Stoichiometry Final

RSM79PhISTCH1
1. IIT–JEE Syllabus
Mole concept, Calculations involving Oxidation – Reduction, neutralisation and
displacement reactions
2. Introduction
Stoichiometry deals with the calculation of the quantities of various reactants and products
involved in a chemical reaction. The numerals used to balance a chemical equation are
known as stoichiometric coefficients. These numerals are essential for solving problems
based on chemical equation, hence called stoichiometric calculation.
In stoichiometric calculations, the mole relationship between different reactants and

products are required as from them the mass-mass, mass-volume and volume-volume
relationship between different reactants and products can be obtained.
Stoichiometric calculations can be carried out by two methods; Gravimetric Analysis and
Volumetric Analysis. In the first method the amount of chemical species is determined by
measurement of mass, whereas, in second method it is determined by measurement of
volume. Stoichiometric calculation can be carried in terms of two important concept: (i) Mole
Concept; (ii) Equivalent concept.
3. Mole Concept
A mole (symbol mol) is defined as the amount of substance that contains as many atoms,
molecules, ions electrons or any other elementary entities as there are carbon atoms in
exactly 12 gm of 12C. The number of atoms in 12 gm of 12C is called Avogadro’s
number (N0).
N0 = 6.023  1023
1 1
One atomic mass unit (amu) =  gm = 1.66  10–24 gm = 1.66  10–27 kg
N0 6.023  10 23
The number of moles of a substance can be calculated by various means depending on

data available, as follows.
Wt . in gm
a) Number of moles of molecules =
Molecular mass
Wt . in gm
b) Number of moles of atoms =
Atomic mass
Volume at STP
c) Number of moles of gases =
S tan dard molar volume
(Standard molar volume at STP = 22.4 lit)
Number of particles
d) Number of moles of particles e.g. atoms, molecules ions etc =
Avogardro number
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e) Number of moles of solute = molarity  volume of solution in litres

molarity  volume in ml
=
1000
f) for a compound AxBy, y moles of A = x moles of B
g) Mole fraction = fraction of the substance in the mixture expressed in terms of mol is
called its mol fraction (X)
E.g. for a mixture of substance A & B
nA nB
XA = XB = (n terms of denote number of moles)
n A  nB n A  nB
XA + XB = 1 & XA= (1 – XB)
Principle of Atom Conservation (POAC)
In chemical reaction atoms are conserved, so moles of atoms shall also be conserved. This
is known as principle of atomic conservation. This principle is helpful in solving problems of
nearly all stoichiometric calculations e.g.
KClO3(s)  KCl(s) + O2(g)
Applying POAC for K atoms
Moles of K atoms in KClO3 = Moles of K atoms in KCl
Since one mole of KClO3 contains 1 mol of K atom. Similarly 1 mol of KCl contains one mole
of K atoms.
WKClO3 WKCl
 1  nKClO3  1 nKCl  1  in gm (Mass-mass relationship)
MKClO3 MKClO3
Applying POAC for ‘O’ atoms

Moles of O atom in KClO3 = Moles of O atom in O2
 3  nKClO 3 = 2  nO 2
w KClO3 in gm Vol. of O2 at STP

 3   2 (Mass volume relationship of reactant
MKClO3 S tan dard Molar Volume
and product)
In this way applying POAC we can break the chemical equation into a number arithmetic
equations without balancing the chemical equation. Moreover number of reactions and their
sequence from reactants to products are not required. It is important to note that POAC can
be applied for the atoms which remain conserved in chemical reaction.
4. Concept of Limiting Reagent

In reactions involving more than one reactant, one has to identify first, of all the reactant,
which is completely consumed (limiting reagent), one can identify the limiting reagent
as follow:
N2 + 3H2  2NH3
Initial mole 5 12 ––
If N2 is the limiting reactant moles of NH3 produced = 10. If H2 is the limiting reactant moles
3
of NH3 produced = 12 = 8. The reactant producing the least number of mole of the
2
product is the limiting reactant, hence H2 is the limiting reactant.
The limiting reactant can also be ascertained by knowing the initial number of equivalents or
milli equivalents of each reactant. The reactant with least number of equivalents or milli
equivalent is the limiting reactant. The equivalent methods to identify the limiting reactant
used not require balancing of chemical equation.
5. Gravimetric Analysis
5.1 Calculation involving in mass – mass relationship
In general, the following steps are adopted in making necessary calculations:

1. Write down balanced molecular equation for the chemical change
2. Write down the no of moles below the formula of each of the reactant and product
3. Write down the relative masses of the reactants and the products with the help of
formula below the respective formula. These shall be the theoretical amounts of
reactants and product.
4. By the applications of unitary method, mole concept or proportionality method, the
unknown factor or factors are determined.
5.2 Calculation involving percent yield
In general, when a reaction is carried out in the laboratory we do not obtain actually the
theoretical amount of the product. The amount of the product that is actually obtained is
called the actual yield. Knowing the actual yield and theoretical yield the percentage yield
can be calculated as
Actual yield
% yield =  100
Theoretica l yield
5.3 Weight – Volume Relationship

2Mg(s) + O 2(g)  2MgO(s)
In the above reaction, one can find out the volume of O 2 at STP required to react with 10
10
gm of Mg. The moles of Mg is . The moles of O 2 required would be ½ the moles of
24
1 10
Mg. Therefore moles of O 2 =  . Since 1 mole of a gas (ideal) occupies 22.4L at
2 24
1 10 1 10
STP, therefore  moles of O 2 would occupy,  22.4L= 4.67L.
2 24 2 24
5.4 Volume – Volume Relationship
Let us consider the reaction H2(g) + ½O2(g)  H2O(l). We are given 10L of H2 at a given
temperature and pressure. How many liters of O2 would react with hydrogen at the same
temperature and pressure?
From the ideal gas equation [PV = nRT] it is clear that the volume of an ideal gas is directly
proportional to its no. of moles. Therefore under the same conditions of P and T,
VH2 nH
 2 . Since the molar ratio is 2:1 (H2:O2),  the volume ratio would also be 2:1.
VO 2 nO 2
Therefore the volume of O2 required would be 5L.
On the other hand if we need to calculate the volume of O2 at a different T and P, then
PH2 VH2 nH2 TH2

PH2 VH2  nH2 R TH2 ,PO2 VO2  nO2 RTO2 , and dividing we get  ,
PO 2 VO 2 nO 2 TO 2
PH2 VH2 nO 2 TO 2
 VO 2  
PO 2 nH2 TH2
Illustration 1: A sample of CaCO3 and MgCO3 weighed 2.21 gm is ignited to constant

weight of 1.152 gm. What is the composition of the mixture. Also calculate
the volume of CO2 evolved at 0°C and 76 cm of pressure.
Solution: CaCO3  CaO + CO2

x gm
MgCO3  MgO + CO2
y gm
(x + y) = 2.21 gm
 100 gm of CaCO3 gives 56 gm of CaO
56
 x gm of CaCO3   ( x )gm CaO
100
Similarly 84 gm of MgCO3 gives 40 gm of MgO
40  ( y )
 y gm of MgCO3 = gm
84
56 x 40 y
 Wt. of residue =  = 1.152 …(2)
100 84
Solving equations (1) and (2)
x = 1.19 gm
y = 1.02 gm
Mole of CO2 formed = Mole of CaCO3 + Mole of MgCO3
1.19 1.02
=  = 0.0241
100 84
 Volume of CO2 at STP = 0.0421  22.4 litre = 539.8 ml
Illustration 2: A mixture of FeO and FeO3 when heated in air to constant weight gains 5%
in weight. Find out composition of mixture.
1
Solution: 2FeO + O2  Fe2O3
2
1
2Fe3O4 + O2  3Fe2O3
2
Let, weight of FeO = x
Weight of Fe3O4 = y
 x + y = 100 …(1)
 2  72 gm of FeO give Fe2O3= 160 gm
160  ( x )
 x gm FeO gives Fe2O3 = gm
144
2  232 gm of Fe3O4 gives Fe2O3 = 3  160 gm
3  160  y
 y gm Fe3O4 gives Fe2O3 = gm
2  232
160 x 3  16  y
  = 105 …(2)
144 464
Solving equation (1) & (2)
x = 20.25 gm
y = 79.95 gm
Illustration 3: Calculate the weight of FeO from 2 gm VO and 5.75 gm of Fe 2O3. Also
report the limiting reagent.
VO + Fe2O3  FeO + V2O5
Solution: Balanced equation

2VO + 3Fe2O3  6FeO + V2O5
2 5.75
Moles before reaction
67 160
= 0.0298 0.0359 0 0
6 1 
Moles after reaction (0.0298 – 0.0359) 0   0.0359    0.0359 
3  3 
As 2 mole of VO react with 3 mole of Fe2O3
3
 0.0298 gm mole of VO =  0.0298 = 0.0447 mole of Fe2O3
2
Moles of Fe2O3 available = 0.0359 only
Hence, Fe2O3 is the limiting reagent
6
Mole of FeO formed =  0.0349
3
 Weight of FeO formed = 0.0359  2  72 = 5.17 gm
 nFeO 6 6
    nFeO   nFe 2 O 3
 nFe O 3  3
 2 3
6
WFeO   nFe 2 O 3  MFe 2 O 3
3
Illustration 4: A mixture of KBr, NaBr weighing 0.56 gm was treated with aqueous
solution of Ag+ and the bromide ion was recovered as 0.97 gm of pure
AgBr. What was the weight of KBr in the sample?
Solution: KBr + NaBr + Ag+  AgBr

a gm (0.56 – a) gm 0.97 gm
Applying POAC for Br atoms
Moles of Br in KBr + moles of Br in NaBr = moles of Br in AgBr
or 1  moles of KBr + 1  moles of NaBr = 1 moles of AgBr
a (0.56  a) 0.97
   (MKBr = 199, MNaBr = 103, MAgBr = 188)
119 103 188
 a = 0.1332 gm
0.1332
Percentage of KBr in the sample =  100 = 23.78
0.560
Illustration 5: In a gravimetric determination of P of an aqueous solution of dihydrogen

phosphate in H2PO4– is treated with a mixture of ammonium and
magnesium ions to precipitate magnesium ammonium phosphate
Mg(NH4)PO4.6H2O. This is heated and decomposed to magnesium
pyrophosphate. Mg2P2O7 which is weighed. A solution of H2PO4– yielded
1.054 gm of (Mg2P2O7) which is weighed. What weight of NaH 2PO4 was
present originally?
Δ
Solution: NaH2PO4 + Mg2+ + NH4+  Mg(NH4)PO4.6H2O  Mg2P2O7
As P atoms are conserved, apply POAC for P atoms, moles of P in
NaH2PO4 = moles of P in Mg2P2IO7
 1  moles of NaH2PO4 = 2  2 moles of Mg2P2O7
WNaH2PO4 WMg 2P2 O 7 WNaH2PO4 1.054
  2   2
MNaH2PO4 MMg 2P2 O 7 120 222
 WNaH2PO 4 = 1.14 gm
Illustration 6: Pyrolusite is an ore of manganese and it contains 80% by mass MnO2, 15%
inert impurities and the rest is water. When MnO 2 is heated it converts to
Mn3O4. A sample of pyrolusite was heated till constant weight is obtained.
Calculate the % of Manganese in the residue.
Solution: First of all think what is being asked. We have to calculate the % of Mn in
the residue. This means that we must have the mass of manganese in
the residue and the total mass of residue. Since the problem does not
mention the mass of pyrolusite that was heated, then probably it was
redundant. So, let us assume the mass of the sample to be x g.
Mass of MnO2 in pyrolusite = 0.8 x g.

 Mass of inert impurities = 0.15 x g.
Now, think about what is meant by 'heated till constant weight is

obtained'. Well, the only thing it can mean is that the sample is heated
due to which some changes took place in its weight and the sample is
being heated till all the changes that were to occur have occurred. This
certainly implies that all the water in the sample must have gone away.
When MnO2 is heated it converts to Mn3O4.
 3MnO2 Mn3O4 + O2 … (1)
We can see that to produce 1 mole of Mn3O4, one would need to heat 3
moles of MnO2.
0 .8 x
Moles of MnO2 in the sample =
87
0.8 x 1
Moles of Mn3O4 produced = 
87 3
 0.8 x 1 
Mass of Mn3O4 produced =    229  g.
 87 3 
Mass of inert impurities = 0.15 x g. (unchanged)
 0.8 x 1 
 Total mass of residue =    229  0.15 x  g.
 87 3 
Now let us find the mass of Mn in the residue.
0 .8 x
Moles of MnO2 in pyrolusite =
87
0 .8 x 0 .8 x
Moles of Mn in = moles of MnO2=
87 87
Since Mn is neither lost nor created in the conversion to Mn3O4, its no. of
moles would remain constant.
 0.8 x 
 mass of Mn in the residue =   55  g.
 87 
0.8 x
 55
% Mn in the residue = 87  100  59.36 %
0.8 x 1
  229  0.15 x
87 3
[Note: You may have noticed that the equation (1) is not balanced. To
balance it , add O2 to the right hand side of the equation.
 we have, 3MnO2  Mn3O4 + O2
Some of you may feel that if MnO2 is heated, the O2 should occur on the
left hand side of the equation. It is not necessary that if something is
heated, it would react with oxygen. It would react with oxygen only if the
product has more % of oxygen than the reactant. In this case it is the
other way round (36.78% O in MnO2, 27.94% O in Mn3O4)].
Illustration 7: Sodium chlorate, NaClO3, can be prepared by the following series of

reactions,
2KMnO4 + 16HCl 2KCl + 2MnCl2 + 8H2O + 5Cl2

6Cl2 + 6Ca(OH)2 Ca(ClO3)2 + 5CaCl2 + 6H2O
Ca(ClO3)2 + Na2SO4 CaSO4 + 2NaClO3
What mass of NaClO3 can be prepared from 100 cc of concentrated HCl

solution (density = 1.18 g/cc, 36% HCl by mass). Assume all other
substances are present in excess amounts.
Solution: We need to find the mass of NaClO3 and we are given the amount of HCl.
100 cc of HCl solution would have a mass= 100  1.18 = 118 g.
36
Mass of HCl in it = 118  = 42.48 g.
100
42.48
Moles of HCl = = 1.1638
36.5
 Moles of Cl2 produced by the first reaction
5 5
=  Moles of HCl  1.1638  0.3636 moles
16 16
Moles of Ca(ClO3)2 produced by the second reaction
1 1
=  Moles of Cl2   0.3636  0.0606 moles
6 6
Moles of NaClO 3 produced
 = 2  moles of Ca(ClO3)2
by the third reaction 
= 2  0.0606 = 0.1212
 Mass of NaClO3 = 0.1212  106.5 gm = 12.9 g.
6. Oxidation and Reduction

Oxidation is
i) the gain of oxygen

ii) the loss of hydrogen
iii) the loss of electrons (de-electronation)
iv) the increase of O.N.
Reduction is
i) the loss of oxygen
ii) the gain of hydrogen
iii) the gain of electron
iv) the decrease in O.N.
Fe  Fe2+ + 2e–
O.N. = 0 +2
 Fe loses electrons
 There is increase in O.N.
 Hence Fe is said to be oxidised
 It is a source of electrons hence it can act as a reducing agent (R.A.)
 Any species that can be oxidised is a reducing agent (R.A.)
Cu2+ + 2e  Cu
O.N. = + 2 0
 Cu2+ gains electron
 There is decrease in O.N.
 Hence Cu2+ is said be reduced.
Since it can gain electrons, hence it can act as an oxidising agent (O.A.)
 Any species that can be reduced is an oxidising agent (O.A.), or oxidant.
Above examples represent half reactions.
A complete reaction showing oxidation and reduction together is called a Redox

reaction.
Fe + Cu2+  Cu + Fe2+
R
O
Now that you are clear on what is oxidation – reduction, we are now in the right position to
know how to balance a redox (oxidation - reduction) reaction. This is important because
many of the problems of stoichiometry would be based on such redox reactions.
6.1 Oxidation State / Oxidation Number
There are several chemical reactions in which oxidation - reduction takes place. Oxidation
refers to a reaction in which electrons are removed from an atom and reduction refers to a
reaction in which electrons are added to an atom. To describe these changes, the concept
of oxidation state becomes necessary. For ionic species, the charge on each ion is said to
be the oxidation state for that atom. For example in NaCl, Na exists as Na + and Cl exists as
Cl. Therefore the oxidation state of Na in NaCl is +1 and that of Cl is 1. But in covalent
molecules, the charge on an atom would be so small that sometimes it becomes impossible
to calculate the exact charge on each atom of a molecule. Therefore, the Oxidation State
(O.S.) or Oxidation Number (O.N.) is defined as the charge, an atom would have in a
molecule if all the bonds associated with this atom in the molecule are considered to
be completely ionic. For example in H2O there are two O–H bonds. If we assume both the
O–H bonds to be completely ionic, then each H would possess a charge of +1, while O
possess a charge of 2. This is because oxygen is more electronegative than hydrogen. On
the other hand, in H2O2 there are two O–H bonds and one OO bond (HOOH).
Considering each O–H bond to be ionic both the oxygen atoms acquire a charge of 1 and
both the H, +1. This is because O–O bond can not be assumed to be ionic as both the
atoms have the same electronegativity.
To calculate the oxidation state of an element in a molecule you need not always know the
structure of the molecule. There are certain set of rules used to assign oxidation states in
polyatomic molecules:
1. The O.S. of all elements (in any allotropic form) is zero.
2. O.S. of oxygen is 2 in all its compounds except peroxides like H2O2 and Na2O2 where it
is 1 and superoxides like KO2 where it is –½.
3. O.S. of hydrogen is +1 in all of its compounds except those with the metals where
it is 1.
4. O.S. of all alkali metals is +1 and alkaline earth metals is +2 in all their compounds.
5. O.S. of all the halogens is 1 in all their compounds except where they are combined
with an element of higher electronegativity. Since fluorine is the most electronegative of
all elements, its O.S. is always –1.
Illustration 8: Calculate the O.S of all the atoms in the following species:
(i) ClO (ii) NO2 (iii) NO3 (iv) CCl4 (v) K2CrO4 (vi) KMnO4
Solution: 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) NO2 : (2  2) + x = 1 (where ‘x’ is O.S. of N)

 x = +3
iii) NO3 : 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).
6.2 Balancing Redox Equations
Some examples of redox reactions are
a) Sn2+ + 2Hg2+ Hg 22 +Sn4+

R
O
b) MnO 4 +5Fe2+ + 8H+  5Fe3+ + Mn2+ + 4H2O

O
R
c) Cr 2 O72 + 6Fe2+ + 14H+  6Fe3+ + 2Cr3+ + 7H2O

O
R
d) 3Cu + 2NO 3 + 8H+  2NO + 3Cu2+ + 4H2O

R
O
 If one of the half reactions does not take place, other half will also not take place. We
can say oxidation and reduction go side by side.
3Cl2 + 6OH–  5Cl– +ClO 3 + 3H2O

O.N. = 0 -1 +5
R
O
In this we find that Cl2 has been oxidised as well as reduced. Such type of redox reaction
is called Disproportionation reaction. Examples are
2Cu+     Cu + Cu2+

Dis proportionates
R
O
2HCHO + OH–  CH3OH + HCOO–

R
O
4ClO 3  3ClO 4 + Cl–

O
R
3MnO 24 + 2H2O  MnO2 + 2MnO 4 + 4OH–

R
O
How to Balance a Redox Reaction
Ion Electron Method
This method involves the following steps :
i) Divide the complete equation into two half reactions, one representing oxidation and the
other reduction.
ii) Balance the atoms in each half reaction separately according to the following steps:
a) First of all balance the atoms other than H and O.
b) In a reaction taking place in acidic or neutral medium, oxygen atoms are balanced by
adding molecules of water to the side deficient in oxygen atoms while hydrogen
atoms are balanced by adding H+ ions to the other side deficient in hydrogen atoms.
On the other hand, in alkaline medium (OH-), for every excess of oxygen atom on
one side is balanced by adding one H2O to the same side and 2OH- to the other
side. In case hydrogen is still unbalanced, then balance by adding one OH-, for every
excess of H atom on the same side and one H2O on the other side.
c) Equalize the charge on both sides by adding suitable number of electrons to the side
deficient in negative charge.
iii) Multiply the two half reactions by suitable integers so that the total number of electrons
gained in one half reaction is equal to the number of electrons lost in the other half
reaction.
iv) Add the two balanced half equations and cancel any term common to both sides.
There have been the common practices to balance the redox reaction by different
methods like O.N. method and electron balance method. In the entrance examination it
is never mentioned what method is to be used. We adopt here “quick” method that will
certainly be a time-saving method.

Illustration 9: a) NO3– + H2S 
 HSO4– + NH4+
H
acidic medium

b) Fe + N2H4  Fe(OH)2 + NH3
OH
alkaline medium
Solution: a) Step 1 N5+ + 8e  N3–

S2–  S6+ + 8e
Step 2 N5+ + S2–  N3– + S6+
Step 3 NO3– + H2S  NH4++ HSO4–
Step 4 NO other atom (except H and O) is unbalanced therefore
no need for this step.
Step 5: Balancing O atom. This is made by using H2O and H+ ions.
Add desired molecules of H2O on the side deficient in O
atom and double H+ on opposite side. Therefore
NO3– + H2S + H2O  NH4+ + HSO4– + 2H+
Step 6 Balance charge by H+

NO3– + H2S + H2O + 3H+  NH4+ + HSO4– + 2H+
 Balanced equation is
NO3– + H2S + H2O + H+  NH4+ + HSO4–
b) Step 1 Fe  Fe2+ + 2e
N22– + 2e  2N3–
Step 2 Fe + N22–  Fe2+ + 2N3–
Step 3 Fe + N2H4  Fe(OH)2 + 2NH3
Step 4 No other atom (except H and O) is unbalanced and
therefore no need for this step.
Step 5 Fe + N2H4 + 4OH–  Fe(OH)2 + 2NH3 + 2H2O
Step 6 Balance charge by H+
 Fe + N2H4 + 4OH– + 4H+  Fe(OH)2 + 2NH3 + 2H2O
Finally Fe + N2H4 + 2H2O  Fe(OH)2 + 2NH3
Oxidation Number Method
This method is based on the principle that the number of electrons lost in oxidation must be
equal to the number of electrons gained in reduction. The steps to be followed are :
i) Write the equation (if it is not complete, then complete it) representing the chemical
changes.
ii) By knowing oxidation number of elements, identify which atom(s) is(are) undergoing
oxidation and reduction. Write down separate equations for oxidation and reduction.
iii) Add required electrons on the right hand side of oxidation reaction and on the left hand
side of reduction reaction. Care must be taken to ensure that the net charge on both the
sides of the equation is same.
iv) Multiply the oxidation and reduction reactions by suitable numbers to make the number
of electrons lost in oxidation reactions equal to the number of electrons gained in
reduction reactions.
v) Transfer the coefficients of the oxidizing and reducing agents and their products to the
main equation.
By inspection, arrive at the co-efficients of the species not undergoing oxidation or

reduction.
Illustration 11: Balance the equation K2Cr2O7 + HCl  KCl + CrCl3 + H2O + Cl2
Solution: Remember that alkali and alkaline earth metals have only one oxidation
number and as long as they remain in the compound they do not undergo
oxidation or reduction.
6 1 3 0
K 2Cr 2O7 + H Cl  KCl + C rCl 3 + H2O + Cl 2
Thus here Cr of K2Cr2O7 is reduced to CrCl3(+6 +3) and Cl of HCl is

oxidised to Cl2(–1  0). In short.
Oxidation: 2Cl–1  Cl 02  2 … (a)
Reduction: Cr 26  2Cr+3  6 … (b)
Step (iii) 2Cl–1 Cl20 + 2e–; Cr2+6 + 6e–  2Cr3+
Step (iv) Multiply equation (a) by 6 and (b) by 2

12Cl–1  6Cl 02 + 12e–
2Cr 26 + 12e–  4Cr+3
—————————————
2Cr2+6 + 12Cl–1  4Cr3 + 6Cl20
or Cr2+6 + 6Cl–  2Cr+3 + 3Cl20
Step (v) K2Cr2O7 + 6HCl  2CrCl3 + 3Cl2
Step (vi) Making provision of KCl and H2O in the product: Since the
reactant has 7 oxygen atoms in the product 7H2O must be
present. For accounting 14 hydrogen atoms of water in the
product, the reactants must have 12 HCl molecules (the only H
containing species). For accounting the 2K atoms and 14 – 12 = 2
additional Cl atoms in the reactant, the product must have 2KCl.
Hence the balanced equation is.
K2Cr2O7 + 14HCl  2KCl + 2CrCl3 + 7H2O + 3Cl2
Exercise 1: MnO 4  3H2O  MnO 2  O2

neutral medium
47 2 4 0
Exercise 2: Write the balanced equation when ferrous sulphate is treated with acidified
(H2SO4) potassium permanganate.
Exercise 3: Balance the equation MnO4 + C2O24  + H+  CO2 + Mn+2 + H2O
7. Volumetric Analysis
Volumetric analysis deals with the determination of the strength of a unknown solution by
another solution of known strength (Titration). Titrations are of various types viz., acid base
titration (neutralisation reaction), redox-titration, iodometric titrations, iodiometric titrations,
precipitation reaction etc.
Method of Expressing Concentration of Solution
i) Molarity (M): The molarity of a solution is the number of moles of solute present in
one litre (1 dm3) of the solution
w  1000
M
m1  V in ml
ii) Normaltiy (N): The normality is the number of equivalents of solute present in one
litre (1 dm3) of the solution
1000  w 1
N
E1V(in ml )
iii) The molality (m): The molality is the number of moles of solute present in one Kg of
solvent
w1  1000
m
m1  w 2
iv) Relation between molarity and molality

1000  M
m (where d = density of solution)
(1000  d  M  m1 )
v) Relation between molarity and normaltiy

Normality = Molarity  n-factor
n-factor: Factor relating molecular weight and equivalent weight
M
n-factor = .
E
M
Equivalent weight =
n  factor
The n-factors in case of acids and bases are basicity and acidity respectively, in case
of salt is the charge on cation or anion, in case of ions, is the charge on the ions, in
case of oxidising agent and reducing agents is the change of oxidation number per
mole of the substance.
8. Law of Equivalence
The fundamental basis of all titrations is the law of equivalence. According to which at the
end point of titration, the volume of the two titrants reacted have same number of
equivalents or milli equivalents.
Equivalent of solute = Normality  Volume in litre
 Meq. = Normaltiy  Volume in mL

Meq .
Also = Eq
1000
 Also moles of solute = Molarity  Volume in litre

 Milli moles of solute = Molarity  Volume in ml
Milli moles
 = Moles
1000
w  W 
 Meq. =  1000  Meq   n  1000 
Equivalent w eight  M 
 For a general reaction

aA + bB  mC + nD
Eq. of A = Eq. of B = Eq. of C = Eq. of D
Or Meq. of A = Meq. of B = Meq. of C = Meq. of D
 In a compound AxBy, Eq. of AxBy = Eq. of A = Eq. of B
For the chemical change
aA + bB  mC 
 nE  X
dD
Meq. of A used = Meq. of B used = Meq. of C formed = Meq. of D used = Meq. of E formed
= Meq. of X formed.
 That is equivalent or meq. of reactants react in equal number to give the same
number of equivalent or meq. of the products separately.
Mole and millimole react according to the equation. It is, therefore, advisable to solve
numerical problems by equivalent or meq. rather than using mole or milli mole. For this
purpose change molarity into normality.
While diluting a solution from one concentration to another
i) M1V1 = M2V2
(conc.) (dilute)
ii) N1V1 = N2V2

(conc.) (dilute)
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).
8.1 ‘n’ Factor
a) In Non Redox Change:
i) n-factor for element: Valency of the element
ii) 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).
e.g. for HCl (n = 1), HNO3 (n =1), H2SO4 (n = 2), H3PO4 (n = 3) and H3PO3 (n=2)
iii) 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).
e.g. NaOH (n = 1), Ba(OH)2 (n = 2), Al(OH)3 (n = 3), etc.
iv) For Salts: A salt reacting such that no atom of the salt undergoes any change in
oxidation state. e.g. 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.
b) In Redox Change: For oxidising agent or reducing agent n-factor is the change in
oxidation number per mole of the substance.
Illustration 12: Calculate the n-factor in the following chemical changes.

H
i) KMnO4  Mn2+
H O
ii) KMnO4 2  Mn4+
OH 
iii) KMnO4   Mn6+
H
iv) K2Cr2O7  Cr3+
v) C2O42  CO2
vi) FeSO4 Fe2O3
vii) Fe2O3 FeSO4
Solution: i) In this reaction, KMnO4 which is an oxidising 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) Here KMnO4 gets reduced to Mn6+ under basic conditions.

n = 1  7  1  6  1
iv) Here K2Cr2O7 which acts as an oxidising agent gets reduced to Cr+3
under acidic conditions. (It does not react under basic conditions).
n = 2   6  2   3  6
v) C 2O42 (oxalate ion) gets oxidised to CO2 when it is reacted with an

oxidising agent.
n = 2   3  2   4  2
vi) Ferrous ions get oxidised to ferric ions

n = 1  2  1  3  1
vii) Here ferric ions are getting reduced to ferrous ions

n = 2   3  2   2  2
Illustration 13: Predict the molar ratio in which the following two substances would react if
they are assumed to be salts of category (a)
Ba3(PO4)2 and AlCl3
Solution: n factor of Ba3 (PO4) = 3 (+2) = 6 = n1

While n factor of AlCl3 = 1 (+3) = 3 = n2
n1 6

n2 3
n1 x
If 
n2 y
y
molar ratio = (inverse of equivalent ratio)
x
 molar ratio in which Ba3(PO4) and AlCl3 will react = 3:6 = 1:2
Illustration 14: Find the n- factor for the reactants in each of the following cases:
i) I  I2
ii) I2  I 
iii) S 2 O 32   S4O62 
iv) IO 3  I+
v) CuS  Cu2+ + SO2
Solution: i) n factor = 1  |0–(–1)| = 1

ii) n factor = 2 | –1–0| = 2
iii) n factor = 2|2.5–2| = 1
iv) n factor = 1 |1–5| = 4
v) n factor = 1 |4–(–2)| = 6
Illustration 15: Calculate the n-factor in the following redox change

FeC2O4 Fe3+ + CO2
Solution: Here Fe2+ is getting oxidised to Fe3+ and C3+ is getting oxidised to C4+.
The n factor w.r.t. Fe is +1 and w.r.t. C 2O42 is 2 (as calculated earlier).
Therefore total n factor is 3.
Exercise 4: Calculate the n factor when FeCr 2O4 gets oxidised to Fe3+ and Cr3+ and
Cu2S gets oxidised to Cu2+ and SO2.
8.2 Applications of the Law of Equivalence
Simple titration
In this, we can find the concentration of a substance with the help of the conc. of another
substance which can react with it.
For example: Let there be a solution of a substance A of unknown concentration. We are

given 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 equivalents, the number of gm equivalents of A is
equal to the number of gm equivalents of B.
 N1V1 = N2V2, where N2 is the conc. of A.
From this we can calculate the value of N2.
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 gms 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 conditions are satisfied (a) A, B and C
should be such compounds 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 A taken should be such that the gm
equivalents of A taken should be  gm equivalents of C in the sample. 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 V1. 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 complete, the
solution is being titrated with B. Let us assume that the volume of B used up is V2.
Gram equivalents of B used in the first titration = N1V1

 gm. equivalents of A initially = N1V1
gm. equivalents of B used in the second titration is N1V2
 gm. equivalents of A left in excess after reacting with C = N1V2
gm. equivalents of A that reacted with C = N1V1  N1V2
gm. equivalents of pure C = N1V1  N1V2.
N V  N1V2
If the n factor of C is x, then the moles of pure C = 1 1
x
N V  N1V2
 the weight of C = 1 1  Molecular weight of C.
x
N V  N1V2 Molecular w t. of C
 percentage of C = 1 1   100
x w
Double titration
The method involves two indicator (Indicators are substances that change their colour
when a reaction is complete) phenolphthalein and methyl orange. This is a titration of
specific compounds. Let us consider a solid mixture of NaOH, Na2CO3 and inert impurities
weighing w g. You are asked to find out the % composition of mixture. You are also given a
reagent that can react with the sample, say, HCl along with its concentration (M1).
We first dissolve the mixture in water to make a solution and then we add two indicators in it,
namely phenolphthalein and methyl orange. Now, we titrate this solution with HCl.
NaOH is a strong base while Na2CO3 is a weak base. So it is safe to assume that NaOH
reacts with HCl first, completely and only then does Na2CO3 react.
NaOH + HCl NaCl + H2O
Once NaOH has reacted, it is the turn of Na2CO3 to react. It reacts with HCl in two steps:
Na2CO3 + HCl NaHCO3 + NaCl and then,
NaHCO3 + HCl NaCl + CO2 + H2O
As can be seen, when we go on adding more and more of HCl, the pH of the solution keeps
on falling. When Na2CO3 is converted to NaHCO3, completely, the solution is weakly basic
due to the presence of NaHCO3 (which is a weaker base as compared to Na2CO3). At this
instant phenolphthalein changes colour since it requires this weakly basic solution to change
its colour. Therefore, remember that phenolphthalein changes colour only when the
weakly basic NaHCO3 is present. As we keep adding HCl, the pH again falls and when all
the NaHCO3 reacts to form NaCl, CO2 and H2O the solution becomes weakly acidic due to
the presence of the weak acid H2CO3(CO2 + H2O). At this instance methyl orange changes
colour since it requires this weakly acidic solution to do so. Therefore, remember methyl
orange changes colour only when H2CO3 is present.
Now, let us assume that the volume of HCl used up for the first and the second reaction,
i.e. NaOH + HCl NaCl + H2O and Na2CO3 + HCl NaHCO3 + NaCl be V1
(this is the volume of HCl from the beginning of the titration up to the point when
phenolphthalein changes colour). Let the volume of HCl required for the last reaction, i.e.,
NaHCO3 + HCl  NaCl + CO2 + H2O be V2 (this is the volume of HCl from the point
where phenolphthalein had changed colour upto the point when methyl orange changes
colour). Then,
moles of HCl used for reacting with NaHCO3 = moles of NaHCO3 reacted = M1V2
moles of NaHCO3 produced by the Na2CO3 = M1V2
moles of Na2CO3 that gave M1V2 moles of NaHCO3 = M1V2
Mass of Na2CO3 = M1V2  106
M1V2  106
% Na2CO3 =  100
w
moles of HCl used for the first two reactions = M1V1
moles of Na2CO3 = M1V2
moles of HCl used for reacting with Na2CO3 = M1V2
moles of HCl used for reacting with only NaOH = M1V1  M1V2
 moles of NaOH = M1V1  M1V2
Mass of NaOH = M1V1  M1 V2   40
% NaOH =
M V  M V   40 100
1 1 1 2
Iodometric and Idiometric titration
The reduction of free iodine to iodide ions and oxidation of iodide ions to free iodine occurs
in these titration’s.
I2 + 2e–  2I– (reduction)
2I–  I2 + 2e– (oxidation)
These are divided into two types
a) Iodometric titration: In iodometric titrations, an oxidising agent in allowed to react in

neutral medium or in acidic medium with excess of potassium iodide to librate free
iodine.
KI + oxidising agent  I2
Free iodine is titrated against a standard reducing agent usually with sodium
thiosulphate Halogen, dichromates, cupric ion, peroxides, etc can be estimated by this
method.
I2 + 2Na2S2O3  2NaI + Na2S4O6
2CuSO4 + 4KI  Cu2I2 + 2K2SO4 + I2
K2Cr2O7 + 6KI + 7H2SO4  Cr2(SO4)3 + 4K2SO4 + 7H2O + 3I2
b) Iodiometric 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  KI3 (Potassium triiodide)
This solution is first standardises before use with the standard solution of I2 substance
such as sulphite, thiosulphate, arsenite etc. are estimated.
The iodimetric and iodometric titrations, starch solution is used as 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.
9. Volume of Strength of H2O2

x volume of H2O2 means x litre of O2 is liberated by 1 litre of H2O2 on decomposition
2H2O2  2H2O + O2

68 gm 22. 4 lit at STP
22.94lit (at STP) of O2 is given by 68 gm of H2O2

68 x 17 x
x litre of O2 is released from gm of H2O2 =
22.4 5 .6
68 x 17 x
 x lit of O2 is given by =  (strength)
22.4 5.6
17x
Strength, S =
5.6
S 17 x x
Normality = = = [ x = N  5.6]
E 5.6  34 / 2 5.6
1 x
Molarity = Normality =
2 11.2
Illustration 16: A polyvalent metal weighing 0.1 gm and having atomic weight of 51 reacted
with dilute H2SO4 to give 43.90 ml of hydrogen at N.T.P. This solution
containing the metal in the lower oxidation state was found to require 58.8
ml of 0.02 M KMnO4 for complete oxidation. What are the oxidation states of
the metal in the two reactions.
Solution: Let lower oxidation state of metal be n

0.1 n 43.90
equivalents of metal = = equivalents of H2 evolved = 2
51 22400
n = 2
Let final oxidation state = n
Then equivalents of metal = equivalents of oxidant
0.1n  2 58.8  0.02  5
  n = 5
51 1000
Illustration 17: 1.20 gm of sample of Na2CO3 and K2CO3 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 neutralisation. Calculate the weight of Na2CO3 in mixture. If
another 20 ml of this solution is treated with excess of BaCl 2 what will be
the weight of the precipitate?
Solution: Let weight of Na2CO3 = x gm
Weight of K2CO3 = y gm
 x + y = 1.20 gm …(1)
For neutralisation reaction of 100 ml of
Meq. of Na2CO3 + Meq. of K2CO3 = Meq. of HCl
x y 40  0.1 100
  2  1000   2  1000 
MNa 2 CO 3 138 20
 69x + 53y = 73.14 …(2)
From equation (1) and (2)
x = 0.5962 gm
y = 0.604 gm
Solution of Na2CO3 and K2CO3 gives ppt. of BaCO3 with BaCl2
(meq. of Na2CO3 + Meq. of K2CO3) in 20 ml = meq. of BaCO3
 Meq. of HCl for 20 ml mixture = Meq. of BaCO3
 Meq. of BaCO3 = 40  0.1 = 4
WBaCO3
 1000 = 40  0.1 = 4
MBaCO3
WBaCO3
 2  1000 = 4
197
 WBaCO3 = 0.394 gm
Illustration 18: What is the weight of sodium bromate and molarity of solution to prepare
85.5 mL of 0.672 N solution when half cell reaction is
BrO3– + 6H+ + 6e  Br– + 3H2O
Solution: Meq. of sodium bromate = 85.5  0.672 = 57.456

Let weight of sodium bromate be w
M
Eq. wt. of sodium bromate = (as n-factor = 6)
6
W
  1000 = 57/456, WNaBrO3 = 1.446 gm
151 / 6
As molarity  n-factor = Normality
0.672 0.672
 Molarity =  = 0.112M
n  factor 6
Illustration 19: A solution 0.1 M KMnO4 is used for the reaction

S2O32– + 2MnO4–+ H2O  MnO2 + SO42– + OH–
What volume of solution in mL will be required to react with 0.158 gm of
Na2S2O3
Solution: Redox changes are: Mn7+ + 3e  Mn+4

S22+  2S6+ + 8e
Meq. of KMnO4 = Meq. of S2O32–
Let volume of KMnO4 required = V
0.158
 V  0.1 3 =  8  1000 ( MNa 2S 2O3 = 158, n-factor = 8)
158
 V = 26.67 ml n-factor for MnO4– = 3)
Illustration 20: A sample of MnO4.4H2O is strongly heated in air. The residue Mn3O4 left
was dissolved in 100 ml of 0.1 N FeSO 4 containing dil. H2SO4. This solution
was completely reacted with 50 ml of KMnO 4 solution. 20 ml of this KMnO4
solution was completely reduced by 30 ml of 0.1 N FeSO 4 solution.
Calculate the amount of MnSO4.4H2O in sample.
Δ
Solution: MnSO4 + H2O  Mn3O4
Redox change 3Mn2+  Mn38/3+ 2e
The residue Mn3O4 is titrated by another FeSO4. The normality of KMnO4
is determined by FeSO4.
Meq. of KMnO4 = Meq. of FeSO4
3
25  N = 30  0.1  N =
25
Meq. of FeSO4 added to Mn3O4 = 100  0.1 = 10
Meq. of FeSO4 left after reaction with Mn3O4
3
= Meq. of KMnO4 used = 50  =6
25
 Meq. of FeSO4 used for Mn3O4 = 10 – 6 = 4

 Meq. of Mn3O4 = 4
 Meq. of MnSO4.4H2O = 4
2
3MnSO4.4H2O  Mn 38 / 3O4 (n-factor = 8/3 – 2 = )
3
 Let weight of hydrated salt be w and molecular weight = M
w 2 W w 2
   1000 = 4 (4s  n  1000 = Meq.)    1000 = 4
M 3 M 223 3
 w = 1.338 gm
Illustration 21: 25 ml of H2O2 solution were added toe excess of acidified solution of KI.
The iodine so liberated required 20 ml of 0.1 N Na2S2O3 for titration.
Calculate the strength of H2O2 in terms of normality and volume strength.
Solution: Redox change is

O2–1 + 2e  2O2–
2I–-  I2 + 2e
2S22+  S4+5/2 + 2e
I2 + 2e  2I–
Meq. of H2O2 = Meq. of I2 = Meq. of Na2S2O3 = 20  0.1 = 2
Meq. 2
 NH2 O 2  
Volume in ml 25
Volume strength (x) = N  5.6
2
 Volume strength =  5.6 = 0.448 volume
25
Exercise 5: i) 0.2M KMnO4 solution completely reacts with 0.05 M FeSO 4 solution
under acidic conditions. The volume of FeSO 4 used is 50 ml. What
volume of KMnO4 was used?
ii) 10 g. of a sample of Ba(OH)2 is dissolved in 10 ml. of 0.5N HCl solution.
The excess of HCl was titrated with 0.2N NaOH. The volume of NaOH
used was 20 cc. Calculate the percentage of Ba(OH)2 in the sample.
iii) 0.2 gm of a solution of mixture of NaOH and Na 2CO3 and inert
impurities was first titrated with phenolphthalein and N/10 HCl 17.5 ml
of HCl was required at the end point. After this methyl organge was
added and 2.5 ml of same HCl was again required for next end point.
Find out percentage of NaOH and Na2CO3 in the mixture.
iv) 50 ml of an aqueous solution of H2O2 was treated with an excess of KI
solution and dilute H2SO4. The liberated iodine required 20 ml 0.1 N.
Na2S2O3 solution for complete intersection.
v) A solution of H2O2, labelled as ‘20 volumes’, was left open. Due to this
some H2O2 decomposed and the volume strength of the solution
decreased. To determine the new volume strength of the H 2O2 solution,
10 mL of the solution was taken and it was diluted to 100 mL. 10mL of
this diluted solution was titrated against 25 mL of 0.0245 M KMnO 4
solution under acidic condition. Calculate the volume strength of the
H2O2 solution.
10. Solution to Exercises

Exercise 1: Effected atoms are balanced
2MnO 4 +3H2O  2MnO2 + 3O2
14(O) 10(O) Cross multiplication
2MnO 4 + 3H2O2 + 4H2O  2MnO2 + 3O2 Add H2O on L.H.S. (excess
O-side)
2MnO 4 + 3H2O2 + 4H2O 2MnO2 + 3O2 + 8OH– Add double OH– on
RHS
We have proceeded in a right way, but we have not considered H due to
H2O2. Hnece H-atoms as well as charge are not balanced. Hence add
6H+ on R.H.S. which will neutralise OH– forming 6H2O and thus final
result will be
2MnO4 + 3H2O  2MnO2 + 3O2 + 2OH– + 2H2O
Exercise 2: Step (i) KMnO4 + H2SO4 + FeSO4  K2SO4 + MnSO4 + Fe2(SO4)3 + H2O
7 2 2 3
Step-(ii) KMnO 4 + H2SO4 + FeSO 4  K2SO4+ MnSO 4 + Fe 2 (SO 4 )3 + H2O
Thus here Mn+7 is reduced to Mn2+ (+ 7  +2) and Fe+2 is oxidised to
Fe+3 (+2+3).
Thus
Oxidation: 2Fe+2  Fe 23  2
Reduction: Mn+7  Mn+2 5
Step (iii) 2Fe+2  Fe2+3 + 2e–
Mn+7 + 5e–  Mn+2
Step (iv) Multiplying equation (a) by 5 and (b) by 2.
10Fe+2  5Fe2+3 + 10e–
2Mn+7 + 10e–  2Mn+2
Adding, 10Fe+3 + 2Mn+7  5Fe2+3 + 2Mn+2 + H2O
Thus the required equation may be written as
10FeSO4 +2KMnO4+H2SO4  5Fe2(SO4)3 +2MnSO4+K2SO4+ H2O
Step (vi) to balance SO 42 ions; multiply H2SO4 by 8
10 FeSO4 + 2KMnO4 + 8H2SO4  5Fe2(SO4)3 + 2MnSO4 + K2SO4 + H2O
7 3 4 2
Exercise 3: MnO 4 + C 2 O 4 2 + H+  C O 2 + Mn  2 + H2O
Thus there Mn+2 is reduced to Mn+2 (+7  +2) and carbon in C2O42 is
oxidised to CO2
Thus here Mn+2 is reduced to Mn+2 (+7  +2) and carbon in C2O4–2 is
oxidised to CO2.
Thus,
3 4
Oxidation: C 2 O 4 2  2CO 2 + 2e–  2
Reduction: Mn+7 + 5e–  Mn+2  5
3
5C2O24   10 CO2 + 10e–
2Mn+7+ 10e–  2Mn+2
——————————————
3
Adding 5C 2 + 2Mn+7  10CO2 + 2Mn+2
2MnO 4 + 5C2O42  2Mn+2 + 10CO2
Making provision of H+ on the L.H.S since these are given in the required
reaction. It must be 16H+ because R.H.S has 8H2O. Thus the balanced
equation is
2MnO4 + 5C2O42 + 16H+  2Mn+2 + 10CO2 + 8H2O
Exercise 4: FeCr2O4  Fe3+ + Cr+3

n factor = 1 (only Fe++ oxidises )
Cu2S  Cu2+ + SO2
n factor = 2 (due to Cu+) + 6 (due to S– – )= 8
Exercise 5: i) 0.2  5  V = 0.05  50

V = 2.5 ml.
ii) Milli eq. of HCl initially = 10  0.5 = 5

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
 eq. of Ba(OH)2 = 3/1000 = 3  10-3
Mass of Ba(OH)2 = 3  10-3  (171/2) = 0.2565 g.
% Ba(OH)2 = (0.2565/20)  100 = 1.28%
iii) Let W 1 gm NaOH and W 2 gm Na2CO3 was present in mixture.

At phenophthalein end point.
 w1 1 w 2  1
    =  17.5  10–3 ------------ (1)
 40 2 53  10
At second end point following reaction takes place
Eq. of NaHCO3 = eq. of HCl used ( in second titration)
1
= eq. of Na2CO3
2
1 W 1
 2 = 25   10–3
2 53 10
W2 = 0.0265 gm
Putting the value of W 2 in equation (1), we get
W1 = 0.06 gm
0.06
Percentage of NaOH =  100 = 30%
0 .2
0.0265
Percentage of Na2CO3 =  100 = 13.25%
0 .2
iv) H2O2 + 2KI + H2SO4 K2SO4 + 2H2O + I2
2Na2S2O3 + I2  Na2S4O6 + 2NaI
34
Equation mass H2O2 = = 17
2
20 ml 0.1 N Na2S2O3 = 20 ml 0.1 N I2 solution.
= 20 ml 0.1 N H2O2 solution
Amount of H2O2 in 50 ml.
v) Volume strength of a H2O2 solution : If a solution of H2O2 is labelled as

‘x volumes’ it means that 1 mL of the H2O2 solution on complete
decomposition would release O2 measuring x mL at STP.
Normality of KMnO4 solution =0.0245  5 = 0.1225 N
0.1225  25
Equivalents of KMnO4 used = =3.0625  10-3
1000
 Equivalents of H2O2 in the 10 mL that
is titrated = 3.0625  10-3
Equivalents of H2O2 in 100 mL=3.0625  10-3  10 = 3.0625  10-2
Equivalents of H2O2 in the original 10 mL = 3.0625  10-2
[ on adding water equivalents of a substance does not change]
3.0625  102
Moles of H2O2 in the original 10 mL = = 1.53  10-2
2
[‘n’ factor of H2O2 is 2 because as reacting with KMnO4
O-1 becomes O-2]
1.53  102
Moles of H2O2 in 1mL of the original 10 mL = = 1.53  103
10
Moles of O2 that it would give on decomposing =
1.53  103  1 
H2O2  H2O  2 O2  = 7.65  10
-4
2  
Volume of O2 at STP in mL = 7.65  10-4  22400= 17.136
 Volume strength = 17.136
11. Solved Problems

11.1 Subjective
Problem 1: 5.5g of a mixture of FeSO4.7H2O and Fe2(SO4)39H2O requires 5.4 ml of 0.1 N

KMnO4 solution for complete oxidation. Calculate the number of moles of
hydrated ferric sulfate in the mixture.
Solution: No. of equivalents of FeSO4.7H2O = No. of equivalents of KMnO4

= 5.4  0.1  10–3
No. of moles of FeSO4.7H2O = 5.4  10–4 ( n = 1 factor)
Weight of FeSO4.7H2O = 5.4  10–4 278
= 0.15g
 Weight of Fe2(SO4)39H2O = (5.5 – 0.15)g
5.35
 No. of moles of Fe2(SO4)39H2O = = 0.0095g
562
Problem 2: 1.1g CH3(CH2)nCOOH was burnt in excess air and the resultant gases
(CO2 + H2O) were passed through a solution of NaOH. The resulting
solution was divided into two equal parts. One part required 30 ml of 2.5 N
HCl for neutralisation using phenolphthalein as indicator. The other part
required 40 ml of 2.5 N HCl for neutralisation using methyl orange as
indicator. Find the value of n.
3
Solution: CH3(CH2)nCOOH + (n + 2)O2
2

(n + 2)CO2 + (n + 2) H2O
Volume of HCl used for neutralisation of NaHCO3 in half portion of
solution
= 40 –30 = 10 ml
10  2.5
Equivalents of NaHCO3 in half of the solution =
1000
10  2.5  2
Equivalents of NaHCO3 in total solution = = 0.05
1000
Moles of NaHCO3 formed = Moles of Na2CO3 formed
= moles of CO2 formed
= 0.05
1.1 (n  2)
Moles of CO2 formed = = 0.05
60  14n
On solving n = 2
Problem 3: When 2.5g of the mixture containing Ag 2CO3 and NaHCO3 was heated
strongly up to full decomposition. The weight of the residue was 1.8g.
Calculate the composition of the mixture.
Solution: 2NaHCO3 
 Na2CO3 + H2O + CO2

b b
84 2(84)
1
Ag2CO3 
 2Ag + CO2 + O2
 2
a 2a
276 76
Let us assume ‘a’ and ‘b’ g of Ag2CO3 and NaHCO3 were present
 a + b = 2.5 …(1)
Correspondingly, the no. of moles of Na2CO3 and Ag produced are
b 2a
and
2(84) 876
Weight of the residue (Na2CO3 + Ag) = 1.8
b 2a
i.e.  106   108 = 1.8 …(2)
2(84) 276
Solving 1 and 2
We get a = 1.5
b = 1.0g
Problem 4: Certain moles of HCN is oxidised completely by 25 ml of KMnO 4. The

products are CO2 and NO3– ion. When all this CO2 is passed through lime
water, 1 g of CaCO3 is obtained. Calculate the molarity of the KMnO4 used.
Solution: 2 3 5 4
H  C  N  NO 3  CO 2
[O]
KMnO 4
Ca(OH) 2
n-factor = 10
CaCO 3
1
Moles of C in CaCO3 = = 0.01
100
 Moles of C in HCN = 0.01
So, moles of HCN = 0.01
 KMnO4 is oxidising in acidic medium, its nfactor = 5
Applying law of chemical equivalence, equivalents of HCN = equivalents
of KMnO4
Moles nfactor = Molarity  nfactor  V in litre
0.01  10 = M  5  25  10–3
M = 0.8
Problem 5: The calcium oxide content in a solution of 1.048g of a substance being

analysed was precipitated with 25 ml of H2C2O4. The excess of C2O42– in one
fourth of the filtrate was back titrated with 5 ml of 0.1025 N KMnO 4. To
determine the concentration of H2C2O4 solution taken, it was diluted
fourfold. The titration of 25 ml of this diluted solution used 24.1 ml of the
same KMnO4 solution. What is the percentage of CaO in the substance?
Solution: Equivalents of KMnO4 used in the last titration
24.1 0.1025
= = 2.47  10–3
1000
 Equivalents of H2C2O4 in 25 ml = 2.47  10–3
 Equivalents in 100 ml = 9.88  10–3
 equivalents of H2C2O4 in the original 25 ml = 9.88  10–3
Equivalents of KMnO4 reacting with one fourth of excess H2C2O4
5  0.1025
= = 5.125  10–4
1000
Equivalents of excess H2C2O4 = 4  5.125  10–4
= 2.05  10–3
Equivalents of H2C2O4 consumed = 9.88  10–3 – 2.05  10–3
= 7.83  10–3
7.83  10 3
Moles of H2C2O4 consumed = = 3.0915  10–3
2
 Moles of CaO = 3.915  10–3
3.915  10 3
% of CaO =  56  100 = 20.92%
1.048
Problem 6: A precipitate of AgCl and AgBr weighs 0.4066g. On heating in a current of

chlorine, the AgBr is converted to AgCl and the mixture loses 0.0725g in
weight. Find the % of Cl in original mixture.
Solution: AgCl Cl2

AgCl (No change)
ag
AgBr  Cl2
AgCl
bg
a + b = 0.4066 ….(1)
Now 188g AgBr changes to 143.5 g AgCl
143 .5  b
b g AgBr changes to g AgCl
188
143 .5  b
 Total weight of AgCl after reaction = a 
188
143 .5  b
 a = 0.4066 – 0.0725 = 0.3341 …(2)
188
Solving 1 and 2
a = 0.1007g
b = 0.3059g
 Wt. of AgCl = 0.1007g

143.5g AgCl has 35.5g Cl
35.5  0.1007
0.1007g AgCl has = g Cl
143 .5
35.5  0.1007  100
 % of Cl in original mixture = = 6.13%
143.5  0.4066
Problem 7: 0.5g of fuming H2SO4 (oleum) is diluted with water. The solution requires
26.7 ml of 0.4 N NaOH for complete neutralisation. Find the % of free SO 3 in
the sample of oleum.
Solution: Fuming H2SO4 contains H2SO4 and SO3. Both react with NaOH. Let ‘a’ g
H2SO4 and ‘b’ g SO3 are present.
Meq. Of (H2SO4 + SO3) = Meq. of NaOH
a b
 1000   1000 = 26.7  0.4
98 / 2 80 / 2
80a + 98b = 41.87 …(1)
a + b = 0.5 …(2)
b = 0.1039 g
0.1039
% of SO3 =  100 = 20.78%
0.5
Problem 8: A solution of specific gravity 1.6g ml–1 is 67% by weight. What will be the %
by weight of the solution of same acid if it is diluted to specific gravity
1.2g ml–1.
Solution: Consider 100 ml of solution 67% by weight
Wt. of solution = 100  1.6 = 160g
67  160
Wt. of solute = = 107.2g
100
Now suppose xg H2O or x ml H2O is added to it ( d H 2O  1 )
Wt. of new solution = (160 + x)g
Also volume of new solution = (100 + x)ml
weight of new solution = (100 + x)  1.2g
= (120 + 1.2x)g
 160 + x = (120 + 1.2x)g
x = 200 ml or 200g
107 .2
 % by weight of new solution =  100 = 29.78%
160  200
Problem 9: A definite amount of BaCl2 was dissolved in HCl solution of unknown

normality 20 ml of this solution was treated with 21.4 ml of N/10 NaOH for
complete neutralization. Further 20 mL of solution was added to 50 ml of
N/10 Na2CO3 and precipitate was filtered off. The filtrate reacted with 10.5
ml of 0.8 N/10 H2SO4 in the presence of phenolphthalein as indicator.
Calculate strength of BaCl2 and HCl in the mixture.
Solution: Meq. of HCl in 20 ml solution = Meq. of NaOH
1
 20  N = 21.4  = 2.14
10
21.4  1
 NHCl = = 0.107
10  20
Strength of HCl = 0.107  36.5 = 3.9055 gm/litre
1
Meq. of Na2CO3 added to 20 ml solution = 50  =5
10
Meq. of Na2CO3 left after reaction in between BaCl2 +NaCO3 and (HCl +
Na2CO3)
= 2  Meq. of H2SO4 using phenolphthalein as indicator
1
( Meq. of Na2CO3 left = Meq. of H2SO4)
2
0.5  0.8
 Meq. of Na2CO3 left = 2  Meq. of H2SO4) = 2  = 1.6
10
Meq. of Na2CO3 usedf for (HCl + BaCl2)
= Meq. of Na2CO3 added – Meq. of Na2CO3 left = (5 – 1.68) = 3.32
 Meq. of HCl + Meq. of BaCl2 = 3.32
 Meq. of BaCl2 = (3.32 – Meq. of HCl)
= 3.32 – 2.14 (meq. of of HCl in 20 ml) = 3.32 – 2.14 = 1.18
WBaCl2
 2  1000 = 1.18 (n-factor for BaCl2 =2)
208
 WBaCl2 in 20 ml = 0.122 of gm
0.122
 WBaCl2 in 1 litre =  1000 = 6.135 gm/lit
20
Problem 10: 1.6 gm 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 this solution when treated with 0.02 M KMnO 4 required 32 mL of
the solution. Find the % of MnO 2 in the sample and also the percentage of
available oxygen.
Solution: Meq. of MnO2 = Meq. of oxalic acid taken – Meq. of oxalic acid left
= 50  0.5  2 – 32  0.02  5  10 (in 250 ml) = 18
Redox changes are C2O42–-  2CO2 (n-factor = 2)
MnO4  Mn
– 2+
(n-factor = 5)
MnO2  Mn 2+
(n-factor = 2)
WMnO 2 WMnO 2
 2  1000  18   2  1000  18 ,  w MnO 2 = 0.7821 gm
MMnO 2 87
0.7821
 % of MnO2 =  100 = 48.88%
1.6
Meq. of MnO2 = Meq. of O2
w O2
 2  1000 = 18,  w O 2 = 0.144 g
16
0.144
% of available O2 = 100 = 9
1 .6
11.2 Objective
Problem 1: The equivalent weight of an element is 4. Its chloride has a vapour density
59.25. Then the valency of the element is
(A) 4 (B) 3
(C) 2 (D) 1
Solution: Molecular weight of MClx = 2  59.25 = 118.5

Molecular w eight
Equivalent weight =
x
Molecular w eight
Equivalent weight of (M + Cl) =
x
Molecular w eight 118 .5
x= = =3
4  35.5 4  35.5
Problem 2: Two metallic oxides contain 27.6% and 30% oxygen respectively. If the
formula of the first oxide is M3PO4, then that of the second
will be
(A) MO (B) MO2
(C) M2O5 (D) M2O3
Solution: In the 1st oxide, oxygen = 27.6 parts

Metal = 100 – 27.6 = 72.4 parts
In the 2nd oxide, oxygen = 30 parts
Metal = 100 – 30 = 70 parts
As 1st oxide is M3O4, 72.4 parts of M = 3 atoms of M and 27.6 parts of O =
4 atoms of O
3
 70 parts of M =  70 atoms of M
72.4
= 2.9 atoms of M
4
30 parts of O =  30 atoms of O
27.6
= 4.35 atoms of O
 Ratio of M : O in the 2nd oxide = 2.9 : 4.35 = 1 : 1.5 = 2:3
Hence the formula is M2O3
(D)
Problem 3: The equivalent weight of iron in Fe2O3 would be

(A) 18.6 (B) 28
(C) 56 (D) 112
Solution: In Fe2O3, 2  56 = 112 parts of Fe combines with 48 parts of oxygen.

112
Hence 8 parts of oxygen will combine with Fe = = 18.6
6
Problem 4: 20 ml of a H3PO4 solution needs 40 ml of 0.1 M NaOH to convert it into

sodium dihydrogen phosphate. How much volume of 0.1 M Ca(OH) 2 is
needed to neutralise the same volume of same H3PO4 completely
(A) 120 ml (B) 20 ml
(C) 40 ml (D) 60 ml
Solution: Equivalents of H3PO4 = equivalents of NaOH

20  10–3  M 1 = 40  0.1 10–3
M = 0.2
Equivalents of Ca(OH)2 = equivalents of H3PO4
V  2  0.1  10–3 = 3  0.2 10–3  20
V = 60 ml
Problem 5: When 0.1 mole of H3BO3 is titrated against NaOH of 1 M using

phenolphthalein indicator what volume of NaOH is used up to the end
point?
(A) 300 ml (B) 100 ml
(C) 3000 ml (D) 1000ml
Solution: H3BO3 is a monobasic acid

equivalents of H3BO3 = equivalents of NaOH
0.1 = 1  V
V = 0.1 litre or 100 ml
Problem 6: A metal oxide has the formula Z2O3. It can be reduced by hydrogen to give
free metal and water. 0.1596g of the metal oxide requires 6 mg of hydrogen
for complete reduction. The atomic weight of the metal is
(A) 27.9 (B) 159.6
(C) 79.8 (D) 55.8
Solution: Valency of metal in Z2O3 = 3

Z2O3 + 3H2  2Z + 3H2O
0.1596g of Z2O3 reacts with 6 mg of H2
0.1596
1g H2 will react with g of Z2O3
0.006
0.1596
 equivalent weight of Z2O3 = = 26.6g
0.006
 equivalent weight of Z2O3 = 26.6
= eq.wt. of Z + eq. wt. of = E + 8
E + 8 = 26.6
E = 18.6
 Atomic weight of Z = 18.6  3 = 55.8
Problem 7: 20g of sample of Ba(OH)2 is dissolved in 50 mL of 0.1 N HCl solution. The

excess of HCl was titrated with 0.1 N NaOH. The volume of NaOH used was
20 ml. The percentage of Ba(OH)2 in the sample is
(A) 1.28 (B) 2.56
(C) 3.24 (D) 4.86
Solution: Equivalents of Ba(OH)2 = eqts of HCl used

W
= 3  10–3
171 / 2
0.256
W = 0.256g  % of Ba(OH)2 =  100 = 1.28%
20
Problem 8: 1.5 litre of a solution of normality N and 2.5 litre of 2M HCl are mixed
together. The resultant solution had a normality 5. The value of N is
(A) 6 (B) 10
(C) 8 (D) 4
Solution: Eq. of 1.5 litre solution + Eq. of 2.5 litre solution = Eq. of resultant of
solution
 1.5 N + 2.5  2 = 4  5
20  5 15
N=  = 10
1.5 1.5
 (B)
Problem 9: The volume of 0.25 M H3PO3 required to neutralise 25 ml of 0.03 M

Ca(OH)2 is
(A) 1.32 mL (B) 3 mL
(C) 26.4 mL (D) 2.0 mL
Solution: Meq. of H3PO4 = Meq. of Ca(OH)2

 V  0.25  2 = 25  0.03  2 (H3PO3 is dibasic acid)
25  3  2
V= = 3mL
25  2
(B)
Problem 10: A 0.1097 gm sample of As2O3 required 26.10 mL of KMnO4 solution for its
titration. The molarity of KMnO4 solution is
(A) 0.02 (B) 0.04
(C) 0.018 (D) 0.3
Solution: n-factor = 5
As2O3 + MnO4–  2AsO43– + Mn2+

n-factor = 4
Let molarity of KMnO4 solution be M
 Eq. of As2O3 = Eq. of KMnO4 solution
0.1097 26.10  M  5 198
4 = (Equivalent weight As2O3 = )
198 1000 4
molarity = 0.017M  0.018
 (C)
12. Assignments
12.1 Subjective
LEVEL – I
1. A definite amount of NH4Cl was boiled with 100 mL of 0.8 N NaOH for complete
reaction of NH4Cl. After the reaction, the reactant mixture containing excess of
NaOH was neutralized with 12.5 mL of 0.75 NH2SO4. Calculate the amount of NH4Cl
taken.
2. In a quality control analysis for sulphur impurity 5.6 gm steel sample was burnt in a
stream of oxygen and sulphur was converted to sulphate by using H2O2 solution to
which had been added 30 mL of 0.04 M NaOH. The equation for reaction is
SO2(g) + H2O2(g) + 2OH–(aq)  SO42– + 2H2O(l)
22.48 ml of 0.624 M HCl was required to neutralize the base remaining after
oxidation reaction. Calculate % of sulphur in given sample.
3. 2.480 gm KClO3 are dissolved in conc. HCl solution and chlorine gas evolved in the
reaction was then passed through a solution of KI and liberated iodine was treated
with 100 mL of hypo solution 12.3 mL of same hypo solution required 24.6 mL of 0.5
N iodine for complete neutralization. Calcualte % purity of KClO3 sample.
4. To a 25 ml H2O2 solution, excess of acidified solution of KI was added. The iodine

liberated required 20 ml 0.3 N Na2S2O3 solution. Calculate the volume strength of
H2O2.
5. 1 gm sample of KClO3 was heated under such conditions that a part of it

decomposed according to the equation
i) 2KClO3  2KCl + 3O2
ii) and the remaining underwent change according to the equation
4KClO3  3KClO4 + KCl
If the amount of O2 evolved was 146.8 ml at STP, calculate percentage by weight of
KClO4 in the residue.
6. A solid mixture (5 gm) consisting of lead nitrate and sodium nitrate was heated below
600°C until the weight of the residue is constant. If the loss in weight is 28% find the
amount of lead nitrate and sodium nitrate in the mixture.
7. A 8.0 g sample contained Fe3O4, Fe2O3 and inert materials. It was treated with an
excess of aqueous KI solution in acidic medium, which reduced all the iron to Fe+2
ions. The resulting solution was diluted to 50.0 cm3 and a 10.0 cm3 of it was taken.
The liberated iodine in this solution required 7.2 cm3 of 1.0 M Na2S2O3 for reduction
to iodide. The iodine from another 25.0 cm3 sample was extracted, after which the
Fe+2 ions was titrated against 1.0 M KMnO4 in acidic medium. The volume of KMnO4
solution used was found to be 4.2 cm3. Calculate the mass percentages of Fe3O4
and of Fe2O3 in the original mixture.
8. 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 20oC and 1 atm. when 200 gm. of 10% by mass H2O2 in water is
treated with 100 ml. of 2 M Sn2+ and then the mixture is allowed to stand until no
further reaction occurs.
9. Calculate the % of MnO2 in a sample of pyrolusite ore, 1.5 g which was made to
react with 10 g of Mohr’s salt (FeSO4.(NH4)2SO4. 6H2O) and dilute H2SO4. MnO2 was
converted 2 Mn2+ . After the reaction the solution was diluted to 250 ml and 50 ml of
this solution, when titrated with 0.1 N K2Cr2O7, required 10 ml of the dichromate
solution.
10. A 1.2 g. of a mixture containing H2C2O42H2O and KHC2O4H2O and impurities of a

neutral salt, consumed 18.9 ml of 0.5 N NaOH for complete neutralization. On
titiration with KMnO4 solution 0.4 g of the same substance needed 21.55 ml of 0.25
N KMnO4. Calculate the percentage composition of the substance.
LEVEL - II
1. A sample of ferrous sulphate and ferrous oxalate was dissolved in dil. H2SO4. The
complete oxidation of reaction mixture required 40 mL of N KMnO4. After the
15
oxidation, the reaction mixture was reduced by Zn and H2SO4. On again oxidation by
same KMnO4, 25mL were required. Calculate the ratio of Fe in ferrous sulphate and
oxalate.
2. A sample of hydrazine sulphate (N2H6SO4) was dissolved in 500 mL water. 10 mL of

this solution was reacted with excess of FeCl3 solution and warmed to complete the
reaction. Ferrous ions formed were estimated and it required 20 mL of N KMnO4
50
solution. Estimate the amount of hydrazine sulphate in one litre solution.
Given that 4Fe3+ + N2H4  N2 + 4Fe2+ + 4H+
MnO4– + 5Fe2+ + 8H+  Mn2++ 5Fe3+ + 4H2O
3. In an experiment 10 litre of air at 1 atmosphere pressure and 27C were passed

through an alkaline KI solution. At the end the iodine entrapped in a solution reacted
with 1.5 mL of 0.01 N Na2S2O3 solution. Calculate the % volume of O3 in the sample
4. 1 gm mixture containing equal number of moles of carbonates of two alkali metals

required 44.4 ml of 0.5 N HCl for complete neutralisation. The atomic weight of one
metal is 7 find the atomic weight of other metal. Also calculate the amount of
sulphate formed on quantitative conversion of 1.0 gm of the mixture into sulphates.
5. 1 gm of mixture of Na2CO3 and K2CO3 was made upto 250 ml in aqueous solution
was neutralised by 20 ml of HCl of unknown concentration. The neutralized solution
required 16.24 ml of 0.1 N AgNO3 for precipitation. Calculate.
a) The % of K2CO3 in mixture
b) Conc. of HCl in gm/litre
c) Molarity of HCl
6. n-Butane is produced by the monobromination of ethane, followed by the Wurtz

reaction. Calculate the volume of ethane at STP that would be required to produce
55 g of n-Butane if the monobromination occurs with 85% (by mole) yield and the
Wurtz reaction occurs with 90% (by mole) yield.
The reactions are :
C2H6 + Br2 C2H5Br + HBr (monobromination)
(Ethane)
2C2H5Br + 2Na C4H10 + 2NaBr (Wurtz reaction)
(Butane)
7. A sample weighing 0.3 g is suspected to contain either pure NaCl, or pure KCl or
pure NH4Cl or a mixture of any of these two mixed in any proportion by weight or a
mixture of all the three mixed in any proportion by weight. What minimum volume of
5% (by weight) of AgNO3 solution (specific gravity = 1.04) must be added to the
sample to ensure complete precipitation of chloride as AgCl in every possible case.
8. A 2.5 g sample containing As2O5, Na2HAsO3 and inert substance is dissolved in

water and the pH is adjusted to neutral with excess NaHCO3. The solution is titrated
with 0.15 M I2 solution, requiring 11.3 ml to just reach the end point, then the solution
is acidified with HCl, KI is added and the liberated I2 requires 41.2 ml of 0.015 M
Na2S2O3 under basic conditions where it converts to SO42-. Calculate % composition
of the mixture.
9. Sufficient amount of H2S gas is passed through 5 ml solution of tincture of iodine to

convert its all iodine into iodide ion. The sulphur precipitated is filtered off and the
solution is made upto 1 litre and the solution is acidified with HCl. 250 ml of this
solution requires 28 ml of 0.05 N Ce4+ for the conversion of entire I– into ICl only. 2
ml of same sample of tincture of iodine gave 0.0313 gm of yellow precipitate in
another experiment when treated with AgNO3 solution. What weight percent of iodine
is present in the form of free iodine. ( Tincture of iodine contains free I– and I2 both)
10. A mixture containing Li2CO3, Na2CO3 and Na2O was strongly heated at 300C, the
gas evolved occupies 59.2 ml at 740 mm pressure. The residue reacts completely
with 15 ml seminormal HCl and further evolves 45 ml gas measured at 27C and at
740 mm pressure. Calculate the percentage of Na2O in the mixture.
12.2 Objective
LEVEL– I Single choice
1. 22.7 ml of N/10 Na2CO3 solution neutralises 10.2 ml of a dilute H2SO4. Then the
volume of water that must be added to 400 ml of same H2SO4 to make
it exactly N/10 is
(A) 245 ml (B) 484.6 ml
(C) 480 ml (D) 490.2 ml
2. The sulphate of a metal M contains 20% of M. This sulphate is isomorphous with

ZnSO4.7H2O. The atomic weight of M is
(A) 12 (B) 24
(C) 36 (D) 48
3. 1.12 ml of a gas is produced at STP by the action of 41.2 mg of alcohol, ROH with
methyl magnesium iodide. The molecular mass of alcohol is
(A) 16.0 (B) 41.2
(C) 84.2 (D) 156.0
4. Rearrange the following (I to IV) in the order of increasing maasses and choose the
correct answer from (A), (B), (C) and (D) (Atomic mass of N = 14, O = 16, Cu = 63).
(I) 1 molecule of oxygen
(II) 1 atom of nitrogen
(III) 1  10–10 gm molecular weight of oxygen
(IV) 1  10–10 gm atomic weight of copper
(A) (II)  (I)  (III)  (IV) (B) (IV)  (III)  (II)  (I)
(C) (II)  (III)  (I)  (IV) (D) (III)  (IV)  (I)  (II)
5. One mole of calcium phosphide on reaction with excess of water gives

(A) One mole of phosphine (B) Two moles of phosphoric acid
(C) Two moles of phosphine (D) One mole of phosphorus pentaoxide
6. An aqueous solution of 6.3 gm 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
(A) 40 ml (B) 20 ml
(C) 10 ml (D) 4 ml
7. If 0.5 mol of BaCl2 is mixed with 0.2 mol of Na3PO4, the maximum number of moles
of Ba3(PO4)2 that can be formed is
(A) 0.7 (B) 0.5
(C) 0.30 (D) 0.10
8. 0.5 mol of H2SO4 is mixed with 0.2 mole of Ca(OH)2. The maximum number of mole
of CaSO4 formed is
(A) 5 (B) 0.5

(C) 0.4 (D) 1.5
9. The hydrated salt Na2SO4.xH2O undergoes 55% loss in weight on heating and
becomes anhydrous. The value of x will be
(A) 5 (B) 3
(C) 7 (D) 10
10. The percent loss in weight after heating a pure sample of KClO3 (molecular
weight = 122.5) will be
(A) 12.25 (B) 24.50
(C) 39.18 (D) 49.0
11. The weight of sodium bromate required to prepare 85.5 ml of 0.672 N solution for cell
reaction BrO3– + 6H+ + 6e  Br– + 3H2O is
(A) 1.56 gm (B) 1.45 gm
(C) 1.23 gm (D) 1.32 gm
12. NaIO3 reacts with NaHSO3 according to equation

IO3– + 3HSO3–  I– + 3H++ 3SO42–
The weight of NaHSO3 required to react with 100 ml of solution containing 0.58 gm
of NaIO3 is
(A) 5.2 gm (B) 4.57 gm
(C) 2.3 gm (D) None of these
13. 25 ml of H2O2 solution were added to excess of acidified solution of KI and iodine so
liberated required 20 ml of 0.1 N Na2S2O3 for titration. The normality H2O2 is?
(A) 0.02 (B) 0.04
(C) 0.08 (D) 0.03
14. A mixture of KBr and NaBr weighing 0.560 gm was treated with aqueous Ag + and all
the bromide ion was recovered as 0.970 gm of pure AgBr. The fraction by weight of
KBr in the sample is
(A) 0.25 gm (B) 0.2378
(C) 0.36 (D) 0.285
15. The number of moles of Fe(OH)3 produced by allowing 1 mol of Fe2S3 2 moles of
H2O and 3 moles of O2 to react according to the equation
2Fe2S3(s) + 6H2O(l) + 3O2(g)  4Fe(OH)3(s) + 6S(s) are
(A) 1.26 (B) 2.4
(C) 1.34 (D) 1.43
16. The volume in ml of 0.1 N HCl required to react completely with 1.0 gm mixture of
Na2CO3 and NaHCO3 containing equimolar amounts of the two compounds is
(A) 157.9 ml (B) 152.6 ml

(C) 200 ml (D) 98.5 ml
17. 25.4 g of iodine and 14.2g of chlorine are made to react completely to yield a mixture
of ICl and ICl3. Calcualte the ratio of moles of ICl and ICl3.
(A) 1:1 (B) 1:2
(C) 1:3 (D) 2:3
18. Calculate the weight of ion which will be converted into its oxide by the action of 18g
of steam on it.
(A) 37.3 gm (B) 3.73 gm
(C) 56 gm (D) 5.6 gm
19 The hourly energy requirement of an astronaut can be satisfied by the energy

released when 34g of sucrose are burnt in his body. How many g of oxygen would
be needed to be carried in space capsule to meet his requirement for one day?
(A) 916.2gm (B) 91.62 gm
(C) 8.162 gm (D) 9.162 gm
20 10 ml of a solution of H2O2 labelled ’10 volume’ just decolorises 100 ml of potassium

permanganate solution acidified with dilute H2SO4. Calculate the amount of
potassium permanganate in the given solution.
(A) 0.1563 gm (B) 0.563 gm
(C) 5.63 gm (D) 0.256 gm
LEVEL– II More than one choice
1. For the following balanced redox reaction,

2MnO4- + 8H+ + Br2 2Mn+2 + 2BrO3- + 2H2O
-
If the molecular wt. of MnO4 , Br2 be Mx, My respectively, then
(A) equivalent wt. of MnO4- is Mx/5
(B) equivalent wt. of Br2 is My/10
(C) the n-factor ratio of Mn+2 to BrO3- is 1 : 1
(D) none of these
2. When non-stoichiometric compound Fe0.95O is heated in presence of oxygen, then it
converts into Fe2O3, then which of the following statements are correct ?
M
(A) equivalent weight of Fe0.95O is where M is molecular weight of Fe0.95O.
0.85
(B) The number of moles of Fe+3 and Fe+2 1 moles Fe0.95O and 0.1 and 0.85 respectively.
(C) The number of moles of Fe+3 and Fe+2 in 1 mole of Fe0.95O are 0.85 and 0.10
respectively
(D) The % composition of Fe+2 and Fe+3 in the non stoichiometric compound is 89.47% and
10.53% respectively.
3. When FeS2 is oxidized with sufficient O2, then its oxidation product is found to be Fe2O3 and
SO2, if the molecular weight of FeS2, Fe2O3 and SO2 are M, M and M, then which of the
following statements are correct ?
(A) equivalent wt. of FeS2 is M/11 (B) the molar ratio of FeS2 to O2 is 4 :11
(C) the molar ratio of FeS2 to O2 is 11 : 4 (D) The molar ratio of Fe2O and SO2 is 1 : 4
4. 40 g NaOH, 106 g Na2CO3 and 84 g NaHCO3 is dissolved in water and the solution is made
1 litre. 20 mL of this stock solution is titrated with 1N HCl, hence which of the following
statements are correct.
(A) the titre reading of HCl will be 40 mL, if phenolphthalein is used indicator from the very
beginning
(B) the titre reading of HCl will be 60 mL if phenolphthalein is used indicator from the very
beginning.
(C) the titre reading of HCl will be 40 mL if the methyl orange is used indicator after the 1st
end point
(D) the tire reading of HCl will be 80 mL, if methyl orange is used as indicator from the very
beginning.
M
5. 150 mL Ba(MnO4)2 in acidic can oxidize completely
10
(A) 150 mL 1M Fe+2 (B) 50 mL 1M FeCrO4
(C) 75 mL 1M C2O4-2 (D) 25 mL 1M K2Cr2O7 solution
6. Which of the following quantities are dependent on temperature?
(A) Molarity (B) Normality (C) Molality (D) Mole fraction.
COOH COOK
7. and
COOH COOH behave as acid are well as reducing agent. Then which of the following
COOH COOK
are the correct statements regarding COOH and COOH
COOH COOK
(A) When COOH and COOH behaves as reducing agent, then its equivalent weights are
equal to half of its molecular weight respectively
(B) 1000 mL of 1N solution of each is neutralized by 1000 mL 1N Ca(OH)2
(C) 1000 mL of 1M solution is neutralized by 1000 mL of 1M Ca(OH)2.
(D) 1000 mL of 1M solution is neutralized by 200 mL 2M of KmnO4 in acidic medium.
8. For the reaction
H3PO4 + Ca(OH)2   CaHPO4 + 2H2O
1 mole 1 mole
then which of the following statements are correct ?
(A) the equivalent weight of H3PO4 is 49.
(B) the resulting solution is neutralized by 1 mole of KOH
(C) 1 mole of H3PO4 is completely neutralized by 1.5 mole of Ca(OH)2
(D) none
9. 1 mol of H2SO4 will exactly neutralize
(A) 2 mol of ammonia (B) 1 mol of Ca(OH)2
(C) 0.5 mol of Ba(OH)2 (D) 2 mol of NaOH
10. During the titration of a mixture of NaOH, Na2CO3 and inert substances against HCl.
(A) Phenolpthalein is used to detect the end point when half equivalent of Na2CO3 and full
equivalent NaOH is consumed
(B) Phenolpthalein is used to detect the second end point
(C) Methyl orange is used to detect the final end point
(D) Methyl orange is used to detect the first end point
LEVEL – III Other Engg. Exams
1. 25.4 g of iodine and 12.2 g of chlorine are made to react completely to yield a mixture of ICl
and ICl3. Calculate the ratio of moles of ICl and ICl3.
(A) 1 : 1 (B) 1 : 2 (C) 1 : 3 (D) 2 : 3
2. Calculate the weight of iron which will be converted into its oxide by the action of 18g of
steam on it.
(A) 37.3 gm (B) 3.73 gm (C) 56 gm (D) 5.6 gm
3. It takes 0.15 mole of ClO to oxidize 12.6 g of chromium oxide of a specific formula to
Cr2O72-. ClO- became Cl-. The formula of the oxide is (atomic weight Cr = 52, O = 16)
(A) CrO3 (B) CrO2 (C) CrO4 (D) CrO
4. 8 g of sulphur is burnt to form SO2 which is oxidized by Cl2 water. The solution is treated
with BaCl2 solution. The amount of BaSO4, precipitate is
(A) 1 mole (B) 0.5 mole (C) 0.24 mole (D) 0.25 mole
5. A 10.0 g samples of a mixture of calcium chloride and sodium chloride is treated with
Na2CO3 to precipitate the calcium as carlcium carbonate. This CaCO3 is heated to convert
all the calcium to CaO and the final mass of CaO is 1.62 gms. The % by mass of CaCl2 in
the original mixture is
(A) 15.2% (B) 32.1% (C) 21.8% (D) 11.7%
6. Equal volumes of 1 M each of KmnO4 and K2Cr2O7 are used to oxidize Fe(II) solution in
acidic medium. The amount of Fe oxidized will be
(A) more with KmnO4 (B) more with K2Cr2O7
(C) equal with both oxidizing agents (D) cannot be determined
7. 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) 0.272 (C) 0.816 (D) 0.0227
8. What volume of 0.3 N Cr2O7  /H+ is needed for complete oxidation of 200ml of 0.6 M
FeC2O4 solution.
(A) 1.2 cc (B) 1.2 litre (C) 120 cc (D) 800 cc
9. The normality of a mixture obtained by mixing 100 ml of 0.2 M H2SO4 with 100 ml of 0.2 M
NaOH will be
(A) 0.05 N (B) 0.1 N (C) 0.15 N (D) 0.2 N
10. 1.82 g of a metal required 32.5 ml of N HCl to dissolve it. Then the equivalent weight of
metal is
(A) 14 (B) 28 (C) 42 (D) 56
11. 25.0 ml of HCl solution gave, on reaction with excess AgNO3 solution 2.125 g of AgCl. The
normality of HCl solution is
(A) 0.25 (B) 0.6 (C) 1.0 (D) 0.75
12. 0.1 g of bleaching powder, on reaction with acetic acid and excess KI solution, gave iodine
which reacted with 50 ml of N/5 hypo. The per cent available Cl2 with sample is
(A) 35.5 (B) 17.5 (C) 28.6 (D) 30.2
13. 11.4 gm of a mixture of 1 butene, C4H8 and butane C4H10, was burned in excess oxygen.
35.2 gm of CO2 and 16.2 gm of H2O were obtained. Calculate the percentage by mass of
butane in original mixture.

(A) 50.87% (B) 49.13% (C) 50% (D) none of these
14. 0.7 g of Na2CO3. xH2O is dissolved in 100 ml water, 20 ml of this solution required 19.8 ml of
0.1 N HCl. The value of x is
(A) 4 (B) 3 (C) 2 (D) 1
15. One mole of N2H4 loses 10 mole of electrons to form a new compound Y. Assuming that all
nitrogen appears in the new compound, what is the oxidation state of nitrogen in Y?
(A) +3 (B) –3 (C) –1 (D) +5
LEVEL – IV Match the Column
1. Match the column
Column – I (Reaction) Column – II (Equivalent weight )
(A) NH3 
 NO3- (p) M/3
(B) FeC2O4 
 Fe3+ + 2CO32- (q) M/6
(C) H2SO5 
 S8 (r) M/8
(D) KMnO4 

acidic medium
 (s) M/5
2. Match the column
Column – I (Acid) Column – II (Nature)
(A) H3PO4 (p) Monobasic
(B) H3PO3 (q) Dibasic
(C) H3BO3 (r) Tri basic
(D) EDTA (s) Tetra basic
LEVEL – V Comprehension Type Questions
WRITE-UP I
Iodine Titration
All such titration which involves the direct titration of Iodine with a reducing agent are
grouped under Iodimetry. Iodimetry is employed to determine the strength of reducing agent
such as sodium those sulphate
I2 + Na2S2O3  I– + S4 O6
If iodine is liberated as a result of chemical reaction involving oxidation of an idodide ion by
a strong oxidizing agent in neutral or acidic medium the liberated iodine is then titrated with
reducing agent. Iodometry is used to estimate the strength of oxidizing agent.
For example the estimation of Cu++ with thiosulphate.
Cu++ + I–  Cu2I2 + I2
I2 + S2O3 
 S4O6  I
Starch used as indicator near the end point which form blue colour complex with I3 . The
blue colour disappears when there is no more of free I2.
1. In Iodine titration Iodine remains in solution in the form of

(A) I3 (B) I2
(C) I3 (D) I–
2. In the reaction, 2CuSO4 + 4KI  Cu2I2 + 2K2SO4 + I2 the ratio of equivalent weight of
CuSO4 to its molecular weight is:
(A) 1/8 (B) ¼
(C) ½ (D) 1
3. When 159.50g of CuSO4 in a solution is reacted with KI, then the liberated iodine required
100 ml 1 M Na 2S2O3 for complete reaction, then what is the percentage purity of CuSO4
sample used in making the solution.
(A) 10% (B) 20%
(C) 5% (D) None of these
4. 100 ml of 0.1 N hypo decolourised iodine by the addition of x g of crystalline blue vitriol to
excess of KI. The value of x is
(A) 5g (B) 2.5g
(C) 10g (D) 1.25g
WRITE-UP II
Like acid base titration, in redox titration also, the equivalence point is reached when the
reducing agent is completely oxidized by the oxidizing agent. But contrary to the acid-base
titrations, oxidizing agents can themselves be used as internal indicator in redox titration e.g.
Cr2O72– (orange yellow), Cr3+ (green), MnO4– (purple), Mn2+ (light pink), where strength of the
solution may be expressed as molarity i.e. number of moles of solute per litre of solution.
5. In a titration experiment, a student finds that 23.48 ml of a NaOH solution are needed to
neutralize 0.5468g of KHP (molecular formula KHC8H4O4). What is the concentration in
molarity of NaOH solution?
(A) 0.114 M (B) 0.228M
(C) 0.057M (D) 0.028 M
6. A 16.42 ml volume of 0.1327M KMnO4 solution is needed to oxidize 25.00 ml of a FeSO4

solution in an acidic medium. What is the number of moles of FeSO 4 being oxidized for the
reaction
5Fe2  MnO4  8H 
 Mn 2  5Fe3  4H2 O
(A) 2.18  10–2 ml (B) 1.09  10–2 ml
(C) 0.545  10–2 ml (D) 0.272  10–2 ml
7. A purple coloured solution is added from a 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+
8. Concentrated aqueous sulphuric acid is 98% H2SO4 by mass and has a density of 1.84 g/ml.
What volume of the concentrated acid is required to make 5 litre of 0.50M H2SO4 solution.
(A) 271.7 ml (B) 13.5 ml
(C) 135.85 ml (D) 27.1 ml
WRITE-UP III
KIO3 is an oxidant which is reduced to I2 or ICl depending on the medium whether it is dil.
HCl or 6 M HCl. KI on the other hand is a reductant, which is oxidized to I 2 or ICl depending
on the condition as mentioned above. In IIT-JEE – 1992, a question based on this concept
was asked and the same in slightly modified form but basic spirit remaining the same, reads
as follows:
1.0g sample of AgNO3 containing some background inert impurities was dissolved in water
and solution was treated with 20 ml KI solution. The precipitated AgI was filtered off. The
filtrate containing unreacted KI was back titrated with 7.5 mL 0.1 M KIO3 in 6 M HCl. In
another titration with 10 mL fresh stock solution of KI exactly required 1.0 mL 0.1 M KIO 3
solution for complete oxidation in 6 M HCl solution. Find percent purity of AgNO 3 in the
sample.
A JEE aspirant solved the problem in the following manner.
KIO3 vs. KI titration:
5 1
K I O3 
 I  Cl
 
n-factor = 4
 0.1 M KIO3 is 0.4N
Strength of stock solution of KI
V1N1 = V2N2
10  N1 = 10  0.4
N1 = 0.4 N
No. of m. equiv. of AgNO3 in the sample
= No. of milli equiv. of KI added – No. of milli equiv. of KIO3 conserved in the back titration
= 20 0.4 – 7.5  0.4 = 5
n-factor of AgNO3 in its reaction with KI (reaction being double displacement) is 1 (= charge
carried by cation or anion).
5
So, No. of m. mole of AgNO3 in the sample = 5
1
% Mass of AgNO3 in the sample = 5  103  100  85
9. Correct statement among the following is?

(A) The solution is correct
(B) The solution is wrong as KIO3 under the conditions given in the figure must be reduced
to I2
(C) The solution is wrong as KI must have oxidized to I2 under the condition as laid down in
the question.
(D) The solution is wrong as there is fallacy in the calculation of no. of m. equiv. of AgNO3
10. The correct final answer according to your calculation should be
(A) the same as calculated above (B) 42.5%

(C) 50% (D) 37.5%
11. The volume (mL) of 0.25 M KIO3 needed to oxidize completely 40.0 mL 0.1 M KI in dil. HCl
medium is:
(A) 8.0 (B) 10.4
(C) 3.2 (D) 4.8
12. An aqueous solution containing 0.10g KIO3 (Formula weight = 214) and an excess of KI was
acidified with HCl. The liberated I2 consumed 45.0 ml of thiosulphate. The molarity of sodium
thiosulphate solution is
IO3  I  H I2  H2O
(A) 0.063M (B) 0.0313M
(C) 0.126M (D) 0.252M
13. Hints to Subjective Assignments

LEVEL – I
5. KClO 3  KCl + O2 (Part – I)

x
KClO 3  KClO 4 + KCl (Part – II)
(1 x ) y
To calculate (x) apply POAC for ‘O’ atom in Part (I)

For calculation of y apply POAC for ‘O’ atom in Part (II) and calculate % of KClO 4 in
the residue as follow.
t
% of KCl4 =  100
WKCl(I)  WKCl  y
( II )
7. Let millimoles of Fe3O4 and Fe2O3 in the mixture is x and y respectively. As Fe3O4
and Fe2+ hence n-factor for both is 2.
 Meq. of Fe3O4 + Meq. of Fe2O3 = Meq. of Na2S2O3
50
 2x + 2y = 7.2  1  …(1)
10
In second redox titration
Fe2+  Fe3+ n=1
MnO4  Mn
– 2+
n=5
For Fe2+, n = 1,  For Fe2+ millimoles = milli equivalent
 Millimoles of Fe2+ from Fe3O4 + Millimole of Fe2+ for
Fe3O4 = Meq. of KMnO4
50
 3x + 2y = 4.2  5  …(2)
2
From equation (1) and (2) calculate x and y and proceed further
LEVEL – II
1. For FeSO4, Fe2+  Fe 3 

oxidation
 Fe2+
reduction
Fe2+
oxidation Fe3+   Fe2+
reduction
For FeC2O4
C2O42–
oxidation CO2
3. O3 + 2KI + H2O  2KOH + I2 + O2

Redox changes are I2 + 2e  2I–

2S22+  S 54 / 2 + 2e
8. Meq. of Na2HAsO3 = Meq. of I2 in first case …(1)

Meq. of Na2HAsO3 + Meq. of As2O5 = Meq. of Na2S2O3 second case …(2)
Δ
10. Li2CO3  LiO + CO2
Δ
Na2CO3  No change
Li2CO3 + Na2CO3   LiCl + NaCl + CO2 + H2O
HCl
Meq. of Li2CO3 + Meq. of Na2CO3 = Meq. of HCl
14. Answers
14.1 Subjective
LEVEL – I
1. 3.78 gm 2. 6.1875%
3. 82.32% 4. 1.344
5. 49.8% 6. Pb(NO3)2 = 3.3246gm
7. FeO4 = 17.4% NaNO3 = 1.6754gm
Fe2O3 = 23.7% 8. 4.54 L
9. 72.5% 10. 14.7%, 80.9%
LEVEL – II
1. 7/3 2. 6.5 gm/lit

3. 1.847  10–3% 4. 0.609 gm, 0.7920gm
5. a) 60%; (b) 2.96 gm lit; (c) 0.0812 6. 55.5 lit
7. 18.33 ml 8. 11.6%, 3.57%
9. 88.2% 10. 14.2%
14.2 Objective
LEVEL – I
1. (D) 2. (C)
3. (C) 4. (A)
5. (C) 6. (A)
7. (D) 8. (A)
9. (D) 10. (D)
11. (B) 12. (B)
13. (C) 14. (B)
15. (C) 16. (A)
17. (A) 18. (A)
19. (A) 20. (B)
LEVEL – II
1. (A, C) 2. (A, B, D) 3. (A, B) 4. (A, C)

5. (A,B,C,D) 6. (A, B) 7. (A,B,D) 8. (A, B,C)
9. (A, B, D) 10. (A, C)
LEVEL – III
1. (A) 2. (A) 3. (B) 4. (D)

5. (B) 6. (B) 7. (D) 8. (B)
9. (B) 10. (B) 11. (B) 12. (A)
13. (A) 14. (C) 15. (A)
LEVEL – IV
1. (A - R), (B - P), (C - Q), (D - S)
2. (A - R), (B - Q), (C - P), (D - S)

3.
LEVEL – V
1. (A) 2. (D) 3. (A) 4. (B)

5. (A) 6. (B) 7. (D) 8. (C)
9. (D) 10. (B) 11. (C) 12. (A)
TABLE OF RELATIVE ATOMIC WEIGHTS
At. Name of Symbol of Atomic At. Name of Symbol of Atomic

No. Element Element Weight No. Element Element Weight
89. Actinium Ac 227.0278 80. Mercury Hg 200.5
13. Aluminium Al 26.981 42. Molybdenum Mo 95.9
95. Americium Am 234.0614 60. Neodymium Nd 144.2
51. Antimony Sb 121.7 10. Neon Ne 20.17
18. Argon Ar 39.94 93. Neptunium Np 237.048
33. Arsenic As 74.922 28. Nickel Ni 58.7
85. Astatine At 209.9871 41. Niobium Nb 92.906
56. Barium Ba 137.3 7. Nitrogen N 14.007
97. Berkelium Bk 247.07 102. Nobelium No 259.1
4. Beryllium Be 9.012 76. Osmium Os 190.2
83. Bismuth Bi 208.981 8. Oxygen O 15.999
5. Boron B 10.81 46. Palladium Pd 106.4
35. Bromine Br 79.904 15. Phosphorus P 30.974
48. Cadmium Cd 112.40 78. Platinum Pt 195.0
55. Cesium Cs 132.905 94. Plutonium Pu 244.06
20. Calcium Ca 40.08 84. Polonium Po 208.98
98. Californium Cf 251.079 19. Potassium K 39.10
6. Carbon C 12.011 59. Praseodymium Pr 140.908
58. Cerium Ce 140.12 61. Promethium Pm 144.91
17. Chlorine Cl 35.453 91. Protactinium Pa 231.036
24. Chromium Cr 51.996 88. Radium Ra 226.025
27. Cobalt Co 58.933 86. Radon Rn 222.017
29. Copper Cu 63.54 75. Rhenium Re 186.2
96. Curium Cm 247.07 45. Rhodium Rh 102.905
66. Dysprosium Dy 162.5 37. Rubidum Rb 85.467
99. Einsteinium Es 252.08 44. Ruthenium Ru 101.07
68. Erbium Er 167.27 104. Rutherfordium Rf 261.11
63. Europium Eu 151.96 62. Samarium Sm 150.4
100. Fermium Fm 257.09 21. Scandium Sc 44.956
9. Fluorine F 18.998 34. Selenium Se 78.9
87. Francium Fr 223.019 14. Silicon Si 28.08
64. Gadolinium Gd 157.2 47. Silver Ag 107.868
31. Gallium Ga 69.72 11. Sodium Na 22.990
32. Germanium Ge 72.61 38. Strontium Sr 87.62
79. Gold Au 196.966 16. Sulphur S 32.06
72. Hafnium Hf 178.49 73. Tantalum Ta 180.947
2. Helium He 4.003 43. Technetium Tc 98.906
67. Holmium Ho 164.930 52. Tellurium Te 127.6
1. Hydrogen H 1.008 65. Terbium Tb 158.925
49. Indium In 114.82 81. Thallium Tl 204.3
53. Iodine I 126.904 90. Thorium Th 232.038
77. Iridium Ir 192.2 69. Thulium Tm 168.934
26. Iron Fe 55.84 50. Tin Sn 118.6
36. Krypton Kr 83.80 22. Titanium Ti 47.9
57. Lanthanum La 138.905 74. Tungsten W 183.8
103. Lawrencium Lr 262.11 92. Uranium U 238.036
82. Lead Pb 207.2 23. Vanadium V 50.941
3. Lithium Li 6.94 54. Xenon Xe 131.30
71. Lutetium Lu 174.97 70. Ytterbium Yb 173.04
12. Magnesium Mg 24.305 39. Yttrium Y 88.906
25. Manganese Mn 54.938 30. Zinc Zn 65.3
101. Mendelevium Md 258.1 40. Zirconium Zr 91.22

Stoichiometry Final

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Stoichiometry Final

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RSM79PhISTCH1

In stoichiometric calculations, the mole relationship between different reactants and

The number of moles of a substance can be calculated by various means depending on

e) Number of moles of solute = molarity  volume of solution in litres

Principle of Atom Conservation (POAC)

Applying POAC for ‘O’ atoms

w KClO3 in gm Vol. of O2 at STP

4. Concept of Limiting Reagent

In general, the following steps are adopted in making necessary calculations:

5.2 Calculation involving percent yield

5.3 Weight – Volume Relationship

5.4 Volume – Volume Relationship

Therefore the volume of O2 required would be 5L.

PH2 VH2 nH2 TH2

Illustration 1: A sample of CaCO3 and MgCO3 weighed 2.21 gm is ignited to constant

Solution: CaCO3  CaO + CO2

Solution: Balanced equation

Solution: KBr + NaBr + Ag+  AgBr

Illustration 5: In a gravimetric determination of P of an aqueous solution of dihydrogen

Mass of MnO2 in pyrolusite = 0.8 x g.

Now, think about what is meant by 'heated till constant weight is

When MnO2 is heated it converts to Mn3O4.

 3MnO2 Mn3O4 + O2 … (1)

 we have, 3MnO2  Mn3O4 + O2

Illustration 7: Sodium chlorate, NaClO3, can be prepared by the following series of

2KMnO4 + 16HCl 2KCl + 2MnCl2 + 8H2O + 5Cl2

What mass of NaClO3 can be prepared from 100 cc of concentrated HCl

6. Oxidation and Reduction

i) the gain of oxygen

i) the loss of oxygen

ii) the gain of hydrogen

iii) the gain of electron

iv) the decrease in O.N.

A complete reaction showing oxidation and reduction together is called a Redox

6.1 Oxidation State / Oxidation Number

1. The O.S. of all elements (in any allotropic form) is zero.

ii) NO2 : (2  2) + x = 1 (where ‘x’ is O.S. of N)

iii) NO3 : x + (3  2) = 1 (where ‘x’ is O.S. of N)

iv) In CCl4, Cl has an O.S. of 1

vi) KMnO4: +1 + x + (4  2) = 0

 x = +7 (where x is O.S. of Mn).

6.2 Balancing Redox Equations

Some examples of redox reactions are

a) Sn2+ + 2Hg2+ Hg 22 +Sn4+

b) MnO 4 +5Fe2+ + 8H+  5Fe3+ + Mn2+ + 4H2O

c) Cr 2 O72 + 6Fe2+ + 14H+  6Fe3+ + 2Cr3+ + 7H2O

d) 3Cu + 2NO 3 + 8H+  2NO + 3Cu2+ + 4H2O

3Cl2 + 6OH–  5Cl– +ClO 3 + 3H2O

2Cu+     Cu + Cu2+

2HCHO + OH–  CH3OH + HCOO–

4ClO 3  3ClO 4 + Cl–

3MnO 24 + 2H2O  MnO2 + 2MnO 4 + 4OH–

How to Balance a Redox Reaction

Ion Electron Method

This method involves the following steps :

a) First of all balance the atoms other than H and O.

Solution: a) Step 1 N5+ + 8e  N3–

Step 6 Balance charge by H+

Oxidation Number Method

By inspection, arrive at the co-efficients of the species not undergoing oxidation or

Thus here Cr of K2Cr2O7 is reduced to CrCl3(+6 +3) and Cl of HCl is

Oxidation: 2Cl–1  Cl 02  2 … (a)

Reduction: Cr 26  2Cr+3  6 … (b)

Step (iii) 2Cl–1 Cl20 + 2e–; Cr2+6 + 6e–  2Cr3+