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Stoichiometry - II
Analysis of Redox Reaction
There are two ways of analysing and solving the stoichiometric problems based on redox reactions :
(a) One is to balance the redox reaction and then approach the problem like a simple balanced chemical
equation using the concept of moles (Application of mole concept as done earlier).
(b) Second, use the concept of gram equivalents (or milli equivalents) as used in neutralisation.
Here gmeq. (or meq) of oxidising agent = gmeq. (or meq) of reducing agent.

First we will learn how to analyse a given redox reaction and different methods used for
balancing it. Then as the chapter progress, you will learn how to proceed while solving
numerical problems based on the redox analysis.

OXIDATION - REDUCTION Section - 1

Oxidation is a process that involves the loss of electrons by the atoms or ions.
Reduction is a process that involves the gain of electrons by the atoms or ions.
Any reaction, in which the electrons are exchanged between atoms or ions, represents simultaneous pro-
cess of oxidation and reduction and is called as a Redox Reaction.
In a Redox Reaction, the species that loses electron (i.e., gets oxidised) is known as reducing agent or
reductant, (since it causes reduction of other species), the species which accepts electrons from reductant
(i.e., gets reduced) is known as oxidising agent or oxidant (as it causes oxidation of other species).

Illustrating the concept :

Mg + Zn2+ 
 Mg2+ + Zn is a redox reaction.

Oxidation : Mg0  Mg2+ + 2e



Reduction : Zn2+ + 2e  Zn0


Mg causes reduction of Zn2+, so it is Reductant.
Zn2+ causes oxidation of Mg, so it is Oxidant.

Note : A redox reaction involves two half reactions: Oxidation half reaction and Reduction half reaction

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Now, a new concept of Oxidation Number and Oxidation State is being introduced in order to study
oxidation and reduction reactions (redox reactions) in a much better way.

Oxidation Number (O.N.) : It refers to the total charge on all atoms of same kind in a compound.
Oxidation State (O.S.) : It refers to the charge per atom of all atoms of same kind in a compoun.
Oxidation state, many a times, is alos referred to as Oxidation Number (Refer to NCERT Book).
This means, oxidation number of an element in a compound is equal to oxidation state of that element
multiplied by total atoms of that element in particular compound.

(i) In ionic compounds, it is simply the charge on corresponding cation and anion which is expressed as
oxidation state of that partiular element. For example, oxidation state of potassium and chlorine in
potassium chloride (KCl) is simply +1 and –1 respectively as KCl is treated as K+ Cl–.

Refer to following examples where oxidation states are written above the atoms : .

+2 –1 +2 –2 +3 –1 +2 –2 +1 –1 +1+6 –2
MgCl2 CaS AlCl3 CaO NaF K2SO4

Note : (a) In MgCl2 and AlCl3, -1 is the oxidation state of Cl atom and its oxidation number is -2 and -3
respectively.
(b) In each of the cases, the sum of oxidation number of all atoms of all kinds is equal to zero (as the
compound is neutral).

(ii) In Covalent Compounds, it is not so easy to assign oxidation state of an atom. In order to simplify
the concept, we are going to define a set of rules which would enable us to assign oxidation state to
every element in any compound.

Rules for Assigning Oxidation State (O.S.) and Oxidation Number (O.N.) :
1. Any element in free state is assigned an oxidation state of zero (0). For example: O.S. of H, P, S, O,
Fe, Br, in H2, P4, S8, O2, Fe, Br2 is equal to 0.
2. The oxidation state of any cation or anion (of form A+ or B ) is equal to the magnitude of its charge.
For example: O.S. of Ca in Ca2+ = +2, O.S. of Al in Al3+ = +3, O.S. of Cl in Cl = 1 and so on.
3. (a) The algebraic sum of the oxidation number of all atoms in a neutral compound is equal to 0.

(b) The algebraic sum of the oxidation numbers of all atoms in an ion (like PO34 etc.) is equal to
the charge on the ion.

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4. The oxidation states of Alkali Metals (Group IA) is +1 in all of their compounds and that of Alkaline
Earth elements (Group IIA) is +2 in all of their compounds.
5. Hydrogen in almost all of its compounds is assigned an oxidation state of +1. The exception occurs
when hydrogen forms compounds with strong metals (metallic hydrides). For example : KH, NaH,
MgH2, CaH2 etc. In all of these, the oxidation state of hydrogen is 1.
6. Oxygen in almost all of its compounds is assigned an oxidation state of 2. In a class of compounds,
Peroxides, oxidation state of oxygen is 1, for example : H2O2, Na2O2 etc. Another exception is
1
OF2, where O.S. is +2. O2F2, where O.S. is +1 and KO2 in which O.S. is  .
2
7. Fluorine is most electronegative element and is assigned an O.S. of 1, in all its compounds. For
other halogens, O.S. is generally 1 except when they are bonded to a more electronegative halo-
gen or oxygen. O.S. of iodine in IF7 is +7, O.S. of chlorine in KClO3 is +5.

Concept of Fractional Oxidation States :

Fractional oxidation state is the average oxidation state of the element under examination and it means
that the element for which fractional oxidation state is realised is present in different oxidation states.
Structure of the species C3O2, Br3O8 and S4O62 reveal the following bonding situations :

The elements marked with asterisk in the above examples are exhibiting different oxidation state from the
rest of the atoms of the same element in each of the species. This means that in C3O2, two carbon atoms are
present in +2 oxidation state each, whereas the third one is present in zero oxidation state and the average
is 4/3. Likewise in Br3O8, each of the two terminal bromine atoms are present in +6 oxidation state and the
middle bromine is present in +4 oxidation state and the average is 16/3. In the same manner, in the species
S 4 O 62  is 2.5, whereas the reality being +5, 0, 0 and +5 oxidation number respectively for each sulphur..
Fe3O4, Mn3O4, Pb3O4 are some of the other examples of the compounds, which are mixed oxides having
the metal in fractional oxidation state. However, the oxidation states may be in fraction as in O 2 and O 2
where it is +1/2 and 1/ 2 respectively..

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Using all these rules, we can now assign oxidatizon states to almost all the elements in various compounds
and ions.
Try Yourself : Find the oxidation state of atoms (written in bold) in the following compounds.
SiO2, OF2, KClO3, HClO4, NH4+, Hg2O, Pb3O4, MnO2, C3H6Cl2, BO33, K2MnO4, Cr2O3,
CrO2Cl2, Mg3N2, N2O5, MgSiO3, Na2S2O3, S4O62, CaC2, H2C2O4, NH4NO3

Analysis of a Redox Reaction

Consider the following Redox Reaction :

CuSO4 + Pb  
 PbSO4 + Cu

1. Assign oxidation state to each atom.

+2 +6 2 0 +2 +6 2 0

Cu S O4 + Pb 
 Pb S O4 + Cu

Note : (i) O.S. of S, O remains same, i.e., neither of the two is oxidised or reduced (by inspection).
(ii) O.S of Pb and Cu2+ has changed from left to right.

Rewriting the equation as two equations (oxidation and reduction) as follows :

Reduction : Cu2+ + 2e 

 Cu0 (gaining 2e)
Oxidation :  Pb2+ + 2e
Pb0  (losing 2e)

Note : (i) O.S of Pb has increased from 0 to +2.

(ii) O.S of Cu2+ has decreased from +2 to 0.

We can now re-define oxidation and reduction as follows :

Oxidation is an increase in oxidation state and Reduction is a decrease in oxidation state.

Note : Pb is oxidised and causes the reduction of Cu2+. Pb is called as reductant. Cu2+ is reduced and causes the
oxidation of Pb. Cu2+ is called as oxidant.

Now an important aspect at this stage is to learn “How to balance the redox reactions”. So first we will learn
balancing the Redox Reactions.

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Balancing of Redox Reactions

For balancing of Redox Reactions, two methods are generally adopted :
(A) Oxidation Number Method
(B) Ion Electron (Half-Reaction) Method

(A) Oxidation Number Method :

While balancing a given reaction by this method, following steps are to be followed :
1. Assign oxidation state to each element (atom) on both sides of the equation and identify which
element has been oxidised and which reduced.
2. Write two oxidation and reduction reactions (two half reactions) separately involving only atoms.
Now balance the atoms on both sides of equation in each half reaction.
3. Balance charge on both sides by adding electrons to whichever side is deficient in electrons. (i.e.,
negative charge)
4. Add two half reactions together. How ? In doing this we want electrons to cancel from both sides. For
this, multiply the equations by appropriate coefficients so that number of electrons produced in oxidation
reaction equals to that used up in reduction reaction.
5. Now compare this balanced equation with original unbalanced equation. Here, notice whether the
given equation is a molecular equation or an ionic equation.
6. For molecular equation, to balance Oxygen (O) and Hydrogen (H), add required water to the side
deficient in H and check for Oxygen atoms on both sides. (They will be equal on both sides)
7. For ionic equation, apart from balancing O and H atoms, charge needs to be balanced. It depends
upon the medium in which the reaction is taking place : Acidic (containing H+ ions or any acid) or
Alkaline (containing OH ions or any base).
(a) In Acidic medium, count total charge on both sides and balance it by adding H+ ions to the
required side (i.e., to the side deficient in +ve charge). Finally add enough water molecules to
balance H and O atoms to the required side.
(b) In Basic medium, balance the charge by adding OH ions to the side with excess of +ve charge
and finally add required number of H2O molecules to the appropriate side to balance O and H.

(B) Ion Electron (Half-Reaction) Method

1. Identify the oxidation and reduction half reactions and write them separately in ionic form. Note that,
write whole of ion in half reaction (unlike the oxidation number method where only atoms undergoing
the change of state were taken).

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For example : Mn in MnO4 in acidic medium generally goes to MnSO4 or Mn2+

Write it like this : MnO4 

 Mn2+ (and not as Mn7+ 
 Mn2+ )
2. Balance each half reaction separately. This is done accordingly to the following procedure.
3. Balance all the atoms of both reactions except O and H.
4. Now first balance O and H atoms (unlike in first method) depending upon the medium of reaction.

Acidic Medium :
To balance O atoms add same number of water (H2O) molecules to the side deficient in O atoms.

MnO4 
 Mn2+ (acidic medium)

Illustration - 1 MnO4 
 Mn2+ + 4 H2O
Now to balance H atoms, add as many H+ ions required to the side deficient in H atoms (generally it is
equal to double the number of water molecules added to the other side while balancing O atoms).

MnO4 + 8 H+ 
 Mn2+ + 4 H2O

Basic Medium :
To balance O atoms, add same number of H2O molecules to the side having excess of O atoms and add the
double the number of OH ions to the other side (i.e., to the side deficient in O atoms).

NO3  
 NH4+ (basic medium)

NO3 + 3 H2O   NH4+ + 6 OH


Now to balance H atoms (if required), add same number of OH ions to the side in excess of H atoms and
then add same number of water molecules to the other side (i.e., the side deficient in H atoms).

NO3 + 3 H2O + 4 H2O 

 NH4+ + 6 OH + 4 OH

NO3 + 7 H2O 
 NH4+ + 10 OH

5. Now add electrons to the side deficient in negative charge in order to balance the charge on both
sides.

MnO4 + 8 H+ + 5e  
 Mn2+ + 4 H2O

NO3 + 7 H2O + 8e 

 NH4+ + 10 OH

These are balanced half reactions in acidic and basic medium respectively.

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6. Now add two half reactions together in such a manner that electrons from both sides cancel. So
multiply by coefficients so that number of electrons produced in oxidation equals the number of electrons
used in reduction (as done in oxidation number method step – 4).

Note : In this method we don’t have to calculate oxidation states as done in first method.

Illustration - 1 Balance the following reaction by Oxidation number and Ion electron method.

KMnO4 + H2SO4 + K2C2O4 

 MnSO4 + CO2 + K2SO4

SOLUTION :
Oxidation Number Method :
Follow the steps given below to balance the 2 Mn7+ + 5 C23+ 
 2 Mn2+ + 10 C4+
reaction given above :
Now compare this balanced equation with the
Assign O.S. to the atoms which are oxidised or molecular unbalanced equation as follows.
reduced. Note that O.S of O, K, H, S are same
on both sides. This is done by oral inspection. 2 KMnO4+ 5 K2C2O4 
 2 MnSO4+10 CO2
We’ll consider O.S of Mn and C on both sides. As the charge is balanced, now balance ‘K’ atoms
+7 +3 on both sides by adding 6 K2SO4 on right.
KMnO4 + H2SO4 + K2C2O4
2 KMnO4 + 5 K2C2O4 

 +2 +4
2 MnSO4 + 10CO2 + 6K2SO4

 MnSO4 + CO2
Now to balance SO42 ions on both sides, add
Write two half reactions and balance the atoms as 8H2SO4 on left.
follows.
2 KMnO4 + 5 K2C2O4 + 8 H2SO4 

(a) Mn7+ 
 Mn2+ (reduction)
2 MnSO4 + 10 CO2 + 6 K2SO4
(b) C23+ 
 2 C4+ (oxidation)
Finally add 8 H2O on right to balance O and H
Balance the charge by adding 5e to left of (a) and atoms to get balanced equation.
2e to the right of (b).
2 KMnO4 + 5 K2C2O4 + 8 H2SO4  
(a) Mn7+ + 5e 
 Mn2+ (reduction) 2 MnSO4 + 10 CO2 + 6 K2SO4 + 8 H2O
(b)  2 C4+ + 2 e
C23+  (oxidation)
Note : You can always make a final check by counting O
atoms on both sides.
Add two half reactions after multiplying (a) by 2
and (b) by 5 in order that electrons cancel from
both sides.

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Ion Electron Method :

First write the given equation in Ionic form having Add 5e in LHS (Note : each e is equivalent to a
ions with Central atom (which has undergone a charge of –1).
change in Oxidation State).
MnO4 + 8H+ + 5e 
 Mn2+ + 4H2O . . . .(i)
 2 2+
MnO4 + C2O4  Mn + CO2

Oxidation :
Note that O and H atoms attached to the Central
atom (shown in bold), have to be retained. C2O42 
 CO2
Now, write the Oxidation and Reduction half and Following the same procedure as above, we have
balance them as shown : :
Reduction :
(i) Balance C atoms : C2O42  
  2 CO2
MnO4 
 Mn
2+
(ii) Balance O atoms : Already balanced.
(i) First, make sure that the element (iii) Balance H atoms : No H atom.
undergone a change in Oxidation State is
balanced. (iv)   2 CO2 + 2e . . . .(ii)
C2O42  
(ii) Balance O atoms by adding 4 H2O on Multiply equation (i) by 2 and (ii) by 5 to balance
right hand side (RHS). the electrons transfer and add to get :

MnO4 
 Mn2+ + 4H2O 2 MnO4+ 5 C2O42 + 16 H+  

(iii) Now, RHS has excess of 8 H atoms. Add 2 Mn2+ + 10 CO2 + 8 H2O
8H+ on left hand side (LHS). Note, the Using the above balanced equation, convert it to
medium is acidic due to the presence of its corresponding given Neutral equation to get :
H2SO4.
2 KMnO4 +5 K2C2O4+ 8H2SO4 
 + 2+
MnO4 + 8H  
 Mn + 4H2O 2MnSO4 + 10 CO2 + 8H2O
(iv) Note, now O and H is balanced. Balance Now, K (12 atoms on LHS) and SO42 (6 atoms
the charge on both sides. on LHS) is unbalanced. Add 6 K2SO4 on RHS to
On LHS : Charge is 1  (1) + 8  (+1) get the final equation as :
= +7
2 KMnO4 + 5 K2C2O4 + 8 H2SO4  
On RHS : Charge is 1  (+2) + 4  (0) 2 MnSO4 + 10 CO2 + 6 K2SO4 + 8H2O
= +2

Note : At the later stages, you will find that it is Ion electron method which is more important.

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Illustration - 2 Balance the following reaction by oxidation number method.

CrO42 + I 
 Cr3+ + IO3 (in alkaline or basic medium)

SOLUTION :
Proceeding on the pattern of last illustration On adding (a) and (b) we get :
+6 1 +3 +5
2 Cr6+ + I 
 2 Cr3+ + I5+
(i) CrO42 + I 
 Cr3+ + IO3 On comparing with given reaction
(ii) (a) Cr6+ 
 Cr3+
2 CrO42 + I 
 2 Cr3+ + IO3
(Reduction : decrease in O.S.) Note that the given reaction is ionic, so first of all
charge needs to be balanced. Balance charge by
(b) I 
  I5+
adding OH ions (in basic medium).
(Oxidation : increase in O.S.) A charge of 5 on left and +5 on right side means
add 10 OH ions to the right side of the equation.
(iii) (a) Cr6+ + 3e 
 Cr3+
2 CrO42 + I 
 2 Cr3+ + IO3 + 10 OH
 
 5+ 
(b) I I + 6e
Finally add 5 H2O molecules on the left to bal-
(iv) (a) [ Cr + 3e6+  
 Cr ] × 2 3+ ance H and O and get the balanced equation.

(b) [ I 
 I5+ + 6e ] × 1 2 CrO42 + I + 5 H2O 

2 Cr3+ + IO3 + 10 OH

Illustration - 3
Balance the following reaction in acidic medium.

CuS + NO3 
 Cu2+ + S8 + NO

SOLUTION :
Proceeding on the same pattern of last illustration (b) N5+ + 3e 
 N2+
2 +5 0 +2
(iv) 24 CuS + 16 NO3 
 3 S8 + 16 NO
 2+
(i) CuS + NO3  
 Cu + S8 + NO
Add 24 Cu2+ ions on right side to balance Cu
before balancing the charge.
(ii) (a) 8 S2 
 S80 (Oxidation)
24 CuS + 16 NO3  

(b) N5+  
 N2+ (Reduction)
24 Cu2+ + 3 S8 + 16 NO
(iii) (a) 8 S2 
 S80 + 16e

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A charge of 16 on left and +48 on right means,

24 CuS + 16 NO3 + 64 H+ 

add 64 H+ ions to the left (acidic). Finally add 32
H2O on right to balance H and O atom s. 24 Cu2+ + 3 S8 + 16 NO + 32 H2O

Illustration - 4 Complete and balance the following in acidic medium.

Ag+ + AsH3 
 H3AsO3

SOLUTION :
+1 3 +3 (b) Ag + 1e  
 Ag

Ag+ + AsH3 
 H3AsO3 As3 + 6 Ag  
 As3 + 6 Ag

(a) As3 
 As3 (Oxidation) AsH3 + 6 Ag 
 6 Ag + H3AsO3
Now balance charge by adding 6 H on right
(b)  Agx
Ag  x=?
side and finally add 3 H2O on left side.
Clearly, (b) must be a reduction, so x must be 0,
as x can’t be ve for Ag (Silver being metal). AsH3 + 6 Ag + 3 H2O 


(a)  As3 + 6e

As3  6 Ag + H3AsO3 + 6 H+

Illustration - 5 Balance the following by ion-electron method in basic medium.

NO3 + Zn 
 Zn2 + NH +
4

SOLUTION :
Two half reactions are : NH4+ + 6 OH + 4OH
Balancing the charge :
(a) NO3 
 NH4+

NO3 + 8e + 7 H2O 


(b) Zn 
 Zn2+
NH4 + 10 OH
+

First balance ‘O’ atoms in basic medium.

(b)  Zn2+ + 2e
Zn 
(a) NO3 + 3 H2O 
 NH4+ + 6 OH
Now overall reaction is :
Balancing H atoms in basic medium
4 Zn + NO3 + 7 H2O 

NO3 + 3H2O + 4 H2O 
 4 Zn2+ + NH4+ + 10 OH

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Illustration - 6 Balance the following by ion-electron in acidic medium.

 IO3 + Cl
ClO3 + I2 

SOLUTION :
Two half reactions are : 5 ClO3 + 3 I2 + 3 H2O  
5 Cl + 6 IO3 + 6 H+
(a) ClO3 
 Cl
(b) I2 
 IO3
Balancing them separately :
 IO3
I2 
ClO3 
 Cl
 2 IO3+ 12 H+
I2 + 6 H2O 
ClO3 + 6 H+ 
 Cl + 3 H2O
 2 IO3 + 10e + 12
I2 + 6 H2O 
ClO3 + 6 e + 6 H+ 
 Cl + 3 H2O +
H
Balancing electrons in two half reactions, and
adding we get :

Illustration - 7 Balance the following by ion-electron method. (Acidic medium)

Mn2+ + S2O8 2 
 MnO4 + HSO4

SOLUTION :
Two half reactions are :  2 MnO4
2 Mn2+ + 5 S2O82 + 8 H2O 
+ 
+ 6 H + 10 HSO4
(a)  MnO4
Mn2+ 
(b) S2O82 
 HSO4
Balancing these two half reactions :
S2O82 + 2 H+ + 2e 
 2 HSO4
 MnO4 + 5e + 8 H+
Mn2+ + 4 H2O 
Adding the two equations, we have the balanced
equation.

Illustration - 8 Balance the following by ion-electron method. (Basic medium)

 I + CrO42
Cr(OH)3 + IO3 

SOLUTION :
Two half reactions are : (b) IO3 
 I
Balancing O atoms
(a) Cr(OH)3 
 CrO42

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(a) Cr(OH)3 + 2 OH 

 CrO42 + H2O Balancing the charge

(b) IO3 + 3 H2O 

 I + 6 OH (a) Cr(OH)3 + 5 OH 
CrO42 + 4 H2O + 3e
Balancing H atoms
(b) IO3 + 3 H2O + 6e 
 I + 6 OH
  

(a) Cr(OH)3 + 2 OH + 3 OH
Adding (a) and (b), we get :’
CrO42 + H2O + 3 H2O
2 Cr(OH)3 + IO3 + 4 OH  
(b) IO3 + 3 H2O  
 I + 6 OH
2 CrO4 + I+ 5 H2O
2

Illustration - 9 Which of the following are examples of disproportionation reactions ?

(a) Ag(NH3)2+ + 2H+ 

 Ag+ + 2NH4+ (b) Cl2 + 2OH 
 ClO + Cl + H2O

(c) CaCO3 
 CaO + CO2 (d) 2HgO 
 2Hg + O2

(e) Cu2O + 2H+ 

 Cu + Cu2+ + H2O (f) CuS + O2 
 Cu + SO2

(g)  Cu + Cu2+ + 4Cl + 2H+

2HCuCl2 + dilute with H2O 

(h) 2H2O2 
 2H2O + O2

SOLUTION :
What is the criteria for a disproportionation reaction ?
A reaction in which same atom is oxidised and reduced at the same time is called as a disproportionation
reaction. Observing very carefully among the above reactions, we note that (b), (e), (g) and (h) are
disproportionation reactions.

Illustration - 10 H SO acts as an oxidising agent, a dehydrating agent and an acid. Among the each of
2 4
following reactions, which behaviour is shown by H2SO4 ?

(a) C6H12O6 + H2SO4(conc.) 

 6C + 6H2O

(b) 5 H2SO4 (conc.) + 4 Zn 

 H2S + 4 Zn2+ + 4 SO42 + 4H2O

(c)  Zn2+ + H2 + SO42

H2SO4 (dil) + Zn 

(d)  Zn2+ + CO2 + SO42 + H2O

H2SO4 (dil) + ZnCO3 

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SOLUTION :
(a) As a dehydrating agent since it simply removes water from glucose.
(b) H2SO4 (S in +6 state)   H S (S in 2 state), i.e., acid is reduced. So it acts as an oxidising agent.
2
(c) All strong acids liberate H2 with an active metals like Zn (i.e., it is reduced) unless SO42 is reduced. In this
case, H+ is reduced to H2. So it acts as an oxidising agent. We can also call it as an acidic property.
(d) Simply an acid.

Illustration - 11 Balance the following reaction by ion-electron method. (Acidic medium)

As2S3 + NO3 
 S + NO2 + AsO43

SOLUTION :
This is a very special case of redox reac-  3 S + 6e
(ii) 3 S2 
tion.
Now add the two equations to get :
Note that, the given reaction involves two oxi-
dations and one reduction. Proceed carefully as
follows. (a) 2As3+ + 3S2 + 8H2O 
 2AsO43 + 3S +
16H+ + 10e
(a) Two half reactions (oxidation) are :
Now balance oxidation half reaction and pro-
(i) As3+ 
 AsO43 ceed as usual.

(ii) S2 
 S (b) NO3 + 2H+ + 1e 
  NO2 + H2O
Adding the two reactions
(b) Reduction half reaction : NO3  
  NO2

First balancing these two half reductions : As2S3 + 10 NO3 + 4H+ 
3
2 AsO4 + 10 NO2 + 3S + 2H2O
(i) 2As3+ + 8H2O 
 2AsO43 + 16
H+ + 4e

Note : In above type of cases, take total change in oxidation number (increase or decrease) for cross multi plica-
tion while adding oxidation and reduction half reactions. For example, in the given case, 10e1s are lost per
mole of As2S3.

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IN - CHAPTER EXERCISE - A
1. Indicate the species which are oxidized and reduced in the following reactions.
(i) CN  + OCl   N 2 + HCO3 + Cl 
(ii) C6 H5OH + O3  CO 2 + H 2O + O 2

(iii) I  + O3  O 2 + I 2

(iv) S2 O32   Cl2  HSO 4  Cl 

(v) C ZnO  Zn  CO
2. Write balanced ionic half equations ( oxidation and reduction) for each of the following reactions.
(i) Te(s)  NO3 (aq)  TeO 2 (s)  NO(g)

(ii) H 2 O 2 (aq)  Fe 2+ (aq)  Fe 3+ (aq)  H 2O(l )

(iii) Mn(s)  NO3 (aq)  Mn 2+ (aq)  NO 2 (g)

(iv) Mn 3+ (aq)  MnO 2 (s)  Mn 2+ (aq)

3. Balance the following half-reactions in acidic medium.
(i) VO2+ (aq)  V 3+ (aq)

(ii) NO3 (aq)  NO 2 (g)

(iii) IO 3 (aq)  I3 (aq)

4. Balance the following half-reactions in basic medium.
(i) CrO 24  (aq)  Cr(OH) 4 (aq)

(ii) Bi3+ (aq)  BiO3 (aq)

(iii) ClO (aq)  Cl (aq)

5. Write balanced net ionic equations for the following reaction in basic solution.
(i) MnO 4 (aq)  IO3 (aq)  MnO 2 (s)  IO 4 (aq)
(ii) Cu(OH)2 (s)  N 2H 4 (aq)  Cu(s)  N 2 (g)

(iii) Fe(OH) 2 (s)  CrO 42  (aq)  Fe(OH)3 (s)  Cr(OH) 4 (aq)

(iv) H 2 O 2 (aq)  ClO 4 (aq)  ClO 2 (aq)  O 2 (g)

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6. Write balanced redox reactions for each of the following reactions.

(i) H 2O 2 (aq) reduces Cr2O 72  (aq) to green coloured Cr3+ (aq) in acidic medium

(ii) H 2O 2 (aq) Oxidises Mn 2+ (aq) to MnO 2 in basic medium

(iii) Sn 2+ (aq) reduces IO 4 ( aq ) to I (aq) and is oxidized to Sn 4+

(iv) A purple solution of aqueous potassium permanganate (KMnO 4 ) reacts with aqueous
2
sodium sulphite (Na 2SO3 ) in basic solution to yield the green manganate ion MnO 4 and  

2
sulphate ion SO4 . 
(v) Potassium dichromate (K 2Cr2O7 ) reacts with hydroiodic acid (HI ) to produce potassium iodide,
chromium (III) iodide and solid iodine, I2 (s).
7. Balance the following chemical reactions. ( It is better to use ion electron method )
(i) CuO + NH3  Cu+ N 2 + H 2O (ii) HI + HNO3  I2 + NO  H 2O

(iii) P4 + H 2 O  PH 3 + H 2PO 2  H + (iv) H 2S SO 2  S + H 2O

(v) CN   MnO 4  H 2O  MnO 2  CNO   OH 

(vi) [Fe(CN) 6 ]3  + N 2 H 4 + OH   [Fe(CN) 6 ]4   N 2 + H 2O

(vii) C2 H 5 OH+ MnO 4  CH 3COO  + MnO 2 + H 2O+ OH 

(viii) P + H + + NO  + H O  H PO  + NO
4 3 2 2 4
(dil)

(ix) HS + HSO3  S2 O 32  + H 2 O

(x) Fe3+ + NH 2 OH  Fe2+ + N 2O+ H  (xi) O2 + H 2O  OH  + O2

(superoxide ion)

(xii) IO 3 + HSO3  I  + H + + SO 42  (xiii) I  + IO3 + H +  H 2 O+ I 2

(xiv) Fe2S3 + H 2O + O2  Fe(OH)3 +S

(xv) IBr+ BrO 3 + H 2 O  IO 3 + Br  + H +

(xvi) CrI3 + H 2O 2 + OH   CrO 42  + IO 4 + H 2O

(xviii) H 2 O 2 + H + + Fe2+  H 2O+ Fe3+

(xviii) As 2S3 + MnO 4 + H +  H 3AsO 4 + Mn 2+ + S

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ANALYSIS BASED ON MOLE CONCEPT Section - 2

Let us now solve some numerical problems based on the analysis of redox reactions. In such type of applications
based problems, first we have to create a chemical equation and then balance it. And then proceed as per the given
problem, using Mole concept.

Illustration - 12 Find the amount of Iron pyrites (FeS ) which is sufficient to produces enough SO on
2 2
roasting (heating in excess of O2) such that (SO2) completely decolourises a 1L solution KMnO4 containing
15.8 g/L of it.

The equation are : FeS2  O2 

 Fe2O3  SO2 and KMnO4  SO2 
 MnSO4  H 2 SO4  K 2 SO4

SOLUTION :
 1.0 L of KMnO4 contains 0.1 moles
First calculate the amount of SO2 required to
declourise 15.8 g/L of KMnO4 solution. For this 5
you need to balance the following chemical Hence moles of So2 required = (0.1)
2
reaction.
= 0.25
KMnO 4  SO2 
 To calculate the amount of pyrites, we have to
MnSO 4  H 2SO4  K 2SO 4 balance the reaction :

Proceeding in the manner as given in above FeS2  O2 

 Fe2 O3  SO2
illustrations, we have balanced equation as :
Balancing the reaction (using Hit and Trial
2 KMnO 4  5SO 2  2H 2 O 
 Method) we have
2 MnSO 4  2H 2SO 4  K 2SO 4
4FeS2  11O2 
 2Fe2 O3  8SO2
Now, using our understanding to solve a
From stoichiometry of roasting, we have :
typical stoichiometric problems, we can solve
this problem as follows : 8 moles of SO2  4 moles of FeS2
From stoichiometry of balanced equation, we 4
have: 0.25 moles of SO2  (0.25) moles of FeS2
8
2 moles of KMnO4  5 moles of SO2
= 0.125 moles of FeS2
Calculate moles in 15.8 g/L of KMnO4 :
 mass of FeS2 = 0.125  120 = 15 gm
Using : Strength (g/L) = M M0

15.8
Molarity = = 0.1 M
158

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Illustration - 13 20 mL of a solution containing 0.2 gm of impure sample of H O reacts with 0.316 gm of

2 2
KMnO4 in presence of H2SO4 as per following reaction.

KMnO4  H2O2  H 2SO4 

 MnSO4  O2  H2O

(a) Find the purity of H2O2 solution (b) Calculate the volume of dry oxygen evolved at 27C and at 750
mm Hg.

SOLUTION :
0.17
First write a complete balanced the reaction :  % age purity of H2O2 = 100
0.2
2 KMnO4 + 5 H2O2 + 3H2SO4 
 = 85 %
2 MnSO4 + K2SO4 + 5 O2 + 8 H2O Now : 2 moles of KMnO4  5 moles of O2
From the balanced reaction, we have : 5 0.316
Moles of O2 produced = 
5 moles of H2O2  2 moles of KMnO4 2 158

0.316 = 5  103
Moles of KMnO4 =
158 Using PV = nRT we have :
5 0.316
 Moles of H2O2 required =  nRT 5×103 ×0.0821×300
2 158 V= =
P 760 / 760
5 0.316
Grams of H2O2 =  34 = 0.17 gm = 0.123 L = 123 mL
2 158

Illustration - 14
Calculate the amount of SeO32  in a solution on the basis of given analysis. 20 mL of M/

60 KBrO3 was added to a sample of SeO32  . The bromine evolved was removed and the excess of KBrO3 was
titrated with 5.1 mL of M/25 solution of NaAsO2 . The reactions involved are : [ASe = 79 gm/mol]

 SeO42   Br2  H 2O and BrO3  AsO2  H 2O 

SeO32   BrO3  H    Br   AsO43  H 

SOLUTION :
In this problem, find the exact amount of KBrO3 Balancing the two equations
used for SeO32- (in the first equation) by
calculating the excess of KBrO3 with the help (i) 5 SeO32   2BrO3  2H  

of second equation.
5 SeO 24   Br2  H 2O

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(ii) BrO3  3AsO 2  3H 2O 

  1 
   20   0.068  0.265 m.moles
Br   3AsO34  6H   60 
From equation (i) :
From the equation (ii) :
2 m.moles of K BrO3  5 m.moles of SeO32 
3 m.moles of AsO 2  1 m.moles of excess of
KBrO3 0.265 m.moles of KBrO3  5/2 (0.265)
m.moles
1 
  5.1 m.moles of AsO 2  5/2 (0.265)  127 mg
25
Mass of SeO32  = 84.13 mg = 0.08413 g
1 5.1
  (= 0.0628) m.moles of excess of
3 25
KBrO3 m.moles of KBrO3 used in equation (i)

Illustration - 15 1.0 gms of AgNO is dissolved in 50 mL of water. It is titrated with 50 mL of KI solution.

3
The Agl precipitated is filtered off. The excess of KI in the filtrate is titrated with M/10 KIO3 in presence of 6
M HCl till all I- is converted to ICl. It requires 50 ml of M/10 KIO3 solution. 20 mL of same KI solution requires
30 mL of M/10 KIO3 under same conditions. Determine the percentage of AgNO3 in the sample.

The reaction involved is : KIO3  KI  HCl 

 ICl  KCl  H 2O

SOLUTION :
The problem considers three experiments : First of all you must balance the equation
involved in experiments 2 and 3. (Note that the
(i) 1.0 gm AgNO3 (50 mL) + 50 mL of KI
reaction is same in both cases)
(M = ?)
I  
 I   2e 
AgNO3 + KI 
 AgI + KNO3
(ii) Excess of KI + 50 mL of M/10 KIO3 in IO3  6H   4e 
 I  3H 2O
6M HCl
 The overall balanced equation is :
KI  KIO3  HCl 
 ICl  KCl  H 2O.
2I   IO3-  6H  
 3I  3H 2O
(iii) Tod determine the molarity of KI (say M)
20 mL KI (original) + 30 mL of M/10  2 m.moles of KI  1 m.moles of KIO3
KIO3­

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Using the above stoichiometry, first find the This gives us initial m.moles of KI in 50 mL
excess of KI and then molarity of KI volume taken initially.
 m.moles of KIO3 used  1/10  50  Initial m.moles of KI = (6/20)  50 = 15
=5
 m. moles of KI used for AgNO3
1 m mole of KIO3  2 m. moles of
= 15 – 10 = 5
KI
Now, 1 m.mole of KI  1 m.mole of AgNO3
 5 m.moles of KIO3  10 m.moles of
KI (excess)  m.moles of AgNO3 = 5
 m.moles of KIO3 used for titrating 20 g
mL KI  1000  5  g  0.85 gram
170
= 1/10  30 = 3
or % AgNO3 = 85%
 m.moles of KI = 6 = M  20
(mass of sample = 1gm)
 M = 6/20

IMP. Not n-factro of KBrO3 in illustration-14 and that of KI in illustration-15 is different in two redox reactions.
It is advised to use concept of mole in such case as done above

NOW ATTEMPT IN-CHAPTER EXERCISE-B BEFORE PROCEEDING AHEAD IN THIS EBOOK

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CONCEPT OF GRAM EQUIVALENTS Section - 3

In the method of gram-equivalents (milli-equivalents), there is no need to balance a redox reaction. For
example, let us consider a typical redox reaction (consisting of two reactants and two main products):

X + Y 
 A + B
Reducing Oxidising
agent agent
According to concept of gram equivalent (or meq) ;
1 gm.eq. of X  1 gm. eq. of Y  1 gm eq. of A  1 gm eq. of B
or meq. of an oxidising agent = meq. of a reducing agent

g g
Note : gm.eq. = and meq = meq   1000
E E

Now to understand the method of gram-equivalents more clearly, let us understand the following illustrations
very carefully.

Illustrating the concept :

What volume of a deci-normal solution of K2Cr2O7 is required to oxidise 1.0 gm of Tin (Sn) in pres-
ence of HCl to its highest oxidation state ?
The involved reaction is :

K2Cr2O7 + Sn + H+ 
 Sn4+ + Cr3+(The highest oxidation state of Sn is +4, so SnCl4 will be formed here)
Here, Sn is a reducing agent (RA) and K2Cr2O7 is an oxidant (OA).
So applying the concept of gram-equivalent, we have : gm.eq of OA (K2Cr2O7) = gm.eq of RA (Sn)

g
Using the definition : N VL  , we get :
E

1 1 119
 VL  ; ESn  where x = electron transfer / mol (also known as valence or n-factor)
10 ESn x

 Sn4+ + 4e
Sn   x=4

V 1 40
   V= = 0.336 L = 336 mL
10 119 / 4 119

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 g 
Note : From definition of gram-equivalents  gmeq.   N VL  , it is very clear that, we must be very confident
 E 
about the concept of equivalent weight (E), for an oxidising or reducing agent. So first let us learn intricacies
of the concept of equivalent weight for an oxidant(s) and reductant(s) in detail.

Equivalent Weight (E) of Oxidant and Reductant :

The equivalent weight of an oxidising or reducing agent is defined as :

M0
Equivalent weight = E 
x
where M0 = molecular mass ; x = number of electrons transferred (loss or gain) by one mole of oxidising or
reducing agent as given by their balanced ionic half reaction.

Illustrating the concept :

 FeSO4 (Ferrous Sulphate)
As reducing agent : As an oxidising agent :

Fe2+ 
 Fe3+ + 1e Fe2+ + 2e 
 Fe + le–
1 mole of e’s are transferred/ mole of FeSO4, so x = 1  x=2
M 152 M 152
 E FeSO   = 152  E FeSO  
4 x 1 4 x 2

Note : FeSO4 (ferrous sulphate) acts both as an oxidant and as a reductant

 H2C2O4 (Oxalic acid) or C2O42 (Oxalate ion)

As reducing agent only

 2 CO2 + 2e or H2C2O4 

C2O42   2 CO2 + 2 H+ + 2 e
90
x = 2 or E H 2C 2O4 
2

134 128
Note : E Na C O  ; E CaC 2O 4  as nfactor for C2O42 is always 2
2 2 4 2 2

Sodium oxalate Calcium oxalate

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 SO2 (Sulphur Dioxide)

As reducing agent

 SO42 + 4H+ + 2e

SO2 + 2H2O 

64
x=2  ESO 2 
2

 HI (Hydrogen Iodide)
As reducing agent only

2HI 
 I2 + 2H+ + 2e  2 mole of e’s / 2 mole of HI

2 128
x= = 1 (for 1 mole of HI)  EHI =
2 1

 Fe2(SO4)3 (Ferric sulphate)  Na2S2O3 (Sodium Thiosulphate)

As oxidising agent only As reducing agent in acidic medium

Fe3+ + 1e  
  Fe2+
 S4O62 + 2e
2 S2O32 
Since 1 mole of Fe2(SO4)3  2 moles of x = 2/2 = 1 for 1 mole of Na2S2O3
Fe3+
 x = 2 for 1 mole of Fe2(SO4)3 158
 E 
Na 2S2 O3 / H  1
400
 E Fe SO    K2Cr2O7 (Potassium Dichromate)
2 4 3 2
As oxidising agent only
 KMnO4 (Potassium Permanganate)
Cr2O72 + 6e + 14 H+  

As oxidising agent in acidic medium
2 Cr3+ + 7 H2O
MnO4 + 8H+ + 5e 
 Mn2+ +
4H2O 294
x = 6  E K 2Cr2O7 
6
158
x=5  E  
KMnO 4 / H 5  MnO2 (Managanese dioxide)
As oxidising agent in strong alkaline As oxidising agent in acidic medium
medium
MnO2 + 4H+ + 2e 
 Mn2+ + 2 H2O
MnO4 + 1e 
 MnO42
158 87
x = 1  E KMnO4  x = 2  E MnO2 
1 2

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As oxidising agent in dilute alkaline As reducing agent in alkaline medium

medium
S2O32 + 10OH 
 2SO42 + 5H2O + 8e
 
MnO4 + 2H2O + 3e 
 MnO2 + x=8

4 OH
158
 E Na 
x = 3  158 2S2O3 /OH

8
E 
KMnO 4 /OH  3

Note : From the above case, you should observe carefully that the equivalent weight depends upon medium.

 HNO3 (Nitric Acid) As oxidising agent (dil. HNO3)

As oxidising agent (conc. HNO3)
NO3 + 4 H+ + 3e 
 NO + 2 H2O
NO3 + 2H+ + 1e 
  NO2 + H2O x=3
x=1
63
 E HNO3 (dil)   21
63 3
 E HNO3 (conc.)   63
1

Note : Equivalent weight depends on dilution for HNO3.

Try to Calculate ‘E’

(a)  NH4+
HNO3 (very dilute)  (b) HNO3 (cold dilute) 
 NH2OH

Note : Some substance act both as OA (oxidants) and reductans (RA) in different reactions. Like FeSO4, H2O2,
HNO2 etc

H2O2 (Hydrogen Peroxide) as OA : H2O2 + 2H+ + 2e 

 2H2O

as RA :   O2 + 2H+ + 2e
H2O2 

FeSO4(Ferrous Sulphate) as OA : Fe2+ + 2e  

 Fe

as RA :   Fe3+ + 1e
Fe2+  

HNO2(Nitrous Acid) as OA : HNO2 + H+ e 

 NO + H2O

as RA :   NO3 + 3H+ + 2e

HNO2 + H2O 
Some other type of oxidants and reductants are also given below.

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 (NH4)2 Cr2O7 
 N2 + Cr2O3
(Ammonium Dichormate)

RA : NH 4 
 N2 OA : Cr2O72  
 Cr2O3

 FeC 2O 4  Fe3+ + CO 2
 Ferrous Oxalate 

RA : Fe2+ 
 Fe3+ + 1e– ; C2O42  
  2CO2 + 2e–  x = 3

Note : In FeC2O4 both cations and anions are oxidised.

  I– + IO3–
I2  (disproportionation reaction)

OA :  2I– ;
I2  RA :   IO3–
I2 
(same compound as OA/RA)

Note : Some compounds act as Acids and RA or OA in separate experiments.


 as acid  x  2  as acid  x  1
  as acid  x  1

H2C2O4 ; HNO3 ; NaHC2O4

 as RA  x  2  as OA  x  1, 3, 6, 8
  as RA  x  2 


Illustration - 16 Complete and balance the following.

(a) H2O2 + I2  
 I + ?? (b) H2O2 + Sn2+ 
 Sn4+ + ??

(c) MnO42 + H+ 
 Mn2+ + ?? (d) NO2 + H2O 
 NO + ??

SOLUTION :
(a) I2 is reduced to I, so H2O2 must be  I + O2
H2O2 + I2 
oxidised, i.e., it acts as a reducing agent.
Hence final product will be O2 gas. The balanced equation will be :

The complete chemical equation is :  2I+ O2 + 2H+

H2O2 + I2 

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(b) Sn2+   Sn4+, i.e., Sn2+ is oxidised.
So H2O2 acts as an oxidising agent, which
means it must be reduced to H2O.
H2O2 + Sn2+ 
 Sn4+ + H2O
The balanced equation will be :
(c) MnO42 is reduced to Mn2+, i.e it is act-
ing as an oxidising agent. Now H+ is al-
ready in the maximum oxidation state, so
MnO42 must also be reduced to Mn7+
state i.e. MnO4 will be formed. Hence it
is a case of disproportionation reaction.

 Mn2+ + MnO4
MnO42 + H+ 
2+
H2O2 + Sn + 2H + 
 Sn4+ + 2H2O
The balanced equation will be :
Important Note :
5 MnO42 + 8H+
H2O2 is chemical species acting both as a re-
ducing agent and as an oxidising agent.  Mn2+ + 4MnO4 + 4H2O
 
as oxidant
H 2O 2  H 2O (d) NO2 (+4 state) disproportionate (like in
as reductant last case) to NO (+2 state) and NO3
 O2
(+5 state).
NO2 + H2O  NO + NO3
The balanced equation will be :

 NO + 2NO 3 
3 NO 2 +H 2 O 
+2 H+

Equivalent weight of a compound undergoing disproportion :

Let a compound ‘A’ contains an ion ‘X’ undergoing disproportionation.

Effective molecular weight of A

Then, EA = Equivalent weight of A =
Number of e transfer

 Total weight of A in   Total weight of A in 

where Effective molecular weight of A =   
 Oxidation half reaction   Re duction half reaction 

1. When number of e- transfer are in oxidation and reduction half reactions

Illustration the concept :

H2O2 undergoes disproportionation in ocidic medium given by the following reaction :

H 2O2 
 H 2O  O 2

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Oxidation half reaction : H2O2 

 O2 + 2H+ + 2e- [2e- transfer] …(i)

Reduction half reaction : H2O2 + 2H+ + 2e- 

 2H2O [2- transfer] …(ii)

Thus, Effective molecular mass of H2O2 = M H 2O2  M H 2O 2  2M H 2O2

from  i  from  ii 

2M H 2O2
 E H 2 O2   34
2

2. When number of e- transfer are different in oxidation and reduction half reaction
Illustrating the concept :
Br2 undergoes disproportionation in basic medium given by the following reaction:

Br2  OH  
 Br   BrO3  H 2O

Oxidation half reaction : Br2 + 12OH– 

 2BrO3– + 6H2O + 10e– [10e– transfer] …(i)

Reduction half reaction : Br2 + 2e– 

 2Br– [2e– transfer] …(ii)

Now, Effective molecular mass of Br2 = M Br2  5M Br2  6M Br2

from  i  from ii 

Note : 5M Br2 is taken because we have to equalize the number of electrons in both oxidation reduction.

6M Br2
Thus, E Br2   0.6 M Br2  96
10

10
This means n-factor of Br2 is
6

Note : However, we should use “Mole concept” while solving problems based on such ractions.

Illustration - 17 1.0 gram of a sample of H O solution containing y% H O by weight requires y mL of

2 2 2 2
KMnO4 solution for complete titration under acidic condition. Find the molarity of KMnO4 solution.

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SOLUTION :  y 
1  
This question involves a redox reaction between  100   1000
meq of H2O2 =
EH O
H2O2 (RA) and KMnO4 (OA). Let us apply 2 2
the concept of gram (milli) equivalents to solve
 34 
this problem.  E H 2 O2  2 
 
i.e., meq of H2O2 = meq of KMnO4
meq of KMnO4 = N (y)
Let us find n-factor (valence factor) of H2O2
and KMnO4 as follows.  y 
1  
 100   1000  N(y) 10
 N =
MnO4 + 8H+ + 5e  
  Mn2+ + 4H2O 17 17
 O2 + 2H+ + 2e
and H2O2   N
And Molarity = ; x = 5 for KMnO4/H+
x = 5 for KMnO4 and x = 2 for H2O2 x

10 / 17 2
 M =  = 0.117
5 17

Illustration - 18 A solution of KMnO /H+ containing 3 gm/L is used to titrate H O solution containing 2
4 2 2
gm/L. What volume of KMnO4 will be required to react with 20 mL of H2O2 solution ? Also find the strength
of H2O2 in terms of available oxygen.

SOLUTION :
It is also called as volume strength of H2O2.
This redox reaction is a typical one.
Volume strength is the volume of O2 given out
strength 3 15 at S.T.P. by 1 volume solution of H2O2.
N KMnO 4   
E 158 / 5 158
2H2O2  
  2H2O + O2
strength 2
N H 2O2  
E 17 2 mol H2O2  1 mol of O2  22.4 L of O2

Now using equation of titration 1 mol H2O2  1/2 mol of O2  11.2 L of O2

per 1.0 L
meq. of OA = meq of RA
 1 M H2O2  11.2 vol of O2 at STP
 NOAVOA = NRAVRA (meq = NVcc)
or 1N H2O2  5.6 vol of O2
15 2
V  20 In the present question :
158 17
2 2
 V = 24.8 mL N H2O2   5.6 = 0.66 L of O2
17 17
What is strength in terms of available
oxygen ? It is written as : 0.66 vol H2O2

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Try yourself : Express the volume strength of H2O2 sample if 100 cc of H2O2 solution were diluted with
100 cc of water. 10 cc of this diluted solution required 20 cc of M/50 KMnO4 in presence
of H2SO4 for complete titration. [Ans : 2.24 vol H2O2]

Illustration - 19 1.25 gm of a sample of bleaching power (CaOCl2) is dissolved in 100 mL of water. 25 mL

of it are treated with KI solution. The iodine so liberated required 12.5 mL of M/25 hypo solution (Na2S2O3 /
H+) for complete titration. Find the percentage of available chlorine from the sample of bleaching powder.

SOLUTION :

CaOCl2 
 Cl2  meq of Cl2 in 100 mL = (0.5  4)
g
Cl2 + 2 KI 
 I2 + 2 KCl   1000 = 2
E

I2 + 2 Na2S2O3  
 2 NaI + Na2S4O6 (Cl2 + 2e  
 2Cl ; E = 71/2)
2 71
  S4O62 + 2e ; x = 1)
(2 S2O32  g  = 0.071 gms
1000 2
In 25 ml sample : % available chlorine
meq of Cl2 in bleaching powder g Cl 2 0.071
=  100   100  5.68 %
= meq of I2 liberated = meq of hypo solution g CaOCl2 1.25

 1 
meq of Hypo = NVcc  1    12.5  0.5
 25 
 meq of Cl2/ 25ml. = 0.5

Try yourself : 5.0 gm of CaOCl2 is dissolved in water to make 500 mL solution. 20 mL of it is acidified
with acetic acid and treated with KI solution. The iodine liberated required 20 mL of M/
10 Na2S2O3 solution. Find the percentage of available chlorine. [Ans: 35.5%]

Illustration - 20
50 ml of an aqueous solution of H2O2 was titrated with an excess of KI solution in dilute
H2SO4, the liberated iodine required 20 ml of 0.1 N Na2S2O3 solution for complete reaction.Calculate volume
strength of H2O2 solution.

SOLUTION :
Both the chemcial equations involved in the H2O2 + KI + H2SO4 

problem are typical redox reactions.
I2 + H2O + K2SO4 . . . (i)

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and I2 + 2 Na2S2O3 
 2 NaI + Now, 1 N H2O2 solution = 5.6 vol. of O2
Na2S4O6 . . . (ii)
1 1
Now : meq. of I2 = meq. of Na2S2O3 (in eq (ii))  N H 2O 2 solution  5.6 
25 25
 meq. of I2 = 20  0.1 = 2 = 0.224 vol of O2
and meq. of H2O2 = meq. of I2 (in eq (i))  Volume Strength of H2O2 solution
2 1 = 0.224 vol.
N H 2O2  VH  2  N H2O2  
2O 2 50 25

Note : In above two problems, Na2S2O3 is used as reducing agent (very common and important reductant). You
must remember its action in acidic and basic both, though acidic medium (hypo solution) is more important.
H OH 
 S4 O 6 2 
Na 2S2O3  ; Na 2S2O3  SO 42 

NOW ATTEMPT IN-CHAPTER EXERCISE-C BEFORE PROCEEDING AHEAD IN THIS EBOOK

SUBJECTIVE SOLVED EXAMPLES

Example - 1 A polyvalent metal weighing 0.1 gm and having atomic weight of 50 reacted with dilute
H2SO4 to give 44.8 mL of hydrogen at STP. The solution containing the metal in this Lower oxidation state,
was found to require 60 mL of 0.1 N KMnO4 solution for complete oxidation. What are valencies of metal ?

SOLUTION :
 Mx+ + xe, i.e., oxidation sate
Thus, M 
Metal (M) + H2SO4 
 H2 is +2
Now M2+ will acquire higher oxidation state
44.8 when oxidized by KMnO4
44.8 mL H2 at STP  moles of H2
22400
M2+ 
 M2 + n + ne-
Now, meq of M = meq of H2
meq of M2+ = meq of KMnO4
+ 
Note : For Hydrogen 2H + 2e 
 H2
0.1
Meq of H2 = 2  m.moles of H2 1000  0.1 60  n 3
50 / n
0.1  44.8  So oxidation state of M is M 2  n  M 5
  2  x 2
50 / x  22400 
Hence the possible valencies are + 2, + 5.

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Example - 2 Hydroxylamine (NH2OH) reduces Fe3+ as per following reaction :

NH 2OH  Fe3 
 N2O  H 2O  Fe2 

Fe2+ produced is estimated by titration with KMnO4. A 10 mL sample of NH2OH is diluted to 1000 mL, 50 mL
of this diluted sample is boiled with excess of Fe3+ solution. The resulting solution required 12 mL of 0.02 M
KMnO4 for complete oxidation. Determine the strength of NH2OH.

SOLUTION :
Consider 50 mL sample : Now meq. of NH2OH in original 10 mL = 24
(meq. remain same on dilution)
NH 2OH  Fe3 
 Fe 2   N 2O
Now find grams of NH 2 OH using
meq of NH2OH  meq of Fe3+  meq of Fe2+
g
2+ 1000  24
Now meq of Fe ions are calculated by titrating E
it against KMnO4.
meq of Fe2+ = meq of KMnO4  N 2O  H 2O  4H   4e
2 NH 2OH 
Now for calculating meq. of KMnO4, convert
4
molarity (M) into normality (N). Now, x  for 1 mole of NH2OH
2
N = xM = 5  0.02 = 0.10 N
33
 E NH 2OH 
x  5; MnO4 
 5e 
 Mn 2
 2

meq of Fe2+ in 50 mL sample = 0.10  12 24   33 / 2 

 g  0.396
= 1.2 = meq of NH2OH 1000

meq of NH2OH in 1000 mL sample 10 mL sample  0.396 grams

= 1.2  20 = 24  1000 mL  39.6 grams

 Strength of NH2OH = 39.6 g/L

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Example - 3 A sample of Pyrolusite (MnO2) weighs 0.5 gm. To this solution 0.594 gm of As2O3 and a
dil. acid are added. After the reaction has ceased, As3+ in As2O3 is titrated with 45 mL of M/50 KMnO4
solution. Calculate the % age of MnO2 in pyrolusite.

SOLUTION :

 Mn2+ + AsO43
MnO2 + As2O3  meq of excess As2O3 = meq of KMnO4

0.5 gm 0.594 gm = 45 [1/50  5 ] = 4.5

For excess of As2O3 :

MnO4 + 5e + 8H+  
  Mn2+ + 4 H2O
(x = 5)
As2O3 + MnO4 
 Mn2+ + AsO43
Note that the number of electron transfer for
E AS2O3 = ? As2O3  As2O3 in two reactions is same.
 AsO43
so meq. of As2O3 used for MnO2 = 12  4.5
 2AsO43 + 10 H+ +
(As2O3 + 5H2O  = 7.5

4e ) meq of MnO2 = 7.5
For 1 mole of As2O3, x = 4 g
  1000 = 7.5
87 / 2
198
 E AS2O3 =
4 (MnO2 + 4H+ 
 Mn2+ + 2H2O ; x = 2)
0.594  g = 0.326
meq of As2O3 taken = 1000  12
198 / 4
0.326
% MnO2 =  100  65.25%
0.5

Example - 4 1 gm of Fe2O3 solid of 55.2 % purity is dissolved in acid and reduced by heating the
solution with Zn dust. The resultant solution is cooled and made upto 100 mL. An aliquot of 25 mL of this
solution, requires 17 mL of 0.0167 M solution of an oxidant. Calculate the number of electrons taken up by
the oxidant in the above reaction.

SOLUTION :

 Fe2+ 
Fe2O3 + Zn   100 mL solution Now meq of Fe2+ in 25 mL = meq of oxidant
25 mL sample 17 mL of 0.0167 M of an = [ 0.0167  n]  17 [N = xM]
oxidant.
meq of Fe2+ in 100 mL = [ 0.0167  n  17 ]  4
Let ‘n’ be the number of electrons taken up by
Also meq of Fe2O3 = meq of Fe2+ in 100 mL
oxidant

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 x = 2 for 1 mole of Fe2O3

0.552
meq of Fe2O3 =  1000
E 160
 E Fe2 O3   80
= (0.0167  68 ) n 2

EFe2O3 = ?  0.552 
 n =   1000   (0.0167 × 68) = 6
 80 
1 mole of Fe2O3  2Fe3+ ; Fe3+ + 1e–  Fe2+
 Electrons taken by oxidant = 6
Example - 5 An equal volume of a reducing agent is titrated separately with 1 M KMnO4 in acid,
neutral and alkaline media. The volumes of KMnO4 required are 20 mL in acid, 33.4 mL in neutral and 100
mL in alkaline media. Find out he oxidation state of manganese in each reduction product. Give the balanced
equations for all three half reactions. Find out the volume of 1 M K2 Cr2O7 consumed, if the same volume of
the reducing agent is titrated in an acid medium.

SOLUTION :
Let meq of RA = P (Since equal volume of RA Balanced half reaction are :
is used in all cases, meq in each case are
same.) (a) MnO4  5e 
 Mn 2 
1 M KMnO4 (in acidic medium)
7
(a) Mn O 4  xe  H  
 Mn 7  x (b) MnO4 1e 
 Mn 6

volume of KMnO4 = 20 mL (in alkaline medium)

7 (c) MnO 4  3e  
 Mn 4
(b) Mn O4  ye   OH  
 Mn 7 y

(in neutral medium)

volume of KMnO4 = 100 mL
Now this mean P = 100
7
(c) Mn O4  ze  
 Mn 7  z meq of RA = meq of K 2Cr2O7
volume of KMnO4 = 33.4 mL
meq of KMnO4 = meq of Ra in each case  Cr O
2 7
2
 14 H   6e 
 2Cr 3  7H 2O 
(a) P = x 1 20 [N = xM] 100  6 1 V

(b) P = y 1100 100

 V = 16.67
6
(c) P = z 1 33.4

 20 x = 100 y = 33.4 z Note : Dil. Alkaline KMnO 4 should be

considered as neutral KMnO4
 x : y : z  5: 1 : 3

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Example - 6 20 mL of a solution containing oxalic acid and sulphuric acid on titration with 0.05 N
NaOH required 40 mL of the base. 20 mL of same solution on titration with 0.02 N KMnO4 required 50 mL of
KMnO4. Determine the strength of oxalic acid and H2SO4.

SOLUTION :
In this problem, two type of titrations viz :  2  x  2  y  meqof NaOH= 40  0.05  2
Neutralisation and Redox are involved. Note that
in both cases, the volume of sample is same,  x+y=1
i.e., mmoles of two constituent are same in both. In second titration, only H2C2O4 (being reducing
Let x = mmoles of H2C2O4 and y = mmoles of agent) reacts with KMnO4.
H2SO4 in first titration, both H2C2O4 and H2SO4
 2  x = meq of KMnO4 = 50  0.02  1
react with base (as acids). [n-factor of both
being 2 due to 2H+ per mole in each].
 H C O 
 CO 2  2H   2e  
 2 2 4 

Note : In the above reaction H2SO4 also reacts with KMnO4 but in the same reaction with H2C2O4 so the meq. of

H2SO4 should not be added separately.  H C O  KMnO  H SO 

 Mn 2   CO 2 
 2 2 4 4 2 4


Hence x = y = 0.5 mmoles

g H 2 C2 O 4 g H 2SO 4
 1000  0.05 Similarly, 1000  0.05
M H 2 C2 O 4 M H 2SO 4

 g  0.045 gm  g  0.049 gm

0.045 0.049
Strenght of H2C2O4 =  2.25 g / L Strengh of H2SO4 =  2.45 g / L
20 / 1000 20 / 1000

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Example - 7 The neutralization of a solution of 1.2 gm of mixture of H2C2O4. 2H2O and KHC2O4.H2O
and same impurities which are neutral, consumed 40.0 mL of 0.25 N NaOH. On the other hand on titration
with KMnO4 in acidic medium, 0.4 gm of mixture required 40.0 mL of 0.125 N KMnO4. Find the molar ratio
of the components.

SOLUTION :
Note that the mass of two samples is different in 2. Rdox reaction with KMnO4 :
tow titrations.
meq of H2C2O4.2H2O + meq of KHC2O4. H2O
Let x = mmoles of H2C2O4. 2H2O
= meq of KMnO4
and y = mmoles of KHC2O4. H2O in 0.4 g
sample 2  x  2  y  0.125  40

So mmoles of oxalic acid in 1.2gm sample = 3x

 HC 2O4 
 2 CO 2  H   2e ; x  2 
and mmoles of bioxalate in 1.2 gm sample = 3y  
 and C O 2   
 2CO2  2e ; x  2 
 2 4 
1. Neutralisation with NaOH :
meq of H2C2O4. 2H2O + meq of KHC2O4. H2O  x + y = 2.5 ... (ii)

= meq of NaOH 5 5
Solve for x and y to get : x  and y 
6 3
2  3 x  1 3y  0.25  40
 x:y=1:2
[oxalic acid has 2 H+ ions while bioxalate has only
1 H+]

10
 2x  y  ...(i)
3

Example - 8 A sample of Fe2(SO4)3 and FeC2O4 was dissolved in H2SO4 . 40 mL of N/16 KMnO4 were
required for complete oxidation. After oxidation, the mixture was reduced by Zn/H2SO4 . On again oxidation
by same KMnO4, 60 mL of it were required. Calculate the ratio of millimoles of Fe2(SO4)3 and FeC2O4.

SOLUTION :
Let m.moles of Fe2(SO4)3 = x Fe2+ 
 Fe3+ + 1e-
and m.moles of FeC2O4 = y y mmol FeC2O4  y mmol Fe2+  y meq Fe2+

Fe3+ + 1e- 
 Fe2+
C2O 42  
 2CO 2  2e
x mmole Fe2 (SO4)  2x mmol meq Fe3
y mmol C2O 42   2y meq C2O 42 
meq Fe3

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In the first titration In the second titration

meq of KMnO4 = meq of Fe2+ + meq of So total meq of Fe2+ = 2x + y
C2O 42  meq of KMnO4 = meq of Fe2+
1/16  60 = (2x + y)
1/16  40 = y + 2y (Fe3+ will not be oxidised
further) 60 70
 2x  y   x
 y = 40/48 16 48
Zn reduces whole of Fe3+ (Fe3+ : original and Ratio of millimoles = x : y = 7 : 4
Fe3+ from FeC2O4) to Fe2+

Example - 9 A 4:3 molar mixture of Cu2S and CuS was titrated with 200 mL of 0.75 M KMnO4 in acidic
medium producing SO2, Cu2+ . The SO2 was boiled off and the excess of MnO4 was titrated with 175 mL of
1 M Fe2+ solution. Find the moles of CuS and Cu2S in the original mixture.

SOLUTION :
Note that in Cu2S, both Cu2+ and S2- will get  meq of Cu2S + meq of CuS = 575 ….(ii)
oxidize
Oxidation of Cu2S
Let x = mmoles of Cu2S ; y = mmoles of CuS
Cu 2 
 2Cu 2   2e
x 4
   3 x  4 y …(i)
y 3
S2  
 SO 2  6e
Now, first find excess of KMnO4
1 mole of Cu2S  8e  n- factor = 8
2 3 
Fe 
 Fe  1e  x 1
Oxidation of Cus
and MnO 4  5e  
 Mn 2   x  5
S2  
 SO 2  6e

meq of Fe2   11 175 175 1 mole of CuS  6e   n – factor = 6

 excess meq. of KMnO4 = 175
Using (ii), x  8  y  6  575
Now, meq of KMnO4 taken
= 200  (0.75  5) = 750 4 
  . y   8  y  6  575 [Using (i)]
3 
 meq of KMnO4 used for Cu2S and CuS
 x = 46 mmoles and y = 34.5 mmoles
= 750 – 175 = 575 meq.

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Example - 10 25 mL of a solution of ferric alum Fe2(SO4)3. (NH4)2SO4.24 H2­O containing 2.41 gm of

salt was boiled with iron then the reaction Fe + Fe2(SO4)3   3Fe(SO4) take place. The un-reacted iron
was filtered off and the solution was treated with 0.1 N KMnO4 in acidic medium. What is the titre value (vol.
of KMnO4) of KMnO4 ? If Cu had been used in place of iron, what would have been titre value ?

SOLUTION :

Fe  Fe 2  SO4  3 
 3FeSO 4  V = 75 mL
 Titre value = 75 mL
1 mole of Fe 2  SO4 3  3 moles of FeSO 4
If Cu were used in place of Fe
1 mole of Fe 2  SO4 3 .  NH 4 2 SO 4 .24H 2O
Cu  Fe2  SO 4 3 
 2FeSO 4  CuSO4
1 mole 2 mole
 1 mole of Fe 2  SO4 3
(only FeSO4 react with KMnO4)
2.41
moles of salt  2.41 mole of Fe 2  SO4 3
9.64 964 2.41 2.41
mol Fe 2  SO4 3  2  mole FeSO4
964 964
3  2.41
 moles of FeSO4 . meq of FeSO4  meq of KMnO4
964

Now, meq of FeSO 4  meq of KMnO 4 .  2  2.41 

   11000  0.1 V
 964 
 3  2.41 
  1000  0.1 V  V = 50 mL
 964 
 Titre value = 50 mL
 Fe 2
 Fe3  1e ; x 1
 
Example - 11 A solution of 0.2 gm of a compound containing cupric and oxalate ions or titration with
0.02 M potassium permanganate in presence of sulphuric acid consumes 22.6 mL of the oxidant. The resultant
solution is neutralised with sodium carbonate, acidified with dil. acetic acid and treated with excess of KI.
The iodine liberated required 11.3 mL of 0.05 M sodium thiosulphate solution for reduction. Find the mole
rate of two ions. Also write down the balanced redox reactions involved in the above titrations.

SOLUTION :
Cu2+ ion can not be oxidised, so only C2O42- 5C 2O42   2MnO 4 16H  

will be oxidised by KMnO4.
2Mn 2   10C O 2  8H 2

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2 millimoles of MnO 4  5 millimoles of 2 millimoles of S2O32   1 millimoles of I2

C2 O42  ions (0.05  11.3)mmole S2O32  

0.02  22.6 m . m o l e s o f MnO 4  5 / 2 1 / 2(0.05  11.3) mmol of I2

 0.02  22.6 m.moles = 1.13 m.moles of
= 0.2825 mmole I2
oxalate ions
Also, 1 mmol I 2  2 mmol Cu 2 
Important :

Cu 2   KI 
 Cu  (not Cu 0 ) 0.2825 m.mol I 2  2  0.2825 mmol Cu 2 

2Cu 2   2I 
 I2  2Cu  = 0.565 mmol Cu2+

2
and I2  2S2O32  
 2I   S4O62  C2 O 4 1.13
So, mole ratio of  2
Cu 2  0.565

Example - 12 25 ml solution containing 6.35 g/L of K H3(C2O4)2 .2H2O required V1 ml of 0.1 N NaOH
and V2 ml of 0.1 N KMnO4 in two separate titrations. Calculate V1 and V2

SOLUTION :
KH3(C2O4)2 . 2H2O : M0 = 254 gm/mol (b) meq of compound (as RA) = meq of
KMnO4
(a) meq of compound (as acid)  meq of
NaOH 25  NRA = V2  0.1
25  Na = V1  0.1 S 6.35
where N RA    0.10
E 254 / 4
S 6.35
 where Na    0.075
E 254 / 3 25  0.1
 V2   25ml
[Note : 3 acidic Hydrogens] 0.1

25  0.075 [Note : n - factor = 4 due to 2 mole of C2 O 42  ]

 V1   18.75 ml
0.1

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Example - 13 Three solution, each 100 ml containing 0.3 M Ag2S2, 4.5M NaOH and 4.5M H2O2 respectiley
were mixed to form AsO43- and SO42- as products.
(i) Give a balanced redox equation.
(ii) Calculate the molarity of each species left at the end of the reaction.
(iii) If the above solution is allowed to stand for sometime, what volume of O2 will be collected at STP ?

SOLUTION :

(i)  AsO43  H 2O  SO42 

Given: As 2S3  NaOH  H 2O2 

Oxidation : As32 16OH  

 2AsO34  8H 2O  4e  ...(i)

S32   24OH  
 3SO42   12H 2O  24e ...(ii)

Adding (i) and (ii), we ger : As32  S32   40OH  

 2AsO34  3SO42   20H 2O  28e ...(iii)
  As2S3 

Reduction : H 2O 2  2e  
 2OH  ...(iv)

Multiply (iii) by 1 and (iv) by 14 and add to get :

As2S3  12OH   14 H 2O2 

 2 AsO34  3SO42   20 H 2O

(ii) Initial mmoles of As 2S3  0.3100  30; Initial mmole of NaOH  4.5 100  450

Initial mmoles of H 2O2  4.5 100  450;

It is clear form the balanced equation and mmoles of reactants that As 2S3 is the limiting regent.

90
moles of NaOH left = 450  12  30  90  M NaOH   0.3M
300

30
mmoles of H 2O 2 left  450 14  30  30  M H 2O2   0.1M
300

60
mmoles of AsO 34 formed  2  30  60  M   0.2 M
AsO34 300

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90
mmoles of SO 24  formed  3  30  90  M   0.3M
SO24  300

600
mmoles of H 2O formed  20  30  60  MH2O  2M
300

(iii) If a H 2O 2 solution is allowed to stand, it decomposes to give O2 and H 2O 2 .

1
H 2O 2 
 H 2O  O 2
2

1
Thus, mmoles of O2 formed  30   15
2

or, volume of O2 at STP 15  22.4 103 L  0.336 L [ 1 mole of O2 at STP  22.4 L]

NOW ATTEMPT OBJECTIVE WORKSHEET TO COMPLETE THIS EBOOK

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Vidyamandir Classes

THINGS TO REMEMBER

1. In a typical redox reaction : X  Y 

AB

meq. of an oxidising agent = meq. of a reducing agent

 g 
2. From definition of gram-equivalents  gmeq.   N VL  , it is very clear that, we must be very confident
 E 
about the concept of equivalent weight (E), for an oxidising or reducing agent.
 The equivalent weight of an oxidising or reducing agent is defined as :

M0
Equivalent weight = E 
x
where M0 = molecular mass ; x = number of electrons transferred (loss or gain) by one mole of
oxidising or reducing agent as given by their balanced ionic half reaction.
3. Variable equivalent weight : Equivalent weight may be variable in many cases. It may depend upon the
medium (acidic/basic) ; dilute/concentrated solution ; whether a reagent is acting as an oxidant or reductant ;
whether a reagent is acting as an oxidant or an acid ; whether a reagent is acting reductant or an acid.
4. A reaction in which same atom is oxidised and reduced at the same time is called as a disproportion-
ation reaction. And the equivalent weight of a compound undergoing disproportionation is :

Effective molecular weight of compound

E 
Number of e  transfer

 Total weight in   Total weight in 

where Effective molecular weight =    
 Oxidation half reaction   Re duction half reaction 
5. Volume strength is the volume of O2 given out at S.T.P. by 1 volume solution of H2O2.
1 M H2O2  11.2 vol of O2 at STP or 1N H2O2  5.6 vol of O2
6. Avoid use of concept of meq in following cases. (Non-typiccal Redox reactions).


H
(a) KMnO4  HCl 
 Cl2  MnCl2  KCl (b) KIO3  KI 
 I2

(c) KMnO4 
 KMnO4  MnO2

7. If a reagent (oxidant or reductant) shows different equivalent weights in two different redox reactions in
a given problem then apply concept of meq carefully. In fact it is advised to use the mole concept in such
cases. (Refer to Illustration 14 & 15)

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Things to
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SOLUTION - IN-CHAPTER EXERCISE - A

1. (i) CN  
 N 2  HCO3 and OCl 
 Cl
(Both C and N areoxidised) (Re duced)

(ii) O3 
 O2 and C6 H5OH 
 CO 2
Reduced Oxidised

(iii) I 
 I2 and O3 
 O2
Oxidised Re duced

(iv) S2O32  
 HSO4 and Cl2 
 Cl
Oxidised Re duced

(v) C 
 CO and ZnO 
 Zn
Oxidised Re duced

2. (i) Te(s)  NO3 (aq.) 

 TeO 2 (s)  NO(g)

 TeO 2 (s)  4H   4e

Oxidation : Te(s)  2H 2O  ; Reduct ion :

NO3 (aq.)  4H   3e 

 NO(g)  2H 2O

(ii) H 2O 2 (aq.)  Fe 2 (aq.) 

 Fe3 (aq.)  H 2O()

Oxidation : Fe 2  (aq.) 
 Fe3 (aq.)  e  ; Reduct ion :

H 2O 2 (aq.)  2H   2e 
 2H 2O()

(iii) Mn(s)  NO3 (aq.) 

 Mn 2  (aq.)  NO 2 (g)

 Mn 2  (aq.)  2e 
Oxidation : Mn(s)  ; Reduct ion :

NO3 (aq.)  2H   1e  
 NO 2 (g)  H 2O()

(iv) Mn 3 (aq.) 
 MnO2 (s)  Mn 2  (aq.) (Disproportionation Rxn.)

Oxidation : Mn 3 (aq.)  2H 2O 
 MnO 2 (s)  4H   e  ; Reduction :

Mn 3  (aq.)  e  
 Mn 2  (aq.)

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3. (i) VO2  (aq.) 

 V3 (aq.)  VO2  (aq.)  2H   e 
 V3 (aq.)  H 2O

(ii) NO3 (aq.) 

 NO2 (g)  NO3 (aq.)  2H   e 
 NO2  H 2O

(iii) IO3 (aq.) 

 I3 (aq.)  3IO3  18H  18e 
 I3  9H2O

4. (i) CrO24  (aq.) 

 Cr(OH)4 (aq.)  CrO24  (aq.)  4H 2O  3e 
 Cr(OH)4  4OH

(ii) Bi3 (aq.) 

 BiO3 (aq.)  Bi3 (aq.)  6OH 
 BiO3 (aq.)  3H 2O  2e

(iii) ClO (aq.) 

 Cl (aq.)  ClO (aq.)  H 2O  2e 
 Cl (aq.)  2OH 

5. (i) MnO4 (aq.)  IO3 (aq.) 

 MnO 2 (s)  IO 4 (aq.)

Re duction : MnO 4 (aq)  2H 2O  3e   MnO2 (s)  4OH 

Oxidation : IO3 (aq.)  2OH    IO 4 (aq.)  H 2O  2e 
________________________________________________
2MnO4  3IO3  H 2O 
 2MnO 2  3IO 4  2OH 

(ii) Cu(OH) 2 (s)  N 2H 4 (aq.) 

 Cu(s)  N 2 (g)

Oxidation : N 2 H 4 (aq.)  4OH   N 2 (g)  4H 2O  4e

Re duction : Cu(OH) 2 (s)  2H 2O  2OH   2e   Cu(s)  4OH   2H 2O
_________________________________________________________
2Cu(OH)2 (s)  N 2H 4 (aq.) 
 2Cu(s)  N 2 (g)  4H 2O

(iii) Fe(OH)2 (s)  CrO 42  (aq.) 

 Fe(OH)3 (s)  Cr(OH)4 (aq.)

Oxidation : Fe(OH) 2 (s)  OH    Fe(OH)3 (s)  e

Re duction : CrO 24  (aq.)  4H 2O  3e  
 Cr(OH) 4  4OH 
_________________________________________________________
3Fe(OH)2  CrO 42  (aq.)  4H 2O 
 3Fe(OH)3  Cr(OH) 4  OH 

(iv) H 2O 2 (aq.)  ClO4 (aq.) 

 ClO2 (aq.)  O2 (g)

Oxidation : H 2O2 (aq.)  2OH    O 2 (g)  2H 2O  2e 

Re duction : ClO4 (aq.)  2H 2O  4e   ClO2 (aq.)  4OH 
____________________________________________________
2H 2O2 (aq.)  ClO 4 (aq.) 
 2O2 (g)  ClO 2 (aq.)  2H 2O

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6. (i) H 2O 2 (aq.)  Cr2O72  (aq.) 

 Cr 3 (aq.)  O2 (g)

Oxidation: H 2O2 (aq.)   O2 (g)  2H   2e 

Re duction : Cr2O72  (aq.)  14H   6e  
 2Cr 3 (aq.)  7H 2O
________________________________________________
Cr2O72  (aq.)  3H 2O2  8H  
 2Cr 3  3O2  7H 2O

(ii) H 2O 2 (aq.)  Mn 2  (aq.) 

 MnO 2 (s)  H 2O

Oxidation : Mn 2  (aq.)  4OH  

 MnO 2 (s)  2H 2O  2e
Re duction : H 2O2 (aq.)  2e  
  2OH 
_______________________________________________
Mn 2  (aq.)  H 2O2 (aq.)  2OH  
 MnO 2  2H 2O

(iii) Sn 2  (aq.)  IO4 (aq.) 

 I (aq.)  Sn 4  (aq.)

Oxidation : Sn 2  (aq.) 
 Sn 4  (aq.)  2e
Re duction : IO 4 (aq.)  8H   8e  
 I (aq.)  4H 2O
_____________________________________________________
4Sn 2  (aq.)  IO4 (aq.)  8H  
 4Sn 4  (aq.)  I   4H 2O

(iv) MnO4 (aq.)  SO32  (aq.) 

 MnO42  (aq)  SO42  (aq.)

Oxidation : SO32  (aq.)  2OH   SO 42  (aq.)  H 2O  2e 

Re duction : MnO 4 (aq.)  e   MnO42  (aq.)
_______________________________________________________________
SO32 (aq.)  2MnO4 (aq.)  2OH  
 SO 42  (aq.)  2MnO 42  (aq.)  H 2O

(v) Cr2O72  (aq.)  HI (aq.) 

 CrI3 (aq.)  I2 (g)  KI

Oxidation : 2HI(aq.)   I 2 (aq)  2H   2e 

Re duction : Cr2O72  (aq.)  14H   6e    2Cr 3  7H 2O
______________________________________________________
Cr2O72  (aq.)  6HI(aq.)  8H  
 2Cr 3 (aq.)  3I 2 (g)  7H 2O

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7. (i) CuO  NH3 

 N 2  Cu  H 2O

Oxidation : 2NH3   N 2  6H   6e

Re duction:CuO  2H   2e    Cu  H 2 O
________________________________
3CuO  2NH3 
 3Cu  N 2  3H 2O

(ii) HI  HNO3 
 I2  NO  H 2O

Oxidation : 2HI   I 2  2H   2e

Re duction : HNO3  3H   3e    NO  2H 2O
__________________________________
6HI  2HNO3 
 3I 2  2NO  4H 2O

(iii)  PH3  H 2 PO2  H 

P4  H 2O 

Oxidation : P4  8H 2O   4H 2PO 2  8H   4e

Re duction :P4  12H   12e   4PH 3
_______________________________________
 4PH3  12H 2 PO 2  12H 
4P4  24H 2O 

(iv) H 2S  SO 2 
 S  H 2O

 S  2H   2e
Oxidation : H 2S 
Re duction : SO 2  4H   4e 
 S  2H 2O
_____________________________
2H 2S  SO 2 
 3S  2H 2O

(v) CN   MnO4  H 2O 
 MnO 2  CNO   OH 

Oxidation : CN   2OH  
 CNO  H 2O  2e
Re duction : MnO 4  2H 2O  3e 
 MnO2  4OH 
_______________________________________________
3CN   2MnO 4  H 2O 
 3CNO  2MnO 2  2OH 

(vi) [Fe(CN)6 ]3  N 2 H 4  OH  

 [Fe(CN)6 ]4   N 2  H 2O

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Re duction :[Fe(CN)6 ]3  e  

 [Fe(CN) 6 ]4 
Oxidation : N 2 H 4  4OH  
 N 2  4H 2O  4e 
______________________________________________________
4[Fe(CN)6 ]3  N 2 H 4  4OH  
 4[Fe(CN) 6 ]4  N 2  4H 2O

(vii) C2 H5OH  MnO 4 

 CH3COO  MnO2  H 2O  OH 

Oxidation : C2 H5OH  5OH    CH3COO  4H 2O  4e 

Re duction : MnO4  2H 2O  3e 
 MnO 2  4OH 
_______________________________________________________
3C 2H5OH  4MnO4 
 3CH3COO  4MnO2  4H 2O  OH 

(viii) P4  H   NO3 (dil)  H 2O 

 H 2PO 4  NO

Oxidation : P4  16H 2O   4H 2PO4  24H   20 e

Re duction : NO3  4H   3e  NO  2H 2O
______________________________________________
3P4  20NO3  8H 2O  8H  
 12H 2 PO 4  20NO

(ix) HS  HSO3 

 S2O32   H2O

Oxidation : HS  3H 2O   S2O32   8H   8e 

Re duction : 2HSO3  4H   4e   S2O32  3H 2O
____________________________________
2HS  4HSO3 
 3S2O32   3H 2O

(x) Fe3  NH2OH 

 Fe2   N 2O  H 

Oxidation : 2NH 2OH   N 2O  H 2O  4H   4e 

Re duction : Fe3  e 
 Fe 2
_____________________________________________
4Fe3  2NH 2OH 
 4Fe 2   N 2O  H 2O  4H 

(xi) O2  H 2O 
 OH   O2

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Oxidation : O 2 
 O 2  e
Re duction:O2  2H 2O  3e 
 4OH 
___________________________
4O 2  2H 2O 
 3O 2  4OH 

(xii) IO3  HSO3 

 I  H  SO42 

Oxidation : HSO3  H 2O   SO42   3H   2e 

Re duction: IO3  6H   6e   I  3H 2O
_________________________________
IO3  3HSO3   3SO 42   I  3H 

(xiii) I  IO3  H  
 I 2  H 2O

Oxidation : 2I   I 2  2e 
Re duction : 2IO3  12H   10e  
 I 2  6H 2O
________________________________
IO3  5I  6H  
 3I2  3H 2O

(xiv) Fe2S3  H2O  O 2 

 Fe(OH)3  S

Oxidation : S2 
 S  2e 
Re duction :O 2  2H 2O  4e  
 4OH 
_______________________________
O2  2S2   2H 2O 
 2S  4OH 

 2Fe2S3  3O2  6H 2O 

 4Fe(OH)3  6S

(xv) IBr  BrO3  H 2O 

 IO3  Br   H 

Oxidation : I  3H 2O   IO3  6H   4e

Re duction : BrO3  6H   6e  Br   3H 2O
_______________________________________
3I  2BrO3  3H 2 O 
 3IO3  2Br   6H 

 3IBr  2BrO3  3H 2O 
 3IO3  5Br   6H 
(xvi) CrI3  H 2O 2  OH  
 CrO42  IO4  H 2O

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Oxidation : CrI3  32OH    CrO 42   3IO 4  16H 2O  27e

Re duction : H 2O 2  2e  
 2OH 
_________________________________________________
2CrI3  27H 2O2  10 OH  
 2CrO 42  6IO4  32H 2O

(xvii) H 2O 2  Fe2   H  
 H 2O  Fe3

Oxidation : Fe 2  
 Fe3  e 
Re duction: H 2O 2  2H   2e  
 2H 2O
___________________________________
2Fe 2   H 2O2  2H  
 2Fe3  2H 2O

(xviii) As2S3  MnO4  H 2O  H  

 H3AsO 4  Mn 2   S

Oxidation : As 2S3  8H 2O   2H3AsO 4  3S  10H   10e 

Re duction : MnO 4  8H   5e   Mn 2   4H 2O
______________________________________________
As 2S3  2MnO 4  6H  
 2H3AsO4  3S  2Mn 2 

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My Chapter Notes

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Illustration - 1

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