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 REDOX & EQUIVALENT CONCEPTS (STOCHIOMETRY-II)
q OXIDATION & REDUCTION
Let us do a comparative study of oxidation and Reduction ;
Oxidation Reduction
(1) Addition of oxygen (i) Removal of oxygen
e.g. 2Mg + O2 ® 2MgO e.g. CuO + C ® Cu + CO
(2) Removal of Hydrogen (ii) Addition of Hydrogen
e.g. H2S + Cl2 ® 2HCl + S e.g. S + H2 ® H2S
(3) Increase in positive charge (iii) Decrease in positive charge
e.g. Fe2+ ® Fe3+ + e– e.g. Fe3+ + e ® Fe2+
(4) Increase in oxidation number (iv) Decrease in oxidation number
(+2) (+4) (+7) (+2)
SnCl2 ® SnCl4 MnO4– ® Mn2+
(5) Removal of electron (v) Addition of electron
e.g. Sn2+ ® Sn4+ + 2e– e.g. Fe3+ + e– ® Fe2+

Oxidation Number :
u It is an imaginary or apparent charge gained by an element when it goes from its elemental
free state to combined state in molecules.
u It is calculated on basis of a arbitrary set of rules.
u It is a relative charge in a particular bonded state.
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Rules governing oxidation number :

The following rules are helpful in calculating oxidation number of the elements in their different
compounds. It is remember that the basis of these rule is the electronegativity of the element.
u Fluorine atom :
Fluorine is most electronegativity atom (known). It always has oxidation no. equal to –1 in all
its compounds.
u Oxygen atom :
In general and as well as in its oxides, oxygen atom has oxidation number equal to –2.
In case of : (i) peroxide (e.g. H2O2, Na2O2) is –1
(ii) super oxide (e.g. KO2) is – ½
(iii) ozonide (KO3) is – 1 3
(iv) oxygen fluoride OF2 is +2 & in O2F2 is +1

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 u Hydrogen atom :
In general, H atom has oxidation number equal to +1. But in metallic hydrides (e.g. NaH, KH)
it is –1.
u Halogen atom :
In general, all halogen atom (Cl, Br, I) has oxidation number equal to –1.
But if halogen atom is attached with an more electronegative atom than halogen atom then it
will show positive oxidation numbers.
+5 +5 +7 +5
e.g. KClO3 HlO3 HClO4 KBrO3
u Metals :
(a) Alkali metal (Li, Na, K, Rb, ..........) always have oxidation number +1.
(b) Alkaline earth metal (Be, Mg, Ca ........) always have oxidation number +2.
Note : Metal may have positive or zero oxidation number.
(c) Aluminium always have +3 oxidation number
u Oxidation number of an element in free state or in allotropic forms is always zero.
0 0 0 0
e.g. O2 ,S8 ,P4 ,O3
u Sum of the charges of elements in a molecule is zero.
u Sum of the charges of all elements in an ions is equal to the charge on the ion.
u If the group no. of an element in periodic table is n then its oxidation number may vary from
n to n – 8 (but it is mainly applicable in p-block elements)
e.g. N-atom belongs to v group in the periodic table therefore as per rule its oxidation number may
vary from
-3 +2 +3 +4 +5
–3 to +5 (NH3 ,NO,N2O3,NO2 ,N2O5 )
Calculation of average oxidation number :
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Solved Examples :
Ex. Calculate oxidation number of underlined element Na2S2O3 :
Sol. Let oxidation number of S-atom is x. Now work accordingly with the rules given before.
(+1) × 2 + (x) × 2 + (–2) × 3 = 0
x=+2
Ex. Na2 S 4O6 :
Sol. Let oxidation number of S-atom is x
(+1) × 2 + (x) × 2 + (–2) × 6 = 0
x = + 2.5
u It's important to note here that Na2S2O3 have two S-atom and there are four S-atom in Na2S4O6
but sulphur atom in both the compound have +2 or +2.5 oxidation number, it is the average
charge (O. No.) Which reside on each sulphur atom therefore we should work to calculate the
individual oxidation number of each sulphur atom in these compound.

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 Ex. Calculate the O.S. of all the atoms in the following species :
(i) ClO–, (ii) NO2–, (iii)NO3– (iv)CCl4 (v) K2CrO4 and (vi)KMnO4
Sol. (i) In ClO–, the net charge on the species is –1 and therefore the sum of the oxidation states
of Cl and O must be equal to –1. Oxygen will have an O.S. of –2 and if the O.S. of Cl
is assumed to be 'x' then x – 2 should be equal to –1.
x is + 1
(ii) NO–2 : (2 × –2) + x = –1 (where 'x' is O.S. of N)
\ x = +3
(iii) NO–3 : x + (3 × –2) = –1 (where 'x' is O.S. of N)
x = +5
(iv) In CCl4, Cl has an O.S. of –1
x + 4 × –1 = 0
\ x = +4 (where 'x' is O.S. of C)
(v) K2CrO4 : K has O.S. of +1 and O has O.S. of –2 and let Cr has O.S. 'x' then,
2 × +1 + x + 4 × –2 = 0
\ x = +6
(vi) KMnO4 : +1 + x + (4 × –2) = 0
\ x = +7 (where x is O.S. of Mn).
q MISCELLANEOUS EXAMPLES
In order to determine the exact or individual oxidation number we need to take help from the struc-
tures of the molecules. Some special cases are discussed as follows :
O O

u The structure of CrO5 is Cr

O O O

From the structure it is evident that in CrO5 there are two peroxide linkages and one double
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bond.
The contribution of each peroxide linkage is –2. Let the O.N. of Cr is x.
\ x + (–2)2 + (–2) = 0 or x = 6
\ O.N. of Cr = +6Ans.
–3
O O
O O
K3CrO8 Cr
O O
O O

From the structure it is evident that in CrO8–3 there are four peroxide linkages.
The contribution of each peroxide linkage is –2. Let the O.N. of Cr is x.
\ x + (–2)4 = –3 or x = +5
\ O.N. of Cr = +5Ans.
O
u The strcuture of H2SO5 is H O O S
O
H O

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 From the structure, it is evident that in H2SO5. there are one peroxide linkage, two sulphur - oxygen
double bond and one OH group. Let the O.N. of S = x.
\ +1 – 2 + x + (–2) 2 + (–2) + 1 = 0
or x+2–8=0
or x–6=0
or x=6
\ O.N. of S in H2SO5 is +6 Ans
q PARADOX OF FRACTIONAL OXIDATION NUMBER
Fractional oxidation state is the average oxidation state of the element under examination and the
structural parameters reveal that the element for whom fractional oxidation state is realised is actually
present in different oxidation states. Structure of the species C3O2, Br3O8 and S4O62– reveal the fol-
lowing bonding situations.
u The element marked with asterisk in each species is exhibiting the different oxidation state
(oxidation number) from rest of the atoms of the same element in each of the species. This
reveals 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. However the realistic picture
is +2 for two terminal carbons and zero for the middle carbon.
+2 0 +2
O = C = C* = C = O

Structure of C3O2
(Carbon suboxide)
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u 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. Once again the average, that is differ-
ent from reality is 16/3.
O +6 +4O O
+6
O = Br = Br* B = O
O O O

Structure of Br3O8 (tribromooctaoxide)

u In the same fashion, in the species S4O62–, is 2.5, whereas the reality being +5,0,0 and +5
oxidation number respectively for each sulphur.
O O
+5 0 0 +5 –
O S S* S* S O
O O

Structure of S4O62– (tetrathionate ion)

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 q OXIDISING AND REDUCING AGENT

u Oxidising agent or Oxidant :

Oxidising agents are those compound which can oxidise others and reduced itself during the
chemical reaction. Those reagents whose O.N. decrease or which gain electrons in a redox
reaction are termed as oxidants

e.g. KMnO4, K2Cr2O7, HNO3, conc. H2SO4 etc, are powerful oxidising agents.

u Reducing agent or Reductant :

Redusing agents are those compound which can reduce others and oxidise itself during the
chemical reaction. Those reagents whose O.N. increase or which loses electrons in a redox
reaction are termed as reductants.

e.g. KI, Na2S2O3 are powerful reducing agents.

Note : There are some compounds also which can work both oxidising agent and reducing agent.

e.g. H2O2, NO–2

q HOW TO IDENTIFY WHETHER A PARTICULAR SUBSTANCE IS AN OXIDISING OR

REDUCING AGENT

Find the O.State of the central atom

If O.S. is=Max. O.S. or (valence electron) If O.S. =Minimum O.S. If O.S. is intermediate b/w max & minimum
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Its Oxidizing It's a reducing It can act both as reducing

agent agent agent & oxidising agent

It can disproportionate
as well

q REDOX REACTION
A reaction in which oxidation and reduction simultaneously take place.
In all redox reactions the total increase in oxidation number must equal the total decrease in oxidation
number.
+2 +7 +3 +2
e.g. 10 Fe SO4 + 2KMnO4 + 8H2SO4 ¾® 5 Fe2 (SO 4 )3 + 2Mn SO 4 + K2SO4 + 8H2O
q TYPE OF REACTION
u Combination Reactions :
When two or more element combine to form compound then such reaction are redox reaction.
For example
A + B ¾® C

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 0 0 +2 –3
(a) D
3 Mg(s) + N 2 (g) ¾¾ ® Mg 3 N 2 (s)
0 0 +4 -2
(b) D
C(s) + O2 (g) ¾¾ ® CO2 (g)
- 4 +1 0 + 4 -2 +1 -2
(c) D
CH 4 (g) + 2O2 (g) ¾¾ ® CO2 (g) + 2H2 O( l )
0 0 +1 -3
(d) D
Li(s) + N 2 (g) ¾¾ ® Li3 N(s)

In reaction (c), there is no change in the oxidation number of hydrogen.

u Decomposition Reactions :
Decomposition reactions are opposite of combination. Decomposition reactions are those in which
when a molecule breaks down to form two or more components, at least one of them must be in the
elemental state. For example :
+ 1 +5 -2 +1 - 1 0
(a) D
2K Cl O3 (s) ¾¾ ® 2M Cl(s) + 3O2 (g)
+2 -1 0 0
(b) D
Ca H2 ¾¾ ® Ca(s) + H2 (g)
+1 -1 0 0
(c) D
2NaH(s) ¾¾ ® 2Na(s) + H2 (g)
+1 -2 0 0
(d) H2O(l) ¾¾
D
® 2H2 (g) + O2 (g)

Exception :
+ 2 +4 -2 +2 -2 +4 -2
D
Ca CO3 (s) ¾¾ ® CaO(s) + CO 2( g)

u Displacement Reactions :
A reaction in which an atom or iron in a compund is replaced by an atom or ion of another element is
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called a displacement reaction. It may be denoted as :

X + YZ ¾® XZ + Y
u Disproportionations reactions :
A redox reaction in which a same element present in a particular compound in a definite oxidation
state is oxidized as well as reduced simultaneously is a disproportionation reactions.
Disproportionation reactions are a special type of redox reactions. One of the reactants in a
disproportionation reaction always contains an element that can exist in at least three oxidation
states. The element in the form of reacting substance is in the intermediate oxidation state and both
higher and lower oxidation states of that element are formed in the reaction.
+ 1 -1
2H2 O2 (aq) ¾® H2 O (l) + O2(g)
0 -2 +2
–
S8 (s) + 12OH (aq) ¾® 4 S2- (aq) + 2 S 2O23- (aq) + 6H2O (l)
0 +1 -1
Cl2 (g) + 2OH (aq) ¾® ClO- (aq) + Cl- (aq) + H2O (l)
–

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 u Consider following reactions :
(a) 2KClO3 = 2KCl + 3O2
KClO3 plays a role of oxidant and reductant both. Because same element is not oxidised and
reduced. Here, Cl present in KClO3 is reduced and O present in KClO3 is oxidized. So its not
a disproportion reaction although it looks like one.
(b) NH4NO2 ¾® N2 + 2H2O
Nitrogen in this compound has –3 and +3 oxidation number so it is not a definite value, so its not
a disproportion reaction. Its a example of comproportionation reaction which is a class of redox
reaction in which a element from two different oxidation state gets converted into a single oxida-
tion state.
(c) 4KClO3 ¾® 3KClO4 + KCl
Its a case of disproportionation reaction in which Cl is the atom disproportionating.
u List of some important disproportionation reaction :
1. H2O2 ¾® H2O + O2
2. X2 + OH– (dil.) ¾® X– + XO–
3. X2 + OH– (conc.) ¾® X– + XO3–
F2 does not (can not) undergo disproportionation as it is the most electronegative element.
F2 + NaOH (dil) ¾® F – + OF2
F2 + NaOH concentration (dil) ¾® F – + O2
u Reverse of disproportionation is called Comproportionation. In some of the disproportion-
ation reactions by changing the medium (from acidic to basic or reverse) the reaction goes in
backward direction and can be taken as an example of Comproportionation.
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I – + IO3– + H+ ¾® I2 + H2O (acidic)

q BALANCING OF REDOX REACTION
All balanced equations must satisfy two criteria
1. Atom balance (mass balance) :
That is there should be the same number of atoms of each kind in reactant and products side.
2. Charge balance :
That is the sum of actual charges on both side of the equation must be equal
There are two methods for balancing the redox equations
(a) Oxidation - number change method
(b) Ion electron method or half cell method
(a) Oxidation number change method :
This method was given by Jonson. In a balanced redox reaction, total increase in oxidation
number must be equal to total decreases in oxidation number. This equivalence provides the
basis for balancing redox reactions.

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 The general procedure involves the following steps :
(i) Select the atom in oxidising agent whose oxidation number decreases and indicate the gain of
electrons.
(ii) Select the atom in reducing agent whose oxidation number increases and write the loss of
electrons.
(iii) Now cross multiply i.e. multiply oxidising agent by the number of loss of electrons and reducing
agent by number of gain of electrons.
(iv) Balance the number of atoms on both sides whose oxidation numbers change in the reaction.
(v) In order to balance oxygen atoms, add H2O molecules to the side deficient in oxygen. Then
balance the number of H atoms by adding H+ ions in the hydrogen.
Ex. Balance the following reaction by the oxidaton number method :
Cu + HNO3 ¾® Cu(NO3)2 + NO2 + H2O
Sol. Write the oxidation number of all the atoms.
0 +1+5–2 +2+5–2 +4 –2 +1 –2
Cu + HNO3 ¾¾¾¾¾® Cu(NO3)2 + NO2 + H2O
There is change in oxidation number of Cu and N.
0 +2
Cu ¾® Cu(NO3)2 ....(1) (Oxidation no. is increased by 2)

+5 +4
HNO3 ¾® NO2 .....(2) (Oxidation no. is decreased
by 1)
To make increase and decrease equal, eq. (2) is multiplied by 2.
Cu + 2HNO3 ¾® Cu(NO3)2 + 2NO2 + H2O
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Balancing nitrates ions, hydrogen and oxygen, the following equation is obtained.
Cu + 4HNO3 ¾® Cu(NO3)2 + 2NO2 + 2H2O
This is the balanced equation.
Ex. Write the skeleton equation for each of the following processes and balance them by ion electron
method :
(i) Permagnet ion oxidizes oxalate ions in acidic medium to carbon dioxide and gets reduced
itself to Mn2+ ions.
(ii) Bromine and hydrogen peroxide react to give bromate ions and water.
(iii) Chlorine reacts with base to form chlorate ion, chloride ion and water in acidic medium.
Sol. (i) The skeleton equation for the process :
MnO4– + C2O42– + H+ ¾® Mn2+ + CO2 + H2O
u Step (1) : Indicating oxidation number :
+7 -2 +3 +4 -2 +1 -2
2+
MnO -4 + C2O24- ¾® Mn + CO2 + H2O
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 u Step (2) : Writing oxidation and reduction half reaction :
+3 +4
C2 O42- ¾® 2CO2 (Oxidation half)
+7 2+
MnO -4 ¾® Mn (Reduction half)
u Step (3) : Adding electrons to make the difference in O.N.
+3 +4
–
C2 O42- ¾® 2CO2 + 2e

+7 – 2+
MnO -4 + 5e ¾® Mn

u Step (4) : Balancing 'O' atom by adding H2O molecules

–
C2 O42- ¾® 2CO2 + 2e

MnO -4 + 5e– ¾® Mn2+ + 4H2O

u Step (5) : Balancing H atom by adding H+ ions
–
C2 O42- ¾® 2CO2 + 2e
– + 2+
MnO -4 + 5e + 8H ¾® Mn + 4H2O
u Step (6) : Multiply the oxidation half reaction by 2 and reduction half reaction by 5 to
equalize the electrons lost and gained and add the two half reactions.
[C2O42– ¾® 2CO2 + 2e–] × 5
[MnO–4 + 5e– + 8H+ ¾® Mn2+ + 4H2O] × 2

2MnO4– + 5C2O2–
4
+ 16H+ ¾® 10CO2 + 2Mn2+ + 8H2O
(ii) The skeleton equation for the given process is
Br2 + H2O2 ¾® BrO3– + H2O (in acidic medium)
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u Step (1) : Indicate the oxidation number of each atom

0 + 1 -2 +6 -2 +1 - 2
Br2 + H2O2 ¾® BrO3
-
+ H2 O

Thus, Br and O changes their oxidation numbers.

u Step (2) : Write the oxidation and reduction half reaction.

2 æç B rO3- ö÷
0 +5
Br2 ¾® (Oxidation half)
è ø
-1 -2
H2O2 ¾® 2H2O (Reduction half)
u Step (3) : Addition of electrons to make up for the difference in O.N.

2 æç B rO3- ö÷ +10e–
0 +5
Br2 ¾®
è ø
H2O2–1 + 2e– ¾® 2H2O–2
u Step (4) : Balance 'O' atoms by adding H2O molecules
Br2 + 6H2O ¾® 2BrO–3 + 10e–
H2O2 + 2e– ¾® 2H2O

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 u Step (5) : Equalize the electrons by multiplying the reduction half with 5 and add the two
half reactions
Br2 + 6H2O ¾® 2BrO–3 + 10e– + 12H+
[H2O2 + 2e– + 2H+ ¾® 2H2O] × 5

Br2 + 5H2O2 ¾® 2BrO3– + 4H2O + 2H+

(iii) The skeleton equation for the given process :
Cl2 + OH– ¾® Cl– + ClO 3– + H2O
u Step (1) : Indicate the oxidation number of each atom
0 -2 +5 +1 - 2
-–
Cl2 + OH - ¾® Cl + ClO3 + H2 O
Thus, chlorine is the only element which undergoes the change in oxidation number. It
decreases its oxidation number from 0 to 1 and also increases its oxidation number from
0 to 5.
u Step (2) : Write the oxidation and reduction half reactions
0 +5
Cl2 ¾® 2 ClO3- (Oxidation half)
0
Cl2 ¾® 2Cl – (Reduction half)
u Step (3) : Add electrons to make up for the difference in O.N.
0 +5
Cl2 ¾® 2 ClO3- + 10e–
0
Cl2 + 2e– ¾® 2Cl–
u Step (4) : Balance O atoms by adding H2O molecules
Cl2 + 6H2O ¾® 2(ClO3)– + 10e–
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Cl2 + 2e– ¾® Cl–

u Step (5) : Since medium is basic, balance H atoms by adding H2O molecules to the side
falling short of H atoms and equal number of OH– ions to the other side.
Cl2 + 6H2O + 12OH – ¾® 2ClO3– + 10e– + 12H2O
Cl2 + 2e– ¾® 2Cl–
u Step (6) : Multiply the reduction half reaction by 5 and add two half reactions.
Cl2 + 5H2O + 2OH – ¾® 2ClO3– + 10e– + 12H2O
[Cl2 + 2e– ¾® 2Cl–] × 5

Cl2 + 5Cl2 + 12OH – ¾® 2ClO3– + 10Cl– + 6H2O

or, 6Cl2 + 12OH – ¾® 2ClO3– + 10Cl– + 6H2O
or, 3Cl2 + 6OH – ¾® ClO3– + 5Cl– + 3H2O
Ex : Balance the following reaction by the oxidation number method :
MnO4– + Fe+2 ¾® Mn+2 + Fe+3

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 Sol : Write the oxidation number of all the atoms.
+7 –2
MnO4– + Fe+2 ¾¾¾¾¾® Mn+2 + Fe+3
change in oxidation number has occurred in Mn and Fe.
+7 +2
MnO4 ¾® Mn
–
......(1) (Decrement in oxidation no. by 5)

Fe+2 ¾® Fe+3 ......(2) (Increment in oxidation no. by 1)

To make increase and decrease equal, eq. (2) is multiplied by 5.
MnO4– + 5Fe+2 ¾® Mn+2 + 5Fe+3
To balance oxygen, 4H2O are added to R.H.S. and to balance hydrogen, 8H+ are added to L.H.S.
MnO4– + 5Fe+2 + 8H+ ¾® Mn+2 + 5Fe+3 + 4H2O
This is the balanced equation.
Ex. Balance the following chemical reaction by oxidation number method and write their skeleton
equation :
(i) Chloride ions reduce maganese dioxide to manganese (II) ions in acidic medium and get
itself oxidized to chlorine gas.
(ii) The nitrate ions in acidic medium oxidize magnesium to Mg2+ ions but itself gets reduced
to nitrous oxide.
Sol. (i) The skeleton equation for the given process is
MnO2 + Cl– ¾® Mn2+ + Cl2 + H2O
+4 -2 +4 +1 -2
– 2+
u Step (1) : MnO2 + Cl ¾® Mn + Cl2 + H2O
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u Step (2) : O.N. decreases by 2 per Mn

+4
MnO2 + Cl– ¾® Mn2+ + Cl2 + H2O

O.N. increases by 1 per Cl

u Step (3) : Equalize the increase/decrease in O.N. by multiplying

MnO2 by 1 and Cl – by 2

MnO2 + 2Cl – ¾® Mn2+ + Cl2 + H2O

u Step (4) : Balance other atoms except H and O. Here they are all balanced.

u Step (5) : Balance O atoms by adding H2O molecules to the side falling short of O atoms.

MnO2 + 2Cl – ¾® Mn2+ + Cl2 + H2O + H2O

u Step (6) : Balance H atoms by adding H+ ions to the side falling short of H atoms.

MnO2 + 2Cl – + 4H+ ¾® Mn2+ + Cl2 + 2H2O

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 (ii) The skeleton equation for the given process is

Mg + NO3– ¾® Mg2+ + N2O + H2O

0 +5 -2 +1 -2 +1 -2
u Step (1) : Mg + ( N O3 )– ¾® Mg2+ + N2O + H2O

Multiply NO–3 by 2 to equalize N atoms

u Step (2) : O.N. increases by 2 per Mg atom

0 +1
Mg + 2NO3– ¾® Mg2+ + N2O + H2O
4 ×2 = 8
O.N. decreases by 4 per N atom

u Step (3) : Equalize increase/decrease in O.N. by multiplying Mg by 4 and 2NO3– by 1.

4Mg + 2NO3– ¾® Mg2+ + N2O + H2O
u Step (4) : Balance atoms other than O and H
4Mg + 2NO3– ¾® 4Mg2+ + N2O + H2O
u Step (5) : Balance O atoms
4Mg + 2NO3– ¾® 4Mg2+ + N2O + H2O + 4H2O
u Step (6) : Balance H atoms as is done in acidic medium.
4Mg + 2NO3– + 10H+ ¾® 4Mg2+ + N2O + 5H2O
(b) Ion electron method or half cell method :
Nucleus Education-(NURTURE_(UNACADEMY)

By this method redox equation are balanced in two different medium

(a) Acidic medium (b) Basic medium
u Balancing in acidic medium
Students are advised to follow the following steps to balance the redox reactions by ion
electron method in acidic medium.
Solved Examples :
Ex : Balance the following redox reaction.
FeSO4 + KMnO4 + H2SO4 ¾® Fe2(SO4)3 + MnSO4 + H2O
Sol : Step-I assign the oxidation No. to each elements present in the reaction.
+2 +6 -2 +1 +7 -2 +1 +6-2 +3 +6-2 +2 +6 -2 +1 -2
Fe S O 4 + KMnO4 + H2 SO 4 ¾® Fe2 ( SO 4 )3 + MnS O 4 + H2 O
Step-II Now convert the reaction in ionic form by eliminating the elements or species which are not
going either oxidation or reduction
+7
Fe2+ + MnO-4 ¾® Fe3+ + Mn2+

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 Step-III Now identify the oxidation / reduction occurring into the reaction.
undergoes reduction
2+ – 3+ 2+
Fe + MnO 4® Fe + Mn
undergoes oxidation

Step-IV Split the ionic reaction in two half one for oxidation and other for reduction
oxidation
Fe2+ ¾¾¾¾¾ ® Fe3+ MnO4– ¾¾¾¾¾
Re duction
® Mn
2+

Step-V Balance the atom other than oxygen and hydrogen atom in both half reactions
Fe2+® Fe3+ MnO4– ® Mn2+
Fe & Mn atom are balanced in both side.
Step-VI Now balance O & H atom by H2O & H+ respectively by the following way for one excess
oxygen atom add one H2O on the other side and two H+ on the same side.
Fe2+ ¾® Fe3+ (no oxygen atom) ..........(i)
+ – 2+
8H + MnO ¾® Mn + 4H2O
4
.........(ii)
Step VII Now see equation (i) & (ii) is balanced atomwise. Now balance both equations chargewise
to balance the charge add electrons to the electrically positive side.
Fe2+ ¾¾¾¾¾
oxidation 3+
® Fe + e
–
..........(1)

5e– + 8H+ + MnO4– ¾¾¾¾¾

Reduction 2+
® Mn + 4H2O ..........(2)
Step VIII The number of electrons gained and lost in each half-reaction are equalised by multiply
suitable factor in both the half reaction and finally the half reactions are added to give the over all
balanced reaction.
Here we multiply equation (i) by 5 and (ii) by one
Nucleus Education-(NURTURE_(UNACADEMY)

Fe2+ ¾® Fe3+ + e– .............(1) × 5

5e– + 8H+ + MnO4– ® M2+ + 4H2O .............(2) × 1

5Fe2+ + 8H+ + MnO–4 ® 5Fe3+ + Mn2+ + 4H2O

(Here at this stage you will get balanced redox reaction in ionic form)
Step IX Now convert the ionic reaction in to molecular form by adding the elements or species which
are removed instep (II).
Now by some manipulation you will get

5
5 FeSO4 + KMnO4 + 4H2SO4 ® Fe2(SO4)3 + MnSO4 + 4H2O or
2

10 FeSO4 + 2KMnO4 + 8H2SO4 ® 5Fe2(SO4)3 + 2MnSO4 + 8H2O + K2SO4

u Balancing in basic medium :
In this case except step VI all the steps are same. We can understand it by following example balance
the redox reaction in basic medium

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 Ex : ClO– + CrO2– + OH– ¾® Cl– + CrO42– + H2O
Sol : By using up to step V we will get
+1 +3 +6
-
Oxidation -
Reduction
ClO – ¾¾¾¾¾ ® Cl – CrO2 ¾¾¾¾¾ ® CrO 24

Now student are advised to follow step VI to balance 'O' and 'H' atom

2H+ + ClO– ¾® Cl– + H2O 2H2O + CrO–2 ¾® CrO42– + 4H+

u Now since we are doing balancing in basic medium therefore add as many as OH– on both
side of equation as there are H+ ions in the equation.
2OH– + 2H+ + ClO– ¾® Cl– + H2O + 2OH– 4OH– + 2H2O + CrO2– ® CrO42– + 4H+ +
4OH–
Finally you will get Finally you will get
H2O + ClO– ¾® Cl– + 2OH– ........(i) 4OH– + CrO2– ® CrO42– + 2H2O .........(ii)
Now see equation (i) and (ii) in which O and H atoms are balanced by OH– and H2O
Now from step VIII
2e– + H2O + ClO– ® Cl– + 2OH– .............(i) × 3
4OH– + CrO2– ® CrO4–2 + 2H2O + 3e– .............(ii) × 2

Adding : 3ClO– + 2CrO2– + 2OH– ® 3Cl– + 2CrO42– + H2O

Equivalent weight (E) :

Molecular weight Mol.wt.

Eq. wt (E) = valency factor (v.f) = n - factor
Nucleus Education-(NURTURE_(UNACADEMY)

mass of a sample
no of Equivalents = eq.wt.of that species

u Equivalent mass is a pure number when expressed in gram, it is called gram equivalent mass.
u The equivalent mass of substance may have different values under different conditions.
Valency factor calculation :
u For Acids :
valence factor = number of replaceable H+ ions
Solved Examples : O
H O P H
Ex : HCl, H2SO4 H3PO 4 H3PO 3 O
H

{see there are only two replaceable H+ ions}

Sol : valence® 1 2 3 2
factor (assume 100%
dissociation)
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 M M M M
Eq.wt.®
1 2 3 2

Self practice problems :

1. Find the valence factor for following acids
(i) CH 3COOH
(ii) NaH2PO 4
(iii) H3BO 3
Answers :
1. (i) 1 (ii) 2 (iii) 1
u For Base :
v.f. = number of replicable OH– ions
Solved Examples :
Ex : NaOH, KOH
Sol : v.f.® 1 1
M M
E.®
1 1
Self practice problems :
1. Find the valence factor for following bases
(i) Ca(OH)2
(ii) CsOH
(iii) Al(OH)3
Answers :
Nucleus Education-(NURTURE_(UNACADEMY)

1. (i) 2 (ii) 1 (iii) 3

u Acid - base reaction :
In case of acid base reaction, the valence factor is the actual number of H+ or OH– replaced in
the reaction. The acid or base may contain more number of replaceable H+ or OH– than actually
replaced in reaction.
v.f. for base is the number of H+ ion form the acid replaced by per molecule of the base.
Solved Examples :
Ex : 2NaOH + H2SO4 ® Na2SO4 + 2H2O
Base Acid
Sol : valency factor of base = 1
valency factor of acid = 2
Here two molecule of NaOH replaced 2H+ ion from the H2SO4 therefore per molecule of NaOH
replaced only one H+ ion of acid so v.f. = 1
u v.f. for acid is number of OH– replaced for the base by per molecule of acid
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 Ex : NaOH + H3PO4 ® NaH2PO4 + H2O
Base Acid
Sol : valence factor of acid = 1
here one of molecule of H3PO4 replaced one OH– from NaOH therefore v.f. for H3PO4 is = 1
mol.wt.of H3PO 4
E=
1
Ex : 2NaOH + H3PO4 ® Na2HPO4 + 2H2O
Base Acid
Sol : valence factor of acid = 2
here one of molecule of H3PO4 replaced two OH– from NaOH therefore v.f. for H3PO4 is = 2
mol.wt.of H3PO 4
E=
2
Ex : Al(OH)3 + HCl ® Al(OH)2Cl + H2O
Base Acid
Sol : valence factor of base = 1
here one of molecule of Al(OH)3 replaced one H+ from HCl therefore v.f. for Al(OH)3 is = 1
mol. wt.of Al(OH)3
E=
1
u For Salts :
(a) In non reacting condition
v.f. = Total number of positive charge or negative charge present into the compound.
Nucleus Education-(NURTURE_(UNACADEMY)

Solved Examples :
Ex : Na2CO 3 Fe2(SO4)3(2Fe3+ + 3SO42–) FeSO4.7H2O
Sol : V.f. 2 2×3=6 2
M M M
E.
2 6 2
(b) Salt in reacting condition :
Solved Examples :
Ex : Na2CO3 + HCl ® NaHCO3 + NaCl
Base Acid
Sol : It is a acid base reaction therefore v.f. for Na2CO3 is one while in non reaction condition it will be two.
Note :- In neutral condition if salt is not given take valency factor as for complete neutrilization.
(c) Eq. wt. of oxidising / reducing agents in redox reaction :
The equivalent weight of an oxidising agent is that weight which accepts one mole electron in
a chemical reaction.

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 (a) Equivalent wt. of an oxidant (get reduced)
Mol.wt.
= No. of electrons gained by one mole
Ex : In acidic medium
6e– + Cr2O72– + 14H+ ¾¾® 2Cr3+ + 7H2O

Mol. wt of K 2 Cr2 O7 Mol. wt.

Eq. wt. of K2Cr2O7 = =
6 6

Note : [6 in denominator indicates that 6 electrons were gained by Cr2O72– as it is clear from the
given balanced equation]
(b) Similarly equivalent wt. of a reductant (gets oxidised)
Mol. wt.
= No. of electrons lost by one mole
Ex: In acidic medium, C2O42– ¾¾® 2CO2 + 2e–

Mol. wt.
Here, Total electrons lost = 2 So, eq. wt. =
2

(c) In different condition a compound may have different equivalent weights. Because, it depends
upon the number of electrons gained or lost by that compound in that reaction.
Ex : (i) MnO4– ¾¾® Mn2+ (acidic medium)
(+7) (+2)

Mol.wt.of KMnO4 158

Here 5 electrons are taken so eq. wt. = = = 31.6
5 5

(ii) MnO4– ¾¾® Mn+4 (neutral medium)

Nucleus Education-(NURTURE_(UNACADEMY)

(+7) (+4)
Mol.wt.of KMnO4 158
Here, only 3 electrons are gained, so eq. wt. = = = 52.7
3 3
(iii) MnO4– ¾¾® MnO4–2 (alkaline medium)
(+7) (+6)

Mol.wt.of KMnO4
Here, only one electron is gained, so eq. wt. = = 158
1

Note : It is important to note that KMnO4 acts as an oxidant in every medium although with different
strength which follows the order.
acidic medium > neutral medium > alkaline medium
Ex : 2S2O3– – ¾¾¾® S4O6– – + 2e–
(Reducing agent)
2M
equivalent weight of S2O3– – = =M
2

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 u Questions based on Equivalent weight :
1. Molecular weight of KMnO4 in acidic medium and neutral medium will be respectively :
(A) 7 × equivalent wt. and 2 × equivalent wt.
(B) 5 × equivalent wt. and 3 × equivalent wt.
(C) 4 × equivalent wt. and 5 × equivalent wt.
(D) 2 × equivalent wt. and 4 × equivalent wt.
2. Equivalent wt. of H3PO4 in each of the reaction will be respectively :
H3PO4 + OH– ¾¾® H2PO4– + H2O
H3PO4 + 2OH– ¾¾® HPO42– + 2H2O
H3PO4 + 3OH– ¾¾® PO43– + 3H2O
(A) 98, 49, 32.67 (B) 49, 98, 32.67 (C) 98, 32.67, 49 (D) 32.67, 49, 98
3. In acidic medium, equivalent weight of K2Cr2O7 (Mol. wt. = M) is –
(A) M/3 (B) M/4 (C) M/6 (D) M/2
Answers :
(1) B (2) A (3) C
NORMALITY
q Normality of solution is defined as the number of equivalent of solute present in one litre (1000 mL)
solutions. Let a solution is prepared by dissolving W g of solute of eq. wt. E in V mL water.
Nucleus Education-(NURTURE_(UNACADEMY)

W
u No. of equivalent of solute =
E
W
u V mL of solution have equivalent of solute
E

W ´ 1000
u 1000 mL solution have
E ´ VmL

W ´ 1000
u Normality (N) =
E ´ VmL

u Normality (N) = Molarity × Valence factor

Normality (N) = molarity × Valence factor (n)

or N × V (in mL) = M × V (in mL) × n
or milli equivalents = millimoles × n
Solved Examples :

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 Ex : Calculate the normality of a solution containing 15.8 g of KMnO4 in 50 mL acidic solution.
W ´ 1000
Sol : Normality (N) =
E ´ VmL

where W = 15.8 g, V = 50 mL
molar mass of KMnO4
E= Valence factor
= 158/5 = 31.6

So, N = 10
Ex : Calculate the normality of a solution containing 50 mL of 5 M solution K2Cr2O7 in acidic medium.
Sol : Normality (N) = Molarity × Valence factor
= 5 × 6 = 30 N
q LAW OF EQUIVALENCE
The law states that one equivalent of an element combine with one equivalent of the other, and in a
chemical reaction equivalent and mill equivalent of reactants react in equal amount to give same no.
of equivalent or milli equivalents of products separately.
According :
(i) aA + bB ® mM + nN
m.eq of A = m.eq of B = m.eq of M = m.eq of N
(ii) In a compound MxNy
m.eq of MxNy = m.eq of M = m.eq of N
Solved Examples :
Nucleus Education-(NURTURE_(UNACADEMY)

Ex : Find the number of moles of KMnO4 needed to oxidise one mole Cu2S in acidic medium.
The reaction is KMnO4 + Cu2S ¾® Mn2+ + Cu2+ + SO2
Sol : From law of equivalence
equivalents of Cu2S = equivalents of KMnO4
moles of Cu2S × v.f = moles of KMnO4 × v.f.
moles of Cu2S × 8 = 1 × 5 Þ moles of Cu2S = 5/8
Ex : The number of moles of oxalate ions oxidized by one mole of MnO4– ion in acidic medium.
5 2 3 5
(A) (B) (C) (D)
2 5 5 3
Sol : Equivalents of C2O42– = equivalents of MnO4–
x (mole) × 2 = 1 × 5
5
x=
2

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 Ex. What volume of 6 M HCl and 2 M HCl should be mixed to get two litre of 3 M HCl ?
Sol. Let, the volume of 6 M HCl required to obtain 2 L of 3M HCl = x L
\ Volume of 2 M HCl required = (2 – x) L

M1V1 + M2V2 = M3V3

6M HCl 2M HCl 3M HCl
6 × (x) + 2 × (2 – x) = 3 × 2
Þ 6x + 4 – 6x = 6 Þ 4x = 2

\ x = 0.5 L

Hence, volume of 6 M HCl required = 0.5 L

Volume of 2M HCl required = 1.5 L
Ex. In a reaction vessel, 1.184 g of NaOH is required to be added for completing the reaction. How
many millilitre of 0.15 M NaOH should be added for this requirement ?
Sol. Amount of NaOH present in 1000 mL of 0.15 M NaOH = 0.15 × 40 = 6 g
6
\ 1 mL of this solution contain NaOH = × 10–3 g
1000
1
\ 1.184 g of NaOH will be present in = × 1.184 = 197.33 mL
6 ´ 10-3
Ex. What weight of Na2CO3 of 85% purity would be required to prepare 45.6 mL of 0.235N H2SO4
?
Sol. Meq. of Na2CO3 = Meq. of H2SO4 = 45.6 × 0.235
WNa2 CO3
\ × 1000 = 45.6 × 0.235
Nucleus Education-(NURTURE_(UNACADEMY)

E Na2CO3

WNa2 CO3
Þ × 1000 = 45.6 × 0.235
106 / 2

\ WNa2 CO3 = 0.5679 g

For 85 g of pure Na2CO3, weighed sample = 100 g
100
\ For 0.5679 g of pure Na2CO3, weighed sample = ´ 0.5679
85
= 0.6681 g
Drawbacks of Equivalent concept :
u Since equivalent weight of a substance for example oxidising or reducing agent may be vari-
able hence it is better to use mole concept.
e.g. 5e– + 8H+ + MnO4– ® Mn2+ + 2H2O

MnO -4 (mol.wt.)
\ Eq. wt of MnO4– =
5

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 e.g. 3e– + 2H2O + MnO4– ® MnO2 + 4OH–

MnO4-
\ Eq. wt. of MnO4– =
3

Thus the no. of equivalents of MnO4– will be different in the above two cases but no. of
moles will be same.
u Normality of any solution depends on reaction while molarity does not.
For example.
Consider 0.1 mol KMnO4 dissolved in water to make 1L solution. Molarity of this solution is
0.1 M. However, its normality is not fixed. It will depend upon the reaction in which KMnO4
participates, e.g. If KMnO4 forms Mn2+, normality = 0.1 × 5 = 0.5 N. This same sample of
KMnO4, if employed in a reaction giving MnO2 as product (Mn in +4 state) will have normal-
ity 0.1 × 3 = 0.3 N.
u The concept of equivalents is handy, but it should be used with care. One must never
equate equivalents in a sequence which involves same element in more than two oxidation
states. Consider an example KIO3 reacts with KI to liberate iodine and liberated iodine is
titrated with standard hypo solution, The reaction are
(i) IO3– + I– ¾® I2
(ii) I2 + S2O32– ¾® S4O62– + I–
meq of hypo = meq of I2 = meq of IO3– + meq of I–
Q IO3 react with I Þ meq of IO3 = meq of I
– – – –

u meq of hypo = 2 × meq of IO3–

Nucleus Education-(NURTURE_(UNACADEMY)

This is wrong. Note that I2 formed by (i) have v.f. = 5/3 & reacted in equation (ii) have v.f. =
2.
Q v.f. of I2 in both the equation are different therefore we cannot equate m.eq is sequence. In
this type of case students are advised to use mole concept.
Solved Example :
Ex : How many milliliters of 0.02000 M KMnO4 solution would be required to exactly titrate 25.00 mL of
0.2000 M Fe(NO3)2 solution.
Sol : Method - 1 : Mole concept method
Starting with 25.00 mL of 0.2000MFe2+, we can write.
Millimoles of Fe2+ = 25.00 × 0.2000
and in volume V (in milliliters of the MnO4–)
Millimoles of MnO4– = V (0.02000)
The balanced reaction is :
MnO4– + 5Fe2+ + 8H+ ¾® Mn2+ + 5 Fe3+ + 4H2O

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 This requires that at the equivalent point,
V(0.02000) (25.00) (0.2000)
= V = 50.00 mL
1 5
Method - 2 : Equivalent Method :
Equivalents of MnO4– = 5 × moles of MnO4–
Normality MnO4– = 5 × molarity of MnO4–
For Fe2+, moles and equivalents are equal,
At the equivalence point,
Equivalents of MnO4– = Equivalents of Fe2+
or V - × Normality of MnO4–
MnO 4

= VFe2+ × Normality of Fe2+

For 0.02000 M MnO –4 solution

Normality of MnO –4 = (5) (0.02000) = 0.1 N and for 0.2000 M Fe2+ solution

æ 0.2000 ö
Normality of Fe2+ = 0.2000 N V = (25.00 mL) ç ÷ = 50.00 mL
-
MnO4 è 0.1000 ø

q FOR ACID-BASE (NEUTRALIZATION REACTION) OR REDOX REACTION

N1V1 = N2V2 is always true.
But M1V1 = M2V2 (may or may not be true )
But M1 × n1 × V1 = M2 × n2 × V2 (always true where n terms represent n-factor).
q 'n' FACTOR : FACTOR RELATING MOLECULAR WEIGHT AND EQUIVALENT
Nucleus Education-(NURTURE_(UNACADEMY)

WEIGHT
M
n-factor =
E

M
E=
n - factor

q n-FACTOR IN VARIOUS CASES

In Non Redox Change
u n-factor for element : Valency of the element
u
For acids : Acids will be treated as species which furnish H+ ions when dissolved in a
solvent.
The n-factor of an acid is the no. of acidic H+ ions that a molecule of the acid would give
when dissolved in a solvent (Basicity).
For example, for HCl (n = 1), HNO3 (n = 1), H2SO4 (n = 2), H3PO4 (n = 3) and H3PO3 (n =2)

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 u For bases : Bases will be treated as species which furnish OH–  ions when dissolved in a
solvent . The n-factor of a base is the no. of OH– ions that a molecule of the base would give
when dissolved in a solvent (Acidity).
For example, NaOH (n = 1), Ba(OH)2 (n = 2), Al(OH)3 (n = 3), etc.
u For salts : A salt reacting such that no atom of the salt undergoes any change in oxidation
state.
For example, 2AgNO3 + MgCl2 ® Mg(NO3)2 + 2AgCl
In this reaction, it can be seen that the oxidation state of Ag, N, O, Mg and Cl remains the
same even in the product. The n-factor for such a salt is the total charge on cation or anion.
In Redox Change
For oxidizing agent or reducing agent n-factor is the change in oxidation number per mole of the
substance.
q SOME OXIDIZING AGENTS/REDUCING AGENTS WITH EQ. WT.

Species Changed to Reaction Electrons Eq. wt.

exchanged
or change in
O.N.
M
MnO4– (O.A.) Mn +2 MnO4– + 8H+ + 5e–¾® Mn2+ + 4H2O 5 E=
in acidic medium 5
M
MnO4– (O.A.) MnO2 MnO4– + 3e– + 2H2O ¾® MnO2 + 4OH– 3 E=
in neutral medium 3

M
MnO4– (O.A.) MnO24- MnO4– + e– ¾® MnO42– 1 E=
in basic medium 1
Nucleus Education-(NURTURE_(UNACADEMY)

M
Cr2O72–(O.A.) Cr 3+ CrO72– + 14H+ + 6e– ¾® 2Cr3+ + 7H2O 6 E=
in acidic medium 6

M
MnO2(O.A.) Mn2 + MnO2 + 4H+ + 2e– ¾® Mn2+ + 2H2O 2 E=
in acidic medium 2
Cl (O.A.) M
2 Cl – Cl2 + 2e– ¾® 2Cl – 2 E=
in bleaching powder
2

CuSO 4 (O.A.) M
Cu+ Cu2+ + e– ¾® Cu+ 1 E=
in iodometric titration
1
2M
S2O32– (R.A.) S4O62– 2S2O32– ¾® S4O62– + 2e– 2 E= =M
2
(for two molecules)
M
H2O2(O.A.) H2O H2O2 + 2H+ + 2e– ¾® 2H2O 2 E=
2
M
H2O2(R.A.) O2 H2O2 ¾® O2 + 2H+ + 2e– (O.N. of 2 E=
2
oxygen in H2O2 is –1 per atom)
M
Fe2+(R.A.) Fe3+ Fe2+ ¾® Fe3+ + e– 1 E=
1
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 Ex. To find the n-factor in the following chemical changes.
2+ + 4+
(i) KMnO4 ¾¾¾
H
® Mn (ii) KMnO4 ¾¾¾
H O
® Mn 2

6+ 3+ +
(iii) KMnO4 ¾¾¾
OH
® Mn
–
(iv) K2Cr2O7 ¾¾¾
H
® Cr

(v) C2O42– ® CO2 (vi) FeSO4 ® Fe2O3

(vii) Fe2O3 ® FeSO4
Sol. (i) In this reaction, KMnO4 which is an oxidizing agent, itself gets reduced to Mn2+ under
acidic conditions.
n = |1 × (+7) – 1 × (+2)| = 5
(ii) In this reaction, KMnO4 gets reduced to Mn4+ under neutral or slightly (weakly) basic
conditions.
n = |1 × (+7) – 1 × (+4)| = 3
(iii) In this reaction, KMnO4 gets reduced to Mn6+ under basic conditions.
n = |1 × (+7) – 1 × (+6)| = 1
(iv) In this reaction, K2Cr2O7 which acts as an oxidizing agent reduced to Cr3+ under acidic
conditions. (It does not react under basic conditions.)
n = |2 × (+6) – 2 × (+3)| = 6
(v) In this reaction, C2O42– (oxalate ion) gets oxidized to CO2 when it is reacted with an
oxidizing agent.
n = |2 × (+3) – 2 × (+4)| = 2
(vi) In this reaction, ferrous ions get oxidized to ferric ions.
n = |1 × (+2) – 1 × (+3)| = 1
(vi) In this reaction, ferric ions are getting reduced to ferrous ions.
n = |2 × (+3) – 2 × (+2)| = 2
Ex. Calculate the molar ratio in which the following two substances would react ?
Nucleus Education-(NURTURE_(UNACADEMY)

Ba3(PO4)2 and AlCl3

Sol. n-factor of Ba3(PO4)2 = 3 × (+2) = 6 = n1
While n-factor of AlCl3 = 1 × (+3) = 3 = n2
n1 6 n1 x
= If =
n2 3 n2 y
y
Molar ratio = (inverse of equivalent ratio)
x
\ Molar ratio in which Ba3(PO4)2 and AlCl3 will react = 3 : 6 = 1 : 2

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 q APPLICATIONS OF THE LAW OF EQUIVALENCE
Simple Titration
In this, we can find the concentration of unknown solution by reacting it with solution of known
concentration (standard solution).
For example, let there be a solution of substance A of unknown concentration. We are given solution
of another substance B whose concentration is known (N1). We take a certain known volume of A in
a flask (V2 ) and then we add B to A slowly till all the A is consumed by B (this can be known with
the help of indicators). Let us, assume that the volume of B consumed is V1. According to the law of
equivalence, the number of g equivalents of B at the end point.
\ N1V1 = N2V2, where N2 is the conc. of A.

From this we can calculate the value of N2.

Ex. 0.4 M KMnO4 solution completely reacts with 0.05 M FeSO4 solution under acidic conditions. The
volume of FeSO4 used is 50 mL. What volume of KMnO4 was used ?
Sol. 0.4 × 5 × V = 0.05 × 50
V = 1.25 mL
Ex. 1.20 g sample of Na 2CO 3 and K 2CO 3 was dissolved in water to form 100 mL of a
Solution. 20 mL of this solution required 40 mL of 0.1 N HCl for complete neutralization.
Calculate the weight of Na2CO3 in the mixture. If another 20 mL of this solution is treated with
excess of BaCl2 what will be the weight of the precipitate ?
Sol. Let, weight of Na2CO3 = x g
Weight of K2CO3 = y g
Nucleus Education-(NURTURE_(UNACADEMY)

\ x + y = 1.20 g ............(i)
For neutralization reaction of 100 mL
Meq. of Na2CO3 + Meq. of K2CO3 = Meq. of HCl
x y 40 ´ 0.1 ´ 100
Þ × 2 × 1000 + × 2 × 1000 =
106 138 20
\ 69 x + 53 y = 73.14 .............(ii)
From Eqs. (i) and (ii), we get
x = 0.5962 g
y = 0.604 g
Solution of Na2CO3 and K2CO3 gives ppt. of BaCO3 with BaCl2
(Meq. of Na2CO3 + Meq. of K2CO3) in 20 mL = Meq. of BaCO3
Þ Meq. of HCl for 20 mL mixture = Meq. of BaCO3

Þ Meq. of BaCO3 = 40 × 0.1 = 4

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 WBaCO3
× 1000 = 40 × 0.1 = 4
M BaCO3

WBaCO3
× 2 × 1000 = 4
197

\ WBaCO3 = 0.394 g

q BACK TITRATION
Back titration is used to calculate % purity of a sample. Let us assume that we are given an impure
solid substance C weighing w gs and we are asked to calculate the percentage of pure C in the
sample. We will assume that the impurities are inert. We are provided with two solutions A and B,
where the concentration of B is known (N1) and that of A is not known. This type of titration will
work only if the following condition is satisfied, i.e. the nature of compounds A, B and C should be
such that A and B can react with each other. A and C can react with each other but the product of A
and C should not react with B.
Now, we take a certain volume of A in a flask ( the g equivalents of A taken should be ³ g equivalents
of C in the sample and this can be done by taking A in excess). Now, we perform a simple titration
using B. Let us assume that the volume of B used is V 1. In another beaker, we again take the
solution of A in the same volume as taken earlier. Now, C is added to this and after the reaction is
completed, the solution is being titrated with B. Let us assume that the volume of B used up is V 2.
Gram equivalents of B used in the first titration = N 1V1.
\ gm. equivalents of A initially = N1V1

gm. equivalents of B used in the second titration = N1V2

Nucleus Education-(NURTURE_(UNACADEMY)

\ gm. equivalents of A left in excess after reacting with C = N1V2

gm. equivalents of A that reacted with C = N1V1 – N1V2

N1 V1 - N1 V2
If the n-factor of C is x, then the moles of pure C =
x
N1 V1 - N1 V2
\ The weight of C = × Molecular weight of C
x
N1 V1 - N1 V2 Molecular wt. of C
\ Percentage of C = × ´ 100
x w

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 q SOME REDOX TITRATIONS (EXCLUDING IODOMETRIC / IODIMETRIC)
Estimation of By titrating Reactions Relation between O.A. and
with R.A.
Fe2+ MnO4– Fe2+ ¾® Fe3+ + e– 5Fe2+ º MnO4–

MnO4– + 8H+ + 5e–¾® Mn2+ + 4H2O Eq. wt. Fe2+ = M/1

Eq. wt. MnO4– = M/5

Fe2+ Cr2O72– Fe2+ ¾® Fe3+ + e– 6Fe2+ º Cr2O72–

Cr2O72– + 14H+ + 6e–¾® 2Cr3++7H2O Eq. wt. Cr2O72– = M/6

C2O42– MnO4– C2O42– ¾® 2CO2 + 2e– 5C2O42– º 2MnO4–

MnO4– + 8H+ + 5e–¾® Mn+2 + 4H2O Eq. wt. C2O42– = M/2

Eq. wt. MnO4– = M/5

H2O2 MnO4– H2O2 ¾® 2H+ + O2 + 2e– 5H2O2 º 2MnO4–

MnO4– + 8H+ + 5e–¾® Mn2+ + 4H2O Eq. wt. H2O2 = M/2

Eq. wt. MnO4– = M/5

As2O3 MnO4– As2O3 + 5H2O® 2AsO43– + 10H+ + 4e– Eq. wt. As2O3= M/4
AsO33– BrO3– AsO33– + H2O ¾® AsO43– + 2H+ + 2e– Eq. wt. AsO33–= M/2
BrO3– + 6H+ + 6e–¾® Br– + 3H2O Eq. wt. BrO3– = M/6
Ex. 20 g of a sample of Ba(OH)2 is dissolved in 10 mL of 0.5 N HCl solution : The excess of HCl
was titrated with 0.2 N NaOH. The volume of NaOH used was 20 cc. Calculate the percentage
of Ba(OH)2 in the sample.
Sol. Milli eq. of HCl initially = 10 × 0.5 = 5
Nucleus Education-(NURTURE_(UNACADEMY)

Milli eq. of NaOH consumed = Milli eq. of HCl in excess = 10 × 0.2 = 2

\ Milli eq. of HCl consumed = Milli eq. of Ba(OH)2 = 5 – 2 = 3
–3
\ Eq. of Ba(OH)2 = 3/1000 = 3 × 10

Mass of Ba(OH)2 = 3 × 10–3 × (171/2) = 0.2565 g

% Ba(OH)2 = (0.2565 / 20) × 100 = 1.28 %
Ex. 3.2 g of pyrolusite was treated with 50 mL of 0.5 M oxalic acid and some sulphuric acid. The oxalic
acid left undecomposed was raised to 250 mL in a flask. 25 mL of this solution when treated with 0.02
M KMnO4 required 32 mL of the solution : Find the % of MnO2 in the sample and also the percentage
of available oxygen.
Sol. Redox changes are C2O42– ¾® 2CO2 (n-factor = 2)
MnO4– ¾® Mn2+ (n-factor = 5)
MnO2 ¾® Mn2+ (n-factor = 2)
Meq. of MnO2 = Meq. of oxalic acid taken - Meq. of oxalic acid left

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 = 50 × 0.5 × 2 – 32 × 0.02 × 5 × 10 (in 250 mL) = 18
WMnO2 WMnO2
× 2 × 1000 = 18 Þ × 2 × 1000 = 18,
MMnO2 87

\ WMnO2 = 0.7821 g
0.7821
\ % of MnO2 = ´ 100 = 24.44 %
3.2
Meq. of MnO2 = Meq. of O2
WO2
× 2 × 1000 = 18, \ WO = 0.144 g
16 2

0.144
% of available O2 = × 100 = 4.5
3.2
Iodometric and Iodimetric Titration :
The reduction of free iodine to iodide ions and oxidation of iodide ions to free iodine occurs in these
titrations.
– –
I 2 + 2e ¾® 2I (reduction)
2I– ¾® I2 + 2e– (oxidation)
These are divided into two types :
Iodometic Titration :
In iodometric titrations, an oxidizing agent is allowed to react in neutral medium or in acidic medium
with excess of potassium iodide to liberate free iodine.
KI + oxidizing agent ¾® I2
Free iodine is titrated against a standard reducing agent usually with sodium thiosulphate. Halogen,
Nucleus Education-(NURTURE_(UNACADEMY)

dichromates, cupric ion, peroxides etc., can be estimated by this method.

I2 + 2NaS2O3 ¾® 2NaI + Na2S4O6
2CuSO4 + 4KI ¾® Cu2I2 + 2K2SO4 + I2
K4Cr2O7 + 6KI + 7H2SO4 ¾® Cr2(SO4)3 + 4K2SO4 + 7H2O + 3I2
Iodimetric Titration
These are the titrations in which free iodine is used as it is difficult to prepare the solution of iodine
(volatile and less soluble in water), it is dissolved in KI solution :
KI + I2 ¾® KI3 (Potassium triiodide)
This solution is first standardized before using with the standard solution of substance such as sulphite,
thiosulphate, arsenite etc, are estimated.
In iodimetric and iodometric titration, starch solution is used as an indicator. Starch solution gives
blue or violet colour with free iodine. At the end point, the blue or violet colour disappears when
iodine is completely changed to iodide.

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 q SOME IODOMETRIC TITRATIONS (TITRATING SOLUTIONS IS Na2S2O3.5H2O)

Estimation of Reaction Relation between O.A. and R.A.

I2 I2 + 2Na2S2O3 ¾® 2Nal + Na2S4O6 I2 = 2I º 2Na2S2O3

or Eq. wt. of Na2S2O3 = M/1

I2 + 2S2O32– ¾® 2I – + S4O62–

CuSO4 2CuSO4 + 4KI ¾® 2Cu2I2 + 2K2SO4 + I2 2CuSO4 º I2 º 2I º 2Na2S2O3

Cu2+ + 4I – ¾® Cu2I2 + I 2 Eq. wt. of CuSO4 = M/1

(White ppt.)

CaOCl2 + H2O ¾® Ca(OH)2 + Cl2

CaOCl2 Cl2 + 2KI ¾® 2KCl + I2

CaOCl 2º Cl 2º I 2º 2I º 2Na 2S 2O 3

Cl2 + 2I – ¾® 2Cl – + I2 Eq. wt. of CaOCl2 = M/2

MnO2 + 4HCl (conc) ¾¾

D
® MnCl2 + Cl2 + 2H2O

Cl2 + 2KI ¾® 2KCl + I2

MnO2 or MnO2 º Cl 2 º I 2 º 2I º 2Na 2S 2O 3

MnO2 + 4H+ + 2Cl– ¾® Mn2+ + 2H2O + Cl2 Eq. wt. of MnO2 = M/2

Cl2 + 2I – ¾® I2 + 2Cl –
Nucleus Education-(NURTURE_(UNACADEMY)

IO3– IO3– + 5I – + 6H+ ¾® 3I2 + 3H2O IO3– º 3I2 º 6I º 6Na 2S 2O 3

Eq. wt. of IO3– = M/6

H2O 2 H2O2 + 2I – + 2H+ ¾® I2 + 2H2O H2O2 º I2 º 2I º 2Na 2S 2O 3

Eq. wt. of H2O2 = M/2

Cl2 Cl2 + 2I – ¾® 2CI – + I2 Cl2 º I2 º 2I º 2Na 2S 2O 3

Eq. wt. of Cl2 = M/2

O3 O3 + 6I – + 6H+¾® 3I 2 + 3H2O O3 º 3I2 º 6I º 6Na 2S 2O 3

Eq. wt. of O3 = M/6

Cr2O72– Cr2O72–+14H+ + 6I – ¾®3I2 + 2Cr3++7H2O Cr2O72– º 3I2 º 6I

Eq. wt. of Cr2O72–

MnO4– 2MnO4–+10I– +16H+ ¾® 2MnO4– + 5I2 + 8H2O 2MnO4– º 5I2 º 10I

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 Eq. wt. of MnO4– = M/5

BrO3– BrO3–+6I– +6H+ ¾® Br– + 3I2 + 3H2O BrO3– º 3I2 º I 2

Eq. wt. of BrO3– = M/6

As(V) H3AsO4 + 2I– + 2H+ ¾® H3AsO3 + H2O + I2 H3AsO4 º I2 º 2I

Eq. wt. of H3AsO4 = M/2

q SOME IODIMETRIC TITRATION (TITRATING SOLUTIONS IS I2 IN KI)

Estimation of Reaction Relation between O.A. and R.A.
H2S H2S + I2 ¾® S + 2I – + 2H+ H2S º I2 º 2I
(in acidic medium) Eq. wt. of H2S = M/2
SO32– SO32– + I2 + H2O ¾® SO32– + 2I – + 2H+ SO32– º I2 º 2I
(in acidic medium) Eq. wt. of SO32– = M/2
Sn2+ Sn2+ + I2 ¾® Sn4+ + 2I – Sn2+ º I2 º 2I
(in acidic medium) Eq. wt. of Sn2+ = M/2
As(III) (at pH = 8) H2AsO3– + I2 + H2O ¾® HAsO42– + 2I – + 2H+ H2AsO3– º I2 º 2I
Eq. wt. of H2AsO3– = M/2
N2H4 N2H4 + 2I2 ¾® N2 + 4H+ + 4I – N2H4 º 2I2 º 4I
Eq. wt. of N2H4 = M/4
Nucleus Education-(NURTURE_(UNACADEMY)

q SUMMARY

wt. in g
1. Number of moles of molecules = Mol.wt.
wt. in g
Number of moles of atoms = Atomic mass
Volume at STP
Number of moles of gases =
Standard molar volume
Number of particles
Number of moles of particles, e.g. atoms, molecular ions etc. = Avogadro No.
Moles of solute in solution = M × V(L)

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 Atomic wt.
2. Equivalent wt. of element =
Valence
Mol.wt.
Equivalent wt. of compound =
Total charge on cationor anion
Mol wt.
Equivalent wt. of acid = Basicity

Mol wt.
Equivalent wt. of base = Acidity

Formula wt.
Equivalent wt. of an ion = Charge on ion

Molecular wt.
Equivalent wt. of acid salt = Replaceable H atom in acid salt
Mol.wt.
Equivalent wt. of oxidizing or reducing agent = Change in oxidation number per mole
wt.in g
No. of equivalent = N × V(L) = Eq.wt.

Ws ´ 1000
3. Molarity (M) = = x ´ d ´ 10
Ms ´ V Ms
where
Ws = wt. of solute in g
Ms = Mol. wt. of solute
x = % by mass of solute
d = density of solution in g/ml
Nucleus Education-(NURTURE_(UNACADEMY)

V = volume of solution in ml
Ws ´ 1000 x ´ d ´ 1000
4. Normality (N) = E ´ V = Es
s

Ws = wt. of solute in g.
Es = eqv. wt. of solute
V = volume of solution in ml
x = % by mass of solute
d = density of solution in g/ml
wt.of solute
5. Moles = M × V(L) =
Mol.wt.
wt.of solute
Millimoles = M × V(ml) = ´ 1000
Mol.wt.
Equivalents of solute = N × V(L)
wt.
Meq. of solute Eq.wt. ´ 1000

6. Molarity equation :
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 If a solution having molarity M1 and volume V1 is diluted to volume V2 so that new molarity
is M2 then total number of moles remains the same.
M1V1 = M2V2
For a balanced equation involving n1 moles of reactant 1 and n2 moles of reactant 2.
M1 V1 M2 V2
=
n1 n2
Normality equation : According to the law of equivalence, the substances combine together
wt.of A Eq.wt.of A
in the ratio of their equivalent masses wt.of B =
Eq.wt.of B
wt.of A wt.of B
Þ =
Eq.wt.of A Eq.wt.of B
Number of gram equivalents of A = Number of gram equivalents of B
N A ´ VA
Number of gram equivalents of A =
1000
N B VB
Number of gram equivalents of B =
1000
N A VA N V
Þ = B B
1000 1000
Þ NA × VB = NB × VB
The above equation is called normality equation.
7. Normality (N) = Molarity (M) × n
(where n = n-factor)
For acid-base (neutralization reaction or redox reaction)
Nucleus Education-(NURTURE_(UNACADEMY)

N1V1 = N2V2 always true

But M1V1 = M2V2 (may or may not be true )
But M1n1V1 = M2n2V2 (always true where n-terms represent n-factor)

Moles of solute
8. Molality (m) =
wt.of solvent (in kg)

9. Strength of solution (S) = N × Eq.wt.

= M × mol. wt.
GLOSSARY
Aliquot. A portion of the whole, usually a simple fraction. A portion of a sample withdraw from a
volumetric flask with a pipet is called an aliquot.

Analytical concentration. The total number of moles per litre of a solute regardless of any reactions
that might occur when the solute dissolves. Used synonymously with formality.

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 Equivalent. The amount of a substance which furnishes or reacts with 1 mol of H+ (acid-base),
1 mol of electrons (redox), or 1 mol of a univalent cation (precipitation and complex formation).

Equivalent weight. The weight in grams of one equivalent of a substance.

Equivalence point. The point in a titration where the number of equivalents of titrant is the same as
the number of equivalents of analyte.

End point. The point in a titration where an indicator changes color.

Formula weight. The number of formula weights of all the atoms in the chemical formula of a
substance.

Formality. The number of formula weights of solute per litre of solution; synonymous with analytical
concentration.

Indicator. A chemical substance which exhibits different colors in the presence of excess analyte or
titrant.

Normality. The number of equivalents of solute per litre of solution.

Primary standard. A substance available in a pure form or state of known purity which is used in
standardizing a solution.

Standardization. The process by which the concentration of a solution is accurately ascertained.

Standard solution. A solution whose concentration has been accurately determined.

Nucleus Education-(NURTURE_(UNACADEMY)

Titrant. The reagent (a standard solution) which is added from a buret to react with the analyte.

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 EXERCISE # (S-I)
Oxidation Number and Balancing of Redox Reaction

1. Calculate the oxidation number of underlined elements in the following compounds :

(a) K[ Co (C2O4)2.(NH3)2] (b) K4P2 O7 (c) CrO2Cl2 (d) Mn3O4
2–
(e) Ca(ClO2)2 (f) ZnO2 (g) Fe0.93O

2 Calculate the O.N. of all atoms in following compounds:-

(1) Fe3O4 (2) FeO (3) Na2S4O6 (4) C2H5OH
(5) FeSO4.(NH4)2SO4.6H2O (6) CO2 (7) FeS2
(8) PbO2 (9) CS2 (10) CrO5 (11) (NH4)2SO4
(12) N2O5 (13) HCN (14) HNC (15) Ba[H2PO2]2
(16) OsO4 (17) H2S2O3 (18) CH3SO3H (19) Ba2XeO6
(20) Ba(SCN)2

3. Find the sum of average oxidation number of S in H2SO5 (peroxy monosulphuric acid) and
Na2S2O3 (sodium thiosulphate).

4. Write balanced net ionic equation for the following reactions in acidic solution.
(a) S4O62– (aq) +Al (s)  H2S (aq) + Al3+ (aq)
(b) S2O32– (aq) + Cr2O72– (aq)  S4O62– (aq) + Cr3+ (aq)
(c) ClO3– (aq) + As2S3 (s)  Cl– (aq) + H2AsO4– (aq) + HSO4– (aq)
Nucleus Education-(NURTURE_(UNACADEMY)

(d) IO3– (aq) + Re (s)  ReO4– (aq) + I– (aq)

(e) HSO4– (aq) + As4 (s) + Pb3O4 (s) PbSO4 (s) + H2AsO4– (aq)
(f) HNO2 (aq)  NO3– + NO (g)
(g) MnO42– + H+  MnO4– + MnO2 + H2O
(h) BCl3 + P4 + H2  BP + HCl
(i) KMnO4 + HCl  MnCl2 + H2O + Cl2 + KCl
(j) KMnO4 + H2O2 + H2SO4 4 MnSO4 + K2SO4 + O2 + H2O
(k) KMnO4  K2MnO4 + MnO2 + O2
(l) Ca(OCl)2 + KI + HCl  I2 + CaCl2 + H2O + KCl.
(m) Cu(NH3)4Cl2 + KCN + H2O  K2Cu(CN)3 + NH3 + KCNO + NH4Cl + KCl

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34 34
 5. Write balanced net ionic equations for the following reactions in basic solution :
(a) C4H4O62–(aq) + ClO3– (aq)  CO32– (aq) + Cl– (aq)
(b) Al (s) + BiONO3 (s)  Bi (s) + NH3 (aq) + Al (OH)4–(aq)
(c) H2O2 (aq) + Cl2O7 (aq) ClO2– (aq) + O2 (g)
(d) Tl2O3 (s) + NH2OH (aq)  TlOH (s) + N2 (g)
(e) Cu(NH3)42+ (aq) + S2O42– (aq) SO32– (aq) + Cu (s) + NH3 (aq)
(f) Mn(OH)2 (s) + MnO4– (aq) MnO2 (s)
(g) C2H5OH + MnO4– + OH–  C2H3O– + MnO2 + H2O
(h) ClO2 + SbO2– + OH–  ClO2– + Sb(OH)6– + H2O
(i) MnO4– + CN– + H2O  MnO2 + CNO– + OH–

Equivalents and Equivalent weight

6. Determine the equivalent weights of the following salts :
(a) NaCl (b) K2SO4 (c) Ca3(PO4)2

7. 1.135 L dry chlorine gas at STP was passed over a heated metal when 5.56 g of chloride of the
metal was formed. What is the equivalent weight of the metal?

8. A mixture of CuS (molecular weight = M1) and Cu2S (molecular weight = M2) is oxidised by
KMnO4
(molecular weight = M3) in acidic medium, where the product obtained are Cu2+, Mn2+ and
SO2. Find the equivalent weight of CuS, Cu2S and KMnO4 respectively.
Nucleus Education-(NURTURE_(UNACADEMY)

9. Determine the equivalent weight of the following oxidising and reducing agents :
(a) KMnO4 (reacting in acidic medium MnO4–  Mn2+)
(b) KMnO4 (reacting in neutral medium MnO4–  MnO2)

10. A dilute solution of H2SO4 is made by adding 5 mL of 3N H2SO4 to 245 mL of water. Find the
normality and molarity of the diluted solution.

Acid – Base titration

11. (a) Calculate volume of 1N H3PO4 required to react with 20 ml 2N Ca(OH)2 solution
(b) Calculate volume of 1N H2SO4 required to react with 20 ml 1 M Al(OH)3 solution

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 12. How many litre of 0.1N HCl are required to react completely with 19 gm mixture of Na2CO3
and NaHCO3 containing equimolar amounts of two ?

13. H3PO4 is a tri basic acid and one of its salt is NaH2PO4. What volume in ml of 1 M NaOH
solution should be added to 12 g of NaH2PO4 to convert it into Na3PO4 ?

14. 50 gm of a sample of Ca(OH)2 is dissolved in 50 ml of 0.5 N HCl solution. The excess of HCl
was titrated with 0.3N – NaOH. The volume of NaOH used was 20cc. Calculate % purity of
Ca(OH)2

15. 10 g CaCO3 were dissolved in 250 ml of 1 M HCl. What volume of 2 M KOH would be
required to neutralise excess HCl.

16. One gm of impure sodium carbonate is dissolved in water and the solution is made up to 250
ml. To 50 ml of this made up solution, 50 ml of 0.1N – HCl is added and the mix after shaking
well required 10 ml of 0.16 N – NaOH solution for complete titration. Calculate the % purity of
the sample.

Redox titration (KMnO4 and K2Cr2O7 titration)

17. (a) Calculate volume of 0.4 M KMnO4 required to react with following in acidic medium.
KHC2O4(1 mol) + H2C2O4(2 mol)
(b) Calculate volume of 0.2 M KMnO4 required to react with following mixture in acidic
medium.
KHC2O4 (128 gm) + H2C2O4 (180 gm)
Nucleus Education-(NURTURE_(UNACADEMY)

18. Calculate the number of milli moles of SO2. If in the following reaction 10 ml of 0.1 M KMnO4
solution are required for titration.
SO2 + MnO4  SO24 + Mn+2

19. In neutral of faintly alkaline medium 18 moles permagnate anion quantitatively oxidise
thiosulphate anion to product „X‟ mole of SO24 . Then „X‟ is –

20. Mass of Cl2 produced by the complete reaction of 230 gm As2O5 with 182.5 gm HCl according
to reaction is
As2O5 + HCl  AsCl3 + Cl2 + H2O
[Atomic mass of As = 75]

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 21. What volume of 0.1 M H2O2 solution will be required to completely reduce 1 litre of 0.1 M
KMnO4 in acidic medium.

22. Moles of K2Cr2O7 used to oxidise 1 mol Fe0.92O to Fe+3 are

23. An equimolar mixture of CuO & Cu2O is titrated with 100 ml 0.1 M KMnO4 solution in acidic
medium. Calculate millimoles of Cu2+ in final solution.

24. How many moles of MnO4 will react with 1 mole of ferrous oxalate in acidic medium.

25. Calculate volume of 0.1 M KIO3 required to produce 254 gm I2 by mixing it with excess KI.

26. Calculate the millimoles of Br2 produced when 10 ml of 0.1 M BrO3– reacts with excess of Br–.

27. It required 40 ml of 1 M Ce4+ to titrate 20 ml of 1 M Sn2+ to Sn4+. What is the oxidation state of
cerrium in the product.

28. A volume of 10.0 ml of 1 M SeO2 reacted with exactly 20 ml of 2 M CrSO4. In the reaction,
Cr2+ was oxidized to Cr3+. To what oxidation state was selenium converted by the reaction.

29. How many mL of 0.3M K2Cr2O7 (acidic) is required for complete oxidation of 5 mL of 0.2 M
SnC2O4 solution.
Nucleus Education-(NURTURE_(UNACADEMY)

K2Cr2O7 + SnC2O4  Sn4+ +Cr3+ +CO2

30. Calculate the number of millimoles of K2Cr2O7 which will completely react with 40 ml 0.1 M
KI Solution.

31. A 1 g sample of H2O2 solution containing x% H2O2 by mass requires x cm3 of a KMnO4
solution for complete oxidation under acidic condition. Calculate the normality of KMnO4
solution.

KMnO4 +H2O2 
 Mn2++ H2O

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 N
32. 20 ml of H2O2 after acidification with dil H2SO4 required 30 ml of KMnO4 for complete
12
oxidation. Detemine the strength of H2O2 solution.

33. Metallic tin in the presence of HCl is oxidized by K2Cr2O7 to stannic shloride, SnCl4. What
volume of deci-normal dichromate solution would be reduced by 11.9 gm of tin [Sn = 119]

Sn + Cr2O72– 
 Sn4+ + Cr3+

34. Potassium acid oxalate K2C2O4. 3H2C2O4.4H2O can be oxidized by MnO4– in acid medium.
Calculate the volume of 0.1 M KMnO4 reacting in acid solution with 5.08 gm of the acid
oxalate.

K2C2O4. 3H2C2O4.4H2O + MnO4– 

 Mn2++ CO2

35. A 100 mL sample of water was treated to convert any iron present to Fe2+. Addition of 25 mL
of 0.002 M K2Cr2O7 resulted in the reaction :
6Fe2+ + Cr2O72– + 14H+ 
 6Fe3+ + 2Cr3+ + 7H2O
The excess K2Cr2O7 was back-titrated with 7.5 mL of 0.01 M Fe2+ solution. Calculate the parts
per million (ppm) of iron in the water sample.

Redox titration (Iodometric/Iodimetric Titration)

36. A mixture containing As2O3 and As2O5 required 20 mL of 0.05 N iodine solution for titration.
Nucleus Education-(NURTURE_(UNACADEMY)

The resulting solution is then acidified and excess of KI was added. The liberated iodine
required 1.116 g hypo (Na2S2O3.5H2O) for complete reaction. Calculate the mass of the
mixture. The reactions are:
As2O3 + 2I2 + 2H2O  As2O5 + 4H+ + 4I–
As2O5 + 4H+ + 4I–  As2O3 + 2I2 + 2H2O (Atomic weight : As = 75)

37. 10 g sample of bleaching powder was dissolved into water to make the solution one litre. To
this solution 35 mL of 1.0 M Mohr salt solution was added containing enough H2SO4. After the
reaction was complete, the excess Mohr salt required 30 mL of 0.1 M KMnO4 for oxidation.
The % of available Cl2 approximately is (mol wt = 71)

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 EXERCISE # (S-II)
1. 520 gm mixture of Fe2O3 and FeO reacts completely with 158 gm KMnO4 in acidic medium
Calculate the mole % of Fe2O3 in mixture.

2. A mixture containing As2O3 and As2O5 required 20 mL of 0.05 N iodine solution for titration.
The resulting solution is then acidified and excess of KI was added. The liberated iodine
required 1.116 g hypo (Na2S2O3.5H2O) for complete reaction. Calculate the mass of the
mixture. The reactions are:
As2O3 + 2I2 + 2H2O 
 As2O5 + 4H+ +4I–
As2O5 + 4H+ + 4I– 
 As2O3 + 2I2 + 2H2O (Atomic weight : As = 75)

3. 10 g sample of bleaching powder was dissolved into water to make the solution one litre. To
this solution 35 mL of 1.0 M Mohr salt solution was added containing enough H2SO4. After the
reaction was complete, the excess Mohr salt required 30 mL of 0.1 M KMnO4 for oxidation.
The % of available Cl2 approximately is (mol wt = 71)

4. A mixture of FeO and Fe2O3 is reacted with acidified KMnO4 solution having a concentration
of 2/5 M, 100 mL of which was used. The solution was then titrated with Zn dust which
converted Fe3+ of the solution to Fe2+. The Fe2+ required 1000 mL of 2/15 M K2Cr2O7 solution.
Find the % by mol of FeO and Fe2O3.

5. A substance of crude copper is boiled in H2SO4 till all the copper has reacted. The impurities
are inert to the acid. The SO2 liberated in the action is passed into 100 mL of 0.4 M acidified
Nucleus Education-(NURTURE_(UNACADEMY)

KMnO4(SO2  SO4–2) The solution of KMnO4 after passage of SO2 is allowed to react with
oxalic acid and requires 25 mL of 1 M oxalic acid. If the purity of copper is 95.25%, what was
the weight of the sample.

6. 24 mL of a solution containing HCl was treated with excess of 0.004 M KIO3 and KI solution
of unknown concentration where I2 liberated is titrated against a standard solution of 0.02 M
Na2S2O3 solution whose 24 mL were used up. Find the molarity of HCl and volume KIO3
solution consumed.

7. H2O2 is reduced rapidly by Sn2+, the products being Sn4+ and water. H2O2 decomposes slowly
at room temperature to yield O2 and water. Calculate the volume of O2 produced at 273 K and
1.00 atm when 200 g of 10.0 % by mass H2O2 in water is treated with 88.2 mL of 1 M Sn2+ and
then the mixture is allowed to stand until no further reaction occurs.
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 8. A 458 g sample containing Mn3O4 was dissolved and all manganese was converted to Mn2+. In
the presence of fluoride ion, Mn2+ is titrated with 3 lit of KMnO4 solution (which was 1.25 N
against oxalate in acidic medium), both reactants being converted to a complex of Mn(III) ,
What was the % of Mn3O4 in the sample ?

9. A 2.024 g sample containing Ba(SCN)2 was dissolved in a bicarbonate solution. 50.0 mL of 1

N iodine solution was added, and the mixture was allowed to stand for five minutes. The
solution was then acidified, and the excess I2 was titrated with 26 mL of 1 M sodium
thiosulphate. Write a balanced equation for the oxidation of SCN– into SO42– and HCN.
Calculate the percent Ba(SCN)2 in sample.

10. 5g sample of brass was dissolved in one litre dil. H2SO4. 20 ml of this solution were mixed with
KI liberating I2 and Cu+ and the I2 required 20 ml of 0.03 N hypo solution for complete
titration. Calculate the percentage of Cu in the alloy.

11. A 0.96 gm sample of Fe2O3 solid of 50% purity is dissolved in acid and completely reduced by
heating the solution with zinc dust. The resultant solution is cooled and made upto 100.0 mL.
An aliquot of 25.0 ml of this solution required 30 mL of 0.01 M solution of an oxidising agent
for titration. Calculate the number of moles of electrons taken up by oxidising agent in the
reaction of the above titration.

12. 5 g of pyrolusite (impure MnO2) were heated with conc. HCl and Cl2 evolved was passed
through excess of KI solution. The iodine liberated required 40 mL of N/10 hypo solution. Find
Nucleus Education-(NURTURE_(UNACADEMY)

the % of MnO2 in the pyrolusite.

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 EXERCISE # (O-I)
Oxidation Number and Balancing of Redox Reaction
1. Which reaction does not represent autoredox or disproportionation :-
(A) Cl2 + OH–  Cl– + ClO3– + H2O (B) 2H2O2  H2O + O2
(C) 2Cu  Cu + Cu
+ +2
(D) (NH4)2Cr2O7  N2 + Cr2O3 + 4H2O

2. Match List-I (Compounds) with List-II (Oxidation states of nitrogen) and select answer using
the codes given below the lists
List-I List-II
(a) NaN3 1. +5
(b) N2H2 2. +2
(c) NO 3. –1/3
(d) N2O5 4. –1
Code : (a) (b) (c) (d)
(A) 3 4 2 1
(B) 4 3 2 1
(C) 3 4 1 2
(D) 4 3 1 2

3. In the reaction
xHI + yHNO3  NO + I2 + H2O
(A) x = 3, y = 2 (B) x = 2, y = 3 (C) x = 6, y = 2 (D) x = 6, y = 1

4. In the reaction X – + XO3– + OH– 

 X2 + H2O, the molar ratio in which X – and XO3– react
Nucleus Education-(NURTURE_(UNACADEMY)

is :
(A) 1 : 5 (B) 5 : 1 (C) 2 : 3 (D) 3 : 2

5. CN– is oxidised by NO3– in presence of acid :

c
a CN– + b NO3– + c H+ 
 (a + b) NO + a CO2 + H2O
2
What are the whole number values of a, b, c in that order :
(A) 3, 7, 7 (B) 3, 10, 7 (C) 3, 10, 10 (D) 3, 7, 10

6. Balance the following equation and choose the quantity which is the sum of the coefficients of
reactants and products :
....... KMnO4 +....... H2O2 +....... H2SO4 
 ....... MnSO4 +....... O2 +....... H2O +....... K2SO4
(A) 26 (B) 23 (C) 28 (D) 22

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 7. Which of the following reactions is a redox reaction ?
(A) H2O2 + KOH 
 KHO2 + H2O (B) Cr2O72– + 2OH– 
 2CrO42– + H2O

(C) Ca(HCO3)2 
 CaCO3 + CO2 + H2O (D) H2O2 
 H2O + O2

8. Which of the following are examples of disproportionation reaction :

(A) H2O2 
 H2O + O2 (B) Cl2 + OH– 
 ClO– + Cl– + H2O
(C) KClO3 
 KClO4 + KCl (D) All of these

9. In the following reaction : Cr(OH)3 + OH– + IO3–   CrO42– + H2O + I–

(A) IO3– is oxidising agent (B) Cr(OH)3 is oxidised
–
(C) 6e are being taken per iodine atom (D) All of these

10. n-factor of Ba(SCN)2 when it reacts with oxidising agent and forms product, SO24 ,CO32 &
NO3 is -
(A) 8 (B) 64 (C) 32 (D) 16

11. The following equations are balanced atomwise and chargewise.

(i) Cr2O72– + 8H+ + 3H2O2 
 2Cr3+ + 7H2O + 3O2
(ii) Cr2O72– + 8H+ + 5H2O2 
 2Cr3+ + 9H2O + 4O2
(iii) Cr2O72– + 8H+ + 7H2O2   2Cr3+ + 11H2O + 5O2
The precise equation/equations representing the oxidation of H2O2 is/are :
(A) (i) only (B) (ii) only (C) (iii) only (D) all the three
Nucleus Education-(NURTURE_(UNACADEMY)

Equivqlents and Equivqlent weight

12. Equivalent mass of Fe0.9 O in reaction with acidic K2Cr2O7 is : (M = Molar mass)
(A) 7 M/10 (B)10 M/7 (C) 7 M/9 (D) 9 M/7

13. x g of the metal gave y g of its oxide. Hence equivalent weight of the metal
yx x x xy
(A) ×8 (B) ×8 (C) × 8 (D) ×8
x (y  x) y x

14. Equivalent wt. of H3PO4 in each of the reaction will be respectively -

H3PO4 + OH–  H2PO4– + H2O
H3PO4 + 2OH–  HPO42– + 2H2O
H3PO4 + 3OH–  PO43– + 3H2O
(A) 98, 49, 32.67 (B) 49, 98, 32, 67 (C) 98, 32.67, 49 (D) 32.67, 49, 98

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 15. 3 g of an oxide of a metal is converted to chloride completely and it yielded 5 g of chloride.
Equivalent weidht of the metal is :
(A) 33.25 (B) 3.325 (C) 12 (D) 20

16. An ion is reduced to the element when it absorbs 6 × 1020 electrons. The number of equivalents
of the ion is:
(A) 0.1 (B) 0.01 (C) 0.001 (D) 0.0001

17. When N2 is converted into NH3, the equivalent weight of nitrogen will be :
(A) 1.67 (B) 2.67 (C) 3.67 (D) 4.67

18. In the ionic equation 2K+BrO3– + 12H+ + 10e–  Br2 + 6H2O + 2K+, the equivalent weight
of KBrO3 will be: (where M = molecular weight of KBrO3)
(A) M/5 (B) M/2 (C) M/6 (D) M/4

19. The equivalent weight of a metal is double that of oxygen. How many times is the weight of its
oxide greater than weight of the metal?
(A) 1.5 (B) 2 (C) 0.5 (D) 3

Acid – Base titration

20. How many millilitres of 0.1N H2SO4 solution will be required for complete reaction with a
solution containing 0.125 g of pure Na2CO3 :
(A) 23.6 mL (B) 25.6 mL (C) 26.3 mL (D) 32.6 mL

21. One litre of a solution contains 18.9 g of HNO3 and one litre of another solution contains 3.2 g
of NaOH. In what volume ratio must these solution be mixed to obtain a neutral solution?
Nucleus Education-(NURTURE_(UNACADEMY)

(A) 3 : 8 (B) 8 : 3 (C) 15 : 4 (D) 4 : 15

22. 1 mol each of H3PO2, H3PO3 and H3PO4 will neutralise respectively x mol of NaOH, y mol of
Ca(OH)2 and z mol of Al(OH)3 (assuming all as strong electrolytes). x, y, z are in the ratio of :
(A) 3 : 1.5 : 1 (B) 1 : 2 : 3 (C) 3 : 2 : 1 (D) 1 : 1 : 1

23. If 25 mL of a H2SO4 solution reacts completely with 1.06 g of pure Na2CO3, what is the
normality of this acid solution :
(A) 1 N (B) 0.5 N (C) 1.8 N (D) 0.8 N

24. The mass of oxalic acid crystals (H2C2O4. 2H2O) required to prepare 50 mL of a 0.2 N solution
is :-
(A) 4.5 g (B) 6.3 g (C) 0.63 g (D) 0.45 g

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 25. 125 mL of 63% (w/v) H2C2O4. 2H2O is made to react with 125 mL of a 40% (w/v) NaOH
solution. The resulting solution is :-
(A) neutral (B) acidic (C) strongly acidic (D) alkaline

Redox titration (KMnO4 and K2Cr2O7 titration)

26. Calculate the moles of KMnO4 required to oxidise 180 gm H2C2O4 in acidic medium. Also
calculate moles and volume of (at STP) of CO2(g) produced.
Moles of KMnO4 Moles of CO2 Volume of CO2 at STP
(A) 2 mol 2 2 × 22.4 lit
4 4 4
(B) × 22.4 lit
5 5 5
4
(C) 4 4 × 22.4 lit
5
4
(D) 4 4 × 22.7 lit
5

27. Calculate the moles of KMnO4 required to react completely with 2 moles of KHC2O4.H2C2O4
in acidic medium
(A) 4/5 (B) 4 (C) 8 (D) 8/5

28. Calculate millimoles moles of compound (KHC2O42H2C2O4) required to reduce 3 litre of 2.8
volume H2O2 solution.
(A) 100 (B) 250 (C) 500 (D) 200
Nucleus Education-(NURTURE_(UNACADEMY)

29. If valence factor (n-factor) of compound NaHC2O42H2 C2O43K2C2O44Al2(C2O4)33FeC2O4 in

acid base titration is x and redox titration with KMnO4 is y then value of y/x is –
(A) 8.4 (B) 9 (C) 11.25 (D) 12

30. 20 ml of KMnO4 solution completely reacts with 10 ml solution of 1 M FeS2 and 2M CuS to
produce Cu+2, Fe+3, SO2. Calculate Normality of KMnO4 solution?
(A) 11.5 (B) 15 (C) 5.75 (D) 10

31. 1 mole of MnO42 disproportionate into MnO4 & MnO2 in acidic medium. % by mass of Mn
converted to MnO4 (Molar mass of Mn = 55 gm)
(A) 66.67 (B) 33.33 (C) 16.67 (D) 50

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 32. Volume V1 mL of 0.1 MK2Cr2O7 is needed for complete oxidation of 0.678 g N2H4 in acidic
medium. The volume of 0.3 M KMnO4 needed for same oxidation in acidic medium will be :-
2 5
(A) V1 (B) V1 (C) 113 V1 (D) can‟t say
5 2

33. If 10 g of V2O5 is dissolved in acid and is reduced to V2+ by zinc metal, how many mole I2
could be reduced by the resulting solution if it is further oxidised to VO2+ ions ?
[Assume no change in state of Zn2+ ions] (V = 51, O = 16, I = 127) :
(A) 0.11 mole of I2 (B) 0.22 mole of I2 (C) 0.055 mole of I2 (D) 0.44 mole of I2

34. H2O2 acts as a reducing agent in:

(A) FeCl2 + HCl + H2O2  FeCl3 + H2O (B) Cl2 + H2O2  HCl + O2
(C) HI + H2O2  I2 + H2O (D) H2SO3 + H2O2  H2SO4 + H2O

35. The number of moles of Cr2O72– needed to oxidize 0.136 equivalents of N2H5+ by the reaction
N2H5+ + Cr2O72–  N2 + Cr3+ + H2O is
(A) 0.136 (B) 0.068 (C) 0.0227 (D) 0.272

36. A solution of KMnO4 is reduced to MnO2. The normality of solution is 0.6. The molarity is:
(A) 1.8M (B) 0.6M (C) 0.1M (D) 0.2M

37. Number of moles of electrons taken up when 1 mole of NO3– ions is reduced to 1 mole of
NH2OH is
(A) 2 (B) 4 (C) 5 (D) 6
Nucleus Education-(NURTURE_(UNACADEMY)

38. When BrO3– ion reacts with Br– ion in acid solution Br2 is liberated.The equivalent weight of
KBrO3 in this reaction is
(A) M/8 (B) M/3 (C) M/5 (D) M/6

39. As2O3 is oxidised to H3AsO4 by KMnO4 in acidic medium. Volume of 0.02M KMnO4 required
for this purpose by 1mmol of As2O3 will be
(A) 10 mL (B) 20 mL (C) 40 mL (D) 80 mL

40. When ozone is passed through dry KOH, KO3 is obtained and O2 is liberated. In this reaction
__________ is oxidised and _________ is reduced.
(A) hydrogen, oxygen (B) potassium, oxygen
(C) oxygen, oxygen (D) oxygen, hydrogen
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 41. In a redox reaction, the equivalent weight of HNO2 is found to be 23.5. The reaction products
might contain
(A) N2O (B) NO (C) NH3 (D) HNO3

42. 100 ml of 0.1M NaAl(OH)2CO3 is neutralised by 0.25 N HCl to form NaCl, AlCl3 and CO2.
Volume of HCl required is
(A) 10 mL (B) 40 mL (C) 100mL (D) 160 mL

43. 70 ml of a solution containing HCl was treated with excess of KBrO3 and KBr solution of
unknown concentration where Br2 liberated is titrated against a standard solution of 21 ml of
2M Na2S2O3 solution. Molarity of HCl solution is
2 36 6 86
(A) (B) (C) (D)
10 100 10 100

44. Dichloroacetic acid (CHCl2COOH) is oxidized to CO2, H2O and Cl2 by 600 meq of an
oxidizing agent. Same amount of acid can neutralize how many moles of ammonia to form
ammonium dichloroacetate?
(A) 0.0167 (B) 0.1 (C) 0.3 (D) 0.6

45. 0.3 g of an oxalate salt was dissolved in 100 mL solution. The solution required 90 mL of N/20
KMnO4 for complete oxidation. The % of oxalate ion in salt is :-
(A) 33% (B) 66% (C) 70% (D) 40%
Nucleus Education-(NURTURE_(UNACADEMY)

46. 2 moles of K3H(C2O4)2 and 1 mole of H2C2O4 is treated separately with KMnO4 in acidic
medium and with Ba(OH)2 having same molarity. Ratio of Volume of KMnO4 to volume of
Ba(OH)2 required is.
(A) 3 (B) 1/3 (C) 1 (D) 2

47. An aq. solution of 0.5M KMnO4 is divided into two parts. One part of it requires 125 ml of
1.5M aq. solution of oxalate ions in acidic medium, while another part requires 270 ml of 0.5M
aq. solution of iodide ions in neutral medium which are converted into I2 only. Calculate total
volume (mL) of the initial KMnO4 solution.
(A) 240 (B) 120 (C) 300 (D) 480

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 Redox titration (Iodometric/Iodimetric Titration)

48. A 0.2 g sample containing copper () was analysed iodometrically, where copper() is reduced
to copper () by iodide ions. 2Cu2+ + 4–   2 Cu + 2
If 20 mL of 0.1 M Na2S2O3 solution is required for titration of the liberated iodine, then the
percentage of copper in the sample will be :
(A) 31.75 % (B) 63.5 % (C) 53 % (D) 37 %

49. One gram of Na3AsO4 is boiled with excess of solid KI in presence of strong HCl. The iodine
evolved is absorbed in KI solution and titrated against 0.2 N hypo solution. Assuming the
reaction to be
AsO43– + 2H+ + 2–  AsO33– + H2O + 2
calculate the volume of hypo consumed. [Atomic weight of As = 75]
(A) 48.1 mL (B) 38.4 mL (C) 24.7 mL (D) 30.3 mL

50. x mmol of XeF4 quantitatively oxidized KI to I2 and liberated Xe, alongwith formation of KF.
This iodine required 20 ml of decinormal hypo solution for exact titration. Thevalue of x is
(A) 0.5 (B) 1.0 (C) 2.0 (D) 5.0

51. What can be the maximum percentage of available chlorine possible in a given bleaching
powder sample (Take formula of bleaching powder as CaOCl2) ?
(A) 52.9% (B) 55.9 % (C) 58% (D) 60%
Nucleus Education-(NURTURE_(UNACADEMY)

52 A solution of Na2S2O3 is standardized iodometrically against 0.167 g of KBrO3 where BrO3

changes to Br–. This process requires 45 mL of the Na2S2O3 solution. What is the strength of
the Na2S2O3 ? [Mw. of KBrO3 = 167]
2 2 1 1
(A) N (B) N (C) N (D) N
15 30 30 60

53. An aqueous solution containing KIO3 was treated with an excess of KI solution. The solution is
acidified with HCl. The liberated iodine consumed 10 ml of 0.1M thiosulphate solution to
decolourise the starch iodine complex. Then millimoles of KIO3 consumed
(A) 1 (B) 1/2 (C) 1/6 (D) 1/3

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 EXERCISE # (O-II)
1. HNO3 oxidises NH4+ ions to nitrogen and itself gets reduced to NO2. The moles of HNO3
required by 1 mol of (NH4)2SO4 is :–
(A) 4 (B) 5 (C) 6 (D) 2

2. During the disproportionation of iodine to iodide and iodate ions, the ratio of iodate and iodide
ions formed in alkaline medium is :-
(A) 1 : 5 (B) 5 : 1 (C) 3 : 1 (D) 1 : 3

3. When arsenic sulphide is boiled with NaOH, sodium arsenite and sodium thioarsenite are formed
y
x As2S3 + y NaOH  Na3AsO3 + x Na3AsS3 + H2O. What are the values of x and y ?
2
(A) 1, 6 (B) 2, 8 (C) 2, 6 (D) 1, 4

4. 35 mL sample of hydrogen peroxide gives of 500 mL of O2 at 27°C and 1 atm pressure.

Volume strength of H2O2 sample will be :–
(A) 10 volume (B) 13 volumes (C) 11 volume (D) 12 volume

5. A mixture of H2SO4 and H2C2O4 (oxalic acid) and some inert impurity weighing 3.185 g was
dissolved in water and the solution made up to 1 litre, 10 mL of this solution required 3 mL of
0.1 N NaOH for complete neutralization. In another experiment 100 mL of the same solution in
hot condition required 4 mL of 0.02M KMnO4 solution for complete reaction. The wt. % of
H2SO4 in the mixture was :–
(A) 40 (B) 50 (C) 60 (D) 80

6. An element A in a compound ABD has oxidation number An–. It is oxidised by Cr2O72– in acid
medium. In the experiment 1.68 × 10–3 moles of K2Cr2O7 were used for 3.26 × 10–3 moles of
Nucleus Education-(NURTURE_(UNACADEMY)

ABD. The new oxidation number of A after oxidation is :–

(A) 3 (B) 3 – n (C) n – 3 (D) +n3

7. Given that 50.0 mL of 0.01 M Na2S2O3 solution and 5 × 10–4 mole of Cl2 react according to
equation,
Cl2 (g) + S2O32–  SO42– + Cl– + S
Answer the following :

(i) How many moles of S2O32– are in the above sample :-

(A) 0.00050 (B) 0.0025 (C) 0.01 (D) 0.02

(ii) How many equivalents of oxidising agents are in this sample for the above reaction :-
(A) 0.001 (B) 0.080 (C) 0.020 (D) 0.010

(iii) What is the molarity of Na2SO4 in this solution :-

(A) 0.080 M (B) 0.040 M (C) 0.020 M (D) 0.010 M
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 8. 50g of pure CaCO3 is heated to liberate CO2. Liberated CO2 required 0.4 mol of moist
ammonia to yield only (NH4)2CO3. Find the volume of CO2 liberated at STP adding excess dil.
HCl to this heated residue.
(A) zero (B) 4.42 L (C) 2.24 L (D) 6.72 L
9. A sample of KMnO4 solution required 50 ml when titrated against 3 mmol of oxalic acid. The
normality of same solution in reaction with alkaline H2O2 is
(A) 0.120 N (B) 0.060 N (C) 0.072 N (D) 0.036 N

MATCH THE COLUMN

10. Column-I Column-II
3M
(A) P2H4  PH3 + P4H2 (p) E=
4
3M
(B) I2  I – + IO3– (q) E=
5
15M
(C) MnO4– + Mn2+ + H2O Mn3O4 + H+ (r) E=
26
5M
(D) H3PO2  PH3 + H3PO3 (s) E=
6
11. Match the column :
Column–I Column–II
(Chemical reactions) ('n' factor of underilined specie
in the given chemical redox reactions)
(A) H2O2  H2O + O2 (p) 4
(B) ClO3– + Fe2+  Cl– + Fe3+ (q) 1
(C) O3 + 2I– + 2H+  I2 + H2O+O2 (r) 2
(D) Zn2++K4[Fe(CN)6]K2Zn3[Fe(CN)6]2+ K+ (s) 1
(t) 6
Nucleus Education-(NURTURE_(UNACADEMY)

Comprehension # 1
Molecular weight / Atomic weight
Equivalent weight =
n  factor
n-factor is very important in redox as well as non-redox reactions. With the help of n-factor we
can predicts the molar ratio of the reactant species taking part in reactions. The reaciprocal of n
factor's ratio of the reactants is the molar ratio of the reactants.
In general n-factor of acid/base is number of moles of H+ /OH– furnished per mole of acid/base.
n-factor of a reactant is no. of moles of electrons lost or gained per mole of reactant.
Example 1 :
1. In acidic medium : KMnO4 (n = 5) Mn2+
2. In neutral medium : KMnO4 (n = 3) Mn2+
3. In basic medium : KMnO4 (n = 1)  Mn6+
Example 2 : FeC2O4  Fe3+ + 2CO2
Total no. of moles of e– lost by 1 mole of FeC2O4 = 1 + 1 × 2  3
 n–actor of FeC2O4 = 3
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 12. n–factor of Ba(MnO4)2 in acidic medium is :
(A) 2 (B) 6 (C) 10 (D) none of these

13. For the reaction,

H3PO2 + NaOH NaH2PO2 + H2O
What is the equivalent weight of H3PO2 ? (mol. wt. is M)
(A) M (B) M/2 (C) M/3 (D) none of these

14. For the reaction, Fe0.95O (molar mass : M)  Fe2O3. What is the eq. wt. of Fe0.95O ?
M M M
(A) (B) (C) (D) none of these
0.85 0.95 0.8075

15. In the reaction, xVO + yFe2O3  FeO + V2O5. What is the value of x and y respectively ?
(A) 1, 1 (B) 2, 3 (C) 3, 2 (D) none of these

Comprehension # 2
Some amount of “20V” H2O2 is mixed with excess of acidified solution of KI. The iodine so
liberated required 200 mL of 0.1 N Na2S2O3 for titration.

16. The volume of H2O2 solution is :

(A) 11.2 mL (B) 37.2 mL (C) 5.675 mL (D) 22.4 mL

17. The mass of K2Cr2O7 needed to oxidise the above volume of H2O2 solution is :
(A) 3.6 g (B) 0.8 g (C) 4.2 g (D) 0.98 g

18. The volume of O2 at STP that would be liberated by above H2O2 solution on disproportionation
is :
(A) 56 mL (B) 113.5 mL (C) 168 mL (D) 224 mL
Nucleus Education-(NURTURE_(UNACADEMY)

19. A small amount of HCl(aq) is added to an aqueous, well stirred solution of NaHCO3 and
K2CO3. Which of the following conditions, when true, will ensure no evolution of CO2?
(A) mmol of HCl added are less than mmol of K2CO3
(B) mmol of HCl added are less than 2 x mmol of K2CO3
(C) mmol of HCl added are less than 0.5 x mmol of K2CO3
(D) none of these

20. x ml and y ml of 0.1 N HCl are required for two separate titrations against a given sample of
NaOH using methyl orange and phenolphthalein as indicators respectively. Which of the
following is true?
(A) x = y
(B) 2x = y
(C) x = 2y
(D) no colour change in titration using methyl orange

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 EXERCISE # (JEE-MAINS)
1. Which of the following is a redox [AIEEE-02]
(1) 2NaAg(CN)2 + Zn Na2Zn (CN)4 + 2 Ag
(2) BaO2 + H2SO4 BaSO4 + H2O2
(3) N2O5 + H2O  2HNO3
(4) AgNO3 + KI AgI + KNO3

2. Oxidation number of Cl in CaOCl2 (bleaching powder is) [AIEEE–02]

(1) Zero, since it contains Cl2
(2) –1, since it contains Cl–
(3) +1, since it contains ClO–
(4) +1 and –1 since it contains ClO– and Cl–

3. MnO4– is good oxidising agent in different medium changing to – [AIEEE–02]

MnO4  Mn2+
   MnO42–
   MnO2
   Mn2O3
 Changes in oxidation number respectively are -
(1) 1, 3, 4, 5 (2) 5, 4, 3, 2 (3) 5, 1, 3, 4 (4) 2, 6, 4, 3
Nucleus Education-(NURTURE_(UNACADEMY)

4. In the coordination compound, K4[Ni (CN)6], the oxidation state of nickel is [AIEEE-03]
(1) +1 (2) +2 (3) –1 (4) 0

5. The oxidation state of chromium in the final product formed by the reaction between Kl and
acidified potassium dichromate solution is - [AIEEE-05]
(1) +6 (2) +4 (3) +3 (4) +2

6. The oxidation state of Cr in [Cr(NH3)4Cl2]+ is – [AIEEE-05]

(1) +2 (2) +3 (3) 0 (4) +1

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 7. Consider the following reaction: [JEE(Main)-2013]
xMnO4  yC2O42  zH 
z
xMn2+ + 2yCO2 + H2O
2
The values of x, y and z in the reaction are respectively :-
(1) 5,2 and 16 (2) 2,5 and 8 (3) 2, 5 and 16 (4) 5,2 and 8

8. Given : [JEE(Main-online)-2013]
X Na2 HAsO3 + Y NaBrO3 +ZHCl  NaBr + H3AsO4 + NaCl
The values of X, Y and Z in the above redox reaction are respectively :
(1) 2, 1, 3 (2) 3, 1, 6 (3) 2, 1, 2 (4) 3, 1, 4

9. In which of the following reaction H2O2 acts as a reducing agent ?

(a) H2O2 + 2H+ + 2e–  2H2O
(b) H2O2 – 2e–  O2 + 2H+
(c) H2O2 + 2e–  2OH–
(d) H2O2 + 2OH– – 2e–  O2 + 2H2O
(1) (a), (c) (2) (b), (d) (3) (a), (b) (4) (c), (d)

10. Consider the reaction [JEE(Main-online)-2014]

4 2
+ H2O(I)  + Sn (aq) + HSO4(aq) + 3H(aa)

Nucleus Education-(NURTURE_(UNACADEMY)

H2SO3(aq) + Sn (aq)

Which of the following statements is correct?

(1) H2SO3 is the reducing agent because it undergoes oxidation
(2) H2SO3 is the reducing agent because it undergoes reduction
(3) Sn4+ is the reducing agent because it undergoes oxidation
(4) Sn4+ is the oxidizing agent because it undergoes reduction

11. How many electrons are involved in the following redox reaction ? [JEE(Main-online)-2014]
Cr2O72– + Fe2+ + C2O42–  Cr3+ + Fe3+ + CO2 (Unbalanced)
(1) 3 (2) 4 (3) 5 (4) 6

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 12. Which of the following reactions is an example of a redox reaction ? JEE(Main)-2017]
(1) XeF4 + O2F2  XeF6 + O2 (2) XeF2 + PF5  [XeF]+PF6–
(3) XeF6 + H2O  XeOF4 + 2HF (4) XeF6 + 2H2O  XeO2F2 + 4HF

13. In the reaction of oxalate with permanganate in acidic medium, the number of electrons
involved in producing one molecule of CO2 is : [JEE Main– 2019 (Jan.)]
(1) 10 (2) 5 (3) 1 (4) 2

14. 25 ml of the given HCl solution requires 30 mL of 0.1 M sodium carbonate solution. What is
the volume of this HCl solution required to titrate 30 mL of 0.2 M aqueous NaOH solution?
[JEE Main– 2019 (Jan.)]
(1) 12.5 mL (2) 50 mL (3) 25 mL (4) 75 mL

15. 50 mL of 0.5 M oxalic acid is needed to neutralize 25 mL of sodium hydroxide solution. The
amount of NaOH in 50 mL of the given sodium hydroxide solution is:[JEE Main–2019 (Jan.)]
(1) 20 g (2) 40 g (3) 80 g (4) 10 g

16. In order to oxidise a mixture of one mole of each of FeC2O4, Fe2(C2O4)3 and Fe2(SO4)3 in
acidic medium, the number of moles of KMnO4 required is : [JEE Main– 2019 (April)]
(1) 1 (2) 3 (3) 2 (4) 1.5

17. The correct order of the oxidation states of nitrogen in NO, N2O, NO2 and N2O3 is:
[JEE Main– 2019 (April)]
Nucleus Education-(NURTURE_(UNACADEMY)

(1) N2O < NO < N2O3 < NO2 (2) N2O < N2O3 < NO < NO2
(3) NO2 < NO < N2O3 < N2O (4) NO2 < N2O3 < NO < N2O

18. An example of a disproportionation reaction is: [JEE Main– 2019 (April)]

(1) 2CuBr  CuBr2 + Cu
(2) 2KMnO4  K2MnO4 + MnO2 + O2
(3) 2MnO4– + 10 I– + 16H+  2Mn2+ + 5I2 + 8H O
(4) 2NaBr + Cl2  2NaCl + Br2

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 EXERCISE # (JEE-ADVANCED)
1. The oxidation number of phosphorus in Ba(H2PO2)2 is : [JEE 1990]
(A) +3 (B) +2 (C) +1 (D) –1

2. The number of electrons to balance the following equation :– [JEE 1991]

NO3– + 4H+ + e–  2H2O + NO is
(A) 5 (B) 4 (C) 3 (D) 2

3. The oxidation states of the most electronegative element in the products of the reaction of BaO2
with dilute H2SO4. [JEE 1991]
(A) 0 and –1 (B) –1 and –2 (C) –2 and 0 (D) –2 and +2

4. For the redox reaction, [JEE 1992]

MnO4– + C2O42– + H+  Mn2+ + CO2 + H2O
the correct coefficients of the reactants for the balanced reaction are :
MnO4– C2O42– H+
(A) 2 5 16
(B) 16 5 2
(C) 5 16 2
(D) 2 16 5

5. A 5.0 cm3 solution of H2O2 liberates 0.508 g of iodine from an acidified KI solution. Calculate
the strength of H2O2 solution in terms of volume strength at STP. [JEE' 1995]

6. The number of mole of KMnO4 that will need to react completely with one mole ferrous
oxalate in acidic solution is : [JEE 1997]
(A) 2/5 (B) 3/5 (C) 4/5 (D) 1
Nucleus Education-(NURTURE_(UNACADEMY)

7. The number of mole of KMnO4 that will be needed to react with one mole of sulphite ion in
acidic solution is : [JEE 1997]
(A) 2/5 (B) 3/5 (C) 4/5 (D) 1

8. One litre of a mixture of O2 and O3 at STP was allowed to react with an excess of acidified
solution of KI. The Iodine liberated required 40 mL of M/10 sodium thiosulphate solution for
titration. What is the percent of ozone in the mixture ? Ultraviolet radiation of wavelength 300
nm can decompose ozone. Assuming that one photon can decompose one ozone molecule, how
many photons would have been required for the complete decomposition of ozone in the
original mixture? [JEE 1997]

9. The equivalent mass of MnSO4 is half its molecular mass when it is converted to : [JEE 1998]
(A) Mn2O3 (B) MnO2 (C) MnO4– (D) MnO42–

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 10. An aqueous solution containing 0.10 g KIO3 (formula wt. 214.0) was treated with an excess of
KI solution. The solution was acidified with HCl. The liberated I2 consumed 45.0 mL of
thiosulphate solution to decolourise the blue starch – iodine complex. Calculate the molarity of
the sodium thiosulphate solution. [JEE 1998]

11. The oxidation number of sulphur in S8, S2F2 and H2S respectively are : [JEE 1999]
(A) 0, +1 and –2 (B) +2, +1 and –2
(C) 0, +1 and +2 (D) –2, +1 and –2

12. How many millilitre of 0.5 M H2SO4 are needed to dissolve 0.5 g of copper II carbonate ?
[JEE 1999]

13. The normality of 0.3 M phosphorus acid (H3PO3) is : [JEE 1999]

(A) 0.1 (B) 0.9 (C) 0.3 (D) 0.6

14. Among the following species in which oxidation state of the element is +6 : [JEE 2000]
(A) MnO4– (B) Cr(CN)63– (C) NiF62– (D) CrO2Cl2

15. A 3.00 g sample containing Fe3O4, Fe2O3 and an inert impure substance, is treated with excess
of KI solution in presence of dilute H2SO4. The entire iron is converted into Fe2+ along with the
liberation of iodine. The resulting solution is diluted to 100 mL. A 20 mL of the diluted
solution require 11 mL of 0.5 M Na2S2O3 solution to reduce the iodine present. A 50 mL of
diluted solution after complete extraction of the iodine requires 12.80 mL of 0.25 KMnO4
solution in dilute H2SO4 medium for the oxidation of Fe2+. Calculate the percentages of Fe2O3
and Fe3O4 in the original sample. [JEE 2000]
Nucleus Education-(NURTURE_(UNACADEMY)

16. An aqueous solution of 6.3 g of oxalic acid dihydrate is made upto 250 mL. The volume of 0.1
N NaOH required to completely neutralise 10 mL of this solution is : [JEE 2001]
(A) 40 mL (B) 20 mL (C) 10 mL (D) 4 mL

17. Hydrogen peroxide solution (20 mL) reacts quantitatively with a solution of KMnO4 (20 mL)
acidified with dilute H2SO4. The same volume of KMnO4 solution is just decolorized by 10 mL
of MnSO4 in neutral medium simultaneously forming a dark brown precipitate of hydrated
MnO2. The brown precipitate is dissolved in 10 mL of 0.2 M sodium oxalate under boiling
condition in the presence of dilute H2SO4. Write the balanced equations involved in the
reactions and calculate the molarity of H2O2. [JEE 2001]

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 18. Reduction of the metal centre in aqueous permanganate ion involves - [JEE-2011]
(A) 3 electrons in neutral medium (B) 5 electrons in neutral medium
(C) 3 electrons in alkaline medium (D) 5 electrons in acidic medium

19. Reaction of Br2 with Na2CO3 in aqueous solution gives sodium bromide and sodium bromate
with evolution of CO2 gas. The number of sodium bromide molecules involved in the balanced
chemical equation is. [JEE- 2011]

20. Which ordering of compounds is according to the decreasing order of the oxidation state of
nitrogen– [JEE- 2012]
(A) HNO3, NO, NH4Cl, N2 (B) HNO3, NO, N2, NH4Cl
(C) HNO3, NH4Cl, NO, N2 (D) NO, HNO3, NH4Cl, N2

21. 25 mL of household bleach solution was mixed with 30 mL of 0.50 M KI and 10 mL of 4 N

acetic acid. In the titration of the liberated iodine, 48 mL of 0.25 N Na2S2O3 was used to reach
the end point. The molarity of the household bleach solution is [JEE- 2012]
(A) 0.48 M (B) 0.96 M (C) 0.24 M (D) 0.024 M

22. For the reaction [JEE- 2014]

I¯ + ClO¯3 + H2SO4  Cl¯ + HSO¯4 + I2
The correct statement(s) in the balanced equation is / are :
(A) Stoichiometric coefficient of HSO¯4 is 6
(B) Iodide is oxidized
(C) Sulphur is reduced
(D) H2O is one of the products

23. In neutral or faintly alkaline solution, 8 moles permanganate anion quantitatively oxidize
thiosulphate anions to produce X moles of a sulphur containing product. the magnitude of X is
[JEE- 2016]
Nucleus Education-(NURTURE_(UNACADEMY)

24. To measure the quantity of MnCl2 dissolved in an aqueous solution, it was completely
converted to KMnO4 using the reaction,
MnCl2 + K2S2O8 + H2O  KMnO4 + H2SO4 + HCl (equation not balanced). Few drops of
concentrated HCl were added to this solution and gently warmed. Further, oxalic acid (225 mg)
was added in portions till the colour of the permanganate ion disappeared. The quantity of
MnCl2 (in mg) present in the initial solution is ____.
(Atomic weights in g mol–1: Mn = 55, Cl = 35.5) [JEE- 2018]

25. The amount of water produced (in g) in the oxidation of 1 mole of rhombic sulphur by conc.
HNO3 to a compound with the highest oxidation state of sulphur is ____
(Given data : Molar mass of water = 18 gmol–1) [JEE- 2019]

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 ANSWER KEY
EXERCISE # (S-I)
1. (a) +3 (b) +5 (c) +6 (d) 8/3 or (2 and 3) (e) +3 (f) +2
(g) 200/93 = 2.15
8
2. (1) + (2) +2 (3) +2.5 (4) –3 (5) +2 (6) +4
3
(7) +2 (8) +4 (9) +4 (10) +5 (11) –3 (12) +5
(13) +2 (14) –3 (15) +1 (16) +8 (17) +4 (18) +6
(19) +8 (20) +4
3. 8
4. (a) S4O62–(aq) + 6Al (s) + 20 H+  4 H2S (aq) + 6Al3+ (aq) + 6H2O
(b) 6S2O32–(aq) + Cr2O72– (aq) + 14 H+  3 S4O62– (aq) + 2 Cr3+ (aq) + 7H2O
(c) 14ClO3–(aq) + 3As2S3(s) + 18 H2O  14 Cl–(aq) + 6H2AsO4–(aq) + 9HSO4–(aq) + 15H+
(d) 7IO3– (aq) + 6Re (s) + 3H2O 6 ReO4– (aq) + 7I – (aq) + 6H+
(e) 30HSO4–(aq) + As4 (s) + 10 Pb3O4(s) + 26H+  30 PbSO4 (s) + 4H2AsO4– (aq) + 24H2O
(f) 3HNO2(aq) HNO3 + 2NO (g) + H2O
(g) 3MnO42– + 4H+  2MnO4– + MnO2 + H2O
(h) 4BCl3 + P4 + 6H2  4BP + 12HCl
(i) 2KMnO4 + 16HCl  2MnCl2 + 5Cl2 + 2KCl + 8H2O
(j) 2KMnO4 + 5H2O2 + 3H2SO4 = 2MnSO4 + K2SO4 + 5O2 + 8H2O
Nucleus Education-(NURTURE_(UNACADEMY)

(k) 2KMnO4 = K2MnO4 + MnO2 + O2

(l) Ca(OCl2) + 4KI + 4HCl  2I2 + 4KCl + CaCl2 + 2H2O
(m) 2Cu(NH3)4Cl2 + 7KCN + H2O = K2Cu(CN)3 + 6NH3 + KCNO + 2NH4Cl + 2KCl
5. (a) 3C4H4O62–(aq) + 5ClO3– (aq) + 18 OH–  12 CO32– (aq) + 5 Cl– (aq) + 15H2O
(b) 11Al (s) + 3BiONO3 (s) + 21H2O + 11OH–  3Bi (s) + 3NH3 (aq) + 11Al (OH)4–(aq)
(c) 4H2O2 (aq) + Cl2O7 (aq) + 2OH–  2ClO2– (aq) + 4O2 (g) + 5H2O
(d) Tl2O3 (s) + 4NH2OH (aq) 2TlOH (s) + 2N2 (g) + 5H2O
(e) Cu(NH3)42+ (aq) + S2O42– (aq) + 4OH–  2SO32– (aq) + Cu (s) + 4NH3 (aq) + 2H2O
(f) 3Mn(OH)2 (s) + 2MnO4– (aq)  5MnO2 (s) + 2H2O + 2OH–
(g) 3C2H5OH + 2MnO4– + OH– = 3C2H3O– + 2MnO2 + 5H2O
(h) 2ClO2 + SbO2– + 2OH– = 2ClO2– + Sb(OH)6– + 2H2O
(i) 2MnO4– + 3CN– + H2O 2MnO2 + 3CNO– + 2OH–
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57 57
 M1 M2 M3
6. (a) 58.5 (b) 87 (c) 51.67 7. 20.1 8. , ,
6 8 5
9. (a) 31.6 (b) 52.67 10. 0.06 N, 0.03 M
11. (a) 40 ml (b) 60 ml 12. V = 3 lit. 13. 200 mL
14. 1.406% 15. V = 25 mL 16. 90.1 17. (a) 3L (b) 6 L
18. 2.5 19. 27/2 20. 71 21. 2500
22. 0.126 23. 75 24. 0.6 25. 10
26. 3 27. +3 28. Zero 29. 2.22 mL.
30. 0.667 31. 0.588 N 32. 2.12 g/L 33. 4 lit
34. V = 160 ml 35. 126 ppm 36. 0.25075 g 37. 7.1%

EXERCISE # (S-II)
1. 16.66% 2. 0.25075 g 3. 7.1% 4. FeO= 40% and Fe2O3= 60%
5. 5g 6. Vol. of KIO3=20mL, [HCl]=0.02 7. 5.6 L

8. 50% 9. 25% ; SCN–+ I2+ 4H2O 

 HCN+7H+ +6I–
10. 38% 11. 5 12. 0.0174g; 3.48%

EXERCISE # (O-I)
1. (D) 2. (A) 3. (C) 4. (B) 5. (D)
Nucleus Education-(NURTURE_(UNACADEMY)

6. (A) 7. (D) 8. (D) 9. (D) 10. (C)

11. (A) 12. (B) 13. (B) 14. (A) 15. (A)
16. (C) 17. (D) 18. (A) 19. (A) 20. (A)
21. (D) 22. (D) 23. (D) 24. (C) 25. (A)
26. (D) 27. (D) 28. (B) 29. (B) 30. (A)
31. (A) 32. (A) 33. (A) 34. (B) 35. (C)
36. (D) 37. (A) 38. (C) 39. (C) 40. (C)
41. (A,D) 42. (D) 43. (C) 44. (B) 45. (B)
46. (C) 47. (A) 48. (B) 49. (A) 50. (A)
51. (B) 52. (A) 53. (C)

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58 58
 EXERCISE # (O-II)
1. (C) 2. (A) 3. (A) 4. (B) 5. (A)
6. (B) 7. (i) (A); (ii)  (A); (iii)  (D) 8. (B)
9. (C) 10. (A) (s); (B) (q); (C) r ; (D)  p
11. (A)  (q); (B)  (t); (C)  (r); (D)  (t) 12. (C) 13. (A)
14. (A) 15. (B) 16. (C) 17. (D) 18. (B)
19. (A,C) 20. (A)

EXERCISE # (JEE-MAINS)
1. (4) 2. (4) 3. (4) 4. (2) 5. (3)
6. (2) 7. (2) 8. (2) 9. (1) 10. (4)
11. (3) 12. (2) 13. (3) 14. (3) 15. Bonus
16. (3) 17. (1) 18. (1)

EXERCISE # (JEE-ADVANCED)
1. (C) 2. (C) 3. (B) 4. (A) 5. (4.48)
6. (B) 7. (A) 8. 6.7% O3 (by weight), 1.2 × 1021 photons
9. (B) 10. (0.0626 M) 11. (A) 12. (8.097 mL) 13. (D)
14. (D) 15. Fe2O3 = 49.33 %, Fe3O4 = 34.8% 16. (A)
Nucleus Education-(NURTURE_(UNACADEMY)

17. (0.1 M) 18. (A,C,D) 19. (5) 20. (B) 21. (C)
22. (A,B,D) 23. (6) 24. (126) 25. (288)

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59 59
 HINT & SOLUTION : REDOX EQUIVALENT
EXERCISE # (S-I)
1. (a) K[Co(C2O4)2 (NH3)2]
1 + x + 2x(–2) + 2 × 0 = 0
x=3
(b) K4 P2 O7
4 × 1 + 2x + 7x(–2) = 0
x = +5
(c) Cr O2 Cl2
x + 2(–2) + 2(–1) = 0
x=+6
(d) Mn3O4
3x + 4x(–2) = 0
8
x=+
3
(e) Ca (Cl O2)2
2 + 2(x + (2x – 2)) = 0
x = +3
(f) Zn O22
x + 2(–2) = –2
x = +2
(g) Fe0.93O
0.93 x – 2 = 0
200
x=
93
8
2. (1) + (2) +2 (3) +2.5 (4) –3 (5) +2 (6) +4
3
Nucleus Education-(NURTURE_(UNACADEMY)

(7) +2 (8) +4 (9) +4 (10) +5 (11) -3 (12) +5

(13) +2 (14) –3 (15) +1 (16) +8 (17) +4 (18) +6
(19) +8 (20) +4

3. 8

4. (a) S4O62–(aq) + 6Al (s) + 20 H+  4 H2S (aq) + 6Al3+ (aq) + 6H2O

(b) 6S2O32–(aq) + Cr2O72– (aq) + 14 H+  3 S4O62– (aq) + 2 Cr3+ (aq) + 7H2O
(c) 14ClO3–(aq) + 3As2S3(s) + 18 H2O  14 Cl–(aq) + 6H2AsO4–(aq) + 9HSO4–(aq) + 15H+
(d) 7IO3– (aq) + 6Re (s) + 3H2O 6 ReO4– (aq) + 7I – (aq) + 6H+
(e) 30HSO4–(aq) + As4 (s) + 10 Pb3O4(s) + 26H+  30 PbSO4 (s) + 4H2AsO4– (aq) + 24H2O
(f) 3HNO2(aq) HNO3 + 2NO (g) + H2O

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 (g) 3MnO42– + 4H+  2MnO4– + MnO2 + H2O
(h) 4BCl3 + P4 + 6H2  4BP + 12HCl
(i) 2KMnO4 + 16HCl  2MnCl2 + 5Cl2 + 2KCl + 8H2O
(j) 2KMnO4 + 5H2O2 + 3H2SO4 = 2MnSO4 + K2SO4 + 5O2 + 8H2O
(k) 2KMnO4 = K2MnO4 + MnO2 + O2
(l) Ca(OCl2) + 4KI + 4HCl  2I2 + 4KCl + CaCl2 + 2H2O
(m) 2Cu(NH3)4Cl2 + 7KCN + H2O = K2Cu(CN)3 + 6NH3 + KCNO + 2NH4Cl + 2KCl

5. (a) 3C4H4O62–(aq) + 5ClO3– (aq) + 18 OH–  12 CO32– (aq) + 5 Cl– (aq) + 15H2O
(b) 11Al (s) + 3BiONO3 (s) + 21H2O + 11OH–  3Bi (s) + 3NH3 (aq) + 11Al (OH)4–(aq)
(c) 4H2O2 (aq) + Cl2O7 (aq) + 2OH–  2ClO2– (aq) + 4O2 (g) + 5H2O
(d) Tl2O3 (s) + 4NH2OH (aq) 2TlOH (s) + 2N2 (g) + 5H2O
(e) Cu(NH3)42+ (aq) + S2O42– (aq) + 4OH–  2SO32– (aq) + Cu (s) + 4NH3 (aq) + 2H2O
(f) 3Mn(OH)2 (s) + 2MnO4– (aq)  5MnO2 (s) + 2H2O + 2OH–
(g) 3C2H5OH + 2MnO4– + OH– = 3C2H3O– + 2MnO2 + 5H2O
(h) 2ClO2 + SbO2– + 2OH– = 2ClO2– + Sb(OH)6– + 2H2O
(i) 2MnO4– + 3CN– + H2O 2MnO2 + 3CNO– + 2OH–

MM
6. Eq. wt. of salt =
Totalcationiccharge (nf )
(a) nf = 1
(b) nf = 2
(c) nf = 6

7. 22.4 L of a gas at STP = 1 mole

Nucleus Education-(NURTURE_(UNACADEMY)

1
1.12 L of a gas at STP = × 1.12 = 0.05 moles
22.4
Mass of chlorine = moles × molar mass = 0.05 × 71 = 3.55 g
Thus mass of metal = Mass of metal chloride – mass of chlorine = (5.56 – 3.55)g = 2.01 g
3.55 gram of chlorine combine with = 2.01 g of metal
2.01
So 35.5 gram of chlorine combines with = × 35.5 = 20.1 g of metal
3.55
8. nf (CuS) =6
nf (Cu2S) =8
nf (KMnO4) =5

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 158
9. (a) Eq. wt. = = 31.6
5
158
(b) Eq. wt. = = 52.67
3
10. N1V1 = N2V2
3 × 5 = N2 × 250
N2 = 0.06 N
N
Also M2 = 2 = 0.03 M
2
11. (a) m.e. of H3PO4 – m.e. of Ca(OH)2
1 × V = 2 × 20
V = 40 ml.
(b) m.e. of H2SO4 = m.e. of Al(OH)3
1 × V = 1 × 3 × 20
V = 60 ml.

12. Let 19 gm mixture contains x moles each of Na2CO3 and NaHCO3.

Therefore
106x + 84x = 19
x = 0.1
Since HCl reacts with mixture as:
HCl + Na2CO3  NaCl + H2CO3
HCl + NaHCO3  NaCl + H2CO3
equivalent of HCl used = equivalent of Na2CO3 + equivalent of NaHCO3
0.1 V = (x × 2) + (x × 1) = 3x
0.1 V = 3 × 0.1
V = 3 lit
Nucleus Education-(NURTURE_(UNACADEMY)

13. NaH2PO4  NaOH Na3PO4 + H2O

n 2 n 1

equivalent of NaH2PO4 = equivalent of NaOH

mole of NaH2PO4 × 'n' factor = M × 'n' factor × V
12
2 = 1 × 1 × V
120
V = 0.2 lt
14. Ca(OH)2 + HCl  CaCl2 + H2O
NaOH + HCl  NaCl + H2O
m.e. of HCl used = m.e. of Ca(OH)2 + m.e. of NaOH
0.5 × 0.5 = m.m. of Ca(OH)2 × 2 + 0.3 × 20
19
m.m. of Ca(OH)2 = m.m.
2

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 19
wt. of Ca(OH)2 = × 10–3 × 74 gm
2
19 103  74
wt % of Ca(OH)2 = 100 = 1.406 %
2  50

15. CaCO3  HCl  CaCl2 + H2CO3

n 2 n 1

KOH HCl  KCl + H2O

n 1 n 1

equivalent of CaCO3 + equivalent of KOH = equivalent of HCl used

 10  11 250
 100  2  + (2 × 1 × V) = 1000
 
V = 25 ml

16. M eq. of Na2CO3 = M eq. of HCl

w
× 1000 = 50 × 0.1 – 10 × 0.16
106
2
w
% purity = × 100 = 90.1%
1

17. (a) 0.4 × 5 × V = 1 × 2 + 2 × 2

V = 3 lit
(b) 0.2 × 5 × V = 1 × 2 + 2 × 2
V = 6 lit

gm eq. of SO2 = gm eq. of MnO4

Nucleus Education-(NURTURE_(UNACADEMY)

18.
10
2 × nSO2 = × 0.1 × 5
1000
Milli moles of SO2 = 2.5

19. Equivalents of MnO4 = eq. of SO24

18 × 5 = 4X
X = 22.5

20. On balancing
As2O5 + 10HCl  2AsCl3 + 5Cl2 + 2H2O
HCl is limiting

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 5
 Moles of Cl2 = ×5
10
= 2.5
Mass of Cl2 = 177.5 gm
21. H2O2 + KMnO4 + H+  Mn2+ + O2(g)
n=2 n=5
Number of equivalent of H2O2 = Number of equivalent of KMnO4
N1V1 = N2V2
2 × 0.1 × V = 5 × 0.1 × 1
V = 2.5 litre
= 2500 ml.

22. Moles × 6 = 0.76 × 1

Moles = 0.1266

100
23. 5 × 0.1 × =x×2
1000
x = 25 × 10–3 moles
= moles of CuO = moles of Cu2O
Milli moles of Cu2+ = 3 × 25 × 10–3 moles
= 75 Milli moles
24. Eq. of MnO4
= Eq of FeC2O4
5 × nKMnO4 = 3 × 1
3
nKMnO4 =
5
25. 0.1 × 5 × V = 2 ×  nf I
2

2 10 5
 nf I2 = 
Nucleus Education-(NURTURE_(UNACADEMY)

12 3
5
0.1 × 5 × V = 2 ×
3
20
V= lit
3
10 5
26. 0.1 × × 5 = moles ×
1000 3
Milli moles = 3 m moles of Br2

4 2
27. Ce  Ce  Sn4+ + Cex
n  4 x n 2
m.e. of Ce4+ = m.e. of Sn2+
1 × (4 – x) × 40 = 1 × 2 × 20
x=3

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 28. SeO2  CrSO4  Ce3+ + Sex
n (4 x) n 1

m.e. of SeO2 = m.e. of CrSO4

1 × (4 – x) × 10 = 2 × 1 × 20
x=0
29. V × 0.03 × 6 = 5 × 0.2 × 4
V = 2.22 ml

30. K2Cr2O7  KI  Cr3+ + I2

n 6 n 1

m.e. of K2Cr2O7 = m.e. of KI

m.m × 6 = 0.1 × 1 × 40
4
m.m. of K2Cr2O7 = = 0.667 m.m.
6
x
31. Weight of H2O2 in the mixture = 1 × gm
100
x
mole of H2O2 in the mixture = mole
100  34
H2O2 + KMnO4  M2n + O2
n 2 n 5
equivalent of H2O2 = equivalent of KMnO4
x
 2 = N × x × 10–3
100  34
20
N= = 0.588
34
1
32. M × 20 × 2 = 30 ×
12
1
M=
Nucleus Education-(NURTURE_(UNACADEMY)

16
1
Strength = M × 34 = × 34 = 2.12 gm/lit
16

33. Sn K2Cr2O7 + HCl  SnCl4 + Cr3+

n 4 n 6
equivalent of Sn = equivalent of K2Cr2O7
11.9 1
4 = V
119 10
V = 4 lit
34. K2C2O4 · 3H2C2O4·4H2O + MnO4 + H+  Mn 2 + CO2
n 8 n 5

equivalent of MnO = equivalent of acid oxalate
4
5.08
0.1 × 5 × V = 8
508
V = 0.16 lit
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 35. Eq. of K2Cr2O7 = Eq. of Fe2+ (initial + back titration)
25 × 0.002 × 6 = 100 × 1 × M + 7.5 × 0.01 × 1
M = 2.25 × 10–4
2.25 104  56
ppm = 106 = 126 ppm
100

36. Meq. of I2 used = 20.10 × 0.05 = 1.005

Let meq. of As2O3 and As2O5 in mixture be a and b respectively.
Addition of I2 to mixture converts As32 into As52 .
Meq. of As2O3 = Meq. of I2 used = Meq. of As52 formed
a = 1.005 …….(i)
After oxidation, the mixture contains all the arsenic in +5 oxidation state, which is then reduced to
As32 by using KI and hypo.
Meq. of As2O3 as As5+ + Meq. of As2O3
= Meq. of I2 liberated = Meq. of hypo used
 1.113 
A+b=   1000
 248 
or a + b = 4.487 …….(ii)
By Eqs. (i) and (ii), we get b = 4.487 – 1.005 = 3.482
 Eq.mass  198 
 Mass of As2O3 =  Meq.  4 
EAs2O3
 1000 
1.005 198
= = 0.0497
4 1000
3.482  230  230 
Mass of As2O5 =
4 1000   EAs2O5
4 
= 0.2002

 Mass of mixture = 0.0497 + 0.2002 = 0.2501 gm

Nucleus Education-(NURTURE_(UNACADEMY)

37. Meq of Mohr’s salt

= 35 × 1 × 1 = 35
Meq of KMnO4 = Meq of excess Mohr salt
= 30 × 0.1 × 5 = 15
Meq of Mohr salt reacted with bleaching powder = 35 – 15 = 20
Meq of Cl2 = 20
71
Weight of Cl2 = 20 × 10–3 × = 0.71 g
2
0.71
Percent of Cl2 = × 100 = 7.1%
10

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 EXERCISE # (S-II)
1. Fe2O3 do not react with KMnO4
KMnO4 + FeO  Fe3+ + Mn+2
equation of KMnO4 = equation of FeO
158
 5 = FeO × 1
158
FeO = 5 WFeO = 360
WFe2O3 = 160 Fe2O3  1
1
Mole % of Fe2O3 = × 100 = 16.67
6

2. Let the m mole of As2O3 = x

As2O5 = y
As2O3 + 2I2 + 2 H2O  As2O5 + 4H+ + 4I–
nf 4 nf  2

equation of As2O3 = equation of I2

x × 4 = 20 × 0.05
x = 25
Total moles of As2O5 after the P × n = x + y
As2O5 + 4H+ + 4I–  As2O3 + 2I2 + 2H2O
nf  4

I2 + Na2S2O3  I– + Na2S4O6
equation of As2O5 = equation of I2 = equation of hypo
1.116
(x + y) × 4 = × 1000 = 4.5
248
x + y = 1.125
y = 0.875
WAS2O3 = 0.25 × 198 × 10–3 = 49.5 × 10–3
WAS2O5 = 0.875 × 230 × 10–3 = 201.25 × 10–3
Nucleus Education-(NURTURE_(UNACADEMY)

Total weight = 0.25075 gm

3. Bleaching powder = CaOCl2

Mohr Salt = (NH4)2SO4 . FeSO4 . 6H2O
CaOCl2 + Fe2  Cl– + Fe3+
nf 2 nf 1

Fe2+ + KMnO4  Fe3+ + Mn2+

meq of Mohr Salt = meq of CaOCl2 + meq of KMnO4
35 × 1 × 1 = millin CaOCl2 × 2 + 30 + 0.1 × 5
m moles of CaOCl2 = 10
man of chlorine = 10 × 10–3 × 71
= 0.71 gm
0.71
% Chlorine = 100 = 7.1 %
10

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 4. Let the m mole of FeO = x
Let the m mole of Fe2O3 = y
KMnO4 + FeO  Fe + Mn
3+ 2+
n f 5 n f 1

meq of KMnO4 = m eq of FeO

2
× 100 × 5 = x × 1
5
x = 200
Total m moles of Fe3+ after the oxidation = x + 2y
Fe3+ + Zn  Fe2+ + Zn2+
Fe2+ + K 2Cr2 O7  Fe3+ + Cr3+
n f 6
2+
meq of Fe = meq of K2Cr2O7
2
(x + 2y) × 1 = × 1000 × 6 = 800
15
y = 300

5. Cu + H2SO4  Cu2+ + SO2

f  2

SO2 + KMnO4  SO42– + Mn2+

f 2 f 5

H2C2O4 + KMnO4  Mn2+ + CO2

f  2 f 5

meq of KMnO4 = meq of SO2 + meq of H2C2O4

100 × 0.4 × 5 = meq of SO2 + 25 × 1 × 2
150 = meq of SO2 + meq of Cu
150
moles of Cu = 10–3
2
Nucleus Education-(NURTURE_(UNACADEMY)

WCu = 75 × 10–3 × 63.5

75 10–3  63.5
Weight of sample = 100 = 5 gm
95.25

6. KI + KIO3 + HCl  I2 + KCl + H2O

5 KI + KIO + 6HCl  3 I2 + 6KCl + 3H2O ....(1)
f 1 f 5 5
f 
3

I2  Na 2S2O3 + I– + Na2S2O3 ....(2)

f 2 f 1

meq of Na2S2O3 = meq of I2 in 2nd R × n

24 × 0.02 × 1 = 2 × I2
moles of I2 = 0.24
meq of I2 in 1st R × n = meq of KIO3

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 5
0.24 × = 0.004 × V × 5
3
1
10 × 6 × = V
3
20 ml = V
 moles of HCl = 6 × moles of KIO3
24 × M = 6 × 20 × 0.004
MHCl = 0.2

7. H2O2 + Sn2+  Sn4+ + H2O

f 2

10
H2O2 
2
2 2
nf = =1
22
20
Initial moles of H2O2 =
34
moles of H2O2 after the with Sn2+
20 88.2 1
= 
34 1000
= 0.5882 – 0.0882
= 0.5
1 1
Moles of produced O2 = 0.5  
2 4
1
Volume of O2 at 1 atm 273K =  22.4 = 5.6 lit
4
Nucleus Education-(NURTURE_(UNACADEMY)

8. Mn3O4  3Mn2+
x mol 3x mol
KMnO4 + C2O42 + H+  Mn2+ + CO2
f 5

1.25
Molarity of KMnO4 sol =  0.25
5
equation of KMnO4 = equation of Mn2+
0.25 × 4 × 3 = 3x × 1
x=1
w 229
% Mn3O4 = 100 = 50%
w 458

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 9. 4H2O + SCN–  SO24 + HCN + 7H+ + 6e–
I2 + 2e–  2I–
4H2O + SCN– + 3I2  SO24 + HCN + 7H+
I2 + Na2S2O3  I– + Na2S4O6
meq of I2 = meq of SCN– + meq of hypo
50 × 6 = 2x × 6 + 26 × 1 × 1
x = 2 moles of Ba(SCN)2
2  253
% w/w of Ba(SCN)2 = ×10–3×100 = 25 %
2.024

10. Cu2+ + KI  I2 + Cu+

If = 1
I2 + Na2S2O3 Na2S4O6 + I–
meq of Cu2+ = meq of I2 = meq of hypo
20  0.03
moles of Cu 20 ml ×1 = = 6×10–4
1000
1000
moles of Cu in 1 litre = ×6×10–4 = 3×10–2
20
2
3  10  64
% w/w Cu = ×100 = 38.4 %
5

11. moles of Fe2O3 = 0.48 gm

0.48
moles of Fe3+ = ×2×10–2 = 6×10–3
160
Fe3+ + Zn  Zn2+ + Fe2+
6moles 6moles
2+
meq of Fe = meq of oxidising agent
Nucleus Education-(NURTURE_(UNACADEMY)

n 25 ml = 30×0.01×n
1 0.01
6× ×1 = 30× ×n
4 100
n=5

12. MnO2 + HCl  Cl2 + Mn2+

Cl2 + KI  I2 + Cl–
I2 + Na2S2O3  I– + Na2 + Na2S4O6
eq of MnO2 = eq of hypo
1 1
n × 2 = 40× 
10 1000
n = 2×10–3
2  103  87
% w/w MnO2 = ×100 = 3.48 %
5
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 EXERCISE # (O-I)
1. A, B & C are disproportionation reaction

1
2. NaN3  N3 (charge on N = )
3
N2H2  N22 (charge of N = –1)
NO (charge on N = +2)
N2O5  (charge on N = +5)

3. On balancing
6HI + 2HNO3  2NO + 3I2 + 4H2O

staichionetriccoefficient of X 5
4. 

staichionetriccoefficient of XO3 1

5. On balancing
3CN– + 7 NO3 + 10H+  10 NO + 3CO2 + 5H2O

6. On balancing
2 KMnO4 + 5 H2O2 + 3 H2SO4  2 MnSO4 + 5 O2 + 8 H2O + K2SO4
Total = 26

7. H2O2  H2O + O2
Oxydation as well as reduction of O atom takes place.
Nucleus Education-(NURTURE_(UNACADEMY)

8. All are disproportion reaction

9. Oxidising agent = IO3

Oxidised = Cr(OH)3
(nf)I = 6

10. Ba(SCN)2  Ba2+ + SO24  CO32  NO3


S C  N
0 2 3

nf = 12 + 4 + 16
= 32

11. Only (i) reaction is balanced.

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 (O.A)
Fe0.9O Fe2O3
12.

% Fe2+ % Fe+3
7 2
=
9 9
Fe+2 
K2Cr2O7
 Fe+3
7
× 0.9
9
7
nf = 1 × × 0.9 = 0.7
9
M 10M
Equivalent mass = 
0.7 7

2
13. Aº  A2Ox
x y
ni
M 2M  16x
Equivalent of M = Equivalent of M2Ox
x y
×x= × 2x
M 2M  16x
x y
=
M 2M 16x
Mn = 8x2 = My
8x 2
M=
yx
M
Eq. wt. of A =
Nucleus Education-(NURTURE_(UNACADEMY)

x
2
8x 8x
= 
(y  x)x y  x

Molar mass
14. Equivalent wt. of Acid =
No.of replaceble H ions

15. A2Ox  AClx

3 gm 5 gm
3 5

E  8 E  35.5
E = 33.25

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 16. Equivalents = Mole  nf
6 1020
= × 1 = 10–3
6 10 23

17. N2  NH3
28
EW(N2 )  = 4.67
6

M
18.
5

19. Equivalents of M = equivalents of O2

Wmetal WO2

(equivalent mass)metal (equivalent mass)O2
Wmetal
=2
WO2
Wmetal  WO2 3
  = 1.5
Wmetal 2

20. Eq. H2SO4 = Eq. Na2CO3

0.125
0.1 × V (lit) = ×2
106
V (ml) = 23.6 ml

21. Eq. (HNO3) = Eq. (NaOH)

M1 n1 V1 = M2 n2 V2
Nucleus Education-(NURTURE_(UNACADEMY)

18.9 3.2
× 1 × V1 = × 1 × V2
63 40
V1 4

V2 15

22. x=1
y=1
z=1

25 1.06
23. N  2
1000 106
N = 0.8

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 24. N V = Mass × nf
50 m
0.2 × = ×2
1000 126
m = 0.63 gm

63 125
25. Eq. (Acid) = × 10 × 2 ×
126 1000
= 1.25
40 125
Eq. (Base) = × 10 × 1 ×
40 1000
= 1.25
Hence neutral

26. In option D ,
4
gm eq KMnO4 = moles of KMnO4 × nf = ×5=4
5
gm eq  H2C2O4 = moles of H2C2O4 × nf = 2 × 2 = 4
Also CO2 produced  4 moles
 4 × 22.7 lit.

27. gm eq. KMnO4 = gm eq  H2O2

n × 5 = 2 × (4)
n = 8/5

28. gm eq. KHC2O4  2H2C2O4 = gm eq. of H2O2

2.8
Moles × 6 = 3 × ×2×2
22.4
Nucleus Education-(NURTURE_(UNACADEMY)

Moles = 0.25
m moles = 250

29. nf when acid =1+4=5=x

nf in redox = 2 + 4 + 6 + (4 × 6) + [3 × (1 + 2)]
= 45

30. nf of FeS2 = 11
nf of CuS = 6
20 10 10
× N = 1 × 11 × +2×6×
1000 1000 1000
N = 11.5

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 31. MnO24  MnO4 + MnO2
Gram eq. of MnO24 = gm eq. of MnO4
 1 2 
1×   = 1 × moles of MnO4
 1 2 
2
Moles of MnO4 =
3
2
Mass of Mn in MnO4 = × 55
3
2
 55
% mass of Mn = 3 × 100
1 55
= 66.66 %
0.678
32. V1 × 0.1 × 6 = × nf …….. (1)
38
0.678
V2 × 0.3 × 5 = × nf …….. (2)
38
(1) / (2)
V1 × 0.1 × 6 = V2 × 0.3 × 5
V1 15 5
 
V2 6 2
2
V2 = V1
5
33. (1) V2O5  V2+
(2) V2+ + I2 VO2+ + I–
Let. Eq. (V2+)1 = Eq. (V2O5) = a
Nucleus Education-(NURTURE_(UNACADEMY)

a
Moles of V2+ =
3
a
Eq. (V2+)2 = × 2 = n I2 × 2
3
a
n I2 
3
10
Eq. (V2O5) = ×6=a
182
10  6
n I2   0.11 moles
182  3

34. In option B
Cl2 is reduced to Cl–

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 35. 0.136 = 6 × moles
Moles = 0.0227

36. N = M × nf
0.6
M= = 0.2
3

5 1
37. NO3  NH2 OH
nf = 6

M
38.
5

39. 1 × 4 = 0.02 × 5 × V (ml)

4 100
= V (ml) = 40 ml
5 2

2
KOH  O30 KO31  O02
40.
Reduced
Oxidized

41. nf = 2
HNO2  N2O / HNO3
Nucleus Education-(NURTURE_(UNACADEMY)

42. Since AlCl3 & NaCl are formed

100 × 0.1 × 4 = 0.25 × V (ml)
V = 160 ml

43. HCl + KBrO3 + KBr  Br2

Br2 + S2O32  Br– + S2O62
Gm eq. of HCl = gm eq. of Br2 = gm eq. of Na2S2O3
70 21
 ×M×1= ×2×1
1000 1000
M = 0.6 M

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 4 0 2 1
44. CHCl2 COOH  2CO2 + H2O + Cl2 (C2 H2 Cl2 O2 )
nf = 6
Moles × 6 = 600
Mole = 100 M moles
100Mmoles 1
For NH3, molesNH3 =
1
= 100 M moles
= 0.1 moles

3 4
45. H2 C2 O4  CO2
a 1 90
×2= 
90 20 1000
81
a=  0.2
400
0.2
% purity = × 100
0.3
= 66%

46. 2mole = 8eq 8eq

K3H(C2O4)2 + KMnO4  CO2
n=4 n=5
1mole=2eq 2eq

H2C2O4 + KMnO4  CO2 + Mn2+

n=2 n =5
Total eq. of KMnO4 used = 10 eq = Normality × volume
10 eq = M × 5 × V1
10
V1 = lit.
Nucleus Education-(NURTURE_(UNACADEMY)

5M

= lit.
M
2mole = 2eq 2eq = 1mole
K3H(C2O4)2 + Ba(OH)2  Ba(K3(C2O4)2)2 + H2O
n=1 n=2
1mole=2eq 2eq=1mole
H2C2O4 + Ba(OH)2  BaC2O4 + H2O
n=2 n =2
Total moles of Ba(OH)2 used = 2 mole = M × V2

V2 = lit.
M
V1
1
V2

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 47. Let V1 & V2 are volumes of KMnO4 in 1st part & 2nd part
Reaction (1) KMnO4 + C2O24 
Acidic
 CO2 + Mn2+
 0.5 × V1 × 5 = 1.5 × 125 × 2  V1 = 150 mL
Reaction (1) KMnO4 + I– 
Basic
 I2 + MnO2
 0.5 × V2 × 3 = 0.5 × 270 × 1  V2 = 90 mL
So initial volume = 150

48. Let x gm be pure copper in the sample

ECu2  EI2   I

x
= ×1
63.5
 x 
 63.5 
 
n I2  
2
 x
127
 
n I2  E Na2S2O3
II

x 20
× 2 = 0.1 × ×1
127 1000
x = 0.127 gm
0.127
% Cu in sample = × 100
0.2
= 63.5%

49. E  AsO34  = E(I2)I

1
Nucleus Education-(NURTURE_(UNACADEMY)

× 2 = E(I2)I
208
 2  1
n(I2)1 =   /2 =
 208  208
E(I2)II = E(Na2S2O3)
1
× 2 = 0.2 × V (lit)
208
V (ml) = 48.1 ml

50. XeF4 + KI  I2 + Xe + KF
I2 + Na2S2O3  Na2S4O6 + I–
20
x × 10–3 × 4 = × 0.1
1000
x = 0.5
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 35.5  2
51. % Cl = 100
40  16  (35.5  2)
71
= × 100  55.9%
127

52. KBrO3 + Na2S2O3  Br– + Na2S4O6

0.167 2
N1V1 = N2V2   6 = 45 × N × 10–3  N = N
167 15

53. (I) KIO3 + KI  I2

(II) I2 + S2O32  I– + S4O62
Gm eq. of S2O32 = gm eq. of I2(II)
10
× 0.1 × 1 = mole I2(II) × 2
1000
10  3
Moles I2(II) = = moles I2(I)
2
Gm eq. of KIO3 = gm eq. of I2(I)
10  3  10  2 
Moles KIO3 × 5 =  
2  12 
1
 M. moles of KIO3 =
6
Nucleus Education-(NURTURE_(UNACADEMY)

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 EXERCISE # (O-II)
1. E HNO3  E NH
4

n×1=2×3
n=6
2. I2 + 60 H–  5 I– + IO3 + 3H2O
n(IO3 ) 1

n(I ] 5
3. Balancing 
AS2O3 + 6 NaOH  Na3ASO3 + Na3AsS3 + 3H2O
x=1
y=6
1
4. H2O2  H2O + O2
2
Vol. of O2 at 27ºC = 500
Vol. of O2 STP
500  273
V=
300
V = 455
35 ml H2O2 give 455 ml O2
1 ml H2O2 give 13 ml O2
Vol. strength = 13 V

5. H2SO4 + H2C2O4 + impurity

n1 n2 n3 moles
n1 n 3
2 2 2 = × 0.1 ……(1)
100 100 1000
n2 4
× 2 = 0.02 × ×5 ……(2)
Nucleus Education-(NURTURE_(UNACADEMY)

10 1000
 n1 = 0.028 n2 = 0.002
w1 = 2.744 w2 = 0.18
2.744
% weight of H2SO4 = 100
2.744  0.18 13.185
 40%
6
6. Cr2O72 + An–  Cr+3 + A+x
ECr O2  EAn
2 7

1.68 × 10–3 × 6 = 3.26 × 10–3 × (n + x)

6=2×n+x
3=n+x
x=3–n

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 0 2 6 0
7. Cl2  S2O32  SO42  Cl  S
nf = 2
(i) moles of S2O32 = M × V
= 0.01 × 50 × 10–3
= 5 × 10–4
= 0.0005
(ii) oxidising agent = Cl2
E = n × nf
= 5 × 10–4 × 2
= 10–3
= 0.001

8. CaCO3  CaO + CO2

n= 0.5 0.5
CO2 + 2NH3 + H2O  (NH4)2CO2
0.5 0.4 0.2
(NH4)2CO3 + 2HCl  2NH4Cl + H2O + CO2
0.2 0.2
Vol. of CO2 = 0.2 × 22.4 = 4.42

3 2 4
9. KMnO4 + H2C2O4  Mn  CO2
EKMnO4  EH2C2O4
M × nf × V = n × nf
50 3 2
M×5× =
1000 1000
24
m=
1000
N = m × nf
Nucleus Education-(NURTURE_(UNACADEMY)

5  24 120
N=  = 0.12 N
1000 1000

23 6
10. nf (P4H4) = 
23 5
2 10 20 5
n(I2) =  
2  10 12 3
13 2 26
n(Mn3O4) = 
13  2 15
4 2 8 4
n(H3PO2) =  
42 6 3

11. (A)  (q); (B)  (t); (C)  (r); (D)  (t)

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 12. Ba(MnO4)2 nf = (in acidic medium) = 5 × 2 = 10

13. nf of H3PO2
O
acid : no. of replaceable H+ = 1
P
HO H nf = 1
H
x 3 3
14. Fe0.95 O  Fe2 O3
(0.95)
 2 
x(0.95) = 2 nf =  3  
 0.95 
2
x= nf = 0.85
0.95
M M
Ew = 
n f 0.95

15. 2VO + 3Fe2O3  6FeO + V2O5

x, y = 2, 3

20 20
16. MH2O2  2 
22.4 11.2
20 200
× V × 2 = 0.1 ×
11.2 1000
V = 5.675 ml

200 m
17. 0.1 × = ×6
1000 294
m = 0.97 gram
Nucleus Education-(NURTURE_(UNACADEMY)

18. 20V H2O2

1L H2O2 liberate 20  O2
20 22.4
11.2 ml H2O2 liberate × 11.2 = = 0.224
1000 100
= 224 ml

19. Use the reactions

K2CO3 + 2 HCl  H2O + CO2 + 2KCl
NaHCO3 + HCl  H2O + CO2 + NaCl

20. x=y

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 EXERCISE # (JEE-MAINS)
1. AgNO3 + KI  AgI + KNO3
is not redox

2. CaOCl2 has Cl– & ClO–

3. MnO4  Mn2+

6
MnO24
4
MnO2
3
M2O3

2
4. K4[Ni(CN)6 ]

5. KI + K2Cr2O7  Cr+3

3
6. [Cr(NH3 )4 Cl2 ]

7. 2MnO4  5C2O42 + 8H+  2Mn2+ + 10CO2 + 4H2O

x = 2, y = 5, z = 8
Nucleus Education-(NURTURE_(UNACADEMY)

8. 6Na2HASO3 + 2NaBrO3 + 12HCl  2NaBr + 6H3AsO4 + 12NaCl

x : y : Z (lowest ratio of whole number)
6 : 2 : 12
3 :1:6

9. R.A. loose electrons

10. (4)

11. Total e– = 6

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 4 1 6 0
12. XeF4  O2F2 
 XeF6  O2

Redn
Oxidation

13. C2O24  MnO4  H 

2CO2  Mn2
e– involved in the reaction = 10
e– involved per mole of CO2 = 5

5 30
14.  M 1   0.1 2
1000 1000
M = 0.24
 0.24×V×1 = 30×0.2×1
6
V= = 25 mL
0.24

15. 50×0.5×2 = 25×M×1

M=2
50
Moles = M×V = 2×  0.1
1000
Mass = 0.1×40
= 4 gm

16. M×5 = 1×[(1+2) + (6) + (1)]

Nucleus Education-(NURTURE_(UNACADEMY)

M×5 = 10
M=2

17. NO +2
N2O +1
NO2 +4
N2O3 +3

18. 2CuBr  CuBr2 + Cu

is a disproportion reaction.

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 EXERCISE # (JEE-ADVANCED)
1. Ba(H2PO2)2
 P = +1

2. NO3 + 4H+ + e–  2H2O + NO

For charge balance 3e–

3. BaO2 + H2SO4  BaSO4 + H2O2

4. 2MnO4  5C2O42 16H  2Mn2+ + 10CO2 + 8H2O

5. Meq. Of H2O2 = Meq. of I2

WH2O2 0.508
  2 1000   2 1000
34 254
 WH2O2  0.06g
1
H2O2  H2O2 + O2
2
 34g H2O2 gives 11.2 litres of O2 at STP
11.2
 0.068 g gives =  0.068 = 22.4 mL O2
34
22.4
 Volume Strength of H2O2 = = 4.48 volume
5

6. FeC2O4 + KMnO4  Mn+2 + Fe+3 + C+4

n×5 = 1×3
Nucleus Education-(NURTURE_(UNACADEMY)

3
n=
5

7. n×5 = 1×2
2
n=
5

8. Let the total moles of O2 and O3 in the mixture be n.

Applying PV = nRT
1×1 = n×0.0821×273
n = 0.044 moles
Moles of O3 = moles of I2 = 1/2 moles of Na2S2O3
1 1 40
   = 0.002 moles
2 10 1000
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 Moles of O2 in the mixture = 0.044 – 0.002 = 0.042 moles
Mass of O2 = 0.042×32 = 1.344 g
Mass of O3 = 0.002×48 = 0.096 g
.096
% O3 = 100 = 6.67
1.44
Number of photons required to decompose 0.002 moles of ozone
= 0.002×6.02×1023
= 1.204×1021

9. When nt = 2
i.e. Mn+2  Mn+4

10. The reaction is as follows :

KIO3 + 5KI  K2O + 3I2
0.1
Moles of KIO3 = 3
214
2Na2S2O3 + I2  2NaI + Na2S4O6
0.1
Moles of Na2S2O3 required = 3  2
214
Number of moles 0.1 1
Molarity = 1000  3   2  1000  0.0623
volumemL 214 45

11. S8 0
S2F2 +1
H2S –2
12. N1V1 = N2V2
N1 = Normality of H2SO4 = 0.5×2 = 1N
Nucleus Education-(NURTURE_(UNACADEMY)

V1 = volume of H2SO4
0.5  2
N2 = Normality of copper (II) carbonate = N
123.5
V2 = Volume of copper (II) carbonate = 1000 mL
0.5  2
Thus, 1.0×V1 = 1000
123.5
Or V1 = 8.09 mL
13. N = M×nf
= 0.3×2  0.6

14. In CrO2Cl2, Cr is in +6

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 15. Fe3O4 is an equimolar mixture of Fe2O=3 and FeO. Thus, the sample contains Fe2O3, FeO and
impurities. The amount of iodine liberated depends on the amount of Fe2O3 and the entire iron is
converted into Fe2+.
Fe3O4 + 2KI + H2SO4  3FeO + H2O + K2SO4 + I2
Fe2O3 + KI + H2SO4  2FeO + H2O + K2SO4 + I2
5×11.0 mL of 0.5 M Na2S2O3  55.0 mL of 0.5 N Na2S2O3 soln.
 55.0 mL of 0.5 N I2soln.
  55.0 mL of 0.5 N Fe2O3 soln.
= 27.5×10–3 equivalent Fe3O4 soln.
= 13.75×10–3 mole Fe2O3
2×12.8 mL of 0.25 M KMnO4soln.
 25.6 mL of 1.25 N KMnO4soln.
 25.6 mL of 1.25 N FeO soln.
= 32.0×10–3 equivalent FeO
= 32.0×10–3 moles FeO
Moles of FeO in Fe2O4 = 0.032 – 0.0275 = 0.0045
Mass of Fe3O4 = 0.0045×232 = 1.044 g
Moles of Fe2O3 = 0.0045×232 = 1.044 g
Moles of Fe2O3 existing separtely
= 0.01375 – 0.0045 = 0.00925
1.044
% Fe3O4 = 100  34.8
3
148
% Fe2O3 = 100  49.33
3

6.3 10
16.   0.1 V
126 250
Nucleus Education-(NURTURE_(UNACADEMY)

V = 40 mL

17. 2KMnO4 + 3H2SO4 + 5H2O2  K2SO4 + 2MnSO4 + 8H2O

2KMnO4 + 3MnSO4 + 2H2O2  5MnO2 + 2H2SO4 + K2SO4
MnO2 + Na2C2O4 + 2H2SO4  MnSO4 + Na2SO4 + 2H2O + 2CO2
Millimoles of Na2C2O4 = 10×0.2 = 2
mEq of Na2C2O4 = 4
mEq of MnO2 = 4
mEq of KMnO2 = 4
mEq of H2O2 = 4
Millimoles of H2O2 = 2×10–3
0.002
Molarity = 1000M
20
Molarity = 0.1 M
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 18. Mn+7 
Acidic
 Mn+2
Mn+7 
Neutral
 Mn+4
Mn+7 
Basic
 Mn+6

19. 3Na2CO + 3Br2  5NaBr + NaBrO3 + 3CO2

20. HNO3 (+5)

NO (+2)
NH4Cl (–3)
N2 (0)

21. Household bleach + 2KI  I2 + Products

I2 + 2Na2S2O3  Na2S4O6 + 2NaI
Amount of Na2S2O3 used = VM = (48×10–3L)(0.25 mol L–1) = 12×10–3 mol
1
Amount of I2 generated = (12×10–3 mol) = 6×10–3 mol
2
Assuming 1 mol of household bleach products 1 mol I2, we will have
Amount of household bleach in 25 mL solution = 6×10–3 mol
n 6 103 mol
Molarity household bleach =   0.24M
V 25 103 L

5
22. 5I– + ClO3 + H2SO4  Cl2 + HSO4  I2
2

23. ClO3 + 6I– + 6H2SO4  3I2 + Cl– + 6HSO4 + 3H2O

24. MnCl2 + K2S2O8 + H2O  KMnO4 + H2SO4 + HCl

Nucleus Education-(NURTURE_(UNACADEMY)

a mg a mg

C2O42  MnO4 
H
 CO2  Mn 2
meq of C2O24 = meq of MnO4
2×0.255/90 = a×5
a = 1×[55 + 71]
= 126 mg

25. Conc. HNO3 oxidises rhombic sulphur (S8) to H2SO4 and itself gets reduced to NO2.
0 5 6 4
S8  48HNO3 
8H2SO4  48NO2 16H2O
1 mole of S8 gives 16 moles of H2O
Mass of H2O = 16×18 = 288 gm

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