STUDY CENTRE

CHAPTER - 05
REDOX REACTIONS

EARLIER CONCEPT OF OXIDATION

Oxidation is the process of addition of oxygen or any electronegative element or group or removal of
hydrogen or any electropositive element of group.

Eg : 2Mg + O 2 ¾¾
® 2MgO
2FeCl 2 + Cl 2 ¾¾
® 2FeCl3
H 2S + Cl 2 ¾¾
® 2HCl + S
K 2 MnO4 + O3 + H 2 O ¾¾
® KMnO 4 + KOH

Reduction is the process of addition of hydrogen or any electropositive element or group or removal of
oxygen or any electronegative element or group.
Eg : H 2 + Cl 2 ¾¾
® 2HCl

2HgCl 2 + SnCl 2 ¾¾
® Hg 2Cl 2 + SnCl 4

ZnO + C ¾¾
® Zn + CO

2FeCl3 + H 2S ¾¾
® FeCl 2 + 2HCl + S
ELECTRONIC CONCEPT
According to the electronic concept, oxidation involves loss of electrons or removal of electrons.

Eg : MnO 24 - ¾¾
® MnO 4- + 1e -
Fe 2+ ¾¾
® Fe3+ + 1e -
® Mg 2+ + 2e -
Mg ¾¾

Here MnO 24 - , Fe 2+ and Mg are donating electrons (electron donor) and are called Reducing agents.
\ Reducing agent is electron donor or we can say that reducing agents are getting oxidised. Similarly
reduction involves gain of electrons or addition of electrons.

Eg : Cl 2 + 2e ¾¾
® 2Cl-
-

Cu 2+ + 1e- ¾¾
® Cu +
Sn 4+ + 2e - ¾¾
® Sn 2+

Cl2 , Sn 4+ and Cu 2 + are accepting electrons and are called oxidising agents.

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\ Oxidising agent is electron acceptor. Hence oxidising agents are getting reduced. We have another
concept for oxidation and reduction, called oxidation number concept.
Oxidation Number concept
Oxidation number is the number of electrons lost or gained when an atom in the free state changes to
the combined state.
OR
It is the positive or negative charge allotted to each atom in a compound assuming all the bonds are
ionic bonds.
In FeCl3, the oxidation number of iron is +3 and that of chlorine is –1.
+3 -1 +1 +5 -2 +1 +4 -2
Eg : Fe Cl3 , H N O 3 , Na 2 C O 3 etc
It is also called oxidation state.
Rules for oxidation number
1. The oxidation number of all elements in free state is zero

Eg : O.N of H atom in H 2 = 0
O.N of O atom in O3 = 0
O.N of P atom in P4 = 0
O.N of S atom in S8 = 0
2. The oxidation number of hydrogen is +1 in usual compounds and –1 in metallic hydrides (ionic hydrides)
+1 +1
Eg : NH 3+1 , CH 4+1 , H 2 O, H 2 SO 4 , NaH -1 , CaH 2-1

-2 -2 -2 -2
3. The oxidation number of oxygen is –2 is usual compounds, SO3 , P2O 5 , Cl 2O 7 , HClO 4

1 -1
–1 in peroxides, H 2 O 2 , BaO 2 and -
-1 -1
in superoxides KO 2 2
2
Oxygen has positive oxidation in oxyfluorides.

æ +1 +2
ö
O
ç 2 2F , O F2 ÷
è ø
4. Fluorine is the most electronegative element with –1 oxidation state.
5. In compounds, the O.N. of Group I metals is +1 and that of Group-II metals is +2.
+1 +1
Na 2 SO 4 , K 2 CO3
+2 +2 +2
Ba Cl2 , Sr SO 4 , Mg CO3
6. The O.N. of a compound is zero and that of an ion is equal to the charge on the ion
7. 1) The algebraic sum of O.N. of all atoms in a neutral compound is zero
2) The algebraic sum of O.N. of all atoms in an ion is equal to the charge on the ion
8. O.N. of covalent bond
1) Each covalent bond contributes one unit for O.N
2) Covalently bonded atoms with less electronegativity acquire positive O.N. While other atom with
more electronegativity acquire negative O.N.
9. O.N. of co-ordinate bond

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1) Give +2 value of O.N. to the atom from which coordinate bond is directed to a more electronegative
atom. +2 to donor atom and –2 to acceptor atom.
2) If co-ordinate bond is directed from a more electronegative atom to a less electronegative atom,
contribution of coordinate bond is neglected.
Oxidation/Reduction in terms of O.N
Oxidation is the process in which O.N. increases. Reduction is the process in which O.N. decreases.
0 +4 -2 +1 +6 -2 +2 +6 -2 +1 -2
Consider the reaction: P b + Pb O 2 + 2 H 2 S O 4 ¾¾
® 2 Pb S O 4 + 2 H 2 O
The O.N. of Pb increases from 0 to +2 \ Pb is oxidised to PbSO4.
The O.N. of Pb in PbO2 decreases from +4 to +2. \ PbO2 is reduced to PbSO4. Such reactions in
which oxidation and reduction occur simultaneously is called a Redox reaction.
Here Pb is the reducing agent and PbO2 is the oxidising agent.
Neutralisation reactions and precipitation reactions are not redox reactions because there is no change
in oxidation number.
3. Disproportionation reaction
The same element in the same oxidation state is simultaneously oxidised and reduced.

(O)

+1 -1 +1 -2
2H 2 O 2 2H 2O + O 2

(R)
(O)

0 -1
hot, conc. + +5
3Cl2 + 6 NaOH 5NaCl NaClO 3 + 3H 2 O

(R)

Reducing agent and oxidising agent

Reducing agent is an electron donor. Hence after oxidation, the O.N. of the reducing agent increases.
Oxidising agent is electron acceptor. Hence after reduction, the oxidation number of oxidising agent
decreases.
+2 +3 +4 +2
SnCl2 + 2FeCl3 SnCl4 + 2FeCl2
Here SnCl2 is the reducing agent and FeCl3 is the oxidising agent.
Exercise :
Determine the oxidation number of
1) P in NaH2PO2
Let O.N. of P = x
\ 1 + 2 + x – 4 = 0; \ x = +1

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2) Cr in Cr2 O72 -
2x – 14 = –2
2x = 12
\ x = +6
RANGE FOR OXIDATION NUMBER
There is a range for oxidation number

Element Oxidation number Range

S -2, 0, +1, +4, +6 -2 to +6

N -3, -2, -1, -1/3, 0, +1, +2, +3, +4, +5 -3 to +5

Cl -1, 0, +1, +3, +4, +5, +7 -1 to +7

H -1, +1 -

P -3, 0, +1, +3, +5 -3 to +5

O -2, -1, -1/2, 0, +1, +2 -2 to +2

C -4, -3, -2, -1, 0, +2, +3, +4 -4 to +4

Cr +3, +6 -

Mn +2, +8/3, +3, +4, +6, +7 +2 to +7

Si -4, +4 -

Fe +8/3, +2, +3 -

Os +8 -

Xe +6 -

Exceptional cases of evaluation of oxidation numbers

The oxidation number is evaluated based on the structure using the concept of chemical bonding.
1. CrO5 (chromium pentoxide or blue per chromate)
By usual method, the oxidation of Cr is +10. But the maximum oxidation of Cr is +6 only. (Cr has only
5e– in 3d orbitals and 1e– in 4s orbital). This is because 4, oxygen atoms are in peroxide linkage.

O O
Cr x + 1´ -2 + 4 ´ -1 x = +6 = 0
O O x - 2 - 4 = 6 \x = +6
O

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2. S in H2SO5 (Peroxomonosulphuric acid, Caro’s acid)

Peroxide linkage
O

H O S O O H

2 ´ +1 + x + 3 ´ -2 + 2 ´ -1 = 0 ; \ x = +6
3. S in H2S2O8 (Peroxi disulphuric acid, Marshall’s acid). It is also has a peroxide linkage

O O

H O S O O S O H

O O

2 ´ +1 + 2 ´ + x + 6 ´ -2 + 2 ´ -1 = 0
for H for S for O for O - O

\ 2x = +12 or x = +6
4. S in Na2S4O6 (Sodium tetra thionate)
+10
2 + 4x - 12 = 0 \ 4x = 10;\ x = = 2.5
4
Fraction : average O.N
-2 -2
O O
+1 -2 0 0 -2 +1
+5 +5
Na O S S S S O Na

O O
-2 -2

5. S in Na2S2O3 (Sodium thiosulphate)

-2
S
+1 -2
+6 -2 +1
Na O S O Na

O
-2

The donor S atom is in +6 and acceptor S atom in –2

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6. C in C3O2

-2 +2 0 +2 -2
O C C C O

7. Cl in CaOCl2 (Bleaching powder)

-2
O Cl+1
+2
Ca one Cl in +1 state and other in –1 state
Cl-1

To predict whether the compound is oxidising agent or reducing agent

1. If the central atom of the compound is in the highest oxidation state, it will act only as oxidising
agent.

+7 +5 +6 +7
Eg : KMnO4, HNO3 , H2SO4, HClO
4

2. If the central atom is in the lowest oxidation state, it will act only as reducing agent.

Eg : SnCl2, FeCl2, HI, NH3, H2S

3. If the central atom is in an intermediate oxidation state, it will act as both oxidising agent and
reducing agent

Eg : H2SO3, HNO2, H2O2, SO2

EQUIVALENT WEIGHT

Equivalent weight of a substance (oxidant or reductant) is equal to molecular weight divided by

number of electrons lost or gained by one molecule of a substance in a redox reaction.

Molecular weight
Eq. wt. of O.A. =
No.ofe gained by one molecule (n - factor or valence factor)
-

Molecular weight
Eq.wt.of. R.A. =
No.ofe lost by one molecule (n - factor or valence factor)
-

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BALANCING OF REDOX REACTIONS

I. Ion-electron method (half reaction method)
i. Write down the reaction in ionic form.
ii. Split it into 2 half reactions (oxidation and reduction)
iii. To balance each half reaction
a. Balance the other atom except H and O
b. Balance the O.N. by adding e–
c. Balance the charge by adding H+ for reactions in acidic medium and OH– for reactions in
basic medium
d. Balance H and O by adding H2O molecules.
iv. Make the no.of electrons equal in both half reactions.
v. Add the 2 balanced half reactions and cancel the common term if any
II. Oxidation number method
i. Write down the reaction in ionic form, and mark the oxidation and reduction
ii. Make the number of atoms equal other than H and O
iii. Find the increase in O.N. and decrease in O.N.
iv. Make the increase and decrease equal. (by multiplication with suitable integer)
v. Balance charge by adding H+ for reactions in acid medium and OH– for reactions in basic medium.
vi. Balance H and O by adding H2O molecules.
REDOX TITRATIONS
Titrations between oxidising agent and reducing agent
I. Permanganometry
KMnO4 is used as O.A. (in acidic medium) H2C2O4 (oxalic acid) or Mohr’s salt is the R.A. KMnO4 itself
acts as a self indicator. End point is the appearance of a permanent pale pink colour.
II. Dichrometry
K2Cr2O7 is used as O.A. (in acidic medium) FeSO4 in the R.A.
External indicator : Potassium ferricyanide . At the end point the prussian blue colour changes.
III. Iodimetry
Estimation of a R.A. using standard I2 solution is called iodimetry.

I 2 + 2Na 2S2 O 3 ¾¾
® 2NaI + Na 2S4 O 6
Starch is used as indicator. At the end point the blue colour disappears.
IV. Iodometry
Here I2 is produced by a reaction between O.A. and KI solution. The I2 liberated is titrated against
Na2S2O3 solution using starch as indicator.

2CuSO 4 + 4KI ¾¾
® 2CuI 2 + 2K 2SO 4 + I2

I 2 + 2Na 2S2 O 3 ¾¾
® 2NaI + Na 2S4 O 6
By this method, the O.A. can be estimated.
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CHAPTER - 06
CHEMICAL THERMODYNAMICS

The branch of chemistry which deals with the study of different forms of energy and their
interconversions is called thermodynamics.
BASICS OF THERMODYNAMICS
System and surroundings
The part of the universe under our experimental observation is called the system. The remaiing part
which exchange energy and matter with the system is called the surrounding.
Thus system + surroundings ® universe
The system is separated from surroundings by real or imaginary boundaries.
If the physical properties and chemical compositions are same throughout the system, the system is
called as homogenous. Otherwise the system is heterogenous.
Different types of systems
1. Open system : A system which can exchange energy and matter with the surroundings is called an
open system.
Eg : Hot water placed in an open beaker
2. Closed system : A system which can exchange only energy but not matter with the surroundings is
called a closed system.
Eg : Hot water placed in a closed beaker.
3. Isolated system : A system which can exchange neither energy nor matter with the surroundings is
called an isolated system.
Eg : Hot water placed in a thermoflask
MACROSCOPIC PROPERTIES OF A SYSTEM
The properties which arise due to the bulk behaviour of matter in the system are called macroscopic
properties.
Eg : Mass, Volume, Energy etc.
1. Extensive properties : The properties which depends upon the amount of substance present in the
system are called extensive properties. Eg : Mass, Volume, Energy etc.
2. Intensive properties : The properties which are independent of the amount of substance present in
the system and depends only on the nature of the substance is called intensive property.
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