Redox Chemistry: Background To Redox Reaction

REDOX CHEMISTRY
By: Ahmed Ewis
Background to redox reaction

A redox reaction involves the simultaneous processes of oxidation and reduction. Originally, the transfer of
oxygen between species in a chemical reaction was the standard upon which oxidation and reduction were
defined, but that changed later on, as transfer of electrons, hydrogen and changes in oxidation numbers were
used for redefining a redox reaction. Examples on each term used to describe a redox reaction are
demonstrated below:
a) Transfer of oxygen:
Fe2O3 + 3CO 2Fe + 3CO2
 Iron (III) oxide is reduce to Iron by losing oxygen
 Carbon monoxide is oxidized to carbon dioxide by gaining oxygen
b) Transfer of electrons:
2Mg + O2 2MgO
 Magnesium is oxidized to magnesium oxide by losing 2 electrons: 2Mg Mg2+ + 2e-
 Oxygen is reduced to magnesium oxide by gaining 2 electrons: O2 + 4e -
2O2-
 The total number of electrons is conserved; the number of electrons on the left side of the equation is the same as
that on the right side of the chemical equation
 Remember OIL RIG (Oxidation Is Loss Reduction Is Gain)
c) Transfer of hydrogen:
H2S + Cl2 S + 2HCl
 Hydrogen sulfide is oxidized to sulfur by losing hydrogen
 Chlorine is reduced to hydrogen chloride by gaining hydrogen
d) Changes in oxidation numbers:

 Before looking at examples, we first need to define what an oxidation number is, and the basic rules followed in
assigning appropriate oxidation numbers. An oxidation number is the charge an ion has, or the charge that it would
have if the species were fully ionic. An increase in the oxidation number of a species in a reaction signifies
oxidation, while a reduction in the same number signifies reduction. The basic rules for assigning oxidation numbers
are:
1) The convention is that the cation is written first in a formula, followed by the anion. For example, in NaH, the H
is H-; in HCl, the H is H+
2) The oxidation number of a free element is always 0. The atoms in He and N2, for example, have oxidation
numbers of 0
3) The oxidation number of a monatomic ion equals the charge of the ion. For example, the oxidation number of
Na+ is +1; the oxidation number of N3- is -3
4) The usual oxidation number of hydrogen is +1. The oxidation number of hydrogen is -1 in compounds containing
elements that are less electronegative than hydrogen, as in CaH2
5) The oxidation number of oxygen in compounds is usually -2. Exceptions include OF2 because F is more
electronegative than O, and BaO2, due to the structure of the peroxide ion, which is [O-O]2-.
6) The oxidation number of a Group I element in a compound is +1.
7) The oxidation number of a Group II element in a compound is +2.
8) The oxidation number of a Group VII element in a compound is -1, except when that element is combined with
one having a higher electronegativity. The oxidation number of Cl is -1 in HCl, but the oxidation number of Cl is +1
in HOCl.
9) The sum of the oxidation numbers of all of the atoms in a neutral compound is 0.
10) The sum of the oxidation numbers in a polyatomic ion is equal to the charge of the ion. For example, the sum of
the oxidation numbers for SO42- is -2.
Cu2O + H2SO4 CuSO4 + Cu + H2O

 Copper (I) oxide is oxidised to copper (II) sulphate through an increase in its oxidation number
 Copper (I) oxide is reduced to copper through a decrease in its oxidation number
 Notice that this also a disproportionation reaction where an element in a species undergoes both oxidation and
reduction
The terms oxidising agent and reducing agent are used to distinguish between the species oxidised or
reduced, as well as be able to identify chemical species of strong oxidising or reducing power. An oxidising
agent is a species that oxidises another species by removing one or more electrons; when an oxidising agent
reacts, it gains electrons and is, therefore, reduced. A reducing agent is a species that reduces another
species by adding one or more electrons; when a reducing agent reacts, it loses electrons and is, therefore,
oxidised.
Constructing ionic equation

An ionic equation shows which ions the reaction depends on; it shows what ions react with each other and
can thus allow reaction manipulation by altering the concentrations of the specified reacting ions. Spectator
ions are ions that do not take part in the reaction, as they appear on both sides of an ionic equation.
In order to construct the ionic equation of a redox reaction, oxidising and reducing agents have to be
identified clearly, in order to show how the electron transfer between the ions happens. The following steps
are used in general to construct the ionic of any reaction:
 Identify oxidizing and reducing agents
 Write Ionic half-equations for both processes of oxidation and reduction
 Balance the number of electrons in both half-equations
 Add both half-equations together
 Cancel out any spectator ions or repeated ions
 Double-check if the steps have been followed correctly
Example 1:
Solid zinc is added to an aqueous solution of copper (II) sulphate. Construct the full ionic equation for the
reaction.
Reducing agent
Chemical equation: Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)
Oxidising agent
Ionic half-equations: Zn(s) Zn2+(aq) + 2e-

Cu2+(aq) + 2e- Cu(s)
Full ionic equation: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
In this straightforward example, we needn’t have balanced the number of electrons in both ionic half-
equations, since they were already equal.
Example 2:
Chlorine gas is bubbled into an aqueous solution of iron (II) chloride, the iron (II) ions are oxidised to into
(III) ions and the chlorine molecules are reduced to chloride ions.
Ionic half-equations: Fe2+(aq) Fe3+(aq) + e-
Cl2(g) + 2e- 2Cl-(aq)
Balanced ionic half-equations: 2Fe2+(aq) 2Fe3+(aq) + 2e-
Cl2(g) + 2e- 2Cl-(aq)
Full ionic equation: 2Fe2+(aq) + Cl(g) 2Fe3+(aq) + 2Cl-(aq)
In this example, the number of electrons in both ionic half-equations was not the same, and thus had to
balanced by multiplying the equation for the oxidation of iron (II) by two.
Example 3:
When an acidified aqueous solution of potassium manganate (VII) is added to an aqueous solution of iron
(II) sulphate, the manganate(VII) ions oxidise iron(II) ions to iron(III) ions. The two half-equations for the
reaction are:
Balanced ionic half-equations: 5Fe2+ 5Fe3+ + 5e-
Full ionic equation: 5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O
Balancing Redox Reactions: Oxidation-Number-Change Method
One way to balance redox reactions is by keeping track of the electron transfer using the oxidation numbers
of each of the atoms. For the oxidation-number-change method, start with the unbalanced skeleton
equation. The example below is for the reaction of iron(III) oxide with carbon monoxide. This reaction is
one that takes place in a blast furnace during the processing of iron ore into metallic iron
(see Figure below):
Step 1: Assign oxidation numbers to each of the atoms in the equation and write the numbers above
the atom.
Step 2: Identify the atoms that are oxidized and those that are reduced. In the above equation, the
carbon atom is being oxidized since its oxidation increases from +2 to +4. The iron atom is being reduced
since its oxidation number decreases from +3 to 0.
Step 3: Use a line to connect the atoms that are undergoing a change in oxidation number. On the line,
write the oxidation-number change.
The carbon atom’s oxidation number increases by 2, while the iron atom’s oxidation number decreases by 3.
As written, the number of electrons lost does not equal the number of electrons gained. In a balanced redox
equation, these must be equal. So, the increase in oxidation number of one atom must be made equal to the
decrease in oxidation number of the other.
Step 4: Use coefficients to make the total increase in oxidation number equal to the total decrease in
oxidation number. In this case, the least common multiple of 2 and 3 is 6. So the oxidation-number increase
should be multiplied by 3, while the oxidation-number decrease should be multiplied by 2. The coefficient is
also applied to the formulas in the equation. So a 3 is placed in front of the CO and in front of the CO2. A 2
is placed in front of the Fe on the right side of the equation. The Fe2O3 does not require a coefficient because
the subscript of 2 after the Fe indicates that there are already two iron atoms.
Step 5: Check the balancing for both atoms and charge. Occasionally, a coefficient may need to be placed
in front of a molecular formula that was not involved in the redox process. In the current example, the
equation is now balanced.

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REDOX CHEMISTRY

By: Ahmed Ewis

Background to redox reaction

d) Changes in oxidation numbers:

Cu2O + H2SO4 CuSO4 + Cu + H2O

Constructing ionic equation

Ionic half-equations: Zn(s) Zn2+(aq) + 2e-

Balanced ionic half-equations: 5Fe2+ 5Fe3+ + 5e-

Full ionic equation: 5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O

Balancing Redox Reactions: Oxidation-Number-Change Method

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