Stoichiometry and Redox Reactions

SYNOPSIS The n-factor of H3PO3 cannot be 3 as it has only two

dissociable H+ ions. So, its n-factor or dissociable pro-
tons is 1 or 2 as one of the H-atoms is linked with P
CALCULATION OF n-FACTOR
atom directly.
For calculating the n-factor of any reactant in any reac-
O
tion. One must know the kind of reaction it is, the reac-
tions may be classified into the following three types. HO P OH

1. Acid-Base Reactions/Neutralization reactions H

2. Redox Reactions  CH 3COO   H 


Similarly, CH 3(COOH
n 1)
3. Precipitation Reactions/Double decomposition re-
actions
Acid-Base Reaction: According, to the Arrhenius, an n-factor of CH3COOH is 1, because it contains only
acid is a substance that furnishes H+ ion(s) in solution, a one dissociable H+ ion.
base is a substance that furnishes OH- ion(s) in solution Now, we will consider the n-factor of some bases.
and neutralization is a reaction in which H+ ion furnished  Na   OH 
NaOH 
by acid combines with OH- ions furnished by base. The (n 1)
number of H+ ion(s) furnished per molecule of the acid
[Ba(OH)]  OH 
Ba(OH) 2 
is its n-factor also called basicity. Similarly the number (n 1)
of OH- ion(s) furnished by the base per molecule is its
n-factor, also called acidity.  Ba 2  2OH 
Ba(OH) 2 
(n  2)
Some Examples
 Al3  3OH 
Al(OH)3 
 H   Cl
HCl  (n 3)
(n 1)

 H   HSO 4
H 2SO4  Similarly, n-factor of Al(OH)3 can also be 1 or 2 or 3,
(n 1) depending upon the number of OH– released.

REDOX REACTIONS
 2H   SO24
H 2SO 4 
(n  2) Those reactions which involve the exchange of electrons
are called redox reactions. For the calculation of n-
 H   H 2 PO 4
H3 PO 4  factor of oxidising agent or reducing agent, the method
(n 1) depends upon the change in oxidation state of the
species considered. We will discuss them one by one.
 3H   PO34
H3 PO 4 
(n 3) i) When only one atom undergoing either reduction or
oxidation e.g.
 H   H 2 PO3
H3 PO3  7 2
H
(n 1) MnO 4 
 Mn 2
n 5
 2H   HPO3
H3 PO3 
In such a case, we consider the change in oxidation
(n  2)
state of atom undergoing oxidation or reduction change
per molecule as the n-factor of the species.
 STIOCHIOMETRY Jr Chemistry E/M
n-factor = |(+2) ×1 – (+7)  1| = 5 iv) Salts which react in such a way that only one
2 3 atom undergoes change in oxidation state in two
Fe 2 
 Fe3 n-factor = |(+3) × 1 – (+2) × 1| = product, in one product with changed oxidation state
n 1
and in other product with same oxidation state as
1
3 2
that of reactant.
4 2
2 In such case also one cannot calculate the n-factor
C O 
2 4 2CO 2 n-factor = |(+4) × 2 – (+3) × 2| =
n2 without knowing the balanced chemical equation
2 because one must know how much of atom has changed
62 32 its oxidation state. For example.
Cr2O72 
 2Cr 3
n-factor = |(+3) × 2 – (+6)× 2| =
n 6
K2Cr2O7 + 14HCl  2KCl + 2CrCl3 +
6 3Cl2 + 7H2O
ii) Salts which reacts in such a way that only one Let us calculate the n-factor of HCl. Out of 14 moles
atom undergoes change in oxidation state but of Cl– (in HCl) only 6 moles of Cl– are changing its
appears in two products with the same oxidation oxidation state from –1 to 0 in the product Cl2 and the
state: oxidation state of remaining 8 Cl– ions remains same in
In such a case the method of calculation of n-factor KCl and CrCl3. So, total no. of moles of electrons lost
remains the same i.e., we will calculate the change in
oxidation state of the atom per mole of that substance by 14 moles of HCl is 6. So each mole of HCl takes up
(reactant). 6/14 i.e., 3/7 moles of electrons and hence n-factor of
6 2 3 3 HCl is 3/7.
Cr2 O72   Cr 3  Cr 3 v) Salts which react in such a way that two or more
In this example, oxidation state of Cr changes from +6 atoms in the salt undergoes change in oxidation
to +3 in both the products. So states as a result of either oxidation or reduction.
n-factor = |(+6) × 2 – (+3) × 2| = 6 Let us consider the following example,
FeC2O4  Fe3+ + 2CO2
iii) Salts which react in such a way that only one
atom undergoes change in oxidation state but goes In this case, the oxidation of both Fe2+ and C3+ are
in two products with different oxidation state as a changing from + 2 and +3 to +3 and +4 respectively.
result of either only oxidation or only reduction. In such a case we will calculate the n-factor of the salt
7 2 6 as the total increase or decrease in oxidation state per
3MnO 4   2Mn 2  Mn  6 mole of the salt. As one can see that one mole of
In such a case, it is impossible to calculate the n-factor FeC2O4 contains one mole of Fe2+ and one mole of
until and unless one knows that how much of MnO 4 is C2O42– (i.e. 2 carbon atoms per mole of C­2O42–.
changing to Mn2+ and how much to Mn6+ and if one Total change in oxidation state
knows the balanced equation then there is no need of = | 1 × (+2) – 1 × (+3) | + | 2 × (+3) – 2 × (+4)
calculation of n-factor. Nevertheless in such case the |
n-factor can be calculated by deducing the total change
in oxidation state divided by total number of atom =1+2=3
undergoing reduction/oxidation change. So, for the So, n-factor of FeC2O4 is 3
calculation of n-factor in the above example, out of three
moles of MnO 4 , two moles are being converted to vi) Salts which react in such a way that two atoms
Mn2+ and one mole changes to Mn6+. So total decrease undergoing change in oxidation state but one
in oxidation state of Mn. undergoing oxidation and other reduction reaction.
= | [2 × (+2) – 2 × (+7)] | + | [1 × (+6) – 1 In such a case one has to calculate the change in
× (+7)]| oxidation state of either the atom being oxidized or
= | 4 – 14 | + | 6 – 7 | = 11 the atom being reduced. For example.
11 3 2 62 0 2 3 2
So, n-factor = (N H 4 ) 2 Cr 2 O7 
 N 2  Cr2 O3  4H 2O
3
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
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In this reaction, the oxidation state of N is increasing BaCl2  Na 2SO 4   BaSO4  2 NaCl
n2 n2
by 6 units and that of Cr is decreasing by 6 unit. So, we
can consider either oxidation or reduction product for for BaCl2
the calculation of n-factor and it will be the same. n-factor = Oxidation state of Ba atom in BaCl2 ×
n-factor of (NH4)2Cr2O7 considering oxidation number of Ba atoms in 1 molecule of BaCl2
= (+2) × 1 = 2
= |(-3) ×2 – (0) × 2| = 6
for Na2SO4
n-factor of (NH4)2Cr2O7 considering reduction
n-factor = Oxidation state of Na × number of Na-atoms
= |(+6) × 2 – (+3) × 2| = 6
in 1 molecule of Na2SO4
= (+1) × 2 = 2
vii) Species which undergoes disproportionation
reaction: Those reaction in which oxidant and
reductant are the same species or the same element TITRATIONS
from the species is getting oxidized as well as The process of determination of concentration of a
reduced. solution with the help of a solution of known
When the number of moles of atoms being oxidized is concentration (standard solution) is called titration.
equal to the number of moles of atoms being reduced. Titration is divided into following four categories.
i) Simple Titration
The n-factor can be calculated by knowing the balanced ii) Double Titration
chemical equation and considering any of the change iii) Back Titration
taking place. Say for example, iv) Iodimetric and Iodometric Titration
2H2O2  2H2O + O2 Simple Titration: A known volume of the solution of
Out of 2 moles of H2O2 consumed in the reaction, one unknown concentration is taken in a flask and required
mole of H 2O 2 is being oxidized reagents are added to it. The solution of known
concentration is added from the burette in the solution
(H2O2  O2) and one mole of H2O2 is being
of unknown concentration till the latter reacts
reduced (H2O2  2H2O). First consider the completely. This process is called titration. At the end
oxidation reaction point (equivalence point) the equivalents or
milliequivalents of the two reacting substances are equal.
( 1) 2 20 Volume of solution (A) = VA litres
H2O 2   O 2
Normality of solution (A) = NA
n-factor = |2 × 0 – (–1) × 2| = 2 Equivalents of substance (A) = NAVA
Similarly, equivalents of substance (B) = NBVB
Again, considering reduction reaction At the equivalence point (end point) the equivalents (not
the moles) of the two substance are equal.
( 1) 2 ( 2 ) 2
H O   2H O NAVA (litre) = NB  VB (litre)
2 2 2

n-factor = |(-2) × 2 – (-1) × 2| = 2 Illustration 19: 40 ml N/10 HCl and 60 ml N/20

KOH are mixed together.
So, n-factor of H2O2 either considering oxidation or Calculate the normality of the
reduction reaction is same i.e. 2. acid or base left. The normality of
PR EC IP ITATI O N/ DO UB LE the salt formed in the solution
DECOMPOSITION REACTIONS: will be
(A) 0.06
In such reaction, there is no change in oxidation state
(B) 0.09
of any atom. The n-factor of the salt can be calculated
by multiplying the oxidation state of the cation/anion by (C) 1
total no. of atoms per molecule of the salt. For example (D) 0.03
 STIOCHIOMETRY
Solution: (D)
Milli equivalents of HCl = N × V
1 40
(ml) = 4
10
Milli equivalents of KOH = N × V
1 60
(ml) = 3
20
One milli equivalent of an acid
neutralizes one milli equivalent of a
base
Milli equivalent of HCl left
=4–3=1
Total volume of the solution
= 40 + 60 = 100 ml
Milli equivalents of HCl =N
× V (ml)
1 = N × 100
Normality (N) of HCl left in solution
= 0.01
Salt formed
= Milli equivalent of acid or base
neutralized
Milli equivalents of the salt formed
= N × V (ml)
3 = N × 100
Normality (N) of salt formed = milli equivalent of NaOH + ½ milli equivalent of Na2CO3
0.03
Double Titration: If an aqueous solution contains a
mixture of any two of the three NaOH, NaHCO3 and
Na2CO3 and it has to be titrated against an acid HCl
or H2SO4, it will require two indicators to determine
the strength of the bases present. The two indicators
used are phenophthalein and methyl orange.
Method: A given volume of the aqueous solution of
the bases is taken and phenophthalein indicator is added
to it. This solution is titrated with an acid of known
normality to the end point the volume of the acid used
is noted. This end point is called first end point. Now in
the same solution methyl orange is added and gain
titrated with an acid of known strength to the end point.
It is called second end point. The volume of acid, used
in the second end point is also noted. The normality of
the bases present is then calculated.
Jr Chemistry E/M
Principle: In the presence of phenolphthalein indicator
i) NaOH is completely neutralized by the acid.
ii) Only half of the milliequivalents of Na2CO3
present are titrated as the phenolphthalein will
show the colour change when only NaHCO3
(weak base) and neutral species are left in the
reaction mixture. The following reactions take
place,
NaOH + HCl   NaCl + H2O
Na2CO3 + HCl  NaHCO
 weak base 3 + NaCl
Since phenolphthalein is a weak organic acid, and it
changes its colour in weakly basic medium (NaHCO3),
so as soon as the Na2CO3 is converted to NaHCO3
phenophthalein shows the colour change indicating the
completion of the reaction.
In the presence of methyl orange, all the basic
substances left in the mixture will be neutralized by acid
and methyl orange will show the colour change when
the medium is weakly acidic
(H2O + CO2 i.e. H2CO3).
Titration of the solution containing both NaOH
and Na2CO3:
A given volume of the aqueous solution is titrated with
an acid of known normality using phenophthalein
indicator. Suppose ‘a’ milli equivalents of acid are used
in the first end point then,
= milli equivalent of
acid = a …(1)
Now in the same already titrated solution methyl orange
indicator is added and again titrated to the end point.
Suppose ‘b’ milli equivalents of the acid are used at the
second end point.
½ milli equivalents of Na2CO3 = milli equivalents of
acid = b …(2)
From equation (1) and (2)
Milli equivalents of acid used by Na2CO3 = 2b
 milli
equivalents of Na2CO3
Milli equivalents of acid used by NaOH = a – b
= milli
equivalent of NaOH
Knowing the milli equivalents of Na2CO3 or NaOH
and the volume of the solution titrated, their normality
can be calculated.
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
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Illustration 20: NaOH and Na2CO3 are dissolved Mass of Na2CO3
in 200 ml aqueous solution. In the = N × E × V (litre)
presence of phenolphthalein (E for Na2CO3 = 53)
indicator. 17.5 ml of 0.1 N HCl are 1
used to titrate this solution. Now =  53  0.2
400
methyl orange is added in the same
solution titrated and it requires 2.5 = 0.0265 gram
ml of the same HCl. Calculate the For NaOH solution: From equation
normality of NaOH and Na2CO3 (1) and (2)
and their mass present in the Milli eq. acid used by NaOH
solution. = a – b = 1.75 – 0.25
Solution: Milli equivalents (a) of HCl used in the = 1.50
presence of phenolphthalein indicator. Volume of NaOH solution = 200 ml
Suppose, Normality of NaOH
= N × V (ml) solution = N
Mili eq. of NaOH = N × V (ml) =
= 0.1 × 17.5 = 1.75 200 N
1.75 (a) = milli. eq. of NaOH + 1/2 Putting the mili eq. of NaOH and
milli eq. of Na­2CO3 ...(1) acid used equal
Milli eq. (b) of HCl used in the presence 200 N = 1.5
of methyl orange indicator (Normality of NaOH solution) N =
= N × V (ml)
= 0.1 × 2.5 = 0.25 1.5
0.25 (b) = 1/2 milli equivalents of 200
Na 2CO 3 Mass of NaOH = N × E ×
…(2) (V litres)
For Na 2CO 3 solution: From 1.5
equation(2) =  40  0.2
200
Milli eq. of acid used by Na2CO3
(E for NaOH = 40) = 0.06g
= 2b
Titration of the solution containing both Na2CO3
= 2 × 0.25 = 0.5
and NaHCO3:
Volume of Na2CO3 solution
Given volume of the solution is titrated by an acid using
= 200 ml
phenolphthalein indicator. Suppose ‘a’ milli equivalents
Suppose, Normality of Na2CO3
of acid are used in the first end point. Then
=N
1/2 milli equivalent of Na2CO3 = milli equivalents of
Milli equivalents of Na2CO3
acid = a …(1)
= N × V (ml) = 200N
Now in the same already titrated solution methyl orange
Putting equivalents of acid and
indicator is added and again titrated to the end point.
Na­2CO3 equal.
Suppose ‘b’ milli equivalents of the acid are used at the
second end point.Then
200N = 0.5
1/2 milli equivalents of Na2CO3 + milli equivalents of
or (Normality of Na­2CO3 solution)
NaHCO3
1 = milli equivalents of acid=b ..(2)
N =
400
 STIOCHIOMETRY
From equation (1) and (2)
Milli equivalents of acid used by Na2CO3 = 2a
milli equivalents of Na2CO3
Milli equivalents of acid used by NaHCO3 = b – a
= milli
equivalent of NaHCO3
Knowing the milli equivalents of the base and volume
of the solution titrated, the normality (strength) of the
bases can be calculated.
Illustration 21: Both Na2CO3 and NaHCO3 are
present in an aqueous solution. In
the presence of phenolphthalein
indicator 10 ml of this solution
requires 2.5 ml of 0.1M H2SO4 for
titration. After this methyl orange
is added in the same solution and
titration requires 5 ml M H2SO4 .
Calculate the concentration of
Na2CO3 and NaHCO3 in g/litre.
Solution: Milli eq. (a) of H2SO4 used in the
presence of phenolphthalein indicator
= N × V (ml) = 0.1 × 2 ×
2.5 = 0.5
a = 0.5 =1/2 milli equivalents of Na2CO3
…(1)
Milli. eq. (b) of NaHCO3 + ½ milli eq. of Na2CO3
…(2)
For Na2CO3 solution: From equation (1)
Milli eq. of acid used by Na­2CO3 =
2 × 0.5 = 1
Suppose, Normality of Na2CO3
solution = N
Volume of Na2CO3 solution taken =
10 ml
Milli eq. of Na2CO3 taken
= N × V (ml) = 10 N
Putting the milli eq. of H2SO4 and
Na2CO3 equal,
1 = 10 N
or (Normality of Na­2CO3)
N = 0.1
Strength (S) in g/litre
=N×E
= 0.1 × 53 (E for Na2CO3 = 53)
= 5.3 g/litre
Jr Chemistry E/M
For NaHCO 3 solution: From
equations (1) and (2) milli eq. of acid
used by
NaHCO3 = b – a =
1.0 – 0.5 = 0.5
Suppose, Normality of NaHCO3
solution= N
Volume of NaHCO3 solution
taken = 10 ml
Milli equivalents of NaHCO3
taken = 10 N
Putting the milli eq. of H2SO4 and
NaHCO3 equal,
0.5 = 10 N
or (Normality of NaHCO­3 solution)
N = 0.05
Strength (S) in g/litre
=N×E
(E for NaHCO3 = 84)
= 0.05 × 84 = 4.2g/litre
Back Titration: Let us consider that we have an impure
solid substance ‘Z’ weighing ‘w’ g and we are required
to calculate the percentage purity of ‘Z’ in the sample.
We are also provided with two solutions ‘X’ and ‘Y’,
where the concentration of ‘Y’ is known (N1) and that
of ‘X’ is unknown. For the back titration to work,
following conditions are to be satisfied
a) Compounds ‘X’, ‘Y’ and ‘Z’ should be such that
‘X’ and ‘Y’ reacts with each other.
b) ‘X’ and pure ‘Z’ also reacts with each other but the
impurity present in ‘Z’ does not react with ‘X’.
Z + X (excess)  Product 1
Remaining (X) + Y  Product 2
Note: Product 1 should not react with Y
Milli equivalent of Y = N2V2
Where N2 and V2 (ml) is the normality and
volume of Y
Initial mili equivalent of X = N1V1
Where N1 and V1 (ml) is the normality and
volume of X
Remaining milli equivalents of X after reacting
with Y = N1V1– N2V2
Remaining milli equivalents of X = milli
equivalents of Z
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
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a  100 i) 2Na2S2O3 + I2 
 Na2S4O6 +
N1V1 – N2V2 =  equivalent weight
2NaI
Where ‘a’ is the weight of pure Z which is ii) Na2SO3 + I2 + H2O Na2SO4 + 2HI
reacted. iii) Na3AsO3 + H2O Na3AsO4 + 2HI
Molecular weight   N1V1  N 2 V2  2. Iodometric Titrations: Iodometric titrations
a
n  factor are defined as those iodine titrations in which
Percentage purity of ‘Z’ some oxidizing agent liberates iodine from an
iodine solution and then lilberated iodine is
 N1V1  N1V1  Molar mass of Z
titrated with a standard solution of a reducing
   100
n  factor w
agent added from a Burette. In such titrations,
a neutral or an acidic solution of oxidizing agent
Illustration 22: 20 g of a sample of Ba(OH)2 is
is employed. The amount of iodine liberated
dissolved in 10 ml. of 0.5N HCl
from an iodide, (i.e. KI) is equivalent to the
solution. The excess of HCl was
titrated with 0.2N NaOH. The quantity of the oxidizing agent present.
volume of NaOH used was 10 cc. Iodometric titrations are used for the
Calculate the percentage of determination of CuSO4, K2Cr2O7, KMnO4,
Ba(OH)2 in the sample. ferric ions, antimonite ions, H­2O2, MnO2,
bromine and chlorine etc. The equations for
Solution: Milli eq. of HCl initially = 10 × 0.5 = 5 some of the reactions are as follows:
Milli eq. of NaOH consumed = i) 2CuSO4 +4KI Cu2I2+ 2K2SO4 + I2
Milli eq. of HCl in excess ii) 2KMnO4 + 3H­2SO4 K2SO4 +
= 10 × 0.2 = 2 2MnSO4 + 3H­2O + 5O
 Milli eq. of HCl consumed = 10KI + 5H­2SO4 + 5O 5K­2SO4 +
Milli eq. of Ba(OH)2 5H2O + 5I2
= 5-2=3 iii) K2Cr­2O7 + 4H2SO4 K2SO4 +
-3
 eq. of Ba(OH)2 = 3/1000 = 310 Cr2(SO4)3 + 4H2O + 3O
Mass of Ba(OH)2 = 310-3(171/2)
6KI + 3H2SO4 + 3O 3K2SO4 +
= 0.2565 g.
% Ba(OH)2 = (0.2565/20) 100 3H2O + 3I2
= 1.28% In the above reactions, the liberated iodine is
Iodimetric and Iodometric Titrations titrated with a standard sodium thiosulphate.
IODIMETRIC AND IDOMETRIC 2Na2S2O3 + I­2 Na2S4O6 + 2NaI
TITRATIONS Illustration 23: 0.5 g sample containing MnO2
The redox-titration using iodine directly or indirectly as is treated with HCl, liberating Cl2.
an oxidizing agent are called Iodine Titrations. These The Cl2 is passed into a solution of
are of two types. KI and 30.0 cm3 of 0.1 M Na2S2O3
1. Iodimetric Titrations: Iodimetric titrations are are required to titrate the liberated
defined as those iodine titrations in which a iodine. Calculate the percentage of
standard iodine solution is used as an oxidant MnO2 in sample. (At. Wt. of Mn =
and iodine is directly titrated against a reducing 55).
agent. Iodimetric procedures are used for the Solution:
determination of strength of reducing agent like M n O 2  H
C l C l 2  K
I  I 2  N
a 2 S 2 O
 3

thiosulphates, sulphites, arsenites and stannous N a I  N a 2 S 4 O 6

chloride etc., by titrating them against standard Redox change are:

solution of iodine taken in a burette. Some cases
 2I 
2e  I02 
of oxidation-reduction reactions are given as
under:
 STIOCHIOMETRY Jr Chemistry E/M
/ 2) Strength (g L–1) = Normality × Equivalent weight
2S22   S(5
 4  2e
17x 34
 N ( n-factor of H2O2 = 2)
2e  Mn 4 
 Mn 2 5.6 2
The reactions suggest that, x = 5.6 × N
Meq. of MnO2 = Meq. of Cl2 i.e., Volume strength of H 2O 2  5.6  Normality
formed = Meq. of I­2 liberated Illustration 24: A sample of H2O2 is x% by mass.
= x ml of KMnO4 are required to oxidize one gram
Meq. of Na2S2O3 used of this H2O2 sample. Calculate the normality of
w KMnO4 solution.
  1000 = 0.1  1  30
M/2
Solution: Suppose, Mass of H2O2 solution =
[  N Na 2S2O3  M Na 2S2O3 since 100g
valency factor = 1, see redox Mass of H2O2 present =x
changes for Na2S2O3] gram
or Mass of H2O2 solution taken = 1
0.1 1 30  M 0.11 30  87 gram
w MnO2   ( M MnOMass
 87)
of H2O2 present in 1 gram
2000 2000 2

x
w MnO2 = 0.1305 solution =
100
0.1305
Purity of MnO2 =  100 = w
0.5 Equivalents of H2O2 =
26.1% E
X
VOLUME STRENGTH OF H2O2 SOLUTION =
100  17
The concentration of H2O2 is usually represented in …(1)
terms of volume. If a sample of H2O2 is labeled as ‘x (E for H2O2) = 17
volume’, it means that 1 volume of H2O2 solution gives Equivalents of KMnO4 = N × V
‘x volumes’ of O 2 gas at STP on complete (litre) = N × X × 10–3
decomposition. Putting equivalents of H2O2 and
Consider the decomposition of H2O2 as X
 KMnO4 equal,  N  x  103
2H 2 O 2  2H 2 O  O2 100  17
234g 22.4 L at STP N = 0.59 (Normality of KMnO4)
 22400 ml of O2 gas is liberated by 68g of H2O2
solution PERCENTAGE LABELING OF OLEUM
68x Oleum or fuming sulphuric acid contains SO3 gas
 x ml of O2 gas will be liberated by = =
dissolved in sulphuric acid. When water is added to
22400
17x oleum, SO3  reacts with H2O to form H2SO4, thus
g of H 2O 2 mass of the solution increases.
5600
SO3 + H2O  H2SO4
17x
It means that g of H2O2 will be present in 1 ml The total mass of H2SO4 obtained by diluting 100g of
5600
sample of oleum with desired amount of water, is equal
of solution.
to the percentage labeling of oleum.
 1000 ml of solution contains H2O2 = % labeling of oleum = Total mass of
H2SO4 present in oleum after dilution.
17x 17x
 1000 
5600 5.6
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
Jr Chemistry E/M
= mass of H2SO4 initially present + 4. 0.1 mole H3POx is completely neutralised by
mass of 5.6 g KOH then the true statement is
H 2S O 4 a)x = 3 and given acid is dibasic
produced on b) x = 4 and given acid has no P-H linkage
c) x = 2 and given acid does not form acid salt
dilution.
d) x = 4 and given acid has P-H linkage
Illustration 25: Calculate the composition of 5. 1 mol each of H3PO2, H3PO3 and H3PO4 will
1 0 9 % neutralise x mole of NaOH, y mol of
oleum. Ca(OH)2 and z mol of Al(OH)3 respectively
Solution: Let the mass of SO3 in the sample be (assuming all as strong electrolytes), x,y,z
‘w’ g, then the mass of H2SO4 would are in the ratio of
b e a) 3:1, 5:1 b) 1:2:3 c) 3 : 2 : 1 d) 1 : 1 : 1
(100 – w)g. On dilution, 6. A mixed solution of potassium hydrixide and
SO3 + H2O  H2SO4 sodium carbonate required 15 mL of an N/
80g 18g 20 HCl solution when titrated with phenol-
phthalein as an indicator. But the same
w amount of the solution when titrated with
Moles of SO3 in oleum = =
80 methyl orange as an indicator required 25
Moles of H2SO4 formed after mL of the same acid. The amount of KOH
dilution. present in the solution is
 Mass of H2SO4 formed on dilution a) 0.014 g b) 0.14 g c) 0.028 g d) 1.4 g
98w 7. 1.60g of a metal were dissolved in HNO­3
=
80 to prepare its nitrate. The nitrate on strong
Total mass of H2SO4 present in
oleum after dilution = heating gives 2g oxide. The equivalent
98w weight of metal is
 (100  w)  109 a) 16 b)32 c) 48 d)12
80
 w = 40. 8. Equal volumes of 1 M each of KMnO4
Thus oleum sample contains 40% SO3 and K2Cr2O7 are used to oxidize Fe(II)
and 60% H2SO4. solution in acidic medium. The amount
of Fe oxidized will be
a) more with KMnO4
SINGLE ANSWER QUESTIONS b) more with K2Cr2O7
c) equal with both oxidizing agents
1. When 5.0 g of a metal is strongly heated, d) cannot be determined
9.44 g of its oxide is obtained. Then the 9. The percentage of copper in a copper (ii) salt
equivalent mass of the metal is ?
can be determined by using a thiosulphate
a) 12 b) 9 c) 32.5 d) 31.75
titration. 0.305 gm of a copper (ii) salt was
2. For the reaction:
dissolved in water and added to an excess
11 of potassium iodide solution liberating iodine
2FeS2  O 2 
 Fe2 O3  4SO 2
2 according to the following equation
What will be the equivalent weight of
 2CuI  S   I 2  aq 
2Cu 2   aq   4 I   aq  
FeS2, if the molecular weight of FeS2 is
M? The iodine liberated required 24.5 cm3 of a
M M M 0.100 mole dm –3 solution of sodium
(a) (b) M (c) d) thiosulphate
8 11 12
3. Gaseous mixture of propane and butane of 2S 2O32  a   I 2  aq   2 I   aq   S2O62  aq 
volume 3 litre on complete combustion pro- the percentage of copper, by mass in the
duces 11.0 litre CO2 under standard condi- copper (ii) salt is. [Atomic mass of copper =
tions of temperature and pressure. The ra- 63.5]
tio of volume of butane to propane is :
a) 64.2 b) 51.0 c) 48.4 d) 25.5
a) 1:2 b) 2:1 c) 3:2 d) 3:1
 STIOCHIOMETRY Jr Chemistry E/M
10. How many moles of KMnO4 are needed 16. In hot alkaline solution, Br2
to oxidised a mixture of 1 mole of each disproportionates to Br - and Bro3-
FeSO4 & FeC2 O4 in acidic medium 1
4 5 3 5 3Br2  6OH   5Br   Bro3  3H 2O . The
a) b) c) d)
5 4 4 3 equivalent weight of Br2 is (mol wt =M)
11. In the mixture of NaHCO3 and Na2CO3,
the volume of HCl required is V1 mL, M M 3M 5M
when phenolphthalein is used as indica- a) b) c) d)
6 5 5 3
tor and further V2 mL is used when
methyl orange is used as indicator after 17. The molecular weight of the compounds
the first end point. Then what is the (i) Na2SO4, (ii) Na3PO4. 12H2 Oand (iii)
volume of HCl required for complete Ca3 (PO4)2 respectively are X, Y and Z.
reaction of original NaHCO3?
a) 2V1/mL b) V2mL the correct set of their equivalent
c) V1/2 mL d) (V2 – V1) mL weights will be -
12. Hydroxyl amine reduces iron (III) X Y Z Y Z
according to following equation a) (i) (ii) (iii) b) (i) X (ii) (iii)
2 3 6 3 3
NH 2 OH  Fe 2 (SO 4 ) 3 

X Z
N 2 (g)  H 2 O  FeSO 4  H 2SO 4 c) (i) (ii) Y (iii) d) (i) X (ii) Y (iii) Z
2 3
which statement is correct
18. A solution contains mixture of H2 SO 4 ,
a) n-factor for Hydroxyl amines is 1
b) equivalent weight of Fe­2(SO4)3 is M/2 H2C2O4. 20 ml of this solution requires 40
c) 6 meq of Fe2(SO4)3 is contained in 3 M
millimoles of ferric sulphate ml of NaOH for neutralization and 20
10
d) all of these.
13. When 159.5g of CuSO4 solution is reacted N
with KI, then the liberated iodine required ml of KMnO4 for oxidation. The molar--
10
100 ml of 1 M Na2S2O3 for complete reac- ity of H2C2O4, H2SO4 are
tion, then what is the percentage purity of
Cu in CuSO4 solution a) 0.1, 0.1 b) 0.1, 0.05
a) 10% b) 20% c) 5% d) 40% c) 0.05, 0.1 d) 0.05, 0.05
19. 500 ml of 0.1 M KCl , 200 ml of 0.01 M
14. 0.80g of impure ( NH 4 )2 SO4 was boiled
NaNO3 and 500 ml of 0.1 M AgNO3 was
with 100mL of a 0.2N NaOH solution till mixed. The molarity of K+ , Ag+ , Cl– , Na+ ,
all the NH 3( g ) evolved. The remaining NO3– in the solution would be
solution was diluted to 250mL. 25mL of a) [K+] = 0.04 ; [Ag+] = 0.04 ; [Na+] = 0.002
b) [K+] = 0.04 ; [Na+] = 0.00166 ; [NO3–] =
this solution was neutralized using 5mL
0.04333
of a 0.2N H 2 SO4 solution. The percent c) [K+] = 0.04 ; [Ag+] = 0.05 ; [Na+] = 0.0025
age purity of the sample is d) [K+] = 0.05 ; [Na+] = 0.0025 ; [Cl–] = 0.05 ;
a) 82.5 b) 72.5 c) 66.5 d) 17.5 [NO3–] = 0.0525
15. 0.5 g mixture of oxalic acid (H2C2O4) and 20. 100 ml of 0.1M aqueous ferric alum solu-
same sodium oxalate (Na2C2O4) with tion is completely reduced with Iron to give
some impurities requires 40 ml of 0.1M Ferrous Ions. The volume of 0.1M acidified
NaOH for complete neutralization and 6
KMnO4 solution required for complete re-
ml of 0.2 M KMnO4 for complete
oxidation. Calculate the % of Na2C2O4 in action with ferrous Ions in the solution will
the mixture be
a) 90% b) 26.8% c) 40% d) 50% a) 60 ml b) 30 ml c) 40 ml d) 100 ml
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
Jr Chemistry E/M
21. What volume of 0.2 M Ba( MnO4)2 solution 27.
is required for complete oxidation of 25 gm
of 89.6% pure Fe Cr2O4 in acidic medium
according to the reaction
MnO4  FeCr2 O4  Fe 3  Cr2 O72  Mn 2
a) 700 ml b) 175 ml c) 350 ml d) 200 ml
22. 10 mL of H2O2 solution on treatment with
KI and titration of liberated I2, required 10
mL of 1 N hypo. Thus H2O2 is :
a) 1N b) 5.6 volume c) 17 g L–1
d) all are corrrect
23. A sample containing 0.496 gm of (NH4)2
C2O4(MW = 124) and inert material was dis-
solved in water and made strongly alkaline
with KOH which converts NH4+ into NH3.
The liberated NH3 was distilled into exactly
50ml of 0.05M H2SO4. The excess H2SO4
was back titrated with 10ml of 0.1M NaOH.
The percentage of (NH4)2 C2O4 with sample
is
a) 40% b) 50% c) 60% d) 75%
24. For decolourisation of 1 mol of KMnO4,
the number of moles of H2O2 used is
1 3 5 7
a) b) c) d)
2 2 2 2
25. A 1.0g sample of pyrolusite ore containing
MnO2 (MW = 87) was dissolved in a
concentrated HCl solution and liberated
Cl2 (g) was passed through a concentrated
KI solution releasing I2. If the liberated
iodine required 16mL of 1.25 M sodium
thiosulphate  Na2 S 2O3  solution, mass
percentage of MnO2 in the given sample is
a) 43.5% b) 87% c) 21.75 % d) 10.875%
26. 20mL of 0.1M solution of compound
Na2 CO3 .NaHCO3 .2 H 2O is titrated
against 0.05M HCl , x mL of HCl is
used when phenolphthalein is used as an
indicator and y mL of HCl is used
when methyl orange is the indicator in
two separate titrations. Hence ( y  x) is
a) 40mL b) 80mL c) 120mLd) 160mL
An equimolar mixture of ferrous oxalate
& stannous chloride is treated with
decinormal acidic KMnO4 giving ferric,
stannic & chlorate ions along with CO2 gas.
If the titre value is 225 ml. Numbers of
millimoles of chlorate ions produced are
a) 1.5 m moles b) 7.5 m moles
c) 3 m moles d) 2.64 m moles
28. A sample of ferrous sulphate and ferrous
oxalate was dissolved in dil.H2SO4. The
complete oxidation of reaction mixture re-
quired 40ml of N 15 KMnO4. After oxi-
dation, the reaction mixture was reduced
by zinc and H2SO4. On again oxidation by
same KMnO4. 25ml were required. The
mole ratio of FeSO4; FeC2O4 in the sample
is
a) 3 : 7 b) 2 : 3 c) 7 : 3 d) 3 : 5
29. A solution of 0.1M KMnO4 is used for the
reaction
S2O3- 2 +2MnO 4 - +H 2 O 

MnO 2 +SO 4 - 2 +OH -
The volume of KMnO4 required to react
0.158gm of Na2S2O3 is (MW = 158)
a) 13.33 ml b) 6.66 ml
c) 3.33 ml d) 26.67 ml
30. V1 ml of NaOH of molarity X and V2 ml of
Ba(OH)2 of molarity Y are mixed together.
The mixture is completely neutralized by 100
ml of 0.1 N HCl. If V1/V2 = 1/4 and X/Y = 4.
Then, what fraction of acid is neutralized by
Ba(OH)2?
a) 0.5 b) 0.25 c) 0.33 d) 0.67
31. When KI in acidic medium were mixed in
50ml H2O2 liberated I2 requires 20ml of 0.1N
hypo. What is strength of H2O2.
a) 6.8 g/litre b) 0.68 g/litre
c) 680 g/litre d) 68.0 g/litre
32. A 0.518 g sample of lime stone is dissolved
in HCl and then the calcium is precipitated
as CaC2O4. After filtering and washing the
precipitate, it requires 40.0 mL of 0.250 N
KMnO4, solution acidified with H2SO4 to ti-
trate it as,
MnO4  H   C2O42 

Mn 2  CO2  2 H 2O
The percentage of CaO in the sample is :
a) 54.0% b) 27.1% c) 42% d) 84%
 STIOCHIOMETRY Jr Chemistry E/M
33. The number of moles of KMnO4 that will be M
needed to react with one mole of sulphite 4. 150 mL Ba(MnO4)2 in acidic can
10
ion in acidic solution is
2 3 4 oxidize completely
(a) 5 (b) 5 (c) 5 (d) 1 (a) 150 mL 1M Fe+2
34. For the balanced chemical reaction (b) 50 mL 1M FeC2O4
x HNO3  y H 2 S 
 a NO  b H 2O  3.S (c) 75 mL 1M C2O4-2
What are the values of x, y, a & b (d) 25 mL 1M K2Cr2O7 solution
respectively 5. 40 g NaOH, 106 g Na2CO3 and 84 g
a) 1,3,2,2 b) 2,3,2,4 NaHCO3 is dissolved in water and the
c) 4,3,2,4 d) 2,3,1,4 solution is made 1 litre. 20 mL of this
stock solution is titrated with 1N HCl,
MULTIPLE ANSWER QUESTIONS hence which of the following statements
are correct.
1. When a mixture of Cu2S and CuS is (A) the titre reading of HCl will be 40 mL, if
titrated with Al(MnO4)3 in acidic medium, phenolphthalein is used indicator from the
very beginning
the oxidation product of Cu2S and CuS
are Cu+2 and SO2. If the molecular weight (B) the titre reading of HCl will be 60 mL if
of Cu2S, CuS and Al(MnO4)3 be M1, M2 phenolphthalein is used indicator from the
very beginning.
and M3 respectively, then which of the
following statement are correct? (C) the titre reading of HCl will be 40 mL if
the methyl orange is used indicator after the
M1 1st end point
(a) Equivalent weight of Cu2S is
8 (D) the tire reading of HCl will be 80 mL, if
(b) Equivalent weight of CuS is M2/5 methyl orange is used as indicator from the
(c) Equivalent weight of Al(MnO4)3 is M3/5 very beginning.
(d) Equivalent weight of Al(MnO4)3 is M3/15 COOH COOK
2. During the titration of a mixture of NaOH, | & | behave as acid are well
6.
Na2CO3 and inert substances against HCl. COOH COOH
(A) Phenolpthalein is used to detect the end as reducing agent. Then which of the
point when half equivalent of Na2CO3 and following are the correct statements
full equivalent NaOH is consumed
(B) Phenolpthalein is used to detect the regarding COOH and COOK
second end point COOH COOH
(C) Methyl orange is used to detect the final
end point (A) When behaves as reducing agent, then
(D) Methyl orange is used to detect the first its equivalent weights are equal to half of its
end point
3. When FeS2 is oxidized with sufficient O2, molecular weight respectively
then its oxidation product is found to be (B) 1000 mL of 1N solution of each is
Fe2O3 and SO2, if the molecular weight of neutralized by 1000 mL 1N Ca(OH)2
FeS2, Fe2O3 and SO2 are M, M¢ and (C) 1000 mL of 1M solution is neutralized by
M¢¢, then which of the following
statements are correct ? 1000 mL of 1M Ca(OH)2.
(a) equivalent wt. of FeS2 is M/11 (D) 1000 mL of 1M solution is neutralized by
(b) the molar ratio of FeS2 to O2 is 4 :11 200 mL 2M of KMnO4 in acidic medium.
(c) the molar ratio of FeS2 to O2 is 11 : 4
(d) The molar ratio of Fe2O and SO2 is 1 : 4
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
Jr Chemistry E/M
7. For the reaction : 4. STATEMENT-1 : H3PO3 is a dibasic acid and
H3PO4 + Ca(OH)2   CaHPO4 + it’s salt Na3PO3 does not exists
2H2O because
1 mole 1 mole STATEMENT-2 : Being dibasic nature, only
then which of the following statements two H are resplaceable.
are correct ? 5. STATEMENT-1 : Addition of water to a
(A) the equivalent weight of H3PO4 is 49. solution containing solute and solvent changes
(B) the resulting solution is neutralized by 1 it’s normality or molarity.
mole of KOH STATEMENT-2 : The milliequivalent and
(C) 1 mole of H3PO4 is completely millimoles of the solute are not changed on
neutralized by 1.5 mole of Ca(OH)2 dilution.
(D) none 6. STATEMENT – 1: In the titrations of
Na 2CO 3 with HCl using methyl orange
ASSERSION & REASON indicator, the volume required at the equivalence
point in twice that of acid required using
Note : phenolphthalein indicator.
(A) Statement – 1 is True, Statement – 2 STATEMENT – 2: Two moles of HCl are
is True; Statement – 2 is a correct required for complete neutralization of one mole
explanation for Statement – 1. of Na2CO3.
(B) Statement – 1 is True, Statement – 2 7. STATEMENT – 1: The molality of the
is True; Statement – 2 is NOT a solution does not change with temperature
correct explanation for Statement – 1. STATEMENT – 2: The molaltiy is expressed
(C) Statement – 1 is True, Statement – 2 in units of moles per 1000 gm of solvent.
is False.
(D) Statement – 1 is False, Statement – 2 8. STATEMENT – 1 :In the roasting of FeS2,
is True. ore is converted into ferric oxide and SO2 gas.
1. STATEMENT-1 : Equivalent weight of The equivalent mass of FeS2 is equal to
a species can be written as molecular molecular weight /11.
weight of the species divided by valence factor. STATEMENT – 2: The n-factor for reducing
because agent is total net change in oxidation number
per formula unit.
STATEMENT-2 : Valence factor represents
valence in element, acidity inbases, basicity in 9. STATEMENT-1: Atomic wt. of P atom in
acids and total charge on cation or anion in an 2yE p
ionic compound the molecule PxOy is where Ep is the
x
2. STATEMENT-1: The percentage of nitrogen equivalent mass of P atom
in urea is 46.6%
because x
STATEMENT-2 : The n factor of P is =
STATEMENT-2: Urea is a convalent y
compound. 10. STATEMENT-1: 109% H2SO4 represent a
3. STATEMENT-1: Molarity and molality of a way to express concentration of industrial
solution both change with density. H2SO4
because because
STATEMENT-2: Density of a solution STATEMENT-2 : It represents that 9g H2O
changes when percentage by mass of a solution reacts with 40g SO3 to produce 49g H2SO4 in
changes. addition to 100g H2SO4
 STIOCHIOMETRY Jr Chemistry E/M
For example the estimation of Cu ++ with
COMPRHENSION QUESTIONS thiosulphate.
Cu++ + I–   Cu2I2 + I2
Passage - I 
I2 + S2 O3   S4 O6  I
20 ml of the solution containg
Starch used as indicator near the end point
Na 2 CO3 and NaHCO 3 is titrated with
0.1M HCl using Phenolphthalein indicator which form blue colour complex with I3 . The blue
the end point was 10ml. colour disappears when there is no more of free
20 ml of the same solution is titrated with I2.
0.1M HCl the end point was 25ml. with 7. In Iodine titration Iodine remains in
Methylorange indicator. solution in the form of
NaHCO3  HCl  NaCl  H 2O  CO2 (a) I3 (b) I2 (c) I3 (d) I–
Na2 CO3  2 HCl  2 NaCl  CO2  H 2O 8. In the reaction, 2CuSO4 + 4KI  
1. What is Molarity of Na2CO3 in solution Cu2I2 + 2K2SO4 + I2 the ratio of
a) 0.05M b) 0.5M equivalent weight of CuSO4 to its
c) 5M d) can not be calculated molecular weight is:
2. What is amount of NaHCO3 present in 1 (a) 1/8 (b) 1/4 (c) ½ (d) 1
liter of solution 9. When 159.50g of CuSO 4 in a solution is
a) 2.1g b) 1.05g c) 8.1 g d) 0.844 g reacted with KI, then the liberated iodine
3. What amount of NaOH is required to
convert NaHCO3 to Na2CO3 in 1 liter of required 100 ml 1 M Na 2S2 O3 for
solution complete reaction, then what is the
a) 2g b) 20g c) 1g d) 0.5g percentage purity of sample used in
Passage - II making the solution.
25 ml solution containing a mixture of Na2CO3 and (a) 10% (b) 20% (c) 5% (d) 30%
NaOH required 20ml of 1N HCl for the phenol- Passage - IV
phthalein end point and in a separate titration 25ml Like acid base titration, in redox titration also,
of the same mixture required 25ml of same HCl the equivalence point is reached when the reducing
for methyl orange end point. Select the correct agent is completely oxidized by the oxidizing agent.
statements. But contrary to the acid-base titrations, oxidizing
4. In the mixture taken, weight of Na2CO3 is agents can themselves be used as internal
a) 5.3g b) 0.53g c) 1.06g d) 0.106g indicator in redox titration e.g. Cr2O72– (orange
5. Ratio of number of moles of Na2CO3 and yellow), Cr3+ (green), MnO4– (purple), Mn2+ (light
NaOH taken is pink), where strength of the solution may be
a) 1:1 b) 1:2 c) 2:1 d) 1:3 expressed as molarity i.e. number of moles of
6. Concentration of NaOH in the solution solute per litre of solution.
taken is 10. In a titration experiment, a student finds
a) 0.6M b) 0.7M c) 0.3M d) 0.1M that 20 ml of a NaOH solution are needed
Passage - III
to neutralize 0.512g of KHP (molecular
All titration which involves the direct titration of
Iodine with a reducing agent are grouped under formula K HC 8 H 4 O 4 ). What is the
Iodimetry. Iodimetry is employed to determine the concentration in molarity of NaOH
strength of reducing agent such as sodium those solution?
sulphate (a) 0.1M b) 0.2M (c) 0.05M (d) 0.02M
–  11. A 16ml volume of 0.2M KMnO4 solution
I2 + Na2S2O3   I + S4 O 6 is needed to oxidize 25.00 ml of a FeSO4
If iodine is liberated as a result of chemical solution in an acidic medium. What is the
reaction involving oxidation of an idodide ion by a number of moles of FeSO4 being oxidized
strong oxidizing agent in neutral or acidic medium for the reaction
the liberated iodine is then titrated with reducing (a) 3.2 × 10–2 (b) 1.6 ×10–2
agent. Iodometry is used to estimate the strength (c) 1.6 ×10 –3
(d) 3.2×10–3
of oxidizing agent.
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
Jr Chemistry E/M
12. A purple coloured solution is added from a 15.
burette to FeSO4 solution kept in the flask.
After sometime, the purple colour changes
to light pink. The ion formed from that
solution is
(a) MnO4 (b) Fe2+ (c) Fe3+ (d) Mn2+
Passage - V
Iodine titrations: Compounds containing iodine
are widely used in titrations, commonly known
as iodine titration. It is of two kinds:
(i) lodometric titrations
(ii) lodimetric titrations.
(i) lodometric titrations : It is nothing but an indirect process by means of which, the percentage
method of estimating the iodine. In this type of
titration, an oxidising agent is made to react with
excess of KI, in acidic medium or, basic medium (combined) is calculated.
in which I- oxidises into I2. Now the liberated I2
can be titrated with Na2S2O3 solution.
KI  Na 2S2 O3 /H + I- +
Oxidising Agent
 I2 
Na2 S4O6
Although solid I2 is black and insoluble in water,
but it converts into soluble I3 ions
I2(s) + I-  I3-
Black dark brown
Starch is used as indicator near the end point or
equivalence point. Even small amount of I2
molecules, gives blue colour with starch. The
completion of the reaction can be detected when
blue colour disappears at the and point. In
iodimetric titration, the strength of reducing agent
is determined by reacting it with I2.
13. When 79.75 g of CuSO4 sample
containing inert impurity is reacted with
KI, the liberated I2 is reacted with 50 mL
(1M) Na2S2O3 in basic medium, where it
oxidises into SO4-2 ions, and I2 reduces
into I-, then what will be the % purity of
CuSO4 in sample ?
(a) 60% (b) 80% (c) 50% (d) 95%
14. When 214 g of KIO3 reacts with excess
of KI in presence of H+, then it produces
I2. Now I2 is completely reacted with 1
M Na2S2O3 solution in basic medium,
where it converts into SO4-2 ions. Then
what volume of Na2S2O3 is needed to
react the end point of the reaction?
(a) 500 ml (b) 800 ml
(c) 1500 ml (d) 750ml.
A solution containing Cu+2 and C2O4-2
ions M which on titration with M/10
KMnO4 requires 50 mL. The resulting
solution is neutralized with K2CO3, then
treated with excess of KI. M The
liberated I2 required 25 mL M/10
Na2S2O3 in acidic solution, then what is
the difference of the number of m mole
of Cu+2 and C2O4-2 ions in the solution ?
(a) 40 (b) 10 (c) 30 (d) 50
Passage - VI
The percentage labelling of oleum is a unique
composition of H 2 SO 4 , SO 3 (free) and SO 3
Oleum is nothing but it is a mixture of H2SO4 and
SO3 i.e., H2S2O7, which is obtained by passing SO3
in solution of H2SO4. In order to dissolve free SO3
in oleum, dilution of oleum is done, in which oleum
converts into pure H2SO4. It is shown by die
reaction as under:
H2SO4 + SO3 + H2O   2 H2SO4 (pure)
or,SO3 + H2O   H2SO4 (pure)
When 100 g sample of oleum is diluted with
desired weight of H2O (in g), then the total mass
of pure H2SO4 obtained after dilution is known as
percentage labelling in oleum.
For example, if the oleum sample is labelled as
“109% H2SO4” it means that 100 g of oleum on
dilution with 9 g of H2O provides 109 g pure H2SO4,
in which all free SO3 in 100 g of oleum is dissolved.
16. For 109% labelled oleum if the number
of moles of H2SO4 and free SO3 be x and
y respectively, then what will be the
value of ?
(a) 1 (b) 18 (c) 1/3 (d) 9.
17. In the above question number 1, what is
die percentage of free SO3 and H2SO4 in
the oleum sample respectively ?
(a) 60%, 40% (b) 30%, 70%
(c) 85%, 15% (d) 40%, 60%.
18. In the above question number 1, what
will be die % of combined SO3 in the
given oleum sample ?
(a) 20% (b) 30% (c) 48.98% (D) 51%.
 STIOCHIOMETRY Jr Chemistry E/M
19. What volume of 1 M NaOH (in mL) will 5. Match the following columns
be required to react completely with 11. Column - I (a,b,c,d)
H2SO4 and SO3 in 109% labelled oleum ? Mol.w.t
(a) 250 mL (b) 1612 mL a) Equivalent w.t 
(c) 750 mL (d) 1800 mL 33
16. (D) 17.(D) 18. (C) 19.(B) Mol.w.t
b) Equivalent w.t 
27
MATRIX MATCHING Mol.w.t
c)Equivalent w.t 
1. Match the following columns 28
Column – I (Reaction) Column – II (Eq wt ) Mol.w.t
-
d) Equivalent w.t 
(a) NH3   NO3 (p) M/3 24
(b) FeC2O4  3+ 2- Column - II (p,q,r,s)
 Fe + 2CO3 (q) M/6
(c) H2SO5  p) When CrI3 oxidies into Cr2O72 and I O4
 S8 (r) M/8
2+ q) When Fe(SCN)2 oxidies in to
(d) KMnO4   Mn (s) M/5
(t) reducing agent Fe3 , SO42 , CO32 and NO3
2. Match the following columns r) When NH4 SCN oxidies into
Column – I (Acid) Column – II (Nature)
SO42 , CO32 , NO3
(a) H3PO4 (p) Monobasic
(b) H3PO3 (q) Protonic acid s) When As2S3 oxidies into AsO3 and SO42
(c) H3BO3 (r) Tri basic
(d) E DT A (s) Tetra basic
INTEGER ANSWER TYPE:
(t) Dibasic
3. Match the following columns 1. 10 ml of mixture of CO, CH 4 and N 2 ex-
Column – I Column – II ploded with excess of oxygen gave a con-
(a) KMnO4  H Mn+2 (p) M/2 traction of 6.5 mL. There was a further con-
2+ traction of 7 ml, when the residual gas
(b) MgC2O4   Mg + CO2 (q) M/5 treated with KOH. What is the volume (ml)
+3
(c) K2Cr2O7   Cr (r) M/6 of CO in the original composition ?
(d) CrO5   Cr2O3 (s) M/3 2. A mixture of NaOH and Na2CO3 required 25
(t) Oxidising agent
4. Match the following columns mL of 0.1 M HCl using phenolphthalein as the
(E = equivalent weight of underlined species) indicator. However, the same amount of the mix
Column - I Column - II
ture required 30 mL methyl orange was used as
3M
a) P2H 4  PH3  P4H 2 p) E  the indicator. The molar ratio of NaOH and
4
3M Na2CO3 in the mixture is x : y. Then the x + y is
b) I2  I   IO3 q) E 
5 (x and y are integers)
 2 
c) M nO 4  M n  H 2O  M n 3O 4  H 3. An 1 is maximum oxidised by acidified KMnO4
15M solution into AO3 . If 2.68 mmoles of A+(n+1) re-
r) E 
26
quires 32.16 mL of a 0.05 M acidified KMnO4
5M
d) H3PO 2  PH3  H3PO3 s) E  solution for complete oxidation, value of n is
6
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
Jr Chemistry E/M
4. Number of moles of OH - ions produced by
MULTIPLE ANSWER QUESTIONS
1 mole of Na 2CO 3 in water 1) a,d 2) a,c 3) a,b 4) a,b,c,d
5. 2 mole, equimolar mixture of Na2C2O4 and 5) a,c 6) a,b,d 7) a,b,c
H 2C2O4 required V1 L of 0.1 M KMnO4 in ASSERTION REASON
acidic medium for complete oxidatiion. The same 1) b 2) b 3) a 4) a
amount of the mixture required V2 L of 0.1 M 5) a 6) a 7) a 8) a
NaOH for neutralization. The ration of V1 to V2 9) c 10) b
is x : y , then the value of x + y is COMPREHENSION TYPE QUESTIONS
(x and y are integers)
1) a 2) a 3) c 4) b
6. 0.01 mole of FeSn (iron (II) sulphide) required
5) d 6) a 7) a 8) d
0.06 mole of AO 34 for complete oxidation. The 9) a 10) a 11) b 12) d
species formed are FeO, SO 2 and A2+ . 13) b 14) d 15) b 16) d
Calculate the value of n. 17) d 18) c 19) d
7. A solution containing 2.68 × 10-3 mol of An+ MATRIX MATCHING TYPE QUESTIONS
ions requires 1.61× 103mol of MnO4- for the 1). (a - r,t), (b - p,t), (c - q), (d - s)
complete oxidation of An+ to AO3- in acidic 2). (a - r,q), (b- t,q),(c - p), (d - s,q)
medium. What is the value of n ? 3). (a – q,t), (b – p), (c – r,t), (d – s,t)
8. Haemoglobin contains 0.25% iron by weight. 4) (a - s), (b - q), (c - r), (d - p)
The molecular weight of Haemoglobin is 5) (a - q), (b - p), (c - s), (d - r)
89600. Calculate the no. of iron atom per INTEGER ANSWER TYPE:
molecule of Haemoglobin. 1) 5 2) 5 3) 1 4) 2
9. Copper froms two oxides. For the same 5) 7 6) 4 7) 2 8) 4
amount of copper, twice as much oxygen 9) 1 10) 2
was used to form first oxide than to form
second one. If valence of Cu in I oxide is 2,
then find the valence of Cu in second oxide ? HINTS
10. 1.575 g of oxalic acid (COOH)2. xH2O are SINGLE ANSWER
dissolved in water and the valume made upto 1. Equivalent weight of
250 mL. On titration 16.68 mL of this
soltuion requires 25mL of N/15 NaOH metal= weight of metal  8
solution for complete neutralization. weight of oxygen
5 40
Calculate x.  8  9
4.44 4.44
3. C3 H 8  5O2  3CO2  4 H 2O
KEY
SINGLE ANSWER QUESTIONS x litres pf propane produce 3x litre of CO2
1) b 2) c 3) b 4) c C4 H10  6.5O2  4CO2  5 H 2O
5) d 6) a 7) b 8) b (3-x) litres of butane produce 4(3-x) lit of
9) b 10) a 11) d 12) d CO2
13) a 14) a 15) b 16) c
17) a 18) d 19) b 20) c 3 x  4 3  x   1 1
21) c 22) d 23) b 24) c 3x  12  4 x  11
25) b 26) b 27) d 28) c 12  x  11
29) d 30) d 31) b 32) a x 1 litre
33) a 34) b volume of butane : propane=2:1
 STIOCHIOMETRY
4. No.of equivalents of H 3 POx = No.of KMnO4  10 FeC2O4  24H 2 SO4
equivalents of KOH  3K 2SO4  6MnSO4  5Fe2  SO4 3 
56
K  0.1  20CO2  24H 2O
56
10 mole of FeC2O4 require= 6 mole of
 K 1
 H 3 POx is a monobasic acid KMnO4

It is H 3 PO2 6 3
1 mole of FeC2O4 requires= 
10 5
x  2 and the acid does not form acidic
salt 1 3 4
Total moles of KMnO4 require=  
6. Let milli moles of KOH= x and 5 5 5

Na2 CO3 =y 11. CO3-- + H+   HCO3 in presence of
1 phenolphthalein
x  y  15  ( with phenolphthalein)
20 HCO3  H  
 H 2CO3
2 x  2 y  1.5 ............( 1) HCO3  H    H 2CO3
1 (initial)
x  2 y  25  ( with methyl orange) Hence, VHCl reacted with original NaHCO3
20
= (V2- V1) ml.
2 x  4 y  2.5 ..............(2)
13. No.of milli equivalents Cu 2  100
2 y  1  y  0.5 milli mole
C u  2  1 0 0  6 3 .5  1 0  3  6 .3 5 g
x  0.25 millimole
159.5 g of CuSO4 should contain =63.5g
weight of KOH = 0.25  103 =0.014g
of copper
9. No.of equivalent of copper (II) salt= but only 6.35g Cu is present
No.of equivalent of Iodine
6.35
= No.of equivalents of hypo. %purity= 100  10%
 No.of equivalent of copper (II) 63.5
14.. Total m.eq. of NaOH taken = 20
salt= 24.5  0.1 =2.45
No.of milli moles of copper(II) salt = 2.45 m.eq. of H 2 SO4 = m.eq. of NaOH reacted
Weight of copper in copper (II) salt 5  0.2
  250  10
= 2.45  63.5 103 =0.078 g 25
0.305g of copper (II) salt contain =0.078g m.eq. of NaOH reacted = 20 – 10 = 10
of Cu
( NH 4 )2 SO4  2 NaOH
0.078
 % copper   100 =51%  Na2 SO4  2 NH 3  2 H 2O
0.305
10.  2KMnO4  10FeSO4  8H2 SO4 m-moles of ( NH 4 )2 SO4 reacted = 5

K2 SO4  2MnSO4  5Fe2  SO4 3  8H 2O wt. of ( NH 4 )2 SO4

10molesg FeSO4 requires2molesof  5 103  132  0.66g

.KMnO4 Percentage of ( NH 4 )2 SO4 in sample
1 mole of FeSO4 require =1/5 0.66
 100  82.5
moles of KMnO4 0.8
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
Jr Chemistry E/M
15. No.of milli equivalents of H 2 C2O4  0.1 500 50
19.  K     0.04167 M
=No.of milli equivalents of NaOH=4 500  200  500 1200
No.of milli equivalents of 0.01 200 2
 Na      0.00167 M
H C O  Na C O = No.of milli
2 2 4 2 2 4 500  200  500 1200
equivalents of KMnO4 = 6  0.2  5  6 0.1 500 50
 Ag      0.04167 M
500  200  500 1200
milli equivalent Na2C2O4 =2
200  0.01 500  0.1 52
weight of Na2C2O4  NO3     0.0433M
500  200  500 1200
= 2  103  67  0.134g 20. Fe 3  Fe  2 Fe 2
100x0.1x2=0.5xV
0.134
%Na2C2O4 =  100 =26.8 100  0.2 200
0.5 V   40ml
0.5 5
16. For 3 Br2 molecules change in oxidation
21. No of milli equivalents of Ba  MnO4  2 
no=5
Change in oxidation number for No of milli equivalents of FeCr2 O4
5 K - factor of Ba  MnO4  2  10
1 molecule=
3
K - factor of FeCr2 O4 = 7
M 3M
equivalent weight of Br2   25  89.6 103
5/3 5  V  0.2 10 
 224 
18. Let molarity of H 2 SO 4  M 1 and 100   
 7 
H 2C 2O 4  M 2
 V  350 ml
No.of milli equivalents of 22. No.of milli equivalent of H 2 SO4 = No.of
 H 2 So4  H 2C2O4  = milli equivalents of hypo
No.of milli equivalent g NaOH 10  N  10 1
N=1N
1
20  2M 1  2 M 2   40  Volume strength=5.6XN=5.6
10
W
40  M 1  M 2   4 N 1
CrEW
M 1  M 2  0.1 -------------(1) W= N  GEW  1 17  17 g / lit

No.of milli equivalents of H 2 C2O4 = 24. No.of equivalents KMnO4  1 5  5

No.of equivalents of H 2 O 2 =5
No.of milli equivalents KMnO4
5
1 No.of moles of H 2 O2 =
20  2 M 2   20  2
10
25. No.of milli equivalents MnO2 =
1
M2   0.05M ------(2) No.of milli equivalents of Cl2 =
20
No.of milli equivalents of KI=
M 1  0.0  0.05  0.05M No.of milli equivalents of hypo
No.of milli equivalents
 STIOCHIOMETRY
5 1 5
MnO2 = 16  1.25  16   20 x  y  25  
4 15 3
No.of milli moles of MnO2 =10  3 x  3 y  5 -----------( 2)
solving ( 1) & ( 2)
weight of MnO2 =10  87  10 3  0.87g
7 1
0.87 x ,y
weight % of MnO2  100  87% 6 2
1
x: y  7:3
26. When phenolphthalein is used as an indicator:
0.05 x  20  0.11  x  40mL . 29. No. of milli equivalents of KMnO4 
When methyl orange is used as an indicator No. of milli equivalents of thiosulphateions
0.05 y  20  0.1 3  y  120mL 0.158
V  0.1  1000
 y  x  80mL  158 
 
 8 
27. Let millimoles of FeC2 O4  SnCl2  x
0.3V  8
k  factor of FeC2 O4  3
80
k  factor of SnCl2  14 V  26.67ml
3
3 x  14 x  0.1 225
30. NaOH=X V1
 17 x  22.5
total no.of milli moles of acid used
22.5 =100x0.1=10
x
17 Let K milli moles of acid used for
millimoles of neutralisation Ba  OH  2  2YV2  K
22.5 milli moles of acid used for neutralising
Cl O3 formed   2  2.64
17 NaOH xV1  10  K 
28. Let milli moles of FeSO4  x Fravtion of acid used for neutralising
Let milli moles of FeC2O4  y NaOH Ba  OH  2
milli equivalents of
milli equivalents of K 2YV2
= K  10  K  =  XV  2YV
 F eSO 4  F eC 2 O 4  =milli equivalents 1 2

of KMnO4 X V1 1
given that y  4 , V  4
2
1 8
x  3 y  40   V1
15 3  X  4 y , V1 
 3 x  9 y  8 ----( 1) 4
Fraction of acid used for neutralising
By zinc and H 2 SO4 only Fe3 ions again
Ba  OH  2
reduced to Fe 2 ions
milli equivalents Fe 2 ions formed again 2YV2 2
   0.67
V
are oxidised by KMnO4 4Y  2  2YV2 3
4
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
Jr Chemistry E/M
31. No of milli equivalents of H 2 O2  COOK
|  2CO2
 n-factor = 2, eq
No of milli equivalents of hypo COOH
No of milli equivalents of wt. = M/2
H 2O2  20  0.1  2 for neutralization meq of one reactant = meq of
other reactant can be neutralized
No of milli moles of H2 O2  1 1000 × 2 = 1000 × 2
1000 7. H3PO4 + Ca(OH)2   CaHPO4 +
1L of H 2 O2 contain  20 milli moles
50 2H2O
n-factor for H3PO4 = 2 (since 2H+ ions are
strength  20  34 103 g
replaced)
 0.68 g / L
M 98
32. No of milli equivalents of lime stone = eq. wt. =   49
2 2
no of milli equivalents of Ca C2 O4  resulting solution of CaHPO4 have only are
no of milli equivalents of KMnO4 replacable H+
so nf = 1
 40  0.25  10 hence no. of eq = 1 for 1 more so can be
No of milli moles of lime stone = neutralized by 1 mole of KOH
No of milli moles of lime = 5 eq of CaHPO4 = eq. of KOH
weight of CaO  5  56 103  0.28 g For complete neutralization - no. of eq. of
H3PO4 = no. of eq. of Ca(OH)2
0.28 1 × 3 = 1.5 × 2
percentage of CaO  100  54.05%
0.518 can be neutralized.

33. Mn O4  SO32  Mn 2  SO42 ASSERTION & REASON

change in oxidation of Mn  5
2. Urea is H2NCONH2
change in oxidation of S  2
28
2MnO4  5SO32  2Mn2  5SO42 % of N = 100  46.6%
60
2 Urea is a covalent compound
1 mol of SO32 require moles KMnO4
5
34. Change in oxidation number of N = 3 10Dx
change in oxidation number of S = 2 3. M= M
s
2 HNO3  3H 2 S  2 NO  4 H 2 O  3S
where D = density of solution
 x  2 , y  3, a  2, b  4 x = % by mass
Ms = molar mass of solute..
MULTIPLE ANSWER QUESTIONS O
||
4. , thus only Na2HPO3
H  O  P O  H
COOH COOK
and NaH2PO3 salts are possible.
6. For | & |
COOH COOH
wt.
When behave as reducing agent 5. meq. = N × V (ml) = Eq. wt 1000 . No
(COOH)2   2CO2 n-factor = 2, eq doubt N decrease with dilution but V
wt. = M/2 increases and thus meq. remain constant
 STIOCHIOMETRY Jr Chemistry E/M
7. Molality does not depend upon volume 14. 214 g KIO3 = 1 mole of KIO3
thus it does not depend temperature = 3 mole of I2 (in the balanced chemical
2 1- 3 4 reaction)
8. O2
Fe S2   Fe 2 O3  SO 2 = 6 eq. of I2 (n f = 2)
= 6000 m eq. of I2
2y
9. n factor of P will be and atomic mass Let the vol. of Na2S2O3 = x mL, then
x
(x ´ 1) ´ 8 = 6000
equavalent mass of P n factor of x = 750 mL
2y 1
P  Ep  15. m mole of KMnO4 used = 50 ´ 5
x 10
m eq. of KMnO4 used (n f = 5) = 25 m eq.
COMPREHENSION TYPE QUESTIONS of C2O4-2
25
M 1V1 M 2V2 m mole of C2O4-2 (n = 2) =  12.5
1.  are the data with methyl
2
n1 n2 m eq. of Na2S2O3 = 2.5 = m eq. of Cu+2 (n
orange. = 1)
2. With phenolpthlien
m eq. of Cu+2 (n = 1) = 2.5
1
nE HCl nE HCl  nE of Na2Co3 Difference in number of m moles of Cu+2 and
2 C2O4-2 = 12.5 – 2.5 = 10
with methyl orange
16. (d) 109% labeled oleum will contain 9 g
nE HCl  nE of Na2Co2  nE of NaHCo3 H2O, 40g free SO3, 60 g H2SO4
3. NaHCo3  NaOH  Na2CO3  H 2 O  Cu 40 g (free) SO3 = mole SO3 (free) = y
84 40 1
2.1 ? 60 g (H2SO4) = mole H2SO4 = x
4,5,6 With phenolpthline 2
1 x y
nE  E of Na2CO3  ENaOH 9
2 Þ
x y
with methyl orange
nE HCl  1ENa2CO3  1E of NaOH 17. (D) In 100 g oleum sample
Wt. of SO3 = 40 g
W wt. of H2SO4 = 60g
10. N U   1000
E
0.512 19 (B) Use, m eq. of NaOH = m eq. of SO3 +
N  20   1000
206 m eq. of H2SO4
11. 1KMnO4  5 FeSO4
INTEGER ANSWER TYPE
16  0.2 10 3  ?
= 16  0.2  10 3  5
1. Let vol of CO=x ml
1.6 102
vol of CH 4 =y ml
13. m eq. of CuSO4 reacted = m eq. of Na2S2O3
reacted (n – f = 8) 1
= 50 ´ 1 ´ 8 = 400 CO  O2  CO2
2
% purity of CuSO4 =
400 CH 4  2O2  CO2  2 H 2 O
=100
Original m eq. of CuSO 4 x
contraction is vol=  2 y  6.5ml
= 80% 2
JR/SR SUBJECT- JEE - NIT - MAINS - VOL - No.
Jr Chemistry E/M
 x  4 y  13ml --------( 1) 8.  100 g Haemoglobin has = 0.25 g Fe
contraction is vol when passed  86600 g Haemoglobin has =
through KOH 0.25  86600
x+y=7------( 1) gFe
100
solving ( 1) & ( 2)
= 224 g Fe
3y=6
y=2ml i.e., 1 mole or N molecules of Haemoglobin
x=5ml vol.of CO=5 ml 224
2. Let milli moles g NaOH=x and has = g atom Fe
56
Na2 CO3 =y = 4 g atom Fe
x+y=25x0.1  1 molecule of Haemoglobin has 4 atom of
x+y=2.5-----( 1) Fe.
x+2y=30x0.1
x+2y=3----( 2) 9. Let valencies of Cu in two oxides be x and y, then
solving ( 1) & ( 2) I oxide is Cu2Ox
x=2 , y=0.5 II oxide is Cu2Oy
x:y=2:0.5=4:1 In I oxide : Equivalent of Cu = equivalent of
x+y=5 oxygen
3. Change in oxidation no.of A=4-n
Change in oxidation no.of Mn=5 w a
 . . . . . .(1)
(4-n)x2.68=5x32.16x0.05 A/x 8
10.72-2.68n=8.04 where x, A, x1 and a are weight of Cu, at.
10.72-8.04=2.68n wt. of Cu, valency of Cu and weight of
2.68 n=2.68 oxygen.
n=1 w a
In II oxide :  . . . .(2)
5. No.of moles of Na2 C2 O4  H 2C2O4 =1 A / x 2 8
4  v1  0.5 ( Oxygen used half of I)
By eqs. (1) and (2)
v1  8 L
x 2
2  v2  0.1  v 2  20 L 
y 1
v1 : v2  8 : 20 2/y = 2/1  y = 1
=2:5=x:y the valancy of Cu second oxide is 1
x+y=7
6. 0.01 × n-f = 0.06 × 3 10. Meq. of oxalic acid in 16.68 mL = Meq of
n-f = 18 NaOH
2  1
18 =   4   n = 25 
n  15
n=4  Meq of oxalic acid in 250 mL =
7. MnO4- would convert to Mn2+. Therefore its
‘n’ factor would be 5. 1 250
25    24.98
 Equivalents of MnO4- = 1.61 × 10-3 × 5 15 16.68
= 8.05 × 10-3 1.575
Equivalents of An+ = 8.05 × 10-3   1000  24.98
(90  18x) / 2
’n’ factor of AO3- = 5 – n
 x  2
 (5 – n) × 2.68 × 10-3 = 8.05 × 10-3
n=2