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CHEMISTRY LECTURE NOTES
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(2012-13)
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Lecture - 01
Classical Concept of Equivalent weight / Mass, Equivalent weight , n-fact or
and Normalit y for Acid, Base and Precipit at e
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CLASSICAL CONCEPT OF EQUIVALENT WEIGHT/MASS :
Number of parts by mass of an element which reacts or displaces from a compound 1.008 parts
by mass of hydrogen, 8 parts by mass of oxygen and 35.5 parts by mass of chlorine, is known as
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the equivalent weight of that element e.g.
2Mg + O2
.
48g 32g
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12g 8g
32 g of O2 reacts with 48 g of Mg
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48 8
8 g of O2 = = 12 g
32
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Equivalent weight of Mg = 12
Similarly, Zn + H2SO4 ZnSO4 + H2
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65.5 g 32.75
65.5
Equivalent weight of Zn = = 32.75 g
2
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3
Al + Cl AlCl3
2 2
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3
27 g × 71 g
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2
111.5 g chlorine reacts with 27 g of Al.
27 35.5
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a factor (say n-factor or valency factor) which is in above three cases is their respective valencies.
Atomic weight
So, equivalent weight (E) = Valency - factor
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M
For acid/base, E Where M = Molar mass
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Basicity / Acidity
M
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For O.A/R.A, E
no. of moles of e – gained / lost
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Page # 2
HCl H+ + Cl–
(v.f. = 1)
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H3PO4 2H+ + HPO4–
(v.f. = 2)
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H3PO4 3H+ + PO43–
(v.f. = 3)
.
H3PO3 H+ + H2PO3–
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(v.f. = 1)
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The valency factor of H3PO3 cannot be 3 as it has only two dissociable H+ ions. So, its valency
factor or dissociable protons is 1 or 2 as one of the H-atom is linked with P atom directly.
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..
:O:
||
nm
HO – P – OH
|
H
CH3COOH CH3COO– + H+
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Similarly,
(v.f. = 1)
(v.f. = 1)
Similarly, valency factor of Al(OH)3 can also be 1 or 2 or 3, depending upon the number of OH–
released.
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salt can be calculated by multiplying the oxidation state of the cation/anion by total no. of atoms
per molecule of the salt. For example
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Equivalent is the term used for amount of substance like mole with the difference that one equivalent
of a substance in different reactions may be different as well as the one equivalent of each
substance is also different.
No. of equivalent is defined as
Wt W W
No. of equivalents of solute =
Eq. wt. E M/n
Page # 3
No. of equivalents of solute = No. of moles of solute × v.f.
NORMALIT Y (N) :
It is defined as the number of equivalents of a solute present in one litre of solution.
Number of equivalent s of solute
Normality (N) = Volume of solution( in litres)
Let the weight of solute be w g, equivalent mass of solute be E g/eqv. and the volume of solution
be V litre.
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Weight of solute w
Number of equivalents of solute =
co
Equivalent mass of solute E
W 1000
N = E V( in ml)
.
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W
Number of equivalents of solute = = N × V (in litre)
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E
Normality = Molarity × v.f.
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Dilution Law N1V1 = N2V2
For two solution, of same solute when mixed, new normality is given as :
N1V1 N 2 V2
nm
N
V1 V2
0.74 1000 2
Sol. (a) N=
74 5
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N 4
N=4 M= =2
v.f . 2
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3.65 1000
(b) N= = 0.5
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36.5 200
N 0 .5
ee
and M= = = 0.5
v.f. 1
1
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2 1000 0 .4
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Lecture - 02
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Equivalentweight,n-factorandNormalityforOxidantandReductant
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Conceptof Equivalentweight/Mass:forRedoxReactions:
For the calculation of n-factor of oxidising agent or reducing agent, the method depends upon the
change in oxidation state of the species considered. We will discuss them one by one.
(i) When only one atom undergoing either reduction or oxidation change e.g.
7 2
H
M n 2
M nO 4
(v.f = 5)
Page # 4
In such a case, we consider the change in oxidation state of atom undergoing oxidation or
reduction change per molecule as the n-factor of the species.
valency factor = 1(7 – 5) = 2
2 3
Fe 2 Fe 3 valency factor = 1 (3 – 2) = 1
(v.f = 1)
3 4
C2O 24 – 2CO 2 valency factor = 2(4 – 3) = 2
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6 3
Cr 2O 72 2Cr 3 valency factor = 2(6 – 3) = 6
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Ex. Calculate the valency factor of the reactant (oxidant or reductant) in the following cases.
.
(i) IO3– I2
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(ii) Zn ZnO22–
(iii) NO3– NH3
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(iv) NH4+ NH2OH
5 0
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Sol. (i) O 3 valency factor = 1(5 – 0) = 5
0 2 2
(ii) ZnO 3 ZnO valency factor = 1(2 – 0) = 2
(iii)
5
NO 3 NH 3
–3 1
nm
valency factor = 1(5 + 3) = 8
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3 1
(iv) N H4 NH2OH valency factor = 1(–1– (– 3)) = 2
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
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(ii) Salts which reacts in such a way that only one atom undergoes change in oxidation state but
appears in two products with the same oxidaiton state.
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In such a case the method of calculation of valency factor remains the same i.e., we will calculate
the change in oxidation state of the atom per mole of that substance (reactant).
6 2 3 3
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Cr2 O 72 Cr 3 Cr 3
In this example, oxidation state of Cr changes from +6 to +3 in both the products.
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state but goes in two products with different oxidation state as a result of either only oxidation or
only reduction.
7 2 6
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3 Mn O 4 2Mn 2 Mn 6
In such a case, it is impossible to calculate the valency factor until and unless one knows that
how much of MnO4– is changing to Mn2+ and how much to Mn6+, and if one knows the balanced
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equation then there is no need of calculation of valency factor. Nevertheless in such case the
valency factor can be calculated by deducing the total change in oxidation state divided by total
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number of atom undergoing reduction/oxidation change. So for the calculation of n-factor in the
above example, out of three moles of MnO4–, two moles are being converted to Mn2+ and one mole
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2(7 2) 1(7 6) 11 11
changes to Mn+6. So total decrease in oxidation state of Mn = . So, v.f.= .
3 3 3
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Ex. Calculate the n-factor of the reactant (oxidant or reductant) in following cases.
(i) 3MnO4– 2Mn2+ + Mn4+
(ii) 2MnO4– Mn2+ + Mn6+
1 13
Sol. (i) v.f. = [2(7 – 2) + 1(7 – 4)] =
3 3
Page # 5
1
(ii) v.f. = [1(7 – 2) + 1(7 – 6)] = 3
2
(iv) Salts which react in such a way that only one atom undergoes change in oxidation state in two
product, in one product with changed oxidation state and in other product with same oxiation
state as that of reactant.
In such case also one cannot calculate the valency factor without knowing the balanced chemical
equation because one must known how much of atom has changed its oxidation state.
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For example.
K2Cr2O7 + 14HCl 2KCl + 2CrCl3 + 3Cl2 + 7H2O
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Let us calculate the valency factor of HCl. Out of 14 moles of Cl– (in HCl) only 6 moles of Cl– are
changing its oxidation state from –1 to 0 in the product Cl2 and the oxidation state of remaining
8 Cl– ions remains same in KCl and CrCl3. So, total no. of moles of electrons lost by 14 moles of
.
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HCl is 6. So each mole of HCl takes up 6/14 i.e., 3/7 moles of electrons and hence valency factor
of HCl is 3/7.
(v) Salts which react in such a way that two or more atoms in the salt undergoes change in oxidation
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states as a result of either oxidation or reduction.
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Let us consider the following example,
3 4
FeC 2 O 4 Fe 3 2 CO2
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In this case, the oxidation of both Fe2+ and C3+ are changing from +2 and +3 to +3 and +4
respectively. In such a case we will calculate the valency factor of the salt as the total increase
or decrease in oxidation state per mole of the salt. As one can see that one mole of FeC2O4
contains one mole of Fe2+ and one mole of C2O42– (i.e. 2 carbon atoms per mole of C2O42–.
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Total change in oxidation state = 1(3 – 2) + 2(4 – 3) = 3
v.f. = 3
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Ex. Calculate the valency factor of the reactant (oxidant or reductant) in following cases
2 1 3 4
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(i) Fe S 2 Fe 2O 3 SO 2
(vi) Salts which react in such a way that two atoms undergoing change in oxidation state but one
undergoing oxidation and other reduction.
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In such a case one has to calculate the change in oxidation state of either the atom being
oxidized or the atom being reduced. For example.
3 6 0 3
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6 unit. So, we can consider either oxidation or reduction product for the calculation or valency
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Ex. Calculate the valency factor of the reactant (oxidant or reductant) in following case
5 –2 1 0
K Cl O 3 K Cl O 2
Sol. v.f. for oxidation = 3 (0–(–2)) = 6
Page # 6
v.f. for reduction = 1 (5–(–1)) = 6
(vii) Species which undergoes disproportionation reaction :
Case 1 : When the number of moles of atoms being oxidized is equal to the number of moles of
atoms being reduced.
The valency factor can be calculated by knowing the balanced chemical equation and considering
any of the change taking place. Say for example
2H2O2 2H2O + O2
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Out of 2 moles of H 2O 2 consumed in the reaction, one mole of H 2O 2 is being oxidized
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(H2O2 O2) and one mole of H2O2 is being reduced
(H2O2 2H2O). First consider the oxidation reaction
.
1 0
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H2 O 2 O 2
v.f. = 2(0–(–1) = 2
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Again, considering reduction reaction
2
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1
H2O 2 H2O
v.f = 2(–1– (–2)) = 2
nm
So, valency factor of H2O2 either considering oxidation or reduction is same i.e. 2.
Case 2 : In those disproportionation reactions where the number of moles of substance getting
oxidised or reduced are not identical.
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The valency factor is calculated by first knowing the total number of moles of electrons exchanged
(lost or gained) by the number of moles of substance appearing in the balanced equation and
then dividing the number of moles of electrons exchanged by the number of moles of substance,
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to get the number of moles of electrons exchanged by one mole of the substance, which is the
valency factor of that substance.
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For example,
12 OH – + 6Br2 10Br– + 2BrO3– + 6H2O.
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In this reaction, the electrons released by the oxidation of some of the Br2 are the someones as
used up in the reduction of rest of the Br2.
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In overall reaction, the number of moles of electrons lost or gained by 6 moles of Br2 are 10.
Therefore, by each mole of Br2, the number of moles of electrons exchanged are 10/6 or 5/3. This
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List of common oxidising and reducing agents (with their valency factor):
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2–
Cr2O 7
Cr3+
v.f. = 2(6 – 3) = 6
Page # 7
O3¯ ¯
v.f. = 1(5 – (–1)) = 6
2 ¯
v.f. = 2(0 –(–1)) = 2
m
v.f. = 1(1 – (–1)) = 2
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v.f. = 2(–1 – (–2)) = 2
.
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NO3¯ NO2
v.f. = 1(5 – 4) = 1
NO3¯ NO
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v.f. = 1(5 – 2) = 3
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NO3¯ N2O
v.f. = 1(5 – 1) = 4
nm
v.f. = 1(5 – (–3)) = 8
2–
O3 O2 + O
v.f. = 1(0 – (–2)) = 2
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K2Cr2O7 is generally not used as O.A. in basic medium, because
In dil basic medium Cr2O72– goes into CrO42– and some of radicals(cations) will get precipitated by
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In basic medium many cationic radicals gets precipitated as hydroxides and hence the titrations will
not be that effective.
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Lecture - 03
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EquivalentConceptforAcidBaseTitrationandPrecipitation
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Reactions:
LAW OF EQUIVALENCE :
The biggest problem you might face when you solve any problem of stoichiometry is the lack of
the knowledge of the chemical reactions involved. A problem might look impossible to solve
because the reactions involved are not known and the same problem looks extremely simple if
the reaction is known. Here we are going to develop a technique by which you would be in a
position to solve a problem without the knowledge of complete balanced reaction. The law that
governs this technique is called law of equivalence. Let us first understand that what information
a balanced chemical equation conveys to us. It tells us the molar ratio of the reactants and
Page # 8
products. Now if we get this molar ratiox without the complete balanced reaction, then it serves
the purpose of the reaction itself. This ratio can be known by knowing the valency factors of
various reactants of the reaction.
Whenever two substances react in such a way that their valency factors are in the ratio
of x : y, they would always react with each other in the molar ratio of y : x in a balanced
chemical reaction.
Since the number of equivalents of a substance is valency factor multiplied by the number of
m
moles, the equivalents of one reactant is x × y and the equivalents of the other is y × x. Hence
they are equal.
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Thus according to the law of equivalence, whenever two substances react the equivalents
of one will be equal to the equivalents of other and is also equal to the equivalents of
.
each of the products.
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i.e. if aA + bB + cC dD + eE + fF then the equivalents of A, B, C, D, E and F are equal to
each other irrespective of the molar ratio in which they are reacting or produced. Thus, the
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advantage with equivalent concept is that a balanced chemical reaction is not needed.
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For an acid base reaction :
At equivalence point, equivalent of Acid = equivalent base.
nm
Ex. The two acids H2SO4 and H3PO4 are neutralised separately by the same amount of an
alkali when sulphate and dihydrogen orthophosphate are formed respectively. Find the ratio of
the masses of H2SO4 and H3PO4.
Sol. H2SO4 2H+ + SO42–
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v.f. = 2
v.f. = 1
Titrations is procedure for determining the concentration of a solution by allowing a carefully measured
volume to react with a standard solution of another substance, whose concentration is known.
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Standard solution : Solution whose concentration is known and is taken in burrette, also called
Titrant.
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Ex :- Oxalic acid, K2Cr2O7 , AgNO3, CuSO4, ferrous ammonium sulphate, hypo etc.
(b) Secondary titrants/standard : These titrants can not be accurately weighed and solutions are to be
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Page # 9
Titrate : Solution consisting of substance to be estimated, generally taken in a beaker .
Equivalence point : When no. of equivalents of titrant added becomes equal to no. of equivalents of
titrate.
At equivalence point :
n1M1V1 = n2M2V2
Indicators : An auxiliary substance added for physical detection of
completion of titration at equivalence point. These generally show
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colour change on completion of titration.
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Types of Titration :
(a) Acid-base titration
.
(b) Redox titration
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(c) Precipitation titration Details not required
(d) Complexometric titrations Details not required
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Acid-base titrations :
The detals of acid-base titration & titration curve will be discussed in ionic equilibrium chapter.
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Here we will discuss only quantitative aspects of acids, bases and salts at equivalence point :
Simple acid base titration :
Acid + Base Salt + water (neutralization reaction)
At equivalence point
eq. of acid = eq. of base.
nm
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Ex. 20 g H3PO4 is dissolved in water & made up to one litre. 50 ml of this solution requires 50 ml of
NaOH solution for complete neutralization. Determine the molarity of NaOH solution. Also determine
the vol of NaOH used if neutralization is carried out upto single stage.
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n=3 n=1
eq. of H3PO4 = eq. of NaOH
20 50 3
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or = 50 × M × 1 × 10–3
1000 98
or M = 0.612
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20 50 1
= V × 0.612 × 1 × 10–3 V = 16.67 ml
1000 98
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Lecture - 04
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Agents&theirRedoxTitration
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Page # 10
160 328
Fe 2O 3 3CO 2Fe 3CO 2
1600 g
3 28
CO required to reduce 1600 g Fe2O3 = 1600 = 3 × 28 × 10 = 840 g
160
1 16 28
C O 2 CO
2
m
16
O2 required to produce 840 g CO = 840 = 480 g.
28
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Method 2 : (Equivalent concept)
Eq. of O2 = eq. of Fe2O3
.
W 1600 ( 3 ) 0
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Fe 2 O 3 Fe
8 160 / 6
v.f = 2(3 – 0) = 6
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8 1600 6
W= = 480 g
160
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Ex. Find the number of moles of kMnO4 needed to oxidise one mole Cu2S in acidic medium.
Sol. The reaction is KMnO4 + Cu2S Mn2+ + Cu2+ + SO2
v.f. = 5 v.f. = 2(2 – 1) + 1 (4 – (–2))
nm
=8
Ex. The number of moles of oxalate ions oxidized by one mole of MnO4– ion in acidic medium .
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5 2 3 5
(A*) (B) (C) (D)
2 5 5 3
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Sol. (A)
H
C2O42– + MnO4–
CO2 + Mn2+
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v.f. = 2 v.f. = 5
5
x(mole) × 2 = 1 × 5 ; x= 2
Ex. How many moles of KMnO4 are needed to oxidised a mixture of 1 mole of each FeSO4 & FeC2O4 in
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acidic medium
4 5 3 5
(A*) (B) (C) (D)
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5 4 4 3
Sol. (A)
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v.f. = 5 v.f. = 3
Page # 11
Ex. 25 gm sample of ferrous sulphate (FeSO4. 7H2O) dissolved in water and dilute H2SO4 and made 1 ltr.
25 ml of solution required 10 ml of 0.04 M KMnO4 solution for complete oxidation. Find the percentage
of FeSO4. 7H2O (molecular weight = 278) in the sample
Sol. m eq. of KMnO4 = 10 × 0.04 × 5 = 2 (in 25 ml)
m eq. of KMnO4 = 2 × 40 = 80 (in 1000 ml)
m eq. of FeSO4 . 7H2O = 80
80 278
% of FeSO4 . 7H2O = × 100 = 88.96
1000 25
m
Ex. How many millititers of 0.02 M KMnO4 solution would be required to exactly titrate 25.00 mL of 0.02 M
co
Fe(NO3)2 solution.
Sol. Method- 1 (Mole Concept) :
Starting with 25.0 mL of 0.2 MFe2+, We can write.
.
Millimoles of Fe2+ = 25.0 x 0.2
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and in volume V (in milliliters of the MnO4¯)
Millimoles of MnO4¯ – V (0.02)
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The balanced reaction is :
MnO4¯ + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
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This requires that at the equivalent point,
V(0.02) ( 25 ) (0.2)
nm
=
1 5
V = 50.00 ml
Method- 2 (Equivalent Concept) :
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Equivalents of MnO4¯ = 5 x moles of MnO4¯
Normality of MnO4¯ = 5 x molarity of MnO4¯
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2
= VFe 2 x normality of Fe
For our 0.02000 M MnO4¯ solution
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Ex. A sample weighing 2.198 gm and containing a mixture of AO and A2O3 takes 0.015 mole of K2Cr2O7 to
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oxidise the sample completely to form AO4¯ and Cr3+. If 0.0187 mole of AO4¯ is famed. What is at.wt.
of A ?
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AO A O
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2 7
6 AO 5K 2 Cr2O 7 6 AO –4 Cr 3
v.f 5 v .f 6 v .f 5
3 7
6 A 2 O 3 4K 2Cr2 O 7 12 AO 4–
v.f 8 v .f 4
Page # 12
5x (2.198 – x ) 8
+ = 0.015 × 6. .....(i)
( A 16) (2A 48)
Also, total molar of AO4– formed.
x 2 (2.198 – x )
= + = 0.0187 .....(ii)
( A 16) (2A 48)
Solving equation (i) and (ii), we get,
A = 100 g/mole.
m
Redox Titration :
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Estimation By titrating Reactions
of with
.
1. Fe2+ MnO4¯ Fe2+ Fe3+ + e–
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MnO4– + 8H+ + 5e– Mn2+ + 4H2O
2. Fe2+ Cr2O72– Fe2+ Fe3+ + e–
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Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
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3. C2O42– MnO4¯ C2O42– 2CO2 + 2e–
MnO4– + 8H+ + 5e– Mn2+ + 4H2O
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4. H2O2 MnO4¯ H2O2 2H+ + O2 + 2e–
MnO4– + 8H+ + 5e– Mn2+ + 4H2O
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5. As2O3 MnO4– As2O3 + 5H2O 2AsO43– + 10H+ + 4e–
MnO4– + 8H+ + 5e– Mn2+ + 4H2O
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(a) Permanganate Titrations : KMnO4 as O.A. in acidic medium (generally) dil H2SO4 is used not HNO3
or HCl to make medium acidic because :
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M
Redox Changes : C23+ 2C4+ +2e– E H2 C 2 O 4
2
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M
5e– + Mn7+ Mn2+ E KMnO 4
5
Indicator : KMnO4 acts as a self indicator.
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M
Redox Changes : Fe2+ Fe3+ + e– EFeSO 4
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1
M
Mn7+ + 5e– Mn2+ E KMnO 4
5
Indicator : KMnO4 is self indicator
Ex. A sample of hydrazine sulphate [N2H6SO4] was dissolved in 100 mL water. 10 mL of this solutions was
treated with excess of FeCl3 solution and named to complete the reaction. Ferrons ions formed were
estimated and it required 20 mL of M/50 KMnO4 solution. Estimate the amount of hydrazine sulphate
in one litre of solution.
Page # 13
Given 4Fe3+ + N2H4 N2 + 4Fe2+ + 4H+
MnO4¯ +5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
1 1 1000
Sol. Amount of hydrazine sulphate in 1 litre solution = 20 × × 5 × 10–3 × × × 130.
50 4 10
= 6.5 g.
(b) Dichromatic Titrations : K2Cr2O7 in acidic medium, mainly for Fe2+, ¯ etc. Diphenylamine is taken
m
as the indicator. After oxidation it becomes blue in colour.
Ex. K2Cr2O7 Vs Ferrous ammonium sulphate.
co
The reaction : 6[FeSO4(NH4)2 SO4 . 6H2O] + K2Cr2O7 + 7H2SO4
3Fe2(SO4)3 + Cr2(SO4)3 + K2SO4 + 6(NH4)2SO4 + 43H2O.
.
es
Redox Changes :
M
Fe2+ Fe3+ + e– EFeSO 4
1
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M
EF2Cr2O 7
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6e– + Cr26+ Cr23+
6
Lecture - 05 nm
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Iodometric/IodimetricTitration,n-factorinDisproportionationand
ComproportionationRedoxReactions,Calcualtionof%Availbale
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Chlorine
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Disproportionation :
List of some important disproportionation reactions
1. H2O2 H2O + O2
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v.f. = 2
v.f. = 2
v.f. = 5/3
v.f. = 3
v.f. = 16
Page # 14
4ClO3– Cl– + 3ClO4–
v.f. = 3/2
Redox Titration :
Estimation By titrating Reactions
of with
m
AsO33– BrO3– AsO33– + H2O AsO43– + 2H+ + 2e–
BrO3– + 6H+ + 6e– Br– + 3H2O
co
Titrationsinvolvingiodine:
.
Compound contains iodine are widely used in titrations.
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(i) Iodide ions can be oxidised to 2 by suitable oxidising agent
2¯ (aq) 2(s) + 2e¯
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(ii) Iodine (V) ions, O3¯ , will oxidise ¯ to 2
od
O¯ (aq) 5¯ (aq) + 6H+ (aq) 32(s) + 3H2O ()
nm
(iii) Thiosulphate ions, S2O32– , can reduce iodine to iodide ions.
2S2O (aq) (s) S4 O62– + 2–
colourless black colourless
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Although solid iodine is black (deep violet) and insoluble in water, it is converted into soluble tri-iodide
ions 3¯ 2 (s) + ¯ ¯ (aq)
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Iodimetric titration :
In iodimetric titration, 2 solution is taken in burette and reducing agent like sodium thiosulphate,
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Indicator - Starch
Iodimetric titrations have been summarised in Table.
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Page # 15
Ex. The sulfur content of a steel sample is determined by converting it to H2S gas absorbing the H2S in
10.0 mL of 0.00500 M I2 and then back titrating the excess I2 with 0.00200 M Na2S2O3. If 10 mL Na2
S2O3 is required for the titration, how many milligrams of sulfur are contained in the sample?
Reactions :
H2S + I2 S + 2I– + 2H+
I2 + 2S2O32– 2I– + S4O62–
Sol. Used mili moles of I2 = .05 - .002x10/2
= .04 = mm of H2S
m
wt of sulfur = 1.28.
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Iodometric Titration :
This is an indirect method of estimation of iodine. An oxidizing agent is made to react with excess of
solid K. The oxidizing agent oxidises – to 2 . The iodine is then made to react with Na2S2O3 solution.
.
es
Na 2 S 2 O 3
O.A. + K 2 Na + Na2S4O6 .
Iodometric titrations have been summarised in table.
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S.No. Estimation of Reaction
od
1. 2 2 + 2Na2S2O3 2Na + Na2S4O6
or, 2 + 2S2O32– 2¯ + S4O62–
nm
2. CuSO4 2CuSO4 + 4K Cu22 + 2K2SO4 + 2
or, Cu2+ + 4¯ Cu22 + 2
white ppt
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3. CaOCl2 CaOCl2 + H2O Ca(OH)2 + Cl2
Cl2 + 2K 2KCl + 2
or, Cl2 + 2¯ 2Cl¯ + 2
ra
4. MnO2 MnO2 + 4HCl(conc.) MnCl2 + Cl2 + 2H2O
pa
Page # 16
Ex. An aqueous solution containing 0.10g KIO3 (formula weight = 214) and an excess of K was acidified
with HCl. The liberated 2 consumed 45.0 ml of thiosulphate. Determine the molarity of sodium
thiosulphate solution is
O3– + – + H+ 2 + H2 O
(A*) 0.063M (B) 0.0313M (C) 0.126M (D) 0.252M
HCl
Sol. KIO3 + 5KI 3I2
v.f. = 5 v.f. = 1
m
0.1 0.3
mole (excess) mole
214 214
co
I2 + 2Na2S2O3
v.f. = 2 v.f. = 1, 45 ml, M(say)
.
es
0.3 2 0.3
mole = 45 × M × 10–3 M = 0.0623 M.
214 214
ul
Ex. A solution of 0.2 g of a compound containing Cu2+ and C2O42– ions on titration with 0.02 M KMnO4 in
presence of H2SO4 consumes 22.6 mL oxidant. The resulting solution is neutralized by Na2CO3,
od
acidified with dilute CH3COOH and titrated with excess of KI. The liberated 2 required 11.3 mL of 0.05
M Na2S2O3 for complete reduction. Find mole ratio of Cu2+ and C2O42– in compound.
nm
H
Sol. 5C2O42– + Mn2+ + CO2
2KMnO4
v.f. = 2 v.f. = 5
5
22.6 × 0.02 m mole
tio
× 22.6 × 0.02 m mole
2
v.f. = 2 v.f. = 1
11.3 0.05
m mole 11.3 × 0.05 m mole
pa
–
2Cu2+ + 4I Cu22 + 2
re
5
C2O42– = × 22.6 × 0.02 m mole
ee
2
Cu2 11.3 0.05 2 1
Required mole ratio of 2– = = 0.5.
en
C 2O 4 5 22.6 0.02 2
.je
The weight % of available Cl2 from the given sample of bleaching powder on reaction with dil acids or
w
CaOCl 2 CO 2 CaCO 3 Cl 2
Page # 17
Method of determination of available chlorine :
CaOCl2 + 2CH3COOH Ca(CH3COO)2 + H2O + Cl2
(Sample of bleaching powder)
m
End point is indicated by disappearance of blue colour.
Let M = Molarity of hypo (Na2S2O3) solution
co
millimoles of Cl2 produced = moles of I2 used by hypo
M V
.
= where V = vol of hypo solution used in ml.
es
2
M V 10 3
mass of Cl2 produced =
ul
× 71
2
= 35.5 × M × V × 10–3
od
35.5 M V 10 3
% of available chlorine = × 100
W
or % of available Cl2 =
3.55 M V nm
where W = amount of belaching powder taken in gm.
tio
W
Ex. 3.55 gm sample of bleaching powder suspended in H2O was treated with enough acetic acid and K
ra
solution. Iodine thus liberated required 80 ml of 0.2 M hypo for titration. Calculate the % of available
chlorine.
pa
3.55 0.2 80
Sol. % of available Cl2 = = 16%
3.55
re
Ex. Calculate the percentage of available chlorine in a sample of 3.55 g of bleaching powder which
tp
was dissolved in 100 mL of water, 25 mL of this solution, on treatment with KI and dilute acid,
required 20 mL of 0.125 N sodium thiosulphate solution.
ee
3.55 20 0.125
Sol. % of available Cl2 = = 10%
3.55
25
en
100
Lecture - 06
.je
Examples
w
Ex. 30 ml of a solution containing 9.15 g of a salt KxH(C2O4)z. nH2O per litre required 27 ml of 0.12 N NaOH
w
for neutralization. The same quantity of solution was also found to require 36 ml of 0.12 N KMnO4
solution for complete oxidation. Calculate the value of x, y, z and n.
Sol. KxHy(C2O4)z. nH2O + NaOH Products
v.f. = y 27 ml, 0.12 N
9.15 30 y
= 27 × 0.12 × 10–3 ... (1)
1000 M
Page # 18
KxHy(C2O4)z. nH2O + KMnO4 CO2 + other products
v.f. = 2z(4–3) = 2z 36 ml, 0.12 N
9.15 30 2z
= 36 × 0.12 × 10–3 ... (2)
1000 M
(2) 2Z 4 Z 2
or
(1) y 3 y 3
m
x 2z
From charge balance x + y – 2z = 0 or 1
y y
co
x 4 1 x 1
1
y 3 3 or y 3
.
es
x:y:z = 1:3:2
x = 1, y = 3, z = 2.
Here we are assuming that x, y, & z are smallest possible integer.
ul
From (1) M = 254
KH3(C2O4)2 .nH2O
od
M = 39 + 3 + 176 + 18 n
or 254 = 218 + 18 n or n = 2.
nm
Back Titration :
Let us consider that we have an impure solid substance ‘Z’ weighing ‘w’gram & we are required to
calculate the percentage purity of Z in the sample. We are also provided with two solutions ‘X’
tio
(Normality = N1) andY (Normality = N2).
For the back titration to work, following conditions are to be satisfied.
(a) Compounds ‘X’, ‘Y’ and ‘Z’ should be such that ‘X’ & ‘Y’ react with each other.
ra
(b) ‘X’ and pure ‘Z’ also reacts with reach other but the impurity present in ‘Z’ does not react with
‘X’.
pa
Relation (3) is true only when valency factor of X in reaction (1) and reaction (2) are same.
Ex. 5 g of a sample of Ca(OH)2 is dissolved in 50 ml of 0.5 N HCl solution. The excess of HCl is back
en
titrated with 0.3 N NaOH. The vol of NaOH used is 10 ml. Calculate % purity of Ca(OH)2.
Sol. Let pure Ca(OH)2 = xg
.je
x2
= 50 × 0.5 × 10–3 – 10 × 0.3 × 10–3
74
or x = 0.814 g
0.814
% purity = × 100 = 16.28%.
5
Page # 19
Double Titration :
Purpose : To find the % composition of an alkali mixture.
Consider a mixture NaOH, Na2CO3 and NaHCO3.
To determine it’s % composition, make a solution of this mixture and then add two indicators in
it, namely phenolphthalein and methyl orange. Now titrate this alkali solution with HCl solution.
NaOH is the strongest base among the mixture of three and NaHCO3 is the weakest. So NaOH
react first with HCl completely then Na2CO3 and then NaHCO3.
m
NaOH + HCl NaCl + H 2O .... (1)
v.f. = 1
co
Na2CO3 + HCl NaHCO3 + NaCl .... (2)
v.f. = 1
.
NaHCO3 + HCl NaCl + H2CO3 .... (3)
es
v.f. = 1
Note that phenolphthalein changes colour only when the weakly basic NaHCO3 is present
ul
& Methyl orange changes colour only when H2CO3 is present in the solution.
When we keep on adding HCl, the pH of the solution decreases. Phenolphthalein changes colour
od
when reaction (2) is complete. This is called phenolphthalein endpoint, At this point.
eq. of HCl used = eq. of NaOH + eq. of Na2CO3 (with v.f. = 1) .... (4)
nm
Also from equation (2),
eq. of NaHCO3 produced in reaction (2) = eq. of Na2CO3 consumed in reaction (2) .... (5)
If we keep on adding HCl, the pH again decreases & when all the NaHCO3 reacts to form NaCl &
H2CO3 the solution becomes weakly acidic due to presence of weak acid H2CO3. At this point,
tio
methyl orange changes colour since it requires weakly acidic solution to do so. This point is
called methyl orange end point.
At this point.
ra
Total eq. of HCl used = eq. of NaOH + eq. of Na2CO3 (v.f. = 1) + eq. of NaHCO3 produced in
reaction (2) + eq. of NaHCO3 present in the original mixture. or,
pa
Total eq. of HCl used = eq. of NaOH + 2 × eq. of Na2CO3 (v.f. = 1) + eq. of NaHCO3. .. (6)
Also,
re
eq. of HCl used after phenolphthalein end point = eq. of Na2CO3 (v.f. = 1) + eq. of NaHCO3. .. (7)
using equation (4) and (6) we can determine % composition of the mixture.
tp
Ex. A solution of 3 gm mixture containing Na2CO3, NaHCO3 and NaOH was titrated with 1 N HCl vol of
HCl used = 34.4 ml when only phenolphthalein is used as indicator and 55.8 ml when methyl
ee
orange is used as indicator from the very beginning. Calculate % composition of the mixture.
Sol. Let NaOH = x g
Na2CO3 = y g
en
x y
1 × 34.4 × 10–3 = ... (1)
40 106
w
x 2y 3 ( x y )
1 × 55.8 × 10–3 = ... (2)
40 106 84
w
1
% of NaHCO3 = × 100 = 33.33%
1 1 1
Page # 20
Similarly % of NaOH = 33.33%
% of Na2CO3 = 33.33%
Ex. One litre of acidified KMnO4 containing 15.8 g KMnO4 is decolorized by passing sufficient SO2.
If SO2 is produced by FeS2, what is the amount of FeS2 to give desired SO2?
H
Sol. 2KMnO4 + 5SO2
Mn2+ + S+6
v.f. = 2 v.f. = 2
m
15.8 1 5 1
mole mole
158 10 2 10
co
FeS2 2SO2
.
1 5 1 5 1
es
mole mole
2 2 10 2 10
ul
= mole
8
od
1
= (56 + 64)g = 15 g.
8
Ex.
nm
1g sample of AgNO3 is dissolved in 50 mL of water. It is titrated with 50 mL of K solution. The Ag
precipitated is filtered off. Excess of KI in filtrate is titrated with M/10 KO3 in presence of 6M HCl till all
¯ converted into ICl. It requires 50 mL of M/10 KIO3 solution. 20 mL of the same stock solution of KI
tio
requires 30 mL of M/10 KIO3 under similar conditions. Calculate % of AgNO3 in sample. The reaction
is : KIO3 + 2KI + 6HCl 3ICl + 3KCl + 3H2O
ra
1 50
re
C + D
E .....(2)
eq. of A reacted = eq. of B reacted = eq. of C = eq. of D reacted = eq. of E produced. .....(3)
w
This statement will be true only when v.f. of C in reaction(1) = v.f. of C in reaction(2) and C
produced in reaction(1) is completely consumed by reaction(2).
w
Page # 21
x
eq. of E produced = n × nC.
C
Note : Thus the equivalent of a substance produced and reacted can be equal only
when in the two reactions its valency factor is same otherwise such modification is
required. So at any point when a substance is produced in a reaction which further
reacts in another reaction, we need to see that such modification is required or not.
m
Ex. When x g of S is burnt it forms SO2 which is oxidized by Cl2 water to SO42– ion. Calculate the
weight of SO42– ion produced ?
Sol. 1st Method : (By Mole Concept)
co
S + O2 SO2
.
x x
es
Mole mole mole
32 32
ul
x x
mole mole
od
32 32
x
=
nm
× 96 = 3x gm.
32
2nd Method : (By Equivalent Concept)
0 ( 4 )
S SO 2 .....(1)
tio
v.f.= 4
xg v.f.=4
ra
( 4 ) ( 6)
SO 2 SO 24– .....(2)
pa
v.f.=2 v.f.=2
re
x
eq. of SO2 produced = eq. of S consume = × 4.
32
tp
4x
or eq. of SO2 produced = (w.r. to v.f. = 4)
32
ee
4x
= (w.r. to v.f. = 1)
32 4
en
4x
= × 2(w.r. to v.f. = 2).
32 4
.je
= × 2 eq. = eq.
32 4 16
w
x
eq. of SO42– produced = eq.
w
16
x
moles of SO42– produced = mole.
16 2
x
mass of SO42– produced = × 96 = 3x gm.
32
Case ii : – When two reactants combine to give same product.
Page # 22
HCl
Ex. KIO3 + KI I2
Given x g of KIO3. Calculate moles of I2 produced.
This problem can be solved by mole concept after balance the equation:
Method : 1 (Mole Concept )
( 5 ) (–5 ) 0
KIO 3 +
KI I2
v.f. = 5 v.f.=1
m
Since v.f. of KIO3 = 5 and KI = 1. So the molar ratio in which they react would be 1 : 5.
KIO3 + 5KI 3I2 (From POAC)
co
x 3x
mole mole
M M
.
es
3x
Moles of I2 produced = mole. (where M = molar mass of KIO3).
M
Case iii : – Back Titration in which excess B is back titrated but the v.f. of B is different in
ul
two reaction.
For Ex.
od
nm
.....(1)
tio
.....(2)
ra
pa
This problem can be solved by mole concept after balance the equation:
re
Case iv : When more than one element of a compound are oxidized and both the elements
goes in different products.
This problem also can be solved by mole concept after balance the equation:
tp
Ex. Hydrogen peroxide solution (20 ml) reacts quantitatively with a solution of KMnO 4
(20 ml) acidified with dilute H2SO4. The same volume of the KMnO4 solution is jest decolourised
en
H
H2O2 + KMnO4 Products ... (1)
v.f. = 2 v.f. = 5
w
20 ml 20 ml
w
( 7 ) ( 2) ( 4 )
+ Neutal ... (2)
K Mn O 4 MnS O 4 Mn O 2
Page # 23
20 ml
v.f. = 3 v.f. = 2 v.f. = 6/5 ( For 5 mole of MnO2, 6 mole of e– is transferred )
( 4 )
H 2+
Mn O 2 + Na2C2O4
Mn + CO2 ... (3)
10 ml, 0.2 M
v.f. = 2 v.f. = 2
m
Meq. of MnO2 used in reaction (3) = 10 × 0.2 × 2 (w.r. to v.f. = 2)
10 0.2 2 6
co
Meq. of MnO2 produced in reaction (2) = (w.r. to v.f. = 6/5)
2 5
Let Molarity of KMnO4 = 4
.
Meq. of KMnO4 = meq. of MnO2
es
10 0.2 2 6
or M × 20 × 3 = or M = 0.04
2 5
ul
Let Molarity of H2O2 = M`
Eq. of H2O2 = Eq. of KMnO4
od
20 × M’ × 2 = 0.04 × 20 × 5
M` = 0.1 Molar
Once balanced reactions are known the problem can be solved easily by mole concept.
Method 2 :
pa
M = 0.1
Although both the methods yields same result but I think you are in a position to decide
ee
that which method is absolutely correct and we think you all will agree with us that the
method-1 given is precise while method-2 is not appropriate since the law of equivalence
in given form cannot be used and modification is to be applied.
en
Ex. 2.616 g of an element X is reacted with an aqueous solution of NaOH and NaNO3 to yield Na2XO2
and NH3. NH3 liberated is absorbed in 100 ml of 0.11 M H2SO4. The excess acid required 48 ml of
.je
(v.f. = 1) (v.f. = 2)
Page # 24
Moles of NaOH consumed against excess of H2SO4 = 48 × 0.25 × 10–3
Moles of excess of H2SO4 = 1/2 × 48 × 10–3 × 0.25
Initial moles of H2SO4 = 0.11 × 100 × 10–3
Moles of H2SO4 used by NH3 = (0.11 × 100 × 10–3) – (24 × 10–3 × 0.25) = 5 × 10–3
Moles of NH3 produced = 5 × 10–3 × 2 = 10 × 10–3 = 0.01
Moles of NaNO3 consumed = 0.01
Moles of X = 0.01 × 4 = 0.04
2.616
m
0.04 =
M
co
2.616
Atomic weight of X = M = = 65.4
0.04
.
Method 2 : (Equivalent concept)
es
100 0.11 2 48 0.5
Equivalent of H2SO4 consumed by NH3 =
1000 1000
ul
= 0.022 – 0.012 = 0.01
od
= Equivalents of NH3 reacted
Moles of NH3 reacted = 0.01
Equivalents of NH3 produced = 0.01 × 8 = 0.08 = Equivalents of Na2XO2
nm
= Equivalents of X reacted
2.616 2
0.08 =
M
Atomic weight of X = M = 65.4
tio
ra
pa
re
tp
ee
en
.je
w
w
w
Page # 25
m
. co
es
ul
od
nm
CHEMISTRY LECTURE NOTES
tio
ra
(2012-13)
en
.je
w
w
w
Lecture - 01
Classical Concept of Equivalent weight / Mass, Equivalent weight ,
n-fact or and Normalit y for Acid, Base and Precipit at e
CLASSICAL CONCEPT OF EQUIVALENT WEIGHT/MASS :
Number of parts by mass of an element which reacts or displaces from a compound 1.008 parts
m
by mass of hydrogen, 8 parts by mass of oxygen and 35.5 parts by mass of chlorine, is known as
the equivalent weight of that element e.g.
co
2Mg + O2
48g 32g
12g 8g
.
es
32 g of O2 reacts with 48 g of Mg
48 8
8 g of O2 = = 12 g
ul
32
Equivalent weight of Mg = 12
od
Similarly, Zn + H2SO4 ZnSO4 + H2
65.5 g 32.75
nm
65.5
Equivalent weight of Zn = = 32.75 g
2
3
tio
Al + Cl AlCl3
2 2
3
ra
27 g × 71 g
2
111.5 g chlorine reacts with 27 g of Al.
pa
27 35.5
35.5 chlorine reacts with = 9.0 g of Al
111 .5
27
re
a factor (say n-factor or valency factor) which is in above three cases is their respective valencies.
ee
Atomic weight
So, equivalent weight (E) = Valency - factor
en
M
For acid/base, E Where M = Molar mass
Basicity / Acidity
.je
M
For O.A/R.A, E
no. of moles of e – gained / lost
w
Page # 2
H2SO4 H+ + HSO4–
(v.f. = 1)
m
H3PO4 3H+ + PO43–
(v.f. = 3)
co
H3PO3 H+ + H2PO3–
(v.f. = 1)
.
H3PO3 2H+ + HPO3–
es
(v.f. = 2)
The valency factor of H3PO3 cannot be 3 as it has only two dissociable H+ ions. So, its valency
factor or dissociable protons is 1 or 2 as one of the H-atom is linked with P atom directly.
ul
..
:O:
od
||
HO – P – OH
|
H
Similarly, CH3COOH CH3COO– + H+
(v.f. = 1)
nm
tio
valency factor of CH3COOH is 1, because it contains only one dissociable H+ ions.
Now, we will consider the valency factor of some bases.
NaOH Na+ + OH–
ra
(v.f. = 1)
(v.f. = 1)
Similarly, valency factor of Al(OH)3 can also be 1 or 2 or 3, depending upon the number of OH–
released.
ee
In such reaction, there is no change in oxidation state of any atom. The valency factor of then
salt can be calculated by multiplying the oxidation state of the cation/anion by total no. of atoms
per molecule of the salt. For example
.je
Equivalent is the term used for amount of substance like mole with the difference that one equivalent
w
of a substance in different reactions may be different as well as the one equivalent of each
substance is also different.
No. of equivalent is defined as
Wt W W
No. of equivalents of solute =
Eq. wt. E M/n
No. of equivalents of solute = No. of moles of solute × v.f.
Page # 3
NORMALIT Y (N) :
It is defined as the number of equivalents of a solute present in one litre of solution.
Number of equivalent s of solute
Normality (N) = Volume of solution( in litres)
Let the weight of solute be w g, equivalent mass of solute be E g/eqv. and the volume of solution
be V litre.
m
Weight of solute w
Number of equivalents of solute =
Equivalent mass of solute E
co
W 1000
N = E V( in ml)
.
es
W
Number of equivalents of solute = = N × V (in litre)
E
ul
Normality = Molarity × v.f.
Dilution Law N1V1 = N2V2
od
For two solution, of same solute when mixed, new normality is given as :
N1V1 N 2 V2
N
nm
V1 V2
Sol. (a) N=
74 5
pa
N 4
N=4 M= =2
v.f . 2
re
3.65 1000
(b) N= = 0.5
36.5 200
tp
N 0 .5
and M= = = 0.5
v.f. 1
ee
1
(c) Eq. of H2SO4 = ×2 ( Eq. = mole × v.f.)
10
en
2 1000 0 .4
N= = 0.4 and M = = 0.2
10 500 2
.je
Lecture - 02
w
w
For the calculation of n-factor of oxidising agent or reducing agent, the method depends upon the
change in oxidation state of the species considered. We will discuss them one by one.
(i) When only one atom undergoing either reduction or oxidation change e.g.
7 2
H
M n 2
M nO 4
(v.f = 5)
Page # 4
In such a case, we consider the change in oxidation state of atom undergoing oxidation or
reduction change per molecule as the n-factor of the species.
valency factor = 1(7 – 5) = 2
2 3
Fe 2 Fe 3 valency factor = 1 (3 – 2) = 1
(v.f = 1)
3 4
C2O 24 – 2CO 2 valency factor = 2(4 – 3) = 2
m
6 3
Cr 2O 72 2Cr 3 valency factor = 2(6 – 3) = 6
co
Ex. Calculate the valency factor of the reactant (oxidant or reductant) in the following cases.
.
(i) IO3– I2
es
(ii) Zn ZnO22–
(iii) NO3– NH3
ul
(iv) NH4+ NH2OH
5 0
od
Sol. (i) O 3 valency factor = 1(5 – 0) = 5
0 2 2
(ii) ZnO 3 ZnO valency factor = 1(2 – 0) = 2
(iii)
5
NO 3 NH 3
–3 1
nm
valency factor = 1(5 + 3) = 8
tio
3 1
(iv) N H4 NH2OH valency factor = 1(–1– (– 3)) = 2
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
ra
(ii) Salts which reacts in such a way that only one atom undergoes change in oxidation state but
appears in two products with the same oxidaiton state.
pa
In such a case the method of calculation of valency factor remains the same i.e., we will calculate
the change in oxidation state of the atom per mole of that substance (reactant).
6 2 3 3
re
Cr2 O 72 Cr 3 Cr 3
In this example, oxidation state of Cr changes from +6 to +3 in both the products.
tp
state but goes in two products with different oxidation state as a result of either only oxidation or
only reduction.
7 2 6
en
3 Mn O 4 2Mn 2 Mn 6
In such a case, it is impossible to calculate the valency factor until and unless one knows that
how much of MnO4– is changing to Mn2+ and how much to Mn6+, and if one knows the balanced
.je
equation then there is no need of calculation of valency factor. Nevertheless in such case the
valency factor can be calculated by deducing the total change in oxidation state divided by total
w
number of atom undergoing reduction/oxidation change. So for the calculation of n-factor in the
above example, out of three moles of MnO4–, two moles are being converted to Mn2+ and one mole
w
2(7 2) 1(7 6) 11 11
changes to Mn+6. So total decrease in oxidation state of Mn = . So, v.f.= .
3 3 3
w
Ex. Calculate the n-factor of the reactant (oxidant or reductant) in following cases.
(i) 3MnO4– 2Mn2+ + Mn4+
(ii) 2MnO4– Mn2+ + Mn6+
1 13
Sol. (i) v.f. = [2(7 – 2) + 1(7 – 4)] =
3 3
1
(ii) v.f. = [1(7 – 2) + 1(7 – 6)] = 3
2
Page # 5
(iv) Salts which react in such a way that only one atom undergoes change in oxidation state in two
product, in one product with changed oxidation state and in other product with same oxiation
state as that of reactant.
In such case also one cannot calculate the valency factor without knowing the balanced chemical
equation because one must known how much of atom has changed its oxidation state.
For example.
K2Cr2O7 + 14HCl 2KCl + 2CrCl3 + 3Cl2 + 7H2O
Let us calculate the valency factor of HCl. Out of 14 moles of Cl– (in HCl) only 6 moles of Cl– are
m
changing its oxidation state from –1 to 0 in the product Cl2 and the oxidation state of remaining
8 Cl– ions remains same in KCl and CrCl3. So, total no. of moles of electrons lost by 14 moles of
co
HCl is 6. So each mole of HCl takes up 6/14 i.e., 3/7 moles of electrons and hence valency factor
of HCl is 3/7.
.
(v) Salts which react in such a way that two or more atoms in the salt undergoes change in oxidation
es
states as a result of either oxidation or reduction.
Let us consider the following example,
ul
3 4
FeC2O 4 Fe 3 2 CO2
od
In this case, the oxidation of both Fe2+ and C3+ are changing from +2 and +3 to +3 and +4
respectively. In such a case we will calculate the valency factor of the salt as the total increase
or decrease in oxidation state per mole of the salt. As one can see that one mole of FeC2O4
nm
contains one mole of Fe2+ and one mole of C2O42– (i.e. 2 carbon atoms per mole of C2O42–.
Total change in oxidation state = 1(3 – 2) + 2(4 – 3) = 3
v.f. = 3
tio
Ex. Calculate the valency factor of the reactant (oxidant or reductant) in following cases
2 1 3 4
(i) Fe S 2 Fe 2O 3 SO 2
ra
(vi) Salts which react in such a way that two atoms undergoing change in oxidation state but one
undergoing oxidation and other reduction.
In such a case one has to calculate the change in oxidation state of either the atom being
en
In this reaction, the oxidation state of N is decreasing by 6 units and that of Cr in increasing by
6 unit. So, we can consider either oxidation or reduction product for the calculation or valency
w
Ex. Calculate the valency factor of the reactant (oxidant or reductant) in following case
5 –2 1 0
K Cl O 3 K Cl O 2
Sol. v.f. for oxidation = 3 (0–(–2)) = 6
v.f. for reduction = 1 (5–(–1)) = 6
Page # 6
(vii) Species which undergoes disproportionation reaction :
Case 1 : When the number of moles of atoms being oxidized is equal to the number of moles of
atoms being reduced.
The valency factor can be calculated by knowing the balanced chemical equation and considering
any of the change taking place. Say for example
2H2O2 2H2O + O2
m
(H2O2 O2) and one mole of H2O2 is being reduced
co
(H2O2 2H2O). First consider the oxidation reaction
1 0
H2O 2 O 2
.
es
v.f. = 2(0–(–1) = 2
Again, considering reduction reaction
ul
1 2
H2O 2 H2O
od
v.f = 2(–1– (–2)) = 2
So, valency factor of H2O2 either considering oxidation or reduction is same i.e. 2.
nm
Case 2 : In those disproportionation reactions where the number of moles of substance getting
oxidised or reduced are not identical.
The valency factor is calculated by first knowing the total number of moles of electrons exchanged
(lost or gained) by the number of moles of substance appearing in the balanced equation and
tio
then dividing the number of moles of electrons exchanged by the number of moles of substance,
to get the number of moles of electrons exchanged by one mole of the substance, which is the
valency factor of that substance.
ra
For example,
pa
–––––––––––––––––––––––
6Br2 10Br– + 2Br+5
en
In overall reaction, the number of moles of electrons lost or gained by 6 moles of Br2 are 10.
Therefore, by each mole of Br2, the number of moles of electrons exchanged are 10/6 or 5/3. This
is the valency factor of Br2 in this reaction.
.je
List of common oxidising and reducing agents (with their valency factor):
It is very very important. Do tell students to mug it up by heart :
w
2–
Cr2O 7
Cr3+
v.f. = 2(6 – 3) = 6
w
O3¯ ¯
v.f. = 1(5 – (–1)) = 6
Page # 7
MnO2 Mn2+ (acid)
v.f. = 1(4 – 2) = 2
2 ¯
v.f. = 2(0 –(–1)) = 2
m
v.f. = 2(–1 – (–2)) = 2
co
v.f. = 1(5 – 3) = 2
.
es
NO3¯ NO
v.f. = 1(5 – 2) = 3
ul
v.f. = 1(5 – 1) = 4
od
NO3¯ NH4+
v.f. = 1(5 – (–3)) = 8
2–
O3 O2 + O
nm
v.f. = 1(0 – (–2)) = 2
In basic medium many cationic radicals gets precipitated as hydroxides and hence the titrations will
not be that effective.
pa
Lecture - 03
Equivalent Concept for Acid Base Titration and Precipitation Reactions :
w
w
LAW OF EQUIVALENCE :
The biggest problem you might face when you solve any problem of stoichiometry is the lack of
w
the knowledge of the chemical reactions involved. A problem might look impossible to solve
because the reactions involved are not known and the same problem looks extremely simple if
the reaction is known. Here we are going to develop a technique by which you would be in a
position to solve a problem without the knowledge of complete balanced reaction. The law that
governs this technique is called law of equivalence. Let us first understand that what information
a balanced chemical equation conveys to us. It tells us the molar ratio of the reactants and
products. Now if we get this molar ratiox without the complete balanced reaction, then it serves
the purpose of the reaction itself. This ratio can be known by knowing the valency factors of
various reactants of the reaction.
Page # 8
Whenever two substances react in such a way that their valency factors are in the ratio
of x : y, they would always react with each other in the molar ratio of y : x in a balanced
chemical reaction.
Since the number of equivalents of a substance is valency factor multiplied by the number of
moles, the equivalents of one reactant is x × y and the equivalents of the other is y × x. Hence
they are equal.
Thus according to the law of equivalence, whenever two substances react the equivalents
of one will be equal to the equivalents of other and is also equal to the equivalents of
m
each of the products.
i.e. if aA + bB + cC dD + eE + fF then the equivalents of A, B, C, D, E and F are equal to
co
each other irrespective of the molar ratio in which they are reacting or produced. Thus, the
advantage with equivalent concept is that a balanced chemical reaction is not needed.
.
es
For an acid base reaction :
At equivalence point, equivalent of Acid = equivalent base.
Ex. The two acids H2SO4 and H3PO4 are neutralised separately by the same amount of an
ul
alkali when sulphate and dihydrogen orthophosphate are formed respectively. Find the ratio of
the masses of H2SO4 and H3PO4.
od
Sol. H2SO4 2H+ + SO42–
v.f. = 2
nm
H2PO4 H+ + H2PO4–
v.f. = 1
Titrations is procedure for determining the concentration of a solution by allowing a carefully measured
volume to react with a standard solution of another substance, whose concentration is known.
Standard solution : Solution whose concentration is known and is taken in burrette, also called
re
Titrant.
There are two type of titrants :
tp
(a) Primary titrants/standard : Reagents which can be accurately weighed and their solutions are not to
be standardised before use :
ee
Ex :- Oxalic acid, K2Cr2O7 , AgNO3, CuSO4, ferrous ammonium sulphate, hypo etc.
(b) Secondary titrants/standard : These titrants can not be accurately weighed and solutions are to be
en
Equivalence point : When no. of equivalents of titrant added becomes equal to no. of equivalents of
titrate.
w
At equivalence point :
n1M1V1 = n2M2V2
w
Types of Titration :
(a) Acid-base titration
(b) Redox titration
(c) Precipitation titration Details not required
(d) Complexometric titrations Details not required
Page # 9
Acid-base titrations :
The detals of acid-base titration & titration curve will be discussed in ionic equilibrium chapter.
Here we will discuss only quantitative aspects of acids, bases and salts at equivalence point :
Simple acid base titration :
Acid + Base Salt + water (neutralization reaction)
At equivalence point
eq. of acid = eq. of base.
m
Ex. 20 g H3PO4 is dissolved in water & made up to one litre. 50 ml of this solution requires 50 ml of
NaOH solution for complete neutralization. Determine the molarity of NaOH solution. Also determine
co
the vol of NaOH used if neutralization is carried out upto single stage.
Sol. For complete neutralization
H3PO4 + 3NaOH Na3PO4 + 3H2O
.
es
n=3 n=1
eq. of H3PO4 = eq. of NaOH
ul
20 50 3
or = 50 × M × 1 × 10–3
1000 98
od
or M = 0.612
For single stage neutralization
nm
H3PO4 + NaOH NaH2PO4 + H2O
n=1 n=1
eq. of H3PO4 = eq. of NaOH
tio
20 50 1
= V × 0.612 × 1 × 10–3 V = 16.67 ml
1000 98
ra
Lecture - 04
pa
We will learn the limitations of law of equivalence once we get equipped with the following things.
Ex. Calculate the amount of oxygen required to produce enough carbon mono oxide on reaction with
ee
160 328
Fe 2O 3 3CO 2Fe 3CO 2
1600 g
.je
3 28
CO required to reduce 1600 g Fe2O3 = 1600 = 3 × 28 × 10 = 840 g
160
1 16 28
w
C O 2 CO
2
w
16
O2 required to produce 840 g CO = 840 = 480 g.
28
w
8 1600 6
W= = 480 g
160
Page # 10
Ex. Find the number of moles of kMnO4 needed to oxidise one mole Cu2S in acidic medium.
Sol. The reaction is KMnO4 + Cu2S Mn2+ + Cu2+ + SO2
v.f. = 5 v.f. = 2(2 – 1) + 1 (4 – (–2))
=8
m
moles of KMnO4 = 8/5
co
Ex. The number of moles of oxalate ions oxidized by one mole of MnO4– ion in acidic medium .
5 2 3 5
(A*) (B) (C) (D)
.
2 5 5 3
es
Sol. (A)
H
C2O42– + MnO4–
CO2 + Mn2+
ul
v.f. = 2 v.f. = 5
od
5
x(mole) × 2 = 1 × 5 ; x= 2
Ex. How many moles of KMnO4 are needed to oxidised a mixture of 1 mole of each FeSO4 & FeC2O4 in
acidic medium
(A*)
4
5
(B)
5
4
nm
(C)
3
4
(D)
5
3
tio
Sol. (A)
KMnO4 + FeSO4 Fe3+ + Mn2+
ra
v.f. = 5 v.f. = 1
pa
4
x= mole.
5
ee
Ex. 25 gm sample of ferrous sulphate (FeSO4. 7H2O) dissolved in water and dilute H2SO4 and made 1 ltr.
25 ml of solution required 10 ml of 0.04 M KMnO4 solution for complete oxidation. Find the percentage
en
1000 25
w
Ex. How many millititers of 0.02 M KMnO4 solution would be required to exactly titrate 25.00 mL of 0.02 M
Fe(NO3)2 solution.
w
Page # 11
This requires that at the equivalent point,
V(0.02) ( 25 ) (0.2)
=
1 5
V = 50.00 ml
Method- 2 (Equivalent Concept) :
Equivalents of MnO4¯ = 5 x moles of MnO4¯
m
Normality of MnO4¯ = 5 x molarity of MnO4¯
For Fe2+, moles and equivalents are equal,
co
At the equivalence point,
Equivalents of MnO4¯ = Equivalents of Fe2+
2
or VMnO 4 X Normality of MnO4¯ = VFe 2 x normality of Fe
.
es
For our 0.02000 M MnO4¯ solution
Normality of MnO4¯ = (5) (0.02000) = 0.1 N
and for Our 0.2000 M Fe2+ solution
ul
Normality of Fe2+ = 0.2000 N
od
0.2000
VMnO = (25.00 mL) = 50.00 mL
4
0.1000
nm
Ex. A sample weighing 2.198 gm and containing a mixture of AO and A2O3 takes 0.015 mole of K2Cr2O7 to
oxidise the sample completely to form AO4¯ and Cr3+. If 0.0187 mole of AO4¯ is famed. What is at.wt.
of A ?
tio
Sol. AO
A O
2 3 2.198 gm.
xg
ra
( 2.198 – x ) g
7
pa
2
6 AO 5K 2 Cr2O 7 6 AO –4 Cr 3
v.f 5 v .f 6 v .f 5
re
3 7
6 A 2 O 3 4K 2Cr2 O 7 12 AO 4–
v.f 8 v .f 4
tp
5x (2.198 – x ) 8
+ = 0.015 × 6. .....(i)
( A 16) (2A 48)
Also, total molar of AO4– formed.
en
x 2 (2.198 – x )
= + = 0.0187 .....(ii)
( A 16) (2A 48)
.je
Redox Titration :
w
Page # 12
4. H2O2 MnO4¯ H2O2 2H+ + O2 + 2e–
MnO4– + 8H+ + 5e– Mn2+ + 4H2O
(a) Permanganate Titrations : KMnO4 as O.A. in acidic medium (generally) dil H2SO4 is used not HNO3
m
or HCl to make medium acidic because :
HNO3 = O.A. HCl = R.A.
co
KMnO4 as self indicator - persistent pink color is indication of end point used mainly for Fe2+ , oxalic
acid ,oxalates, H2O2 etc.
.
es
Ex. KMnO4 vs oxalic acid
Reaction : 2KMnO4 + 3H2SO4 + 5H2C2O4 K2SO4 + 2MnSO4 + 8H2O + 10CO2
ul
M
Redox Changes : C23+ 2C4+ +2e– E H2C 2O 4
2
od
M
5e– + Mn7+ Mn2+ E KMnO 4
5
nm
Indicator : KMnO4 acts as a self indicator.
M
Redox Changes : Fe2+ Fe3+ + e– EFeSO 4
1
pa
M
Mn7+ + 5e– Mn2+ E KMnO 4
5
re
Indicator : KMnO4 is self indicator
tp
Ex. A sample of hydrazine sulphate [N2H6SO4] was dissolved in 100 mL water. 10 mL of this solutions was
treated with excess of FeCl3 solution and named to complete the reaction. Ferrons ions formed were
ee
estimated and it required 20 mL of M/50 KMnO4 solution. Estimate the amount of hydrazine sulphate
in one litre of solution.
Given 4Fe3+ + N2H4 N2 + 4Fe2+ + 4H+
en
(b) Dichromatic Titrations : K2Cr2O7 in acidic medium, mainly for Fe2+, ¯ etc. Diphenylamine is taken as
w
M
6e– + Cr26+ Cr23+ EF2Cr2O 7
6
Page # 13
Lecture - 05
Iodometric/Iodimetric Titration, n-factor in Disproportionation and
Comproportionation Redox Reactions, Calcualtion of % Availbale Chlorine
Disproportionation :
List of some important disproportionation reactions
m
1. H2O2 H2O + O2
v.f. = 2
co
2. X2 + OH–(dil.) X¯ + XO¯
v.f. = 2
.
es
v.f. = 5/3
ul
v.f. = 3
od
5. S8
v.f. = 16
nm
v.f. = 2/3
v.f. = 2
Redox Titration :
Estimation By titrating Reactions
en
of with
Page # 14
Although solid iodine is black (deep violet) and insoluble in water, it is converted into soluble tri-iodide
ions 3¯ 2 (s) + ¯ ¯ (aq)
black dark brown
Small amount of iodine molecules, 2, gives blue colour with starch, hence completion of the reaction
can be detected when blue colour disappears at the end-point.
Iodimetric titration :
In iodimetric titration, 2 solution is taken in burette and reducing agent like sodium thiosulphate,
m
As2O3, etc. are taken in flask.
+ 2Na2S2O3 Na2S4O6 + 2Na
co
2I + As2O3 + 5H2O 2AsO43– + 4H+
These titrations are usually performed in neutral or mildly alkaline (pH 8) to weakly acid solutions.
If the pH is too alkaline, 2 will disproportionate to hypoiodate and iodide ions.
.
es
+ 2OH¯ H2O
Weakly acidic medium is preferred since
starch used for the end-point detection tends to hydrolyse or decompose in strong acid.
ul
reducing power of several reducing agent is increased in neutral solution.
¯ produced in the reaction tends to be oxidised by dissolved O2 in acid solution.
od
4¯ + O2 + 4H+ 22 + 2H2O
The pH for the titration of arsenic () with 2 can be maintained neutral by adding NaHCO3,
nm
Indicator - Starch
Iodimetric titrations have been summarised in Table.
S.No. Estimation of Reaction
S + 2¯ + 2H+
tio
1. H2S H2 S + 2
(in acidic medium)
2. SO32– SO32– + 2 + H2O SO42– + 2¯ + 2H+
ra
Ex. The sulfur content of a steel sample is determined by converting it to H2S gas absorbing the H2S in
tp
10.0 mL of 0.00500 M I2 and then back titrating the excess I2 with 0.00200 M Na2S2O3. If 10 mL Na2
S2O3 is required for the titration, how many milligrams of sulfur are contained in the sample?
Reactions :
ee
Iodometric Titration :
This is an indirect method of estimation of iodine. An oxidizing agent is made to react with excess of
w
solid K. The oxidizing agent oxidises – to 2 . The iodine is then made to react with Na2S2O3 solution.
w
Na 2 S 2 O 3
O.A. + K 2 Na + Na2S4O6 .
Iodometric titrations have been summarised in table.
w
Page # 15
3. CaOCl2 CaOCl2 + H2O Ca(OH)2 + Cl2
Cl2 + 2K 2KCl + 2
or, Cl2 + 2¯ 2Cl¯ + 2
4. MnO2 MnO2 + 4HCl(conc.) MnCl2 + Cl2 + 2H2O
Cl2 + 2K 2KCl + 2
or MnO2 + 4H+ + 2Cl¯ Mn2+ + 2H2O + Cl2
Cl2 + 2¯ 2 + 2Cl¯
m
5. O3¯ O3¯ + 5¯ + 6H+ 32 + 3H2O
co
6. H2O2 H2O2 + 2¯ + 2H+ 2 + 2H2O
7. Cl2 Cl2 + 2¯ 2Cl¯ + 2
.
es
8. O3 O3 + 6¯ + 6H+ 32 + 3H2O
9. ClO¯ ClO¯ + 2¯ + 2H+ H2O + Cl¯ + 2
ul
10. Cr2O72– Cr2O72– + 14H+ + 6¯ 32 + 2Cr3+ + 7H2O
od
11. MnO4– 2MnO4– + 10¯+ 16H+ 2Mn2+ + 52 + 8H2O
12. BrO3– BrO3– + 6¯ + 6H+ Br– + 32 + 3H2O
nm
13. As(V) H2AsO4¯ + 2¯+ 3H+ H3AsO3 + H2O + 2
14. HNO2 2HNO2 + 2¯ + 2H+ 2 + 2NO + 2H2O
tio
15. HClO HClO + 2¯ + H+ Cl¯ + 2 + H2O
Ex. An aqueous solution containing 0.10g KIO3 (formula weight = 214) and an excess of K was acidified
ra
with HCl. The liberated 2 consumed 45.0 ml of thiosulphate. Determine the molarity of sodium
thiosulphate solution is
O3– + – + H+ 2 + H2 O
pa
v.f. = 5 v.f. = 1
0.1 0.3
tp
I2 + 2Na2S2O3
v.f. = 2 v.f. = 1, 45 ml, M(say)
en
0.3 2 0.3
mole = 45 × M × 10–3 M = 0.0623 M.
214 214
.je
Ex. A solution of 0.2 g of a compound containing Cu2+ and C2O42– ions on titration with 0.02 M KMnO4 in
presence of H2SO4 consumes 22.6 mL oxidant. The resulting solution is neutralized by Na2CO3,
acidified with dilute CH3COOH and titrated with excess of KI. The liberated 2 required 11.3 mL of 0.05
w
M Na2S2O3 for complete reduction. Find mole ratio of Cu2+ and C2O42– in compound.
H
Sol. 5C2O42– + 2KMnO4 Mn2+ + CO2
w
v.f. = 2 v.f. = 5
w
5
× 22.6 × 0.02 m mole 22.6 × 0.02 m mole
2
11.3 0.05
m mole 11.3 × 0.05 m mole
2
–
2Cu2+ + 4I Cu22 + 2
2 11.3 0.05 11.3 0.05
m mole
2 2
Page # 16
Cu2+ = 11.3 × 0.05 m mole
5
C2O42– = × 22.6 × 0.02 m mole
2
Cu2 11.3 0.05 2 1
Required mole ratio of 2– = = 0.5.
C 2O 4 5 22.6 0.02 2
m
BLEACHNG POWDER–
The weight % of available Cl2 from the given sample of bleaching powder on reaction with dil acids or
co
CO2 is called available chlorine.
CaOCl 2 H2SO 4 CaSO 4 H2 O Cl 2
.
es
CaOCl 2 2HCl CaCl 2 H2 O Cl2
CaOCl 2 2CH3 COOH CaCH 3 Coo 2 H2 O Cl 2
ul
CaOCl 2 CO 2 CaCO 3 Cl 2
od
Method of determination of available chlorine :
CaOCl2 + 2CH3COOH Ca(CH3COO)2 + H2O + Cl2
nm
(Sample of bleaching powder)
M V
= where V = vol of hypo solution used in ml.
2
re
M V 10 3
mass of Cl2 produced = × 71
tp
2
= 35.5 × M × V × 10–3
ee
35.5 M V 10 3
% of available chlorine = × 100
W
en
Ex. 3.55 gm sample of bleaching powder suspended in H2O was treated with enough acetic acid and K
w
solution. Iodine thus liberated required 80 ml of 0.2 M hypo for titration. Calculate the % of available
chlorine.
w
3.55 0.2 80
Sol. % of available Cl2 = = 16%
w
3.55
Ex. Calculate the percentage of available chlorine in a sample of 3.55 g of bleaching powder which
was dissolved in 100 mL of water, 25 mL of this solution, on treatment with KI and dilute acid,
required 20 mL of 0.125 N sodium thiosulphate solution.
3.55 20 0.125
Sol. % of available Cl2 = = 10%
3.55
25
100
Page # 17
Lecture - 06
Back Titration, Acid Base Double Indicator Titration, Miscellaneous / Difficult
Examples
Ex. 30 ml of a solution containing 9.15 g of a salt KxH(C2O4)z. nH2O per litre required 27 ml of 0.12 N NaOH
for neutralization. The same quantity of solution was also found to require 36 ml of 0.12 N KMnO4
solution for complete oxidation. Calculate the value of x, y, z and n.
m
Sol. KxHy(C2O4)z. nH2O + NaOH Products
co
v.f. = y 27 ml, 0.12 N
9.15 30 y
= 27 × 0.12 × 10–3 ... (1)
.
1000 M
es
KxHy(C2O4)z. nH2O + KMnO4 CO2 + other products
v.f. = 2z(4–3) = 2z 36 ml, 0.12 N
ul
9.15 30 2z
= 36 × 0.12 × 10–3 ... (2)
1000 M
od
(2) 2Z 4 Z 2
or
(1) y 3 y 3
x = 1, y = 3, z = 2.
Here we are assuming that x, y, & z are smallest possible integer.
pa
or 254 = 218 + 18 n or n = 2.
tp
Back Titration :
Let us consider that we have an impure solid substance ‘Z’ weighing ‘w’gram & we are required to
ee
calculate the percentage purity of Z in the sample. We are also provided with two solutions ‘X’
(Normality = N1) andY (Normality = N2).
For the back titration to work, following conditions are to be satisfied.
en
(a) Compounds ‘X’, ‘Y’ and ‘Z’ should be such that ‘X’ & ‘Y’ react with each other.
(b) ‘X’ and pure ‘Z’ also reacts with reach other but the impurity present in ‘Z’ does not react with
.je
‘X’.
Z + X (excess) Product 1 .... (1)
X + Y Product 2 .... (2)
w
(Remaining)
w
Relation (3) is true only when valency factor of X in reaction (1) and reaction (2) are same.
Ex. 5 g of a sample of Ca(OH)2 is dissolved in 50 ml of 0.5 N HCl solution. The excess of HCl is back
titrated with 0.3 N NaOH. The vol of NaOH used is 10 ml. Calculate % purity of Ca(OH)2.
Sol. Let pure Ca(OH)2 = xg
Ca(OH)2 + 2HCl CaCl2 + 2H2O
(excess)
Page # 18
HCl + NaOH NaCl + H2O
(left over)
m
0.814
% purity = × 100 = 16.28%.
co
5
Double Titration :
Purpose : To find the % composition of an alkali mixture.
.
Consider a mixture NaOH, Na2CO3 and NaHCO3.
es
To determine it’s % composition, make a solution of this mixture and then add two indicators in
it, namely phenolphthalein and methyl orange. Now titrate this alkali solution with HCl solution.
ul
NaOH is the strongest base among the mixture of three and NaHCO3 is the weakest. So NaOH
react first with HCl completely then Na2CO3 and then NaHCO3.
od
NaOH + HCl NaCl + H 2O .... (1)
v.f. = 1
nm
Na2CO3 + HCl NaHCO3 + NaCl .... (2)
v.f. = 1
NaHCO3 + HCl NaCl + H2CO3 .... (3)
tio
v.f. = 1
Note that phenolphthalein changes colour only when the weakly basic NaHCO3 is present
ra
& Methyl orange changes colour only when H2CO3 is present in the solution.
When we keep on adding HCl, the pH of the solution decreases. Phenolphthalein changes colour
pa
when reaction (2) is complete. This is called phenolphthalein endpoint, At this point.
eq. of HCl used = eq. of NaOH + eq. of Na2CO3 (with v.f. = 1) .... (4)
Also from equation (2),
re
eq. of NaHCO3 produced in reaction (2) = eq. of Na2CO3 consumed in reaction (2) .... (5)
If we keep on adding HCl, the pH again decreases & when all the NaHCO3 reacts to form NaCl &
tp
H2CO3 the solution becomes weakly acidic due to presence of weak acid H2CO3. At this point,
methyl orange changes colour since it requires weakly acidic solution to do so. This point is
ee
Also,
eq. of HCl used after phenolphthalein end point = eq. of Na2CO3 (v.f. = 1) + eq. of NaHCO3. .. (7)
using equation (4) and (6) we can determine % composition of the mixture.
w
Ex. A solution of 3 gm mixture containing Na2CO3, NaHCO3 and NaOH was titrated with 1 N HCl vol of
w
HCl used = 34.4 ml when only phenolphthalein is used as indicator and 55.8 ml when methyl
orange is used as indicator from the very beginning. Calculate % composition of the mixture.
w
Page # 19
At methyl orange end point
x 2y 3 ( x y )
1 × 55.8 × 10–3 = ... (2)
40 106 84
Solving (1) & (2) we get
x=1g
y=1g NaHCO3 = 3 – (1 + 1) = 1 g
m
1
% of NaHCO3 = × 100 = 33.33%
1 1 1
co
Similarly % of NaOH = 33.33%
% of Na2CO3 = 33.33%
.
es
Ex. One litre of acidified KMnO4 containing 15.8 g KMnO4 is decolorized by passing sufficient SO2.
If SO2 is produced by FeS2, what is the amount of FeS2 to give desired SO2?
H
ul
Sol. 2KMnO4 + 5SO2
Mn2+ + S+6
v.f. = 2 v.f. = 2
od
15.8 1 5 1
mole mole
158 10 2 10
FeS2
1 5 1
mole
2SO2
5 1
mole nm
tio
2 2 10 2 10
1
= mole
ra
1
pa
= (56 + 64)g = 15 g.
8
re
Ex. 1g sample of AgNO3 is dissolved in 50 mL of water. It is titrated with 50 mL of K solution. The Ag
precipitated is filtered off. Excess of KI in filtrate is titrated with M/10 KO3 in presence of 6M HCl till all
¯ converted into ICl. It requires 50 mL of M/10 KIO3 solution. 20 mL of the same stock solution of KI
tp
requires 30 mL of M/10 KIO3 under similar conditions. Calculate % of AgNO3 in sample. The reaction
is : KIO3 + 2KI + 6HCl 3ICl + 3KCl + 3H2O
ee
1 50
Initial millimoles of KI = 30 2 = 15 m mole
10 20
millimoles of KI used in reaction (1) = 15 – 10 = 5 m mole
w
= 5 × 10–3 × 170 g = 0.85 g
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Page # 20
When v.f. of C is different then :
Let v.f of C in reaction (1) = nC
and v.f. of C in reaction(2) = nC.
Given that eq. of A reacted = x
eq. of C produced in reaction (1) = x (w.r. to v.f. = nC)
x
eq. of C consumed in reaction (2) = n × nC (w.r. to v.f. = nC).
C
m
x
eq. of E produced = n × nC.
co
C
Note : Thus the equivalent of a substance produced and reacted can be equal only when in the
two reactions its valency factor is same otherwise such modification is required. So at any point
.
when a substance is produced in a reaction which further reacts in another reaction, we need to
es
see that such modification is required or not.
Ex. When x g of S is burnt it forms SO2 which is oxidized by Cl2 water to SO42– ion. Calculate the
ul
weight of SO42– ion produced ?
Sol. 1st Method : (By Mole Concept)
od
S + O2 SO2
nm
x x
Mole mole mole
32 32
x
= × 96 = 3x gm.
32
pa
S SO 2
v.f.= 4
tp
xg v.f.=4
( 4 ) ( 6)
.....(2)
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SO 2 SO 24–
v.f.=2 v.f.=2
en
x
eq. of SO2 produced = eq. of S consume = × 4.
32
.je
4x
or eq. of SO2 produced = (w.r. to v.f. = 4)
32
w
4x
= (w.r. to v.f. = 1)
32 4
w
4x
=
w
x
eq. of SO42– produced = eq.
16
Page # 21
x
moles of SO42– produced = mole.
16 2
x
mass of SO42– produced = × 96 = 3x gm.
32
Case ii : – When two reactants combine to give same product.
HCl
Ex. KIO3 + KI I2
m
Given x g of KIO3. Calculate moles of I2 produced.
This problem can be solved by mole concept after balance the equation:
co
Method : 1 (Mole Concept )
( 5 ) (–5 ) 0
KIO 3 +
KI I2
.
es
v.f. = 5 v.f.=1
Since v.f. of KIO3 = 5 and KI = 1. So the molar ratio in which they react would be 1 : 5.
ul
KIO3 + 5KI 3I2 (From POAC)
x 3x
od
mole mole
M M
3x
Moles of I2 produced = mole. (where M = molar mass of KIO3).
M
nm
Case iii : – Back Titration in which excess B is back titrated but the v.f. of B is different in
two reaction.
For Ex.
tio
ra
.....(1)
pa
re
.....(2)
tp
This problem can be solved by mole concept after balance the equation:
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Case iv : When more than one element of a compound are oxidized and both the elements
goes in different products.
en
This problem also can be solved by mole concept after balance the equation:
( 1) (–2 ) (0 ) 2 (–2 ) 4 (–2 )
Ex. Cu2 S 2 O 2 2 Cu O SO 2
.je
Ex. Hydrogen peroxide solution (20 ml) reacts quantitatively with a solution of KMnO 4
(20 ml) acidified with dilute H2SO4. The same volume of the KMnO4 solution is jest decolourised
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in the presence of dilute H2SO4. Write the balanced equations involved in the reaction and calculate
the molarity of H2O2.
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Page # 22
( 4 )
H 2+
Mn O 2 + Na2C2O4
Mn + CO2 ... (3)
10 ml, 0.2 M
v.f. = 2 v.f. = 2
m
2 5
Let Molarity of KMnO4 = 4
co
Meq. of KMnO4 = meq. of MnO2
10 0.2 2 6
or M × 20 × 3 = or M = 0.04
.
2 5
es
Let Molarity of H2O2 = M`
Eq. of H2O2 = Eq. of KMnO4
20 × M’ × 2 = 0.04 × 20 × 5
ul
M` = 0.1 Molar
od
Balanced reactions are :
2KMnO4 + 5H2O2 + 3H2SO4 K2SO4 + 2MnSO4 + 8H2O + 5O2
2KMnO4 + 3MnSO4 + 2H2O 5MnO2 + 2H2SO4 + K2SO4
nm
MnO2 + Na2C2O4 + 2H2SO4 MnSO4 + 2CO2 + Na2SO4 + 2H2O
tio
Once balanced reactions are known the problem can be solved easily by mole concept.
Method 2 :
ra
Although both the methods yields same result but I think you are in a position to decide
that which method is absolutely correct and we think you all will agree with us that the
tp
method-1 given is precise while method-2 is not appropriate since the law of equivalence
in given form cannot be used and modification is to be applied.
ee
Ex. 2.616 g of an element X is reacted with an aqueous solution of NaOH and NaNO3 to yield Na2XO2
and NH3. NH3 liberated is absorbed in 100 ml of 0.11 M H2SO4. The excess acid required 48 ml of
en
Page # 23
2.616
0.04 =
M
2.616
Atomic weight of X = M = = 65.4
0.04
m
Equivalent of H2SO4 consumed by NH3 =
1000 1000
co
= 0.022 – 0.012 = 0.01
= Equivalents of NH3 reacted
Moles of NH3 reacted = 0.01
.
Equivalents of NH3 produced = 0.01 × 8 = 0.08 = Equivalents of Na2XO2
es
= Equivalents of X reacted
2.616 2
0.08 =
ul
M
Atomic weight of X = M = 65.4
od
nm
tio
ra
pa
re
tp
ee
en
.je
w
w
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Page # 24