REDOX REACTIONS

Redox reactions are those reactions in which oxidation and

reduction takes place simultaneously
Classical View of Redox Reactions
Oxidation is the addition of oxygen / electronegative element to a
substance or removal of hydrogen / electropositive element from a
substance
Example:
● 2 𝑀𝑔 (𝑠) + 𝑂2 (𝑔) → 2𝑀𝑔𝑂 (𝑠)
● 𝐶𝐻4 + 2 𝑂2 → 𝐶𝑂2 (𝑔) + 2 𝐻2𝑂 (𝑙)
● 2 𝐻2𝑆 (𝑔) + 𝑂2 (𝑔) → 2 𝑆 (𝑠) + 2𝐻2𝑂 (𝑙)
● 𝑀𝑔 (𝑠) + 𝑆 (𝑠) → 𝑀𝑔𝑆 (𝑠)§§
● 2 𝐾4 [𝐹𝑒(𝐶𝑁)6 ](𝑎𝑞) + 𝐻2𝑂2(𝑎𝑞) →2 𝐾3[𝐹𝑒(𝐶𝑁)6](𝑎𝑞) + 2 𝐾𝑂𝐻 (𝑎𝑞)

Reduction is removal of oxygen / electronegative element from a

substance or addition of hydrogen / electropositive element to a
substance
Example:
● 2 𝐻𝑔𝑂 (𝑠) → 2 𝐻𝑔(𝑙) + 𝑂2(𝑔) [Heat is required]
● 2 𝐹𝑒𝐶𝑙3(𝑎𝑞) + 𝐻2(𝑔) → 2 𝐹𝑒𝐶𝑙2(𝑎𝑞) + 2 𝐻𝐶𝑙(𝑔)
● 𝐶𝐻2 = 𝐶𝐻2(𝑔) + 𝐻2(𝑔) → 𝐶𝐻3 − 𝐶𝐻3
● 2 𝐻𝑔𝐶𝑙2(𝑎𝑞) + 𝑆𝑛𝐶𝑙2(𝑎𝑞) → 𝐻𝑔2𝐶𝑙2(𝑠) + 𝑆𝑛𝐶𝑙4(𝑎𝑞)

Redox Reactions in Terms of Electron Transfer

Oxidation is defined as loss of electrons by any species. Half
reactions that involve loss of electrons are called oxidation reactions
Reduction is defined as the gain of electrons by any species. The
half reactions that involve gain of electrons are called reduction
reactions

2 Na(s) → 2 Na+ (g) + 2e– [Oxidation]

−
𝐶𝑙2(𝑔) + 2𝑒 − → 2 𝐶𝑙 (𝑔) [Reduction]
+ −
2 𝑁𝑎(𝑠) + 𝐶𝑙2(𝑔) → 2 𝑁𝑎 𝐶𝑙 (𝑠) 𝑜𝑟 2 𝑁𝑎𝐶𝑙 (𝑠) [Redox]

In oxidation reactions there is loss of electrons or an increase in

positive charge or decrease in negative charge
In reduction reactions there is gain of electrons or a decrease in
positive charge or increase in negative charge
Oxidising agents are species which gain one or more electrons and
get reduced themselves
Reducing agents are the species which lose one or more electrons
and gets oxidized themselves
Oxidation number denotes the oxidation state of an element in a
compound ascertained according to a set of rules. These rules are
formulated on the basis that electrons in a covalent bond belongs
entirely to the more electronegative element.
Competitive Electron Transfer Reactions
Metals which are more reactive are going to react with less reactive
metals to form redox reactions.

As we can see copper being more reactive than silver releases

electrons and it is oxidised. Also silver gains electrons and hence is
reduced.
This can also be witnessed in reactions like,
𝑍𝑛(𝑠) + 𝐶𝑢 (𝑎𝑞) → 𝑍𝑛 (𝑎𝑞) + 𝐶𝑢(𝑠) ; where Zn is oxidised and
2+ 2+

copper is reduced.
There will be no reaction when metallic copper is placed in a
solution of zinc sulphate. Hence neither copper nor zinc will be
oxidised or reduced.
Oxidation Number
In order to keep track of electron shifts in chemical reactions
involving formation of covalent compounds, a more practical
method of using oxidation number has been developed.
In this method, it is always assumed that there is a complete
transfer of electrons from a less electronegative atom to a more
electronegative atom.
Some covalent reactions with their oxidation numbers:
Oxidation number denotes the oxidation state of an element in a
compound ascertained according to a set of rules formulated on the
basis that electron pair in a covalent bond belongs entirely to more
electronegative element.
Rules for Assigning Oxidation Number to an Atom:
● Oxidation number of Hydrogen is always +1 (except in
hydrides, it is -1).
● Oxidation number of oxygen in most of compounds is -2. In
peroxides it is (-1). In superoxides, it is (-1/2). In 𝑂𝐹2 oxidation
number of oxygen is +2. In 𝑂2𝐹2 oxidation number of oxygen is
+1.
● Oxidation number of Fluorine is -1 in all its compounds.
● For neutral molecules sum of oxidation number of all atoms is
equal to zero.
● In the free or elementary state, the oxidation number of an
atom is always zero. This is irrespective of its allotropic form.
● For ions composed of only one atom, the oxidation number is
equal to the charge on the ion.
 ● The algebraic sum of the oxidation numbers of all the atoms in
a compound must be zero.
● For ions the sum of oxidation number is equal to the charge
on the ion.
● In a polyatomic ion, the algebraic sum of all the oxidation
numbers of atoms of the ion must be equal to the charge on
the ion
● Oxidation state and oxidation number are often used
interchangeably
● According to Stock notation the oxidation number is expressed
by putting a Roman numeral representing the oxidation
number in parentheses after the symbol of the metal in the
molecular formula
Types of Redox Reactions
● Combination Reactions:
Chemical reactions in which two or more substances (elements
or compounds) combine to form a single substance
A+B➝C
Either A or B or both must be in elemental form for such a
reaction to be a redox reaction.
Some examples of combination redox reactions are:
● Decomposition Reactions:
Chemical reactions in which a compound breaks up into two
or more simple substances
C➝A+B
Some examples of decomposition redox reactions are:

● Displacement Reactions:
Reaction in which one ion(or atom)in a compound is replaced
by an ion(or atom) of other elements.
X + YZ ➝ XZ + Y
● Metal Displacement Reactions:
Reactions in which a metal in a compound is displaced by
another metal in the uncombined state.
Part of displacement redox reactions.
 Some examples of metal displacement redox reactions are:

● Non-Metal Displacement Reactions:

Such reactions are mainly hydrogen displacement or oxygen
displacement reactions.
Some examples of non-metal displacement redox reactions
are:
● Disproportionation Reactions:
Reactions in which an element in one oxidation state is
simultaneously oxidized and reduced.
One of the reacting substances in a disproportionation
reaction always contains an element that can exist in at least
three oxidation states.
Some examples of disproportionation redox reactions are:
 Among halogens fluorine doesn't show disproportionation
tendency. This is due to the fact that fluorine is highly
electronegative and cannot exhibit any positive oxidation state.
Balancing of Redox Reactions
One method of balancing redox reactions is based on the change in
the oxidation number of reducing agent and the oxidising agent.
Steps Involved in Balancing a Redox Reaction by Oxidation Number
Method are:
I. Write the skeletal redox reaction for all reactants and products
of the reaction.
II. Indicate the oxidation number of all the atoms in each
compound above the symbol of element.
III. Identify the element/elements which undergo change in
oxidation numbers.
IV. Calculate the increase or decrease in oxidation number per
atom.
V. Equate the increase in oxidation number with decrease in
oxidation number on the reactant side by multiplying formula
 of oxidizing agent and reducing agents with suitable
coefficients.
VI. Balance the equation with respect to all other atoms except
hydrogen and oxygen.
VII. Finally balance hydrogen and oxygen. For balancing oxygen
atoms add water molecules to the side deficient in it.
Balancing of hydrogen atoms depend upon the medium.
VIII. For reactions taking place in acidic solutions add H+ ions to
the side deficient in hydrogen atoms.
IX. For reactions taking place in basic solutions add H2O
molecules to the side deficient in hydrogen atoms and
simultaneously add equal number of OH– ions on the other
side of the equation.
X. Finally balance the equation by cancelling common species
present on both sides of the equation.
An example of balancing a redox reaction using this method is:
The second method is based on
splitting the redox reaction
into two half reactions — one
involving oxidation and the
other involving reduction.
Steps Involved in Balancing a Redox Reaction by Ion-Electron
Method (Half Reaction method) are:
I. Find the elements whose oxidation numbers are changed.
Identify the substance that acts as an oxidizing agent and
reducing agent.
II. Separate the complete equation into oxidation half reaction
and reduction half reaction.
 III. Balance the half equations by following steps.
IV. Balance all atoms other than H and O.
V. Calculate the oxidation number on both sides of the equation.
Add electrons to whichever side is necessary to make up the
difference.
VI. Balance the half equation so that both sides get the same
charge.
VII. Add water molecules to complete the balancing of the
equation.
VIII. Add the two balanced equations. Multiply one or both half
equations by suitable numbers so that on adding two
equations the electrons are balanced.

An example of balancing a redox reaction using this method is:

Redox Reactions as the Basis for Titrations
In redox systems, the titration method can be adopted to determine
the strength of a reductant/oxidant using a redox sensitive
indicator.
Potassium permanganate (𝐾𝑀𝑛𝑂4) is a very strong oxidizing agent
and is used in determination of many reducing agents like Fe2+,
oxalate ions etc. It acts as a self indicator in redox reactions.
Equation showing 𝐾𝑀𝑛𝑂4 as an oxidising agent in acidic medium is:
4− + − 2+
𝑀𝑛𝑂 + 8𝐻 + 5𝑒 → 𝑀𝑛 + 4𝐻2𝑂

𝐾2𝐶𝑟2𝑂7is used as an oxidizing agent in redox reactions. Titrations

involving K2Cr2O7 uses diphenylamine and potassium ferricyanide
(external indicator).
Equation showing K2Cr2O7 as an oxidising agent in acidic medium
is:
2− + −
𝐶𝑟2𝑂7 + 14𝐻 + 6𝑒 → 2𝐶𝑟3 + 7𝐻2𝑂

Iodine (𝐼2) in redox reactions: 𝐼2 acts as mild oxidising agent in

solution according to equation
− −
𝐼2 + 2𝑒 → 2𝐼

Direct redox reaction:

Redox reactions in which reduction and oxidation occurs in the
same solution (i.e. same reaction vessel). In these reactions
transference of electrons is limited to very small distance.
An example of this is:
● If a zinc rod is dipped in copper sulphate solution. The redox
reaction takes place and during the reaction, zinc is oxidised
 to zinc ions and copper ions are reduced to metallic copper
due to direct transfer of electrons from zinc to copper ion.
Indirect redox reactions:
Redox reactions in which oxidation and reduction reactions take
place in different reactions vessels and thus transfer of electrons
from one species to another does not take place directly
Electrochemical cell is a device that converts chemical energy
produced in a redox reaction into electrical energy. These cells are
also called Galvanic cells or Voltaic cells
The electrode at which oxidation occurs is called anode and is
negatively charged
The electrode at which reduction takes place is called cathode and
is positively charged
In an electrochemical cell the transfer of electrons takes place from
anode to cathode
In an electrochemical cell the flow of current is from cathode to
anode
In an electrochemical cell, the electrical circuit is completed with a
salt bridge. Salt bridge also maintains the electrical neutrality of the
two half cells
A salt bridge is a U shaped tube filled with solution of inert
electrolyte like sodium chloride or sodium sulphate or a solution of
potassium chloride or ammonium nitrate which will not interfere in
the redox reaction. The ions are set in a gel or agar agar so that
only ions flow when inverted
Electrical potential difference developed between the metal and its
solution is called electrode potential. It can also be defined as the
tendency of an electrode in a half cell to gain or lose electrons
Oxidation potential is the tendency of an electrode to lose electrons
or to get oxidized
Reduction potential is the tendency of an electrode to gain electrons
or get reduced
In an electrochemical cell, by the present convention, the electrode
potentials are represented as reduction potential
The electrode having a higher reduction potential will have a higher
tendency to gain electrons
By convention, the standard electrode potential of hydrogen
electrode is 0.00 volts
A redox couple is defined as having together oxidized and reduced
forms of a substance taking part in an oxidation or reduction half
reaction
The difference between the electrode potentials of eth two electrodes
constituting the electrochemical cell is called EMF (Electromotive
force) or the cell potential
EMF = E⊖ cathode – E⊖ anode
A negative E⊖ means that the redox couple is a stronger reducing
agent than the H+/H2 couple
A positive E⊖ means that the redox couple is a weaker reducing
agent than the H+/H2 couple
An example of this is:
The left beaker (anode) has zinc sulphate solution with a zinc rod or
strip in it and is getting oxidised. While the right beaker (cathode)
has copper sulphate solution with a copper rod or strip in it.