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.
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
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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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
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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, 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
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
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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
On the other hand if we need to calculate the volume of O2 at a different T and P, then
Illustration 2: A mixture of FeO and FeO3 when heated in air to constant weight gains 5%
in weight. Find out composition of mixture.
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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
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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?
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.
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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.
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)].
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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.
Reduction is
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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.
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.
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 OO bond (HOOH).
Considering each O–H bond to be ionic both the oxygen atoms acquire a charge of 1 and
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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:
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
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
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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.
In this we find that Cl2 has been oxidised as well as reduced. Such type of redox reaction
is called Disproportionation reaction. Examples are
R
O
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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:
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
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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
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.
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
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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.
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 MnO4 + 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.
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
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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
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.
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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.
i) M1V1 = M2V2
(conc.) (dilute)
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).
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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.
ii) In this reaction, KMnO4 gets reduced to Mn4+ under neutral or slightly
(weakly) basic conditions.
n = 1 7 1 4 3
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
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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
Illustration 14: Find the n- factor for the reactants in each of the following cases:
i) I I2
ii) I2 I
iv) IO 3 I+
v) CuS Cu2+ + SO2
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.
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.
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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.
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.
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.
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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.
Once NaOH has reacted, it is the turn of Na2CO3 to react. It reacts with HCl in two steps:
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
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The reduction of free iodine to iodide ions and oxidation of iodide ions to free iodine occurs
in these titration’s.
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.
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.
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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.
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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
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
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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.
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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 23 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 C2O42 is
oxidised to CO2
Thus here Mn+2 is reduced to Mn+2 (+7 +2) and carbon in C2O4–2 is
oxidised to CO2.
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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 + 5C2O42 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
2MnO4 + 5C2O42 + 16H+ 2Mn+2 + 10CO2 + 8H2O
w1 1 w 2 1
= 17.5 10–3 ------------ (1)
40 2 53 10
1
= eq. of Na2CO3
2
1 W 1
2 = 25 10–3
2 53 10
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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
34
Equation mass H2O2 = = 17
2
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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
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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
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 nfactor = 5
Applying law of chemical equivalence, equivalents of HCN = equivalents
of KMnO4
Moles nfactor = Molarity nfactor V in litre
0.01 10 = M 5 25 10–3
M = 0.8
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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
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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
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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
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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
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
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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
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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 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
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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
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.
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.
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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.
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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.
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
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.
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10. A mixture containing Li2CO3, Na2CO3 and Na2O was strongly heated at 300C, 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 27C and at
740 mm pressure. Calculate the percentage of Na2O in the mixture.
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12.2 Objective
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
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)
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
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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
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
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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
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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
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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
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(A) NH3
NO3- (p) M/3
(B) FeC2O4
Fe3+ + 2CO32- (q) M/6
(C) H2SO5
S8 (r) M/8
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.
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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.
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
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
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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 = 5 103 100 85
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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
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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
Fe2+
oxidation Fe3+ Fe2+
reduction
For FeC2O4
C2O42–
oxidation CO2
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Δ
Na2CO3 No change
Li2CO3 + Na2CO3 LiCl + NaCl + CO2 + H2O
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
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)
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LEVEL – II
LEVEL – III
LEVEL – IV
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