REDOX REACTION

“Where there is oxidation, there is always reduction –Chemistry is essentially a study of redox systems.”

INTRODUCTION
Chemical Reaction: is the process which leads to the transformation of one set of
chemical substances to other substances. Many chemical reactions involve transfer of electrons from one
chemical substance to another these electron transfer reaction are termed as oxidation- reduction or
Redox reaction.
 Oxidation and reduction reactions are complementary to each other.

Oxidation: There are number of ways to define oxidation:

(i) Oxidation is a process which involves addition of oxygen.

(ii) Removal of hydrogen

e.g., H2S + Cl2 → 2HCl + S (H2S is oxidized to s)
(iii) Addition of non-metal / electronegative element
e.g., Mg + F2 → MgF2 (Mg is oxidized)
2Na + Cl2 → 2NaCl (Na is oxidized)
(iv) Removal of metal / electropositive element.
e.g., 2KI + H2O2 → 2KOH + I2 (KI is oxidized to I2 with the removal of K)

(v) Increase in positive valency

e.g., Fe+2 → Fe+3 + e-
(vi) Loss of electron by an tom or species (also known as de-electronation)

(vii) Increase in oxidation number

𝑀𝑔0  𝑀𝑔2+ (From 0 to + 2)
[Fe2+ (CN)6 ]4−  [Fe3+ (CN)6 ]3− (From +2 to +3)
2𝐶𝑙 − 𝐶𝑙2 (From –1 to 0)

Reduction: is defined as a process which involves

(i) Addition of hydrogen.
e.g., Cl2 + H2 → 2HCl (Chlorine is reduced to HCl)
(ii) Removal of oxygen.
e.g., CuO + C → Cu + CO ( CuO is reduced to Cu)
(iii) Addition of metal / electropositive element

(iv) Removal of non-metal / electronegative element.

(v) Decrease in positive valency

e.g., Sn+4 + 2e- → Sn+2
(vi) Gain of e- by an atom or species.(also known as electronation)

(vii) Decrease in oxidation number

𝑀𝑔2+  𝑀𝑔0 (From + 2 to 0)

[Fe3+ (CN)6 ]]3−  [Fe2+ (CN)6 ]]4− (From +3 to +2)
Difference between Oxidation and Reduction:

Sr.No. Oxidation Reduction

1. Addition of oxygen to an element or compound Addition of hydrogen to an element or compound
or Removal of hydrogen from a compound or Removal of oxygen from a compound
2. Oxidation is loss of e- by an atom , ion or Reduction is gain of e- by an atom , ion or
molecule molecule
3. It involves increase in oxidation number It involves decrease in oxidation number
4. Oxidation is caused by a oxidizing agent Reduction is caused by a reducing agent.
5. It is also known as De-electronation It is also known as electronation
6. Ex. Fe+2 → Fe+3 + e- Ex. Sn+4 + 2e- → Sn+2

Note: Electro negativity is a measure of the tendency of an atom to attract a bonding pair of
electrons.
 Applying the classical definition of oxidation and reduction can be tricky sometime.
Refer the example given in the next page

Oxidizing agent:
is a chemical substance which can accept two or more electron and causes oxidation of
other substance.

 It is also known as oxidant and is acceptor of e-.

 It involves decrease in oxidation number of Oxidant.
 Non metals are oxidizing agent because they accept e- being more electronegative

Imp Oxidant:
 Molecules of high electronegative e.g., O3, O2, & halogens (F is the strongest oxidizing agent).
 Oxides of few elements e.g., Mgo , Cuo, CrO3, CO2 , P4O10 etc.
 Compound having element in higher O.S. (oxidation state)
e.g., KMnO4, Na2Cr2O7, K2Cr2O7, HClO4, H2SO4, HNO3, KClO3, Ce(SO)4 , H2O2, FeCl3 , SO3 etc.
 Reducing agent:
is a chemical substance which can give one or more electron and causes reduction
of other substance.

 It is also known as reductant and is donor of e-

 It involves increase in oxidation number of reductant.
 All metals are reducing agent because they donate e- being more electropositive

Imp Reductant:

 All metals e.g. Na, Zn, Fe, Al, etc. (Lithium is the strongest reducing agent in solution.)
 A few non-metals e.g. C, H2, S etc.
 Hydracids : HCl, HBr, HI, H2S etc.
 A few compounds containing an element in the lower oxidation state (ous).
Example: , FeCl2, FeSO4, SnCl2 ,Hg2Cl2 ,Cu2O etc.
 Metallic hydrides e.g. NaH, LiH etc.
 Organic compounds like HCOOH and (COOH)2 and their salts, aldehydes, alkanes etc.
 Hypo prefix indicates that central atom of compound has the minimum oxidation state
so it will act as a reducing agent.
Example : H3PO2 (hypophosphorous acid).

Oxidising agent: Reducing agent:

 Itself gets reduced  Itself gets oxidized
 High oxidation number(O.N.)  Low oxidation number(O.N.)
 Electron acceptor  Electron donor

Redox Reaction:
The reactions in which oxidation and reduction reaction occur simultaneously
are called Redox reaction

 When substances loses electrons, undergoes oxidation and its oxidation number increases Hence,
it acts as reducing agent.

 When substances gains electrons, undergoes reduction and its oxidation number decreases Hence, it
acts as oxidizing agent.

For example:
Loss of electron

Gain of electron
Oxidation: Zn → Zn2+ + 2e-
Reduction: Cu2+ + 2e- → Cu
Electron transfer reaction is also known oxidation-reduction (Redox) reaction.
In Redox reaction,

No. of electron gain = no. of electron lost

Increase in O.N = Decrease in O.N

Keywords:

OIL = Oxidation is loss RIG = Reduction is gain

OR
LEO = Loss of electron is Oxidation GER = Gain of electron is Reduction

Tips for the identification of oxidising and reducing agents

1) If an element is in its highest possible oxidation state in a compound, the compound can function as an
oxidising agent.
Example: KMnO4 , K2CrO7, HNO3 , H2SO4 , HClO4 etc.
2) If an element is in its lowest possible oxidation state in a compound, the compound can function only
as a reducing agent.
Example: H2S, H2C2O4 , FeSO4 , Na2 S2 O3 , SnCl 2 etc.
3) If an element is in its intermediate oxidation state in a compound, the compound can function both as
an oxidising agent as well as reducing agent.
Example: H2O2 , H2SO3 , HNO2 , SO2, FeCl2 etc.

Note: There are some compounds also which can work both oxidising agent and reducing
agent. e.g. H2O2, 𝐒𝐎𝟐

Oxidation number or Oxidation state:

Charge on an atom produced by donating or accepting electrons is
called oxidation number or oxidation state.
OR

It is the apparent charge assigned to an atom of an element in a molecule or in a ion.

Distinguish between Valency and Oxidation number:

Sr.no. Valency Oxidation number

1. Valency is the combining capacity of an It is apparent charge assigned to an atom of an
element. element in a molecule or in a ion.
2. It is number only. It has no plus or minus It may be positive or negative number.
sign with it.
3. It cannot be zero except noble gases. It may be zero.
4. It is always a whole number. It may be whole number or in fraction.

Nomenclature:
Sometimes an element forms two monoatomic cations & represents different O.S.,
the two ions are distinguished by using the ending-ous and ic.

 The suffix – ous is used for the cation with lower oxidation state and and the suffix – ic is used for the
cation with higher oxidation state.

For example : Cu+ (oxidation number +1) cuprous Cu2+ (oxidation number +2) cupric

Stock Notation:
The oxidation number/state of a metal in a compound is sometimes presented
according to the notation given by German chemist, Alfred Stock.

 It is popularly known as Stock notation.

 According to this, the oxidation number is expressed by putting a Roman numeral representing the
oxidation number in parenthesis after the symbol of the metal inthe molecular formula.
 Rules for assigning oxidation number:

1. O.N. of all the elements in their elemental and allotropic form is taken as zero.
For example: Oxidation state of elements in 𝐶𝑙2 , 𝑂2 , 𝑃4 , 𝐻2 , 𝑍𝑛(𝑆) , 𝐹𝑒(𝑠) , 𝑆8 , 𝑂3 , is zero.
2. Oxidation state of alkali metals (Group-I elements) is +1, While alkaline earth metals (Group II) have +2
oxidation states.
3. O.N. of an atom in a monoatomic ion is equal to charge on it.
Eg. 𝐵𝑎2+ 𝐶𝑟 3+ 𝑆 2−

+2 +3 -2

4. O.N. of oxygen is -2 in most of the compound except in

In ozonides e.g., KO3 O.N. of oxygen is -1/3 .

Hydrogen peroxide structure: H−O − O − H

-1 -1

In case of oxygen difluoride (O𝐹2 ) O.N. of oxygen is +2.

While in case of O2F2 (dioxygen difluoride) O.N. of oxygen is +1.

5. The O.N. of hydrogen is +1 but when bonded with metal its oxidation state is -1
Eg. [H − O − H] Li – H H −Ca − H

+1 -1 -1

6. The O.N. of F is always -1 in all of its compounds. Cl, Br, I also have -1 oxidation state but if these
halogens (Cl, Br, I) are bonded to oxygen then O.N. is +1
Eg. H−Cl K−Br H−O − Cl Na-O-Cl

-1 -1 +1 +1

In interhalogen compounds, the more electronegative halogens get the O.N. of –1.
For example: in BrCl3 the oxidation number of Cl is –1 while that of Br is +3.

7. Oxidation number of a metal in carbonyl complex and amalgam is always zero.

Example: Ni has zero oxidation state in [𝑁𝑖(𝐶𝑂)4 ]

8. O.N. of nitrogen is –3 when it is bonded to less electronegative atom as in NH3 but in NF3,
O.N. of N is + 3 as it is bonded to more electronegative.

9. The Algebraic sum of the oxidation state of all atoms in neutral molecule is equal to zero.
Eg. NaCl
O.N. of Na + O.N. of Cl = 0

10. The Algebraic sum of the oxidation state of all atoms in polyatomic ion is equal to charge on it.
Eg. SO42-
O.N. of S + 4 x O.N. of oxygen = -2

Note:

 If there is a covalent bond between two same atoms then oxidation numbers of these two atoms
are zero. Because electronegative difference is 0.
A: A or A – A → A* + A*
For example, Oxidation number of Cl in Cl2, O in O2 and N in N2 is zero.
 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.

 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.

Higher oxidation of element = Group no. or no. of electron in valence shell

Lower oxidation of element = 8- Group no. or no. of electron in valence shell

 Variable oxidation number is most commonly shown by p-block elements as well as transition
elements.
Transition elements: for e.g., Fe(+2, +3) ; Cu(+1, +2) ; Mn (+7,+6,+5,+4,+3,+2,+1) etc.
P-block elements: for e.g., Sn(+2, +4) ; Sb(+3, +5) ; As(+3, +5) etc.

Common oxidation numbers

Group Number Outer shell configuration
except zero in free state
IA 1 ns1 +1
II A 2 ns2 +2
13
III A ns2np1 +3, +1
(Boron Family)
14 +4,+3,+2,+1, –1, –2, –3, –4
IV A ns2np2
(Carbon family) Range( +4 to -4)
15 +5,+3,+1, –1, –3
VA ns2np3
(Nitrogen family) Range (-3 to +5)
16 +6,+4,+2,–2
VI A ns2np4
(Oxygen family) Range (-2 to +6)
17 +7,+5,+3, +1, –1
VII A ns2np5
(Halogen family) Ramge(-1 to +7)

Formula for calculating the O.N. of Carbon in organic compound which contains C, H, O.

2 × 𝑛𝑜. 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛 − 𝑛𝑜. 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛

Oxidation no. of ‘C’ =
𝑛𝑜. 𝑜𝑓 𝑐𝑎𝑟𝑏𝑜𝑛

Calculation of oxidation number:

For Example: i] S2O2−

3

Solution: The sum of the oxidation numbers of all atoms is -2

2 x oxidation number of S + 3 x oxidation number of O = -2

2 𝑥 + 3 x (-2) = -2 ⇒ 2 𝑥 + (-6) = -2
 2 𝑥 = -2 + 6  2 𝑥 = +4
 𝑥 = +2

Therefore Oxidation number of S is +2

 ii] S4O2−
6
Solution:
The sum of the oxidation numbers of all atoms is -2
4 x O.N. of Sulphur + 6 x O.N. of Oxygen = -2
 𝑥 + 6 x (-2) = -2
4
 4 𝑥 + (-12) = -2
 4 𝑥 = -2 + 12
 4𝑥 = +10

 𝑥 = +2.5 Therefore Oxidation number of S is +2.5

Question for practice

Find the oxidation number of underline species in the following compound or ion.
i. PF6− ii. NaIO3 iii. K2Cr2O7 iv. ClF3 v. NaBH4
vi. Mn(OH)3 vii. C2H5OH viii. K4 [Fe (CN)6]

N-atom belongs to v group in the periodic table therefore as per rule its oxidation number may vary from –3
to +5

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 following cases. In these cases, to determine the exact oxidation
number of element we need to take help from the structures of the molecules. Some special cases are discussed
as follows:

CrO5(Blue perchromate)

Oxidation number of Cr in CrO5

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.

In Cro5, one of the oxygen is doubly bonded to Cr(Cr= O) and has been
assigned an oxidation number of -2, whereas four of the oxygen have
peroxo linkage(O−O) and should be assigned -1 oxidation number.

Therefore, the evaluation of o.n. of Cr should be made as follows

x + 1 × (– 2) + 4 (–1) = 0

(for Cr) (for Cr= O) (for O–O)

x=+6

H2SO5 (Caro's Acid)

H2S2O8(Marshall’s Acid)
Na2S2O3 (Sodium thiosulfate)

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.

Na2S4O6 (Sodium tetrathionate)

The two S-atoms which are linked to each other have oxidation number
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.

Oxidation number of chlorine in CaOCl2

(bleaching powder) -1
In bleaching powder, Ca(OCl)Cl, the two Cl atoms are in different +2
oxidation states i.e.
-1
one Cl– having oxidation number of –1 and
the other as OCl– having oxidation number of +1.
-2
C2O3 Carbon suboxide

The carbon in the middle has 0oxidation state, whereas the carbons
bonded to oxygen have a +2 oxidation state.

On average, the oxidation state at carbon is [(2 + 2 + 0)/3] = +1.3.

On the other hand, both oxygens have an oxidation state of -2.

Br3O8 (Tribromine Octoxide )

Each of the two terminal Bromine atoms has 3 oxygen atoms attached to
it. So, the bromine atom on the terminals will have an oxidation state of
+6. The bromine atom in the middle has 2 oxygen atoms attached to it. It
will have an oxidation state of +4.

Since, the three bromine atoms have different oxidation states in the
same compound, the average of the oxidation states is calculated and
considered as the oxidation state of the atom in the compound. Let oxidation of Br be x

3x+8 (-2)=0
Thus, the oxidation state of Bromine in Br₃O₈ is 16/3.
3x-16=0

3x= 16

x= 16/3
Pb3O4
Let oxidation of Pb be x

3x+4 (-2)=0

This is because the net charge on the given compound is 0 and oxidation
state of oxygen is considered as -2

So, x=+8/3

Oxidation of Pb in PbO is +2
Oxidation of Pb in PbO2 is +4

NOCl

Fe3O4