Oxidation-Reduction Reaction

Covalency, Oxidation Number and Oxidation State

Covalency of an element represents (i) the number of H-atoms with which an atom of that element can
combine (ii) the number of single bonds which an atom of that element can form 'iii, the number of electrons
its atom is able to share with other elements. Thus, in every case covalency of an element is a pure number
and has no plus or minus sign associated with it. For example, covalency of nitrogen in NH3 is 3.
Oxidation number of an element is defined as the formal charge which an atom of that element appears to
have when electrons are counted. Oxidation number of an atom may be positive or negative. For example
(i) oxidation number of K and Br in KBr is +1 and - 1 respectively. (ii) Oxidation number of N in NH3 is -3.
Differences between Oxidation Number (ON.) and Valency
 ▪ Oxidation state of an element is its oxidation number of per atom. For example: the oxidation state of Al
in A13O3 = + 6/2 = + 3.
▪ In ionic compounds the oxidation state of an element is the same as the charge on the ion formed from
the atom of the element. For example: in KBr, K is said to be in +1 oxidation state while Br is said to be in
-1 oxidation state.

Rules for Calculating Oxidation Number: The rules are followed -

• The oxidation number of an element in the free or uncombined state is zero.
• Fluorine, the most electronegative element, has an oxidation number of -1 in all its compounds.
• The oxidation number of hydrogen is +1 in all its compound except in the ionic metal hydrides where its O.N.
is -1. For example the O.N. of H in H2O is +1 while its U.N. in NaH is equal to -1.
• The O.N. of oxygen is generally equal to -2 except in F2O in which the O.N. of oxygen is equal to +2. In H2O2
molecule, O.N. of O-atom in H2O2 molecule (or its derivatives like BaO2 etc.) is equal to -1. Because, the
electron pair shared between H and O atoms is counted with 0-atom, since it is more
electronegative than H-atom. Therefore the number of electrons counted with each
O-atom is equal to seven instead of its outermost shell six electrons.
Therefore O-atom in H2O2, molecule appears to have -1 charge on it.
• The net charge on a given ion is equal to the sum of the oxidation numbers of all the atoms present in the ion.
• The oxidation number of a neutral molecule is always zero and is equal to the sum of oxidation numbers of the
individual atoms, each multiplied by the number of atoms of the element in the molecule.
Oxidation and Reduction:

Oxidation is a reaction in which an

atom or an ion loses one or more
electrons and thus increases its valency,
i.e. in oxidation the atomic or ionic
system loses one or more electrons and
is changed into more electropositive or
less electronegative state. Due to the
loss of electrons, oxidation is also called
de-electronation.
Reduction is a reaction in which an
atom or an ion gains one or more
electrons and thus decreases its valency,
i.e. in reduction the atomic or ionic
system gains one or more electrons and
is changed into less electropositive or
more electronegative slate. Due to gain
of electrons, reduction is also called
electronation.
 Redox Reactions, Half Reactions, Oxidising Agents & Reducing Agents:
▪ The oxidation (i.e. loss of electrons) and reduction (i.e. gain of electrons) reactions go hand in hand and
such reactions in which oxidation and reduction take place simultaneously are known as oxidation-
reduction reactions or redox reactions. For example the reaction between Zn and CuSO4 solution.
▪ The reaction showing oxidation is called oxidation half-reaction while that representing reduction is called
reduction half-reaction.
▪ An oxidising agent (atom, ion or molecule) is that substance which oxidises some other substance, and is
itself reduced to a lower valency state by gaining one or more electrons while a reducing agent (atom, ion
or molecule) is that substance which reduces some other substance, and is itself oxidised to a higher valency
state by losing one or more electrons.

Zn + CuSO4 = ZnSO4 + Cu
Or
Zn + Cu2+ = Zn2+ + Cu
 Equivalent Weights of Oxidising Agents

The equivalent weight of an

oxidising agent (molecule or
ion) is its that weight which
can take up one electron, i.e.
the equivalent weight of an
oxidizing agent is equal to its
molecular weight or ion
weight divided by the number
of electrons gained by its per
molecule or per ion.
 Equivalent Weights of Reducing Agents

The equivalent weight of a reducing agent

(molecule or ion) is its that weight which
can loss one electron. i.e. the equivalent
weight of a reducing agent is equal to its
molecular weight or ion weight divided by
the number of electrons lost by its per
molecule or per ion.
 Auto-oxidation
There are substances like turpentine, olefinic compounds, P and some metals (e.g. Zn and Pb) which have a
tendency to absorb O2 from the air and then become active. These active substances can oxidise other substances
which are not normally oxidised by them.

In order to explain the phenomenon of auto-oxidation,

Bach suggested that the other substance is supposed to
combine with O2 to form an unstable addition compound,
called moloxide which then gives up oxygen. This oxygen
is used up by H2O to form H2O2. Bach called lead an
activator, since it activated O2 to combine with H2O to
form H2O2 and water was called an acceptor.

The turpentine or other unsaturated compounds which act

as activators are supposed to take up O2 molecule in the
form of —O-O— at the double bond position to form the
unstable peroxide (moloxide). This moloxide gives up
oxygen which is used up by H2O molecule to form H2O2.
 Induced Oxidation
▪ The phenomenon in which one substance while undergoing oxidation itself on exposure to air brings
about oxidation of another substance also which of itself cannot take up oxygen is known as induced
oxidation.
▪ It has been observed that if a solution of Na2SO3 is exposed to air, it gets oxidised to Na2SO4. But, if a
solution of Na2AsO3 is exposed to air, it does not get oxidised to Na2AsO4. However, if a solution of
Na2SO3 is mixed with that of Na2AsO3 and then the mixture be exposed to air, both undergo oxidation.
▪ Induced oxidation can be explained by Brodie's theory and by Bach's theory.

(a) Brodie's theory: (b) Bach's theory:

According to this theory H2O2 is formed which The theory is based on the formation of moloxide
brings about the oxidation of Na2AsO3 to Na2AsO4. by the reaction between Na2SO3 and O2.
Balancing Redox Equations by Oxidation Number Method
 Balancing Redox Equations by Ion-electron Method—By the Use of Half-reactions
This method was developed in 1927 by Jatte and Lamer and various steps involved in the method are as follows:
1). Break up the complete equation in two half reactions, one for the change undergone by the reducing agent
and the other for the change undergone by the oxidising agent.
2). Balance each half reaction as to the number of atoms of each element. For this purpose-
(a) Balance the atoms other than H and O for each half-reaction by using simple multiples.
(b) In neutral and acid solutions, H2O and H+ are added for balancing oxygen and hydrogen atoms.
First balance the oxygen atoms. For each excess oxygen atom on one side of the equation,
add one H2O to the other side. Now use H+ to balance hydrogen atoms.
In alkaline solutions, OH- may be used. For each excess on one side, balance is secured by adding
one H2O to the same side and 2H+ to the other side. If hydrogen is still unbalanced, balance
is secured by adding one OH- for each excess hydrogen on the same side as the excess and
one H2O to the other side.
3). Equalise the charges on both sides by adding electrons to the side deficient in negative charges.
4). Multiply one or both half-reactions by a suitable number so that on adding the two equations, the electrons
are balanced.
5). Add the two balanced half reactions and cancel any terms common to both sides. Also see that all electrons
cancel.