5e− + 8H+ (aq)  Mn2+ (aq) + 4H2O (l)

C2H2O4 (aq)  2CO2 (g) + 2e− + 2H+ (aq)

Trinity College Dublin, The University of Dublin CH1101 General Chemistry

Words to formulae in redox chemistry
We’re in acid, so add H+ to balance hydrogens:

MnO4− (aq) + 5e− + 8H+ (aq)  Mn2+ (aq) + 4H2O (l)

C2H2O4 (aq)  2CO2 (g) + 2e− + 2H+ (aq)

At this point, we can combine the half-equations to give a complete equation.

We want the electrons to cancel out:

2[MnO4− (aq) + 5e− + 8H+ (aq)  Mn2+ (aq) + 4H2O (l)]

5[C2H2O4 (aq)  2CO2 (g) + 2e− + 2H+ (aq)]

2MnO4− (aq) + 10e− + 16H+ (aq) + 5C2H2O4 (aq)

 2Mn2+ (aq) + 8H2O (l) + 10CO2 (g) + 10e− + 10H+ (aq)

Trinity College Dublin, The University of Dublin CH1101 General Chemistry

Words to formulae in redox chemistry
2MnO4− (aq) + 10e− + 16H+ (aq) + 5C2H2O4 (aq)
 2Mn2+ (aq) + 8H2O (l) + 10CO2 (g) + 10e− + 10H+ (aq)

Start simplifying:

2MnO4− (aq) + 16H+ (aq) + 5C2H2O4 (aq)

 2Mn2+ (aq) + 8H2O (l) + 10CO2 (g) + 10H+ (aq)

2MnO4− (aq) + 6H+ (aq) + 5C2H2O4 (aq)  2Mn2+ (aq) + 8H2O (l) + 10CO2 (g)

Trinity College Dublin, The University of Dublin CH1101 General Chemistry