Chemistry

Redox Reaction

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Table of Content

1. Molecular and Ionic equations.

2. Oxidation – Reduction and Redox reactions.
3. Oxidizing and Reducing agents (Oxidants & Reductants).
4. Oxidation number or Oxidation state.
5. Balancing of oxidation – reduction reactions.
6. Autoxidation.
7. Disproportionation.
8. Important applications of Redox reactions.

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Chemical reactions involve transfer of electrons from one chemical substance to another. These electron
– transfer reactions are termed as oxidation-reduction or redox-reactions.

Redox reactions play an important role in our daily life. These reactions are accompanied by energy
changes in the form of heat, light, electricity etc. Generation of electricity in batteries and many industrial
processes such as production of caustic soda, KMnO 4 extraction of metals like sodium, iron and
aluminum are common examples of redox reactions.

1. Molecular and Ionic equations.

(1) Molecular equations: When the reactants and products involved in a chemical change are written in
molecular forms in the chemical equation, it is termed as molecular equation.

Examples: (i) MnO 2  4 HCl  MnCl 2  2 H 2 O  Cl 2

(ii) 2 FeCl 3  SnCl 2  2 FeCl 2  SnCl 4
In above examples, the reactants and products have been written in molecular forms, thus the equation
is termed as molecular equation.

(2) Ionic equations: When the reactants and products involved in a chemical change are ionic
compounds, these will be present in the form of ions in the solution. The chemical change is written in
ionic forms in chemical equation, it is termed as ionic equation.
Examples: (i) MnO 2  4 H   4 Cl   Mn 2   2Cl   2 H 2 O  Cl 2
(ii) 2 Fe 3  6 Cl   Sn 2  2Cl   2 Fe 2  4 Cl   Sn 4   4 Cl 
In above examples, the reactants and products have been written in ionic forms, thus the equation is
termed as ionic equation.

(3) Spectator ions: In ionic equations, the ions which do not undergo any change and equal in number
in both reactants and products are termed spectator ions and are not included in the final balanced
equations.
Example: Zn  2 H   2Cl   Zn 2   H 2  2Cl  (Ionic equation)
Zn  2 H   Zn 2   H 2 (Final ionic equation)
In above example, the Cl  ions are the spectator ions and hence are not included in the final ionic
balanced equation.

2
(4) Rules for writing ionic equations
(i) All soluble ionic compounds involved in a chemical change are expressed in ionic symbols and
covalent substances are written in molecular form. H2O, NH3, NO2, NO, SO2, CO, CO2, etc., are expressed
in molecular form.
(ii) The ionic compound which is highly insoluble is expressed in molecular form.
(iii) The ions which are common and equal in number on both sides, i.e., spectator ions, are
cancelled.
(iv) Besides the atoms, the ionic charges must also be balanced on both the sides.

The rules can be explained by following examples,

Example: Write the ionic equation for the reaction of sodium bicarbonate with sulphuric acid, the
molecular equation for the chemical change is,
NaHCO3 + H2SO4  Na2SO4 + H2O + CO2
NaHCO3, H2SO4 and Na2SO4 are ionic compounds, so these are written in ionic forms.
Na   HCO 3  2 H   SO 42   2 Na   SO 42   H 2 O  CO 2
Na  and SO 42  ions are spectator ions; hence these shall not appear in the final equation.
HCO 3  2 H   H 2 O  CO 2
To make equal charges on both sides, HCO 3 should have a coefficient 2.
2 HCO 3  2 H   H 2 O  CO 2
In order to balance the hydrogen and carbon on both sides, the molecules of H2O and CO2
should have a coefficient 2 respectively.
2 HCO 3  2 H   2 H 2 O  2CO 2 or HCO 3  H   H 2 O  CO 2
This is the balanced ionic equation.
Conversion of ionic equation in molecular form can be explained by following example,

Example: Write the following ionic equation in the molecular form if the reactants are
chlorides.
2Fe3++Sn2+  2Fe2++Sn4+
For writing the reactants in molecular forms, the requisite number of chloride ions are added.
2 Fe 3   6 Cl   Sn 2   2Cl  or 2FeCl3 + SnCl2

Similarly 8 Cl ions are added on R.H.S. to neutralize the charges.
2 Fe 2   4 Cl   Sn 4   4 Cl  or 2FeCl2 + SnCl4

Thus, the balanced molecular equation is, 2FeCl3+SnCl2 = 2FeCl2 + SnCl4

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2. Oxidation-reduction and Redox reactions.

(1) Oxidation : Oxidation is a process which involves; addition of oxygen, removal of hydrogen, addition
of non-metal, removal of metal, Increase in +ve valency, loss of electrons and increase in oxidation
number.
(i) Addition of oxygen
(a) 2Mg + O2  2MgO (Oxidation of magnesium)
(b) S + O2  SO2 (Oxidation of sulphur)
(c) 2CO + O2  2CO2 (Oxidation of carbon monoxide)
(d) Na2SO3+H2O2  Na2SO4+H2O (Oxidation of sodium sulphite)

(ii) Removal of hydrogen

(a) H2S + Cl2  2HCl + S (Oxidation of hydrogen sulphide)
(b) 4HI + O2  2H2O + 2I2 (Oxidation of hydrogen iodide)
(c) C2H5OH   CH3CHO + H2 (Oxidation of ethanol)
o

Cu / 300 C

(d) 4HCl + MnO2  MnCl2 + 2H2O + Cl2 (Oxidation of hydrogen chloride)

(iii) Addition of an electronegative element or addition of Non-metal

(a) Fe + S  FeS (Oxidation of iron)
(b) SnCl2 + Cl2  SnCl4 (Oxidation of stannous chloride)
(c) 2Fe + 3F2  2FeF3 (Oxidation of iron)

(iv) Removal of an electropositive element or removal of metal

(a) 2KI + H2O2  2KOH + I2 (Oxidation of potassium iodide)
(b) 2K2MnO4 + Cl2  2KCl + 2KMnO4 (Oxidation of potassium magnate)
(c) 2KI + Cl2  2KCl + I2 (Oxidation of potassium iodide)

(v) Increase in +ve valency and Decrease in – ve valency

Increase in +ve valency

–4, –3, –2, –1, 0, +1, +2, +3, +4

Decrease in –ve valency

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 (a) Fe 2   Fe 3   e  (+ve valency increases)
(b) Sn 2
 Sn 4
 2e 
(+ve valency increases)
(c) [Fe (CN )6 ] 4
 [Fe(CN )6 ] 3
e 
(–ve valency decreases)
(d) MnO 42   MnO 4  e  (–ve valency decreases)
(vi) Loss of electrons (also known as de-electronation)

4 3 2 1 0 1 2 3 4
M M M M M M M M M

–e– –e– –e– –e– –e– –e– –e– –e–

Loss of electrons

(a) H 0  H   e  (Formation of proton)

(b) H 20  H 2 e 
(De-electronation of hydrogen)
(c) Fe 2
 Fe 3
e 
(De-electronation of Fe 2  )
(d) Mg  Mg 2   2e  (De-electronation of Magnesium)
(e) MnO 42   MnO 4  e  (De-electronation of MnO 42  )
(f) 2Cl   Cl 2  2e  (De-electronation of chloride ion)
(g) 2 Fe 0  2 Fe 3   6 e  (De-electronation of iron)

(vii) Increase in oxidation number

(a) Mg 0  Mg 2  (From 0 to +2)


(b) Fe  2 (CN )6  4

 Fe  3 (CN )6 
3
(From +2 to +3)

(c) 2Cl  Cl 20 (From –1 to 0)

(2) Reduction: Reduction is just reverse of oxidation. Reduction is a process which involves; removal of
oxygen, addition of hydrogen, removal of non-metal, addition of metal, decrease in +ve valency, gain of
electrons and decrease in oxidation number.

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(i) Removal of oxygen
(a) CuO  C  Cu  CO (Reduction of cupric oxide)
(b) H 2 O  C  CO  H 2 (Reduction of water)
Steam Coke  
Water gas

(c) Fe 3 O 4  4 H 2  3 Fe  4 H 2 O (Reduction of Fe 3 O 4 )
(d) C 6 H 5 OH  Zn  C 6 H 6  ZnO (Reduction of phenol)

(ii) Addition of hydrogen

(a) Cl 2  H 2  2 HCl (Reduction of chlorine)
(b) S  H 2  H 2 S (Reduction of sulphur)
(c) C 2 H 4  H 2  C 2 H 6 (Hydrogenation of ethane)

(iii) Removal of an electronegative element or removal of Non-metal

(a) 2 HgCl 2  SnCl 2  Hg 2 Cl 2  SnCl 4 (Reduction of mercuric chloride)
(b) 2 FeCl 3  H 2  2 FeCl 2  2 HCl (Reduction of ferric chloride)
(c) 2 FeCl 3  H 2 S  2 FeCl 2  2 HCl  S (Reduction of ferric chloride)

(iv) Addition of an electropositive element or addition of metal

(a) HgCl 2  Hg  Hg 2 Cl 2 (Reduction of mercuric chloride)
(b) CuCl 2  Cu  Cu 2 Cl 2 (Reduction of cupric chloride)

(v) Decrease in +ve valency and Increase in –ve valency

Decrease in +ve valency

–4, –3, –2, –1, 0, +1, +2, +3, +4

Increase in –ve valency

(a) Fe 3   Fe 2  (+ve valency decreases)

(b) Sn 4   Sn 2  (+ve valency decreases)
(c) [Fe (CN )6 ]3   [Fe(CN )6 ]4  (–ve valency increases)
(d) MnO 4  MnO 42  (–ve valency increases)

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(vi) Gain of electrons (also known as electronation)
4 3 2 1 0 1 2 3 4
M M M M M M M M M

+e– +e– +e– +e– +e– +e– +e– +e–

Gain of electrons

(a) Zn 2  (aq)  2e   Zn(S ) (Electronation of Zn 2  )

(b) Pb 2   2e   Pb 0 (Electronation of Pb 2  )
(c) Mn 7   5 e   Mn 2  (Electronation of Mn 7  )
(d) Fe 3   e   Fe 2  (Electronation of Fe 3  )
(e) Sn 4   2e   Sn 2  (Electronation of Sn 4  )
(f) Cl  e   Cl  (Formation of chloride ion)
(g) [Fe(CN )6 ]3   e   [Fe(CN )6 ]4  (Electronation of [Fe(CN )6 ]3  )

(vii) Decrease in oxidation number

(a) Mg 2   Mg 0 (From +2 to 0)
(b) Fe(CN )6 3   Fe(CN )6 4  (From +3 to +2)
(c) Cl 20  2Cl  (From 0 to –1)

(3) Redox-reactions

(i) An overall reaction in which oxidation and reduction takes place simultaneously is called redox or
oxidation-reduction reaction. These reactions involve transfer of electrons from one atom to another.
Thus every redox reaction is made up of two half reactions; One half reaction represents the oxidation
and the other half reaction represents the reduction.
(ii) The redox reactions are of following types
(a) Direct redox reaction: The reactions in which oxidation and reduction takes place in
the same vessel are called direct redox reactions.
(b) Indirect redox reaction: The reactions in which oxidation and reduction takes place in
different vessels are called indirect redox reactions. Indirect redox reactions are the basis
of electro-chemical cells.
(c) Intermolecular redox reactions: In which one substance is oxidized while the other is
reduced. For example,
2 Al  Fe 2 O3  Al 2 O3  2 Fe

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 Here, Al is oxidized to Al 2 O 3 while Fe 2 O 3 is reduced to Fe.
(d) Intramolecular redox reactions: In which one element of a compound is oxidized
while the other is reduced. For example,

2 KClO 3  2 KCl  3 O 2
Here, Cl 5 in KClO 3 is reduced to Cl 1 in KCl while O 2  in KClO 3 is oxidized to O 20 .

(iii) To see whether the given chemical reaction is a redox reaction or not, the molecular reaction is
written in the form of ionic reaction and now it is observed whether there is any change in the valency of
atoms or ions. If there is a change in valency, the chemical reaction will be a redox reaction otherwise
not. For example,
(a) BaO2  H 2 SO 4  BaSO 4  H 2 O 2
(b) CuSO 4  4 NH 3  Cu (NH 3 )4  SO 4
In above examples there is no change in the valency of any ion or atom, thus these are not redox
reactions.

(iv) Some examples of redox reactions are,

–2e–

(a) Oxidation

2 HgCl+22e SnCl 2  Hg 2 Cl 2  SnCl 4

–

Reduction

Here mercuric ion is reduced to mercurous ion and stannous ion is oxidized to stannic
ion, i.e., mercuric ion acts as an oxidizing agent while stannous ion acts as a reducing
agent.

(b) +2e–

SnCl 2  2Reduction
FeCl 3  2 FeCl 2  SnCl 4
– 2e–

Here ferric ion is reduced to ferrous ion by gain of one electron while stannous ion is
Oxidation

oxidized to stannic ion by loss of two electrons. The ferric ion acts as an oxidizing agent
while stannous ion acts as a reducing agent.

(c) +2e –

2 Na 2 S 2 O 3  I 2  Na 2 S 4 O 6  2 NaI
Reduction
–2e–

Oxidation

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Here thiosulphate ion is oxidized to tetrathionate ion by loss of electrons while iodine is
reduced to iodide ion by gain of electrons. Thiosulphate ion acts as a reducing agent and
iodine acts as an oxidizing agent.

(d) –2e–
0 
2Oxidation 0
Zn  Cu SO 4  ZnSO 4  Cu
+2e –

Reduction

(e) –2e –
0 0
Oxidation  
H2  X 2  2 H X (Where X = F, Cl, Br, I)
+2e–

Reduction
–2e–

Oxidation0 0 2 1
(f) Zn  I 2  Zn I 2
+2e–

Reduction

(g) +2e–
0 1 0 2
Reduction
Zn  2 Ag CN  2 Ag  Zn(CN )2
–2e–

Oxidation

(h) +2e–

0 1 2
Reduction 0
Cu  2 Ag NO 3  Cu ( NO 3 )2  2 Ag
–2e–

Oxidation

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3. Oxidizing and Reducing agents (Oxidants and Reductants).

(1) Definition: The substance (atom, ion or molecule) that gains electrons and is thereby reduced to a
low valency state is called an oxidizing agent, while the substance that loses electrons and is thereby
oxidized to a higher valency state is called a reducing agent.
Or
An oxidizing agent is a substance the oxidation number of whose atom or atoms decreases while a
reducing agent is a substance the oxidation number of whose atom increases.

(2) Important oxidizing agents

(i) Molecules made up of electronegative elements, e.g. O2, O3 and X2 (halogens).
(ii) Compounds containing an element which is in the highest oxidation state e.g. KMnO 4 , K 2 Cr2 O7 ,
Na 2 Cr2 O7 , CrO 3, H 2 SO 4 , HNO 3 , NaNO 3 , FeCl 3 , HgCl 2 , KClO 4 , SO 3 , CO 2 , H 2 O 2 etc.
(iii) Oxides of elements e.g. MgO, CuO , CrO 3 , CO 2 , P4 O10 , etc.
(iv) Fluorine is the strongest oxidizing agent.

(3) Important reducing agents

(i) All metals e.g. Na, Zn, Fe, Al, etc.
(ii) A few non-metals e.g. C, H2, S etc.
(iii) Hydracids: HCl, HBr, HI, H2S etc.
(iv) A few compounds containing an-element in the lower oxidation state (ous), e.g. FeCl 2 , FeSO 4 ,
SnCl 2 , Hg 2 Cl 2 , Cu 2 O Etc.
(v) Metallic hydrides e.g. NaH, LiH etc.
(vi) Organic compounds like HCOOH and (COOH)2 and their salts, aldehydes, alkanes etc.
(vii) Lithium is the strongest reducing agent in solution.
(viii) Cesium is the strongest reducing agent in absence of water. Other reducing agents are Na 2 S 2 O 3
and KI.
(ix) Hypo prefix indicates that central atom of compound has the minimum oxidation state so it will act
as a reducing agent. e.g., H 3 PO 2 (hypophosphorous acid).

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(4) Substances which act as oxidizing as well as reducing agents
Example: H 2 O2 , SO 2 , H 2 SO 3 , HNO 2 , NaNO 2 , Na 2 SO 3 , O3 etc.

(5) Tips for the identification of oxidizing and reducing agents

(i) If an element is in its highest possible oxidation state in a compound, the compound can function as
an oxidizing agent, e.g. KMnO 4 , K 2 Cr2 O7 , HNO 3 , H 2 SO 4 , HClO 4 etc.
(ii) If an element is in its lowest possible oxidation state in a compound, the compound can function only
as a reducing agent, e.g. H 2 S , H 2 C 2 O 4 , FeSO 4 , Na 2 S 2 O 3 , SnCl 2 etc.
(iii) If an element is in its intermediate oxidation state in a compound, the compound can function both
as an oxidizing agent as well as reducing agent, e.g. H 2 O 2 , H 2 SO 3 , HNO 2 , SO 2 etc.
(iv) If a highly electronegative element is in its highest oxidation state in a compound, that compound
can function as a powerful oxidizing agent, e.g. KClO 4 , KClO 3 , KBrO 3 , KIO3 etc.
(v) If an electronegative element is in its lowest possible oxidation state in a compound or in Free State,
it can function as a powerful reducing agent, e.g. I  , Br  , N 3  etc.

(6) Tests for oxidizing agents

(i) Aqueous solutions of oxidizing agents react with,
(a) Hydrogen sulphide to give a milky yellow precipitate of sulphur.
H 2 S  Oxidizing agent  S (milky yellow ppt.)
(b) Potassium iodide solution and evolve iodine which gives intense blue color with starch solution
KI  Oxidizing agent  I 2    intense blue color
Starch solution

(c) Freshly prepared solution of ferrous ammonium sulphate in presence of dil. H 2 SO 4 . Ferric ions
(Fe 3 ) can be detected by adding ammonium thiocyanate solution when a deep red coloration is
produced.


Oxidizing agent + Fe 2   Fe 3    Fe(CNS )3 (deep red coloration)
CNS

(ii) Insoluble oxidizing agents on,

(a) Strong heating evolve oxygen which relights a glowing splinter.
(b) Warming with concentrated hydrochloric acid evolve chlorine which bleaches the moist litmus paper.

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(7) Tests for reducing agents
(i) Aqueous solutions of reducing agents react with,
(a) Acidified potassium permanganate solution and decolorize it.
(b) Few drops of acidified potassium dichromate solution, green coloration is produced.
(c) Few drops of ferric chloride solution. The ferrous ions thus formed give a deep blue coloration
with potassium ferricyanide (K 3 [Fe(CN )6 ]) .
Insoluble reducing agents on,
(d) Heating with concentrated nitric acid, evolve brown fumes of nitrogen dioxide.
(e) Heating with powdered cupric salt, form a red deposit of copper which does not dissolve in
warm dilute sulphuric acid.

(8) Equivalent weight of oxidizing and reducing agents

(i) Equivalent weight of a substance (Oxidant or Reductants) is equal to molecular weight divided by
number of electrons lost or gained by one molecule of the substance in a redox reaction.
Molecular weight
Equivalent weight of oxidizing agent =
No. of electrons gained by one molecule
Molecular weight
Equivalent weight of reducing agent =
No. of electrons lost by one molecule

(ii) In other words, it is equal to the molecular weight of oxidant or Reductants divided by the change in
oxidation number.
Molecular weight
Equivalent weight of oxidizing agent =
Change in O.N. per mole
Molecular weight
Equivalent weight of reducing agent =
Change in O.N. per mole

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Equivalent weight of few oxidizing/reducing agents

Agents O. N. Product O. N. Change in Total Eq. wt.

O. N. per Change in
atom O. N. per mole

Cr2 O7
2
+6 Cr 3  +3 3 3×2=6 Mol. wt./6

C 2 O4
2
+3 CO 2 +4 1 1×2=2 Mol. wt./2

S 2 O3
2
+2 S 4 O6
2
+ 2.5 0.5 0.5 × 2 = 1 Mol. wt./1

H 2 O2 –1 H 2O –2 1 1×2=2 Mol. wt./2

H 2 O2 –1 O2 0 1 1×2=2 Mol. wt./2
MnO4 +7 Mn2  +2 5 5×1=5 Mol. wt./5
(Acidic medium)
MnO4 +7 MnO2 +4 3 3×1=3 Mol. wt./3
(Neutral
medium)
MnO4 +7 MnO42  +6 1 1×1=1 Mol. wt./1
(Alkaline
medium)

4. Oxidation number or Oxidation state.

(1) Definition: Charge on an atom produced by donating or accepting electrons is called oxidation
number or oxidation state. It is the number of effective charges on an atom.

(2) Valency and oxidation number: Valency and oxidation number concepts are different. In some
cases (mainly in the case of electrovalent compounds), valency and oxidation number are the same but
in other cases they may have different values. Points of difference between the two have been tabulated
below

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 Valency Oxidation number

It is the combining capacity of the element. No O.N. is the charge (real or imaginary) present on the
plus or minus sign is attached to it. atom of the element when it is in combination. It may
have plus or minus sign.

Valency of an element is usually fixed. O.N. of an element may have different values. It
depends on the nature of compound in which it is
present.

Valency is always a whole number. O.N. of the element may be a whole number or
fractional.

Valency of the element is never zero except of O.N. of the element may be zero.
noble gases.

(3) Oxidation number and Nomenclature

(i) When an element forms two monoatomic cations (representing different oxidation states), the two
ions are distinguished by using the ending-ous and ic. The suffix – ous is used for the action with lower
oxidation state and the suffix – ic is used for the action with higher oxidation state.
For example: Cu+ (oxidation number +1) cuprous: Cu2+ (oxidation number +2) cupric

(ii) Albert Stock proposed a new system known as Stock system. In this system, the oxidation states are
indicated by Roman numeral written in parentheses immediately after the name of the element. For
example,

Cu2O Copper (I) oxide SnO Tin (II) oxide

FeCl2 Iron (II) chloride Mn2O7 Manganese (VII) oxide
K2Cr2O7 Potassium dichromate (VI) Na2CrO4 Sodium chromate (VI)
V2O5 Vanadium (V) oxide CuO Copper (II) oxide
SnO2 Tin (IV) oxide FeCl3 Iron (III) chloride

Note: Stock system is not used for non-metals.

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(4) Rules for the determination of oxidation number of an atom
The following rules are followed in ascertaining the oxidation number of an atom,

(i) If there is a covalent bond between two same atoms then oxidation numbers of these two atoms will
be zero. Bonded electrons are symmetrically distributed between two atoms. Bonded atoms do not
acquire any charge. So oxidation numbers of these two atoms are zero.
A: A or A – A  A* + A*
For e.g. Oxidation number of Cl in Cl2, O in O2 and N and N2 is zero.

(ii) If covalent bond is between two different atoms then electrons are counted towards more
electronegative atom. Thus oxidation number of more electronegative atom is negative and oxidation
number of less electronegative atom is positive. Total number of charges on any element depends on
number of bonds.
A–B  A+ +B: –
A–B  A+2 + : B : –2
The oxidation number of less electronegative element (A) is + 1 and + 2 respectively.

(iii) If there is a coordinate bond between two atoms then oxidation number of donor atom will be + 2
and of acceptor atom will be – 2.
A  B  A2+ + B-2
(iv) The oxidation number of all the atoms of different elements in their respective elementary states is
taken to be zero. For example, in N 2 , Cl 2 , H 2 , P4 , S 8 , O2 , Br2 , Na, Fe, Ag etc. the oxidation number of
each atom is zero.

(v) The oxidation number of a monoatomic ion is the same as the charge on it. For example, oxidation
numbers of Na  , Mg 2  and Al 3  ions are + 1, + 2 and + 3 respectively while those of Cl  , S 2  and N 3 
ions are –1, –2 and –3 respectively.

(vi) The oxidation number of hydrogen is + 1 when combined with non-metals and is –1 when combined
with active metals called metal hydrides such as LiH, KH, MgH2, CaH2 etc.

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(vii) The oxidation number of oxygen is – 2 in most of its compounds, except in peroxides like
H 2 O2 , BaO2 etc. where it is –1. Another interesting exception is found in the compound OF2 (oxygen
difluoride) where the oxidation number of oxygen is + 2. This is due to the fact that fluorine being the
most electronegative element known has always an oxidation number of –1.

(viii) In compounds formed by union of metals with non-metals, the metal atoms will have positive
oxidation numbers and the non-metals will have negative oxidation numbers. For example,
(a) The oxidation number of alkali metals (Li, Na, K etc.) is always +1 and those of alkaline
earth metals (Be, Mg, Ca etc.) is + 2.
(b) The oxidation number of halogens (F, Cl, Br, I) is always –1 in metal halides such as KF,
AlCl3, MgBr2, CdI2. Etc.

(ix) In compounds formed by the union of different elements, the more electronegative atom will have
negative oxidation number whereas the less electronegative atom will have positive oxidation number. For
example,
(a) N is given an oxidation number of –3 when it is bonded to less electronegative atom as in
NH3 and NI3, but is given an oxidation number of + 3 when it is bonded to more
electronegative atoms as in NCl3.
(b) Since fluorine is the most electronegative element known so its oxidation number is always
–1 in its compounds i.e. oxides, interhalogen compounds etc.
(c) In interhalogen compounds of Cl, Br, and I; the more electronegative of the two halogens
gets the oxidation number of –1. For example, in BrCl3, the oxidation number of Cl is –1 while
that of Br is +3.

(x) For neutral molecule, the sum of the oxidation numbers of all the atoms is equal to zero. For example,
in NH3 the sum of the oxidation numbers of nitrogen atom and 3 hydrogen atoms is equal to zero. For a
complex ion, the sum of the oxidation numbers of all the atoms is equal to charge on the ion. For
example, in SO 42  ion, the sum of the oxidation numbers of sulphur atom and 4 oxygen atoms must be
equal to –2.

(xi) It may be noted that oxidation number is also frequently called as oxidation state. For example, in
H2O, the oxidation state of hydrogen is +1 and the oxidation state of oxygen is – 2. This means that
oxidation number gives the oxidation state of an element in a compound.

(xii) In the case of representative elements, the highest oxidation number of an element is the same as its
group number while highest negative oxidation number is equal to (8 – Group number) with negative

16
sign with a few exceptions. The most common oxidation states of the representative elements are shown
in the following table,

Group Outer shell Common oxidation numbers (states)

configuration except zero in free state
IA ns1 +1
II A ns2 +2
III A ns2np1 +3, +1
IV A ns2np2 +4,+3,+2,+1, –1, –2, –3, –4
VA ns2np3 +5,+3,+1, –1, –3
VI A ns2np4 +6,+4,+2,–2
VII A ns2np5 +7,+5,+3, +1, –1

(xiii) Transition metals exhibit a large number of oxidation states due to involvement of (n –1) d electron
besides ns electron.
(xiv) Oxidation number of a metal in carbonyl complex is always zero, e.g. Ni has zero oxidation state in
NiCO 4 .

(xv) Those compounds which have only C, H and O the oxidation number of carbon can be calculated by
following formula,
(n O  2 - n H )
Oxidation number of ' C ' 
nC

Where, n O is the number of oxygen atom, n H is the number of hydrogen atom, n C is the number of carbon
atom.
*
For example, (a) CH 3 OH ; n H  4, nC  1, nO  1
(1  2  4 )
Oxidation number of ‘C’ =  2
1
*
(b) HCOOH ; n H  2, nO  2, nc  1
(2  2  2)
Oxidation number of carbon =  2
1

17
(5) Procedure for calculation of oxidation number: By applying the above rules, we can calculate the
oxidation numbers of elements in the molecules/ions by the following steps.
(i) Write down the formula of the given molecule/ion leaving some space between the atoms.
(ii) Write oxidation number on the top of each atom. In case of the atom whose oxidation number has to
be calculated write x.
(iii) Beneath the formula, write down the total oxidation numbers of each element. For this purpose,
multiply the oxidation numbers of each atom with the number of atoms of that kind in the molecule/ion.
Write the product in a bracket.
(iv) Equate the sum of the oxidation numbers to zero for neutral molecule and equal to charge on the
ion.
(v) Solve for the value of x.

Oxidation number of some elements in compounds, ions or chemical species

Element Oxidation Compounds, ions or chemical species

Number
Sulphur –2 H2S, ZnS, NaHS, (SnS3)2–, BaS, CS2
(s)
0 S, S4, S8, SCN–
+1 S2, F2, S2Cl2
+4 SO2, H2SO3, (SO3)2–, SOCl2, NaHSO3, Ca[HSO3]2, [HSO3]–, SF4
+6 H2SO4, (SO4)2-, [HSO4]–, BaSO4, KHSO4, SO3, SF6, H2S2O7,
(S2O7)2–
Nitrogen –3 NH3, (NH4)+, AlN, Mg3N2, (N)3–, Ca3N2, CN–
(N)
–2 N2H4, (N2H5)+
–1 NH2OH
–1/3 NaN3, N3H
0 N2
+1 N2O
+2 NO
+3 HNO2, (NO2)–, NaNO2, N2O3, NF3
+4 NO2
+5 HNO3, (NO3)–, KNO3, N2O5

18
Chlorine –1 HCl, NaCl, CaCl2, AlCl3, ICl, ICl5, SOCl2, CrO2Cl2, KCl, K2PtCl6,
HAuCl4, CCl4

(Cl) 0 Cl, Cl2

+1 HOCl, NaOCl, (OCl)–, Cl2O

+3 KClO2, (ClO2)–, HClO2

+4 ClO2
+5 (ClO3)–, KClO3, NaClO3, HClO3

+7 HClO4, Cl2O7, KClO4, (ClO4)–

Hydrogen –1 NaH, CaH2, LiAlH4, LiH

(H) +1 NH3, PH3, HF

Phosphor –3 PH3, (PH4)+, Ca3P2

us
(P) 0 P4
+1 H3PO2, KH2PO2, BaH4P2O4

+3 PI3, PBr3, PCl3, P2O3, H3PO3

+5 (PO4)3–, H3PO4, Ca3(PO4)2, H4P2O7, P4O10, PCl5, (P2O7)4–,

Mg2P2O7, ATP

Oxygen –2 H2O, PbO2, (CO3)2–, (PO4)2–, SO2, (C2O4)2–, HOCl, (OH)–, (O)2-

(O) –1 Na2O2, BaO2, H2O2, (O2)2–, Peroxides

– 1/2 KO2

0 O, O2, O3

+1 O2F2

+2 OF2

Carbon –4 CH4

(C) –3 C2H6

–2 CH3Cl, C2H4

–1 CaC2, C2H2

0 Diamond, Graphite, C6H12O6, C2H4O2, HCHO, CH2Cl2

+2 CO, CHCl3, HCN

+3 H2C2O4, (C2O4)2–

19
 +4 CO2, H2CO3, (HCO3)–, CCl4, Na2CO3, Ca2CO3, CS2, CF4, (CO3)–2

Chromiu +3 Cr2(SO4)3, CrCl3, Cr2O3, [Cr(H2O)4Cl3]

m
(Cr) +6 K2CrO4, (CrO4)2–, K2Cr2O7, (Cr2O7)2–, KCrO3Cl, CrO2Cl2,
Na2Cr3O10, CrO3

Mangane +2 MnO, MnSO4, MnCl2, Mn(OH)2

se
(Mn) + 8/3 Mn3O4
+3 Mn(OH)3
+4 MnO2, K2MnO3
+6 K2MnO4, (MnO4)2–
+7 KMnO4, (MnO4)–, HMnO4
Silicon –4 SiH4, Mg2Si

(Si) +4 SiO2, K2SiO3, SiCl4

Iron 
8 Fe3O4
3
(Fe)
+2 FeSO4 (Ferrous ammonium sulphate), K4Fe(CN)6, FeCl2
+3 K3[Fe(CN)6], FeCl3
Iodine +7 H 4 IO 6 , KIO4
(I)
Osmium +8 OsO4
(Os)
Xenon +6 XeO3, XeF6
(Xe)

(6) Exceptional cases of evaluation of oxidation numbers: The rules described earlier are usually
helpful in determination of the oxidation number of a specific atom in simple molecules but these rules
fail in the following cases. In these cases, the oxidation numbers are evaluated using the concepts of
chemical bonding involved.

20
Type I. In molecules containing peroxide linkage in addition to element-oxygen bonds. For example,
(i) Oxidation number of S in H2SO5 (Permonosulphuric acid or Caro's acid).
By usual method; H 2 SO 5
2  1  x  5  (2)  0 or x  8
But this cannot be true as maximum oxidation number for S cannot exceed + 6. Since S has only 6
electrons in its valence shell. This exceptional value is due to the fact that two oxygen atoms in H2SO5
shows peroxide linkage as shown below,
O Peroxide linkage

H O S O O H
O
Therefore the evaluation of o.n. of sulphur here should be made as follows,
2 × (+1) + x + 3 × (–2) + 2 × (–1)
(For H) (For S) (For O) (For O–O)
or 2 + x–6–2=0 or x = + 6.

(ii) Oxidation number of S in H2S2O8 (Peroxidisulphuric acid or Marshall's acid)

By usual method; H 2 S 2 O8
1 × 2 + 2x + 8 (–2) = 0
2x = + 16 – 2 = 14 or x=+7
Similarly Caro's acid, Marshall's acid also has a peroxide linkage so that in which S shows +6 oxidation
Peroxide linkage
state.
O O
H O S O O S O H
O O
Therefore the evaluation of oxidation state of sulphur should be made as follow,
2 × (+1) + 2 × (x) + 6 × (–2) + 2 × (–1) = 0
(for H) (for S) (for O) (for O–O)
or 2 + 2x – 12 – 2 = 0 or x = + 6.

(iii) Oxidation number of Cr in CrO5 (Blue perchromate)

By usual method CrO5 ; x – 10 = 0 or x = + 10
This cannot be true as maximum o.n. of Cr cannot be more than + 6. Since Cr has only five electrons in
3d orbitals and one electron in 4s orbital. This exceptional value is due to the fact that four oxygen
atoms in CrO5 are in peroxide linkage. The chemical structure of CrO5 is

21
 O O
Peroxide linkage Cr Peroxide linkage

O O
O
Therefore, the evaluation of o.n. of Cr should be made as follows
x + 1 × (– 2) + 4 (–1) = 0
(For Cr) (For O) (For O–O)
or x – 2 – 4 = 0 or x = + 6.

Type II. In molecules containing covalent and coordinate bonds, following rules are used for evaluating
the oxidation numbers of atoms.
(i) For each covalent bond between dissimilar atoms the less electronegative element is assigned the
oxidation number of + 1 while the atom of the more electronegative element is assigned the oxidation
number
of –1.
(ii) In case of a coordinate-covalent bond between similar or dissimilar atoms but the donor atom is less
electronegative than the acceptor atom, an oxidation number of +2 is assigned to the donor atom and
an oxidation number of –2 is assigned to the acceptor atom.
Conversely, if the donor atom is more electronegative than the acceptor atom, the contribution of the
coordinate bond is neglected.

Example:

(a) Oxidation number of C in HC  N and HN  C
The evaluation of oxidation number of C cannot be made directly by usual rules since no
standard rule exists for oxidation numbers of N and C.
In such cases, evaluation of oxidation number should be made using indirect concept or by the
original concepts of chemical bonding.

(b) Oxidation number of carbon in H – N  C
The contribution of coordinate bond is neglected since the bond is directed from a more
electronegative N atom (donor) to a less electronegative carbon atom (acceptor).

Therefore the oxidation number of N in HN  C remains – 3 as it has three covalent bonds.
1 × (+ 1) + 1 × (– 3) +x=0
(For H) (For N) (For C)
or 1 + x – 3 = 0 or x = + 2.

22
 (c) Oxidation number of carbon in HC  N
In HC  N , N is more electronegative than carbon, each bond gives an oxidation number of –1
to N. There are three covalent bonds, the oxidation number of N is HC  N is taken as – 3
Now HC  N  +1 + x – 3 = 0  x = + 2

Type III. In a molecule containing two or more atoms of same or different elements in different
oxidation states.

(i) Oxidation number of S in Na2S2O3

By usual method Na 2 S 2 O 3
 2 × (+1) + 2 × x + 3 (–2) = 0 or 2 + 2x – 6 = 0 or x = 2.

But this is unacceptable as the two sulphur atoms in Na2S2O3 cannot have the same oxidation
number because on treatment with dil. H2SO4, one sulphur atom is precipitated while the other is
oxidized to SO2.
Na 2 S 2 O 3  H 2 SO 4  Na 2 SO 4  SO 2  S  H 2 O
In this case, the oxidation number of sulphur is evaluated from concepts of chemical bonding. The
chemical structure of Na2S2O3 is
S
 
Na O S O Na 
O
Due to the presence of a co-ordinate bond between two sulphur atoms, the acceptor sulphur atom
has oxidation number of – 2 whereas the other S atom gets oxidation number of + 2.
2 × (+1) + 3 × (–2) + x ×1 + 1 × (– 2) = 0
(For Na) (For O) (For S) (For coordinated S)
or +2–6 + x–2=0 or x = + 6

Thus two sulphur atoms in Na2S2O3 have oxidation number of – 2 and +6.

(ii) Oxidation number of chlorine in CaOCl2 (bleaching powder)

In bleaching powder, Ca (OCl) Cl, the two Cl atoms are in different oxidation states i.e., one Cl–
having oxidation number of –1 and the other as OCl– having oxidation number of +1.

(iii) Oxidation number of N in NH4NO3

23
 By usual method N2H4O3 ; 2x + 4 × (+1) + 3 × (–1) = 0
2x + 4 – 3 = 0 or 2x = + 1 (wrong)
No doubt NH4NO3 has two nitrogen atoms but one N has negative oxidation number (attached
to H) and the other has positive oxidation number (attached to O). Hence the evaluation should
be made separately for NH 4 and NO 3
NH 4 x + 4 × (+1) = +1 or x = – 3
NO 3 x + 3 (– 2) = –1 or x = + 5.

(iv) Oxidation number of Fe in Fe3O4

In Fe3O4, Fe atoms are in two different oxidation states. Fe3O4 can be considered as an
equimolar mixture of FeO (iron (II) oxide) and Fe2O3 (iron (III) oxide). Thus in one molecule of
Fe3O4, two Fe atoms are in + 3 oxidation state and one Fe atom is in + 2 oxidation state.

(v) Oxidation number of S in sodium tetrathionate (Na2S4O6). Its structure can be represented
as follows:
O O
Na O S S S S O Na 


O O
The two S-atoms which are linked to each other have oxidation number of zero. The oxidation
number of other S-atoms can be calculated as follows
Let oxidation number of S = x.
2 × x + 2 × 0 + 6 × (– 2) = – 2
(For S) (For S–S) (For O)
x = + 5.

24
5. Balancing of oxidation-reduction reactions.

Though there are a number of methods for balancing oxidation – reduction reactions, two methods are
very important.
These are:
(1) Oxidation number method
(2) Ion – electron method

(1) Oxidation number method: The method: for balancing redox reactions by oxidation number
change method was developed by Johnson. In a balanced redox reaction, total increase in oxidation
number must be equal to the total decrease in oxidation number. This equivalence provides the basis for
balancing redox reactions. This method is applicable to both molecular and ionic equations. The general
procedure involves the following steps,

(i) Write the skeleton equation (if not given, frame it) representing the chemical change.
(ii) Assign oxidation numbers to the atoms in the equation and find out which atoms are
undergoing oxidation and reduction. Write separate equations for the atoms undergoing oxidation
and reduction.
(iii) Find the change in oxidation number in each equation. Make the change equal in both the
equations by multiplying with suitable integers. Add both the equations.
(iv) Complete the balancing by inspection. First balance those substances which have undergone
change in oxidation number and then other atoms except hydrogen and oxygen. Finally balance
hydrogen and oxygen by putting H2O molecules wherever needed.
The final balanced equation should be checked to ensure that there are as many atoms of each
element on the right as there are on the left.
(v) In ionic equations the net charges on both sides of the equation must be exactly the same. Use
H+ ion/ions in acidic reactions and OH– ion/ions in basic reactions to balance the charge and
number of hydrogen and oxygen atoms.

The following example illustrate the above rules:

Step: I Cu  HNO 3  Cu (NO 3 )2  NO 2  H 2 O (Skeleton equation)

Step: II writing the oxidation number of all the atoms.
0 1 5  2 2 5 2 4 2 1 2
Cu  H N O 3  Cu ( N O 3 )2  N O 2  H 2 O
Step: III Change in oxidation number has occurred in copper and nitrogen.
0 2
Cu  Cu (NO 3 )2 ......(i)

25
 5 4
H N O3  N O2 ......(ii)
Increase in oxidation number of copper = 2 units per molecule Cu
Decrease in oxidation number of nitrogen = 1 unit per molecule HNO3
Step: IV To make increase and decrease equal, equation (ii) is multiplied by 2.
Cu  2 HNO 3  Cu (NO 3 )2  2 NO 2  H 2 O
Step: V Balancing nitrate ions, hydrogen and oxygen, the following equation is obtained.
Cu  4 HNO 3  Cu (NO 3 )2  2 NO 2  2 H 2 O
This is the balanced equation.

(2) Ion-electron method (half reaction method)

The method for balancing redox-reactions by ion electron method was developed by Jette and LaMev
in 1927. It involves the following steps

(i) Write down the redox reaction in ionic form.

(ii) Split the redox reaction into two half reactions, one for oxidation and other for reduction.
(iii) Balance each half reaction for the number of atoms of each element. For this purpose,

(a) Balance the atoms other than H and O for each half reaction using simple multiples.
(b) Add water molecules to the side deficient in oxygen and H+ to the side deficient in hydrogen.
This is done in acidic or neutral solutions.
(c) In alkaline solution, for each excess of oxygen, add one water molecule to the same side and
2OH– ions to the other side. If hydrogen is still unbalanced, add one OH– ion for each excess
hydrogen on the same side and one water molecule to the other side.

(iv) Add electrons to the side deficient in electrons as to equalize the charge on both sides.
(v) Multiply one or both the half reactions by a suitable number so that number of electrons
become equal in both the equations.
(vi) Add the two balanced half reactions and cancel any term common to both sides.

The following example illustrate the above rules

Step: I I 2  OH   IO3  I   H 2 O (Ionic equation)
Step: II Splitting into two half reactions, I 2  OH   IO3  H 2 O ; I2  I 
(Oxidation half reaction) (Reduction half reaction)

Step: III Adding OH ions, I 2  12OH  2 IO3  6 H 2 O


Step: IV Adding electrons to the sides deficient in electrons,

26
 I 2  12OH   2 IO3  6 H 2 O  10 e  ; I 2  2e   2 I 
Step: V Balancing electrons in both the half reactions.
I 2  12OH   2 IO3  6 H 2 O  10 e  ; 5 [I 2  2e   2 I  ]
Step: VI Adding both the half reactions.
6 I 2  12OH   2 IO3  6 H 2 O  10 I  ; Dividing by 2, `
3 I 2  6 OH   IO3  5 I   3 H 2 O

6. Autoxidation.

(1) Turpentine and numerous other olefinic compounds, phosphorus and certain metals like Zn and Pb
can absorb oxygen from the air in presence of water. The water is oxidized to hydrogen peroxide. This
phenomenon of formation of H2O2 by the oxidation of H2O is known as autoxidation. The substance
such as turpentine or phosphorus or lead which can activate the oxygen is called activator. The activator
is supposed to first combine with oxygen to form an addition compound, which acts as an autoxidator
and reacts with water or some other acceptor so as to oxidize the latter. For example;
Pb  O 2  PbO 2 PbO 2  H 2 O  PbO  H 2 O 2
(activator ) (autoxidat or) (acceptor )

(2) The turpentine or other unsaturated compounds which act as activators are supposed to take up
oxygen molecule at the double bond position to form unstable peroxide called moloxide, which then
gives up the oxygen to water molecule or any other acceptor.
RCH  CHR  O 2  RHC CHR
O O
RHC CHR  2 H 2 O  RCH  CHR  2 H 2 O 2
O O
2 KI  H 2 O 2  2 KOH  I 2

The evolution of iodine from KI solution in presence of turpentine can be confirmed with starch solution
which turns blue.

(3) The concept of autoxidation help to explain the phenomenon of induced oxidation. Na 2 SO 3 Solution
is oxidized by air but Na 3 AsO 3 solution is not oxidized by air. If a mixture of both is taken, it is observed
both are oxidized. This is induced oxidation.
Na 2 SO 3  O 2  Na 2 SO 5

27
Moloxide

Na 2 SO 5  Na 3 AsO 3  Na 3 AsO 4  Na 2 SO 4
Na 2 SO 3  Na 3 AsO 3  O 2  Na 2 SO 4  Na 3 AsO 4

7. Disproportionation.

One and the same substance may act simultaneously as an oxidizing agent and as a reducing agent with
the result that a part of it gets oxidized to a higher state and rest of it is reduced to lower state of
oxidation. Such a reaction, in which a substance undergoes simultaneous oxidation and reduction is
called disproportionation and the substance is said to disproportionate.

Following are the some examples of disproportionation,

increase
decrease

1 0 5 7 1
(1) H 2 O2  H 2 O 2  H 2 O  O 2 (2) 4 K Cl O3  3 K Cl O4  KCl
–1 –2
increase
decrease
decrease decrease

0 1 3
(3) 4 P  3 NaOH  3 H 2 O  3 NaH 2 PO 2  PH 3 (4)
0 1 5
3 Cl 2  6 NaOH 

hot
5 Na Cl  Na ClO 3  3 H 2 O
increase increase
(conc.)

28
8. Important applications of redox-reactions.

Many applications are based on redox reactions which are occurring in environment. Some important
examples are listed below;
(1) Many metal oxides are reduced to metals by using suitable reducing agents. For example Al 2 O 3 is
reduced to aluminum by cathodic reduction in electrolytic cell. Fe 2 O 3 is reduced to iron in a blast furnace
using coke.
(2) Photosynthesis is used to convert carbon dioxide and water by chlorophyll of green plants in the
presence of sunlight to carbohydrates.
6 CO 2(g)  6 H 2 O(l)    C 6 H 12 O 6(aq.)  6 O 2 (g)
Chlorophyll
Sunlight
In this case, CO 2 is reduced to carbohydrates and water is oxidized to oxygen. The light provides the
energy required for the reaction.

(3) Oxidation of fuels is an important source of energy which satisfies our daily need of life.
Fuels  O 2  CO 2  H 2 O  Energy
In living cells, glucose C 6 H 12 O 6  is oxidized to CO 2 and H 2 O in the presence of oxygen and
energy is released, C 6 H 12 O6 (aq.)  6 O 2 (g)  6 CO 2 (g)  6 H 2 O(l)  Energy

(4) The electrochemical cells involving reaction between hydrogen and oxygen using hydrogen and
oxygen electrodes in fuel cells meet our demand of electrical energy in space capsule.
(5) Respiration in animals and humans is also an important application of redox reactions.

29