CHEMISTRY LECTURE NOTES

COURSE : VIKAAS & VIPUL

(LECTURE No. 1 TO 11)

TOPIC : EQUIVALENT CONCEPTS

(2012-13)
 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
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.
2Mg + O2 
48g 32g
12g 8g
 32 g of O2 reacts with 48 g of Mg
48  8
 8 g of O2 = = 12 g
32
 Equivalent weight of Mg = 12
Similarly, Zn + H2SO4  ZnSO4 + H2
65.5 g 32.75
65.5
 Equivalent weight of Zn = = 32.75 g
2
3
Al + Cl  AlCl3
2 2
3
27 g × 71 g
2
 111.5 g chlorine reacts with 27 g of Al.
27  35.5
 35.5 chlorine reacts with = 9.0 g of Al
111 .5
27
 Equivalent weight of aluminium = = 9.0
3
As we can see from the above examples that equivalent weight is the ratio of atomic weight and
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

M
For acid/base, E Where M = Molar mass
Basicity / Acidity

M
For O.A/R.A, E
no. of moles of e – gained / lost
Therefore, in general, we can write.
Atomic or moleculear weight
Equivalent weight (E) = (v.f. = valency factor)
v.f.

CALCULATION OF VALENCY FACTOR :

For Acid-Base Reaction :
n-factor of acid = basicity = no. of H+ ion(s) furnished per molecule of the acid.
n-factor of base = acidity = no. of OH– ion(s) furnised by the base per molecule.
Some Examples :

Page # 2
 HCl  H+ + Cl–
(v.f. = 1)

H2SO4  H+ + HSO4–

(v.f. = 1)

H2SO4  2H+ + SO42–

(v.f. = 1)

H3PO4  H+ + H2PO4–

(v.f. = 1)

H3PO4  2H+ + HPO4–

(v.f. = 2)

H3PO4  3H+ + PO43–

(v.f. = 3)

H3PO3  H+ + H2PO3–

(v.f. = 1)

H3PO3  2H+ + HPO3–

(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.
..
:O:
||
HO – P – OH
|
H
Similarly, CH3COOH  CH3COO– + H+
(v.f. = 1)

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–
(v.f. = 1)

Ba(OH)2  [Ba(OH)]– + OH–

(v.f. = 1)

Ba(OH)2  Ba2+ + 2OH–

(v.f. = 2)

Al(OH)3  Al3+ + 3OH–

(v.f. = 3)

Similarly, valency factor of Al(OH)3 can also be 1 or 2 or 3, depending upon the number of OH–
released.

For Precipitation /Double Decomposition Reactions :

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
BaCl2 + Na2SO4  BaSO  + 2NaCl
v.f = 2 v.f = 2

Concept of number of equivalents :

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.
Weight of solute w
Number of equivalents of solute = 
Equivalent mass of solute E

W 1000
 N = E  V( in ml)

W
 Number of equivalents of solute = = N × V (in litre)
E
Normality = Molarity × v.f.
Dilution Law N1V1 = N2V2
For two solution, of same solute when mixed, new normality is given as :
N1V1  N 2 V2
N
V1  V2

Ex. Calculate normality and molarity of the following :

(a) 0.74 g of Ca(OH)2 in 5 mL of solution.
(b) 3.65 g of HCl in 200 mL of solution.
(c) 1/10 mole of H2SO4 in 500 mL of solution.
0.74  1000  2
Sol. (a) N=
74  5

N 4
N=4  M=  =2
v.f . 2
3.65  1000
(b)  N= = 0.5
36.5  200

N 0 .5
and M= = = 0.5
v.f. 1
1
(c) Eq. of H2SO4 = ×2 (  Eq. = mole × v.f.)
10

2  1000 0 .4
 N= = 0.4 and M = = 0.2
10  500 2

Lecture - 02
Equivalentweight,n-factorandNormalityforOxidantandReductant
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

6 3
Cr 2O 72   2Cr 3  valency factor = 2(6 – 3) = 6

Ex. Calculate the valency factor of the reactant (oxidant or reductant) in the following cases.
(i) IO3–  I2
(ii) Zn  ZnO22–
(iii) NO3–  NH3
(iv) NH4+  NH2OH
5 0
Sol. (i)  O 3   valency factor = 1(5 – 0) = 5

0 2 2 
(ii) ZnO 3  ZnO valency factor = 1(2 – 0) = 2
5 –3 1
(iii) NO 3  NH 3 valency factor = 1(5 + 3) = 8

3 1
(iv) N H4  NH2OH valency factor = 1(–1– (– 3)) = 2
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
(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.
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
Cr2 O 72   Cr 3   Cr 3 
In this example, oxidation state of Cr changes from +6 to +3 in both the products.
So v.f. = 2(6 – 3)= 6
(iii) Salts which react in such react in such a way that only one atom undergoes change in oxidation
state but goes in two products with different oxidation state as a result of either only oxidation or
only reduction.
7 2 6
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
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
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
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

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.
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
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
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
states as a result of either oxidation or reduction.
Let us consider the following example,
3 4
FeC 2 O 4  Fe 3   2 CO2
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–.
Total change in oxidation state = 1(3 – 2) + 2(4 – 3) = 3
 v.f. = 3
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

(ii) [Fe(CN)6]4–  Fe3+ + CO2 + NO3–

(iii) Cu2S  Cu2+ + SO2

(iv) Fe2(SO4)3  Fe2+ + SO2
Sol. (i) v.f. = 1(3 – 2) + 2(4 – (–1)) = 1 + 10 = 11
(ii) v.f. = 1(3 – 2) + 6(4 – 2) + 6(5–(–3)) = 61
(iii) v.f. = 2(2 – 1) + 1(4 – (–2)) = 2 + 6 = 8
(iv) v.f. = 2(3 – 2) + 3(6 – 4) = 8
(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
oxidized or the atom being reduced. For example.
3 6 0 3
(NH4 )2 Cr2O 7  N2  Cr2O 3  4H2O .
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
factor and it will be the same.
v.f. of (NH4)2 Cr2O7 considering oxidation 2(0–(–3)) = 6
v.f. of (NH4)2 Cr2O7 considering reduction 2(6 –3) = 6

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

Out of 2 moles of H 2O 2 consumed in the reaction, one mole of H 2O 2 is being oxidized

(H2O2  O2) and one mole of H2O2 is being reduced
(H2O2  2H2O). First consider the oxidation reaction
1 0
H2 O 2  O 2
v.f. = 2(0–(–1) = 2
Again, considering reduction reaction
1 2
H2O 2  H2O
v.f = 2(–1– (–2)) = 2
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.
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,
to get the number of moles of electrons exchanged by one mole of the substance, which is the
valency factor of that substance.
For example,
12 OH – + 6Br2  10Br– + 2BrO3– + 6H2O.
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.
Br2  2Br+5 + 10e–
5Br2 + 10e–  10Br–
–––––––––––––––––––––––
6Br2  10Br– + 2Br+5

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.

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 :
Common Oxidising Agents
2–
Cr2O 7
 Cr3+
v.f. = 2(6 – 3) = 6

MnO4¯  Mn2+ (acid)

v.f. = 1(7 – 2) = 5

MnO4¯  MnO2 (basic/neutral)

v.f. = 1(7 – 4) = 3

MnO4¯  MnO42– (highly basic)

v.f. = 1(7 – 6) = 1

Page # 7
 O3¯  ¯
v.f. = 1(5 – (–1)) = 6

MnO2  Mn2+ (acid)

v.f. = 1(4 – 2) = 2

2  ¯
v.f. = 2(0 –(–1)) = 2

ClO¯  Cl¯ (basic)

v.f. = 1(1 – (–1)) = 2

H2O2  H2O

v.f. = 2(–1 – (–2)) = 2

NO3¯  NO2¯

v.f. = 1(5 – 3) = 2

NO3¯  NO2

v.f. = 1(5 – 4) = 1

NO3¯  NO
v.f. = 1(5 – 2) = 3

NO3¯  N2O

v.f. = 1(5 – 1) = 4

NO3¯  NH4+

v.f. = 1(5 – (–3)) = 8
2–
O3  O2 + O
v.f. = 1(0 – (–2)) = 2

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
CrO42– and will hinder in titration.
In basic medium many cationic radicals gets precipitated as hydroxides and hence the titrations will
not be that effective.

Common reducing agents and their valency factor :

Fe2+  Fe3+ ; NO2¯  NO3¯
v.f. = 1(3 – 2) = 1 v.f. = 1(5 – 3) = 2

Sn2+  Sn4+ ; H2O2  O2

v.f. = 1(4 – 2) = 2 v.f. = 2(0 – (–1) = 2.

S2O32–  S4O62– ; C2O42–  CO2

v.f. = 2(2.5 –2) = 1 v.f. = 2(4 – 3) = 2

S2–  S ; Zn  ZnO22– (basic)

v.f. = 1(0 –(–2)) = 2 v.f. = 1(2 – 0) = 2

Lecture - 03
EquivalentConceptforAcidBaseTitrationandPrecipitation
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
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
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
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.

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
alkali when sulphate and dihydrogen orthophosphate are formed respectively. Find the ratio of
the masses of H2SO4 and H3PO4.
Sol. H2SO4  2H+ + SO42–
v.f. = 2

H2PO4  H+ + H2PO4–

v.f. = 1

Eq. of alkali = Eq. of H2SO4 = Eq. of H3PO4

Wt. of H2SO 4 Wt. of H3PO 4
 
Eq. wt. of H2SO 4 Eq. wt. of H3PO 4
49 1
 Wt. of H2SO4/Wt. of H3PO4 = 
98 2
TITRATIONS :
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
Titrant.
There are two type of titrants :
(a) Primary titrants/standard : Reagents which can be accurately weighed and their solutions are not to
be standardised before use :
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
standardised before use
Ex - NaOH, KOH, HCl, H2SO4, 2, KMnO4 etc.

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
colour change on completion of titration.

Types of Titration :
(a) Acid-base titration
(b) Redox titration
(c) Precipitation titration Details not required
(d) Complexometric titrations Details not required

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.

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.
Sol. For complete neutralization
H3PO4 + 3NaOH  Na3PO4 + 3H2O
n=3 n=1
eq. of H3PO4 = eq. of NaOH
20 50  3
or  = 50 × M × 1 × 10–3
1000 98
or M = 0.612
For single stage neutralization
H3PO4 + NaOH  NaH2PO4 + H2O
n=1 n=1
eq. of H3PO4 = eq. of NaOH
20 50  1
 = V × 0.612 × 1 × 10–3  V = 16.67 ml
1000 98

Lecture - 04
EquivalentConceptforRedoxreactions,KMnO4 /K2Cr2O7 v/sReducing
Agents&theirRedoxTitration
LAW OF EQUIVALENCE (FOR A REDOX REACTION ) :

At equivalence point, equivalent of oxidising agent = equivalent of reducing agent.

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
carbon which can reduce 1.6 kg Fe2O3.
Sol. Method 1 : (Mole concept)

Page # 10
 160 328
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
16
O2 required to produce 840 g CO =  840 = 480 g.
28
Method 2 : (Equivalent concept)
Eq. of O2 = eq. of Fe2O3
W 1600 ( 3 ) 0
  Fe 2 O 3  Fe
8 160 / 6
v.f = 2(3 – 0) = 6

8  1600  6
W= = 480 g
160
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

From law of equivalence

equivalents of Cu2S = equivalents of KMnO4
or, moles of Cu2S × v.f = moles of KMnO4 × v.f
or, 1 × 8 = moles of KMnO4 × 5
 moles of KMnO4 = 8/5

Ex. The number of moles of oxalate ions oxidized by one mole of MnO4– ion in acidic medium .
5 2 3 5
(A*) (B) (C) (D)
2 5 5 3
Sol. (A)
H
C2O42– + MnO4– 
 CO2 + Mn2+
v.f. = 2 v.f. = 5

Equivalents of C2O42– = equivalents of MnO4–

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
4 5 3 5
(A*) (B) (C) (D)
5 4 4 3
Sol. (A)
KMnO4 + FeSO4  Fe3+ + Mn2+
v.f. = 5 v.f. = 1

KMnO4 + FeC2O4  Mn2+ + Fe3+ + CO2

v.f. = 5 v.f. = 3

Equivalents of KMnO4 = equivalent of FeSO4 + equivalent of FeC2O4

x×5=1×1+1×3
4
x= mole.
5

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

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.
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
and in volume V (in milliliters of the MnO4¯)
Millimoles of MnO4¯ – V (0.02)
The balanced reaction is :
MnO4¯ + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O
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¯
Normality of MnO4¯ = 5 x molarity of MnO4¯
For Fe2+, moles and equivalents are equal,
At the equivalence point,
Equivalents of MnO4¯ = Equivalents of Fe2+
or VMnO 4 X Normality of MnO4¯
2
= VFe 2  x normality of Fe
For our 0.02000 M MnO4¯ solution
Normality of MnO4¯ = (5) (0.02000) = 0.1 N
and for Our 0.2000 M Fe2+ solution
Normality of Fe2+ = 0.2000 N
 0.2000 
VMnO  = (25.00 mL)   = 50.00 mL
4
 0.1000 

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 ?

 
 
Sol. AO
   A 2 O 3   2.198 gm.
 xg  
 ( 2.198 – x ) g 

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

eq. of AO + eq. of A2O3 = eq. of K2CrO4 .

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.

Redox Titration :
Estimation By titrating Reactions
of with
1. Fe2+ MnO4¯ Fe2+  Fe3+ + e–
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O
2. Fe2+ Cr2O72– Fe2+  Fe3+ + e–
Cr2O72– + 14H+ + 6e–  2Cr3+ + 7H2O
3. C2O42– MnO4¯ C2O42–  2CO2 + 2e–
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O

4. H2O2 MnO4¯ H2O2  2H+ + O2 + 2e–

MnO4– + 8H+ + 5e–  Mn2+ + 4H2O

5. As2O3 MnO4– As2O3 + 5H2O  2AsO43– + 10H+ + 4e–

MnO4– + 8H+ + 5e–  Mn2+ + 4H2O

(a) Permanganate Titrations : KMnO4 as O.A. in acidic medium (generally) dil H2SO4 is used not HNO3
or HCl to make medium acidic because :
HNO3 = O.A. HCl = R.A.
KMnO4 as self indicator - persistent pink color is indication of end point used mainly for Fe2+ , oxalic
acid ,oxalates, H2O2 etc.
Ex. KMnO4 vs oxalic acid
Reaction : 2KMnO4 + 3H2SO4 + 5H2C2O4  K2SO4 + 2MnSO4 + 8H2O + 10CO2
 M
Redox Changes : C23+  2C4+ +2e–  E H2 C 2 O 4  
 2

 M
5e– + Mn7+  Mn2+  E KMnO 4  
 5
Indicator : KMnO4 acts as a self indicator.
Ex. KMnO4 vs ferrous ammonium sulphate.
Reaction : 2KMnO4 + 10[FeSO4(NH4)2SO4. 6H2O] + 8H2SO4 
5Fe2(SO4)3 + 10(NH4)2SO4 + K2SO4 + 2MnSO4 + 68H2O
 M
Redox Changes : Fe2+  Fe3+ + e–  EFeSO 4  
 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
as the indicator. After oxidation it becomes blue in colour.
Ex. K2Cr2O7 Vs Ferrous ammonium sulphate.
The reaction : 6[FeSO4(NH4)2 SO4 . 6H2O] + K2Cr2O7 + 7H2SO4 
3Fe2(SO4)3 + Cr2(SO4)3 + K2SO4 + 6(NH4)2SO4 + 43H2O.
Redox Changes :
 M
Fe2+  Fe3+ + e–  EFeSO 4  
 1
 M
6e– + Cr26+  Cr23+  EF2Cr2O 7  
 6

Lecture - 05
Iodometric/IodimetricTitration,n-factorinDisproportionationand
ComproportionationRedoxReactions,Calcualtionof%Availbale
Chlorine
Disproportionation :
List of some important disproportionation reactions
1. H2O2  H2O + O2
v.f. = 2

2. X2 + OH–(dil.)  X¯ + XO¯

v.f. = 2

3. 6X2 + 12OH–(conc.)  10X¯ + 2XO3¯ + 6H2O.

v.f. = 5/3

F2 does not undergo disproportionation as it is the most electronegative element

4. P4 + 3OH– + 2H2O  PH3 + 3H2PO2¯ (basic)
v.f. = 3

5. S8 + 12OH–  4S2– + 2S2O32– + 6H2O.

v.f. = 16

6. 3MnO42–  2MnO4¯ + MnO2 + 2H2O. (acid)

v.f. = 2/3

7. Oxyacids of Phosphorus ( +1, +3 oxidation number)

3H3PO2  PH3 + 2H3PO3
v.f. = 4/3

2H3PO2  PH3 + H3PO4 (hot)

v.f. = 4

8. Oxyacids of Chlorine( Halogens)( +1, +3, +5 Oxidation number)

2ClO–  Cl– + ClO2–
v.f. = 2

3ClO2–  Cl– + 2ClO3–

v.f. = 4/3

Page # 14
 4ClO3–  Cl– + 3ClO4–
v.f. = 3/2

Redox Titration :
Estimation By titrating Reactions
of with

AsO33– BrO3– AsO33– + H2O  AsO43– + 2H+ + 2e–

BrO3– + 6H+ + 6e–  Br– + 3H2O

Titrationsinvolvingiodine:
Compound contains iodine are widely used in titrations.
(i) Iodide ions can be oxidised to 2 by suitable oxidising agent
2¯ (aq)  2(s) + 2e¯

(ii) Iodine (V) ions, O3¯ , will oxidise ¯ to 2

O¯ (aq) 5¯ (aq) + 6H+ (aq)  32(s) + 3H2O ()

(iii) Thiosulphate ions, S2O32– , can reduce iodine to iodide ions.

2S2O (aq) (s)  S4 O62– + 2–
colourless black colourless
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,
As2O3, etc. are taken in flask.
 + 2Na2S2O3  Na2S4O6 + 2Na
 + As2O3 + 5H2O  2AsO43– + 4H+
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.
 + 2OH¯   H2O
Weakly acidic medium is preferred since
 starch used for the end-point detection tends to hydrolyse or decompose in strong acid.
 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.
4¯ + O2 + 4H+  22 + 2H2O
 The pH for the titration of arsenic () with 2 can be maintained neutral by adding NaHCO3,
Indicator - Starch
Iodimetric titrations have been summarised in Table.
S.No. Estimation of Reaction
1. H2S H2 S +  2  S + 2¯ + 2H+
(in acidic medium)
2. SO32– SO32– + 2 + H2O  SO42– + 2¯ + 2H+
(in acidic medium)
3. Sn2+ Sn2+ + 2  Sn4+ + 2¯
(in acidic medium)
4. As(III) (at pH 8) H2AsO3¯ + 2 + H2O  HAsO42– + 2¯ + 2H+
5. N2H4 N2H4 + 22  N2 + 4H+ + 4¯

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
wt of sulfur = 1.28.

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.
Na 2 S 2 O 3
O.A. + K  2    Na + Na2S4O6 .
Iodometric titrations have been summarised in table.

S.No. Estimation of Reaction

1. 2 2 + 2Na2S2O3  2Na + Na2S4O6
or, 2 + 2S2O32–  2¯ + S4O62–
2. CuSO4 2CuSO4 + 4K  Cu22 + 2K2SO4 + 2
or, Cu2+ + 4¯  Cu22 + 2
white ppt
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¯
5. O3¯ O3¯ + 5¯ + 6H+  32 + 3H2O
6. H2O2 H2O2 + 2¯ + 2H+  2 + 2H2O
7. Cl2 Cl2 + 2¯  2Cl¯ + 2
8. O3 O3 + 6¯ + 6H+  32 + 3H2O
9. ClO¯ ClO¯ + 2¯ + 2H+  H2O + Cl¯ + 2
10. Cr2O72– Cr2O72– + 14H+ + 6¯  32 + 2Cr3+ + 7H2O
11. MnO4– 2MnO4– + 10¯+ 16H+  2Mn2+ + 52 + 8H2O
12. BrO3– BrO3– + 6¯ + 6H+  Br– + 32 + 3H2O
13. As(V) H2AsO4¯ + 2¯+ 3H+  H3AsO3 + H2O + 2
14. HNO2 2HNO2 + 2¯ + 2H+  2 + 2NO + 2H2O
15. HClO HClO + 2¯ + H+  Cl¯ + 2 + H2O

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

0.1 0.3
mole (excess) mole
214 214

I2 + 2Na2S2O3 
v.f. = 2 v.f. = 1, 45 ml, M(say)

0.3 2  0.3
mole = 45 × M × 10–3  M = 0.0623 M.
214 214

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
M Na2S2O3 for complete reduction. Find mole ratio of Cu2+ and C2O42– in compound.
H
Sol. 5C2O42– +  Mn2+ + CO2
2KMnO4 
v.f. = 2 v.f. = 5

5
× 22.6 × 0.02 m mole 22.6 × 0.02 m mole
2

I2 + 2Na2S2O3  products

v.f. = 2 v.f. = 1

11.3  0.05
m mole 11.3 × 0.05 m mole
2

–
2Cu2+ + 4I  Cu22 + 2
2  11.3  0.05 11 .3  0.05
m mole
2 2

 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

CALCULATION OF AVAILABLE CHLORINE FROM A SAMPLE OF

BLEACHNG POWDER–
The weight % of available Cl2 from the given sample of bleaching powder on reaction with dil acids or
CO2 is called available chlorine.
CaOCl 2  H2SO 4  CaSO 4  H2 O  Cl 2
CaOCl 2  2HCl  CaCl 2  H2 O  Cl2
CaOCl 2  2CH3 COOH  CaCH 3 Coo 2  H2 O  Cl 2

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)

Cl2 + 2KI  2KCl + I2

Starch as indicator
I2 + 2Na2S2O3    Na2S4O6 + 2Nal
v.f. = 2 v.f. = 1
End point is indicated by disappearance of blue colour.
Let M = Molarity of hypo (Na2S2O3) solution
 millimoles of Cl2 produced = moles of I2 used by hypo
M V
= where V = vol of hypo solution used in ml.
2

M  V  10 3
mass of Cl2 produced = × 71
2
= 35.5 × M × V × 10–3

35.5  M  V  10 3
 % of available chlorine = × 100
W
where W = amount of belaching powder taken in gm.
3.55  M  V
or % of available Cl2 =
W

Ex. 3.55 gm sample of bleaching powder suspended in H2O was treated with enough acetic acid and K
solution. Iodine thus liberated required 80 ml of 0.2 M hypo for titration. Calculate the % of available
chlorine.
3.55  0.2  80
Sol. % of available Cl2 = = 16%
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

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.
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
x 2z
From charge balance x + y – 2z = 0 or 1
y y
x 4 1 x 1
 1 
y 3 3 or y 3
 x:y:z = 1:3:2
 x = 1, y = 3, z = 2.
Here we are assuming that x, y, & z are smallest possible integer.
From (1) M = 254
 KH3(C2O4)2 .nH2O
M = 39 + 3 + 176 + 18 n
or 254 = 218 + 18 n or n = 2.

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’
(Normality = N1) andY (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.
(b) ‘X’ and pure ‘Z’ also reacts with reach other but the impurity present in ‘Z’ does not react with
‘X’.
Z + X (excess)  Product 1 .... (1)
X + Y  Product 2 .... (2)
(Remaining)

(c) Product 1 should not react with Y.

 eq. of Z = eq. of X – eq. of Y ... (3)

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)
HCl + NaOH  NaCl + H2O
(left over)

equivalent of Ca(OH)2 = eq. of HCl – eq. of NaOH

x2
= 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.

NaOH + HCl  NaCl + H 2O .... (1)

v.f. = 1
Na2CO3 + HCl  NaHCO3 + NaCl .... (2)
v.f. = 1
NaHCO3 + HCl  NaCl + H2CO3 .... (3)
v.f. = 1
Note that phenolphthalein changes colour only when the weakly basic NaHCO3 is present
& 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
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),
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,
methyl orange changes colour since it requires weakly acidic solution to do so. This point is
called methyl orange end point.
At this point.
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,
Total eq. of HCl used = eq. of NaOH + 2 × eq. of Na2CO3 (v.f. = 1) + eq. of NaHCO3. .. (6)
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.
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
orange is used as indicator from the very beginning. Calculate % composition of the mixture.
Sol. Let NaOH = x g
Na2CO3 = y g
& NaHCO3 = 3 – (x + y) gm.

At phenolphthalein end point

x y
1 × 34.4 × 10–3 =  ... (1)
40 106
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

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

15.8 1 5 1
 mole  mole
158 10 2 10

FeS2  2SO2

1 5 1 5 1
  mole  mole
2 2 10 2 10

1
= mole
8

1
= (56 + 64)g = 15 g.
8

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 KO3 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
requires 30 mL of M/10 KIO3 under similar conditions. Calculate % of AgNO3 in sample. The reaction
is : KIO3 + 2KI + 6HCl  3ICl + 3KCl + 3H2O
Sol. AgNO3 + KI  AgI + KNO3 .... (1)
1g(impure) 50ml

2KI + KIO3 + 6HCl  3Cl + 3KCl + 3H2O .... (2)

(left over)

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
= m mole of AgNO3 in the sample
 AgNO3 = 5 m mole
= 5 × 10–3 × 170 g = 0.85 g
% of pure AgNO3 = 85%

MODIFICATION IN LAW OF EQUIVALENCE :

Case i : – A + B  C .....(1)
C + D
 E .....(2)
eq. of A reacted = eq. of B reacted = eq. of C = eq. of D reacted = eq. of E produced. .....(3)
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).
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

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.
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)
S + O2  SO2
x x
Mole mole mole
32 32

SO2 + Cl2 + 2H2O  4H+ + SO42– + 2Cl–

x x
mole mole
32 32

x
= × 96 = 3x gm.
32
2nd Method : (By Equivalent Concept)
0 ( 4 )
S  SO 2 .....(1)
v.f.= 4
xg v.f.=4
( 4 ) (  6)
SO 2  SO 24– .....(2)
v.f.=2 v.f.=2

x
eq. of SO2 produced = eq. of S consume = × 4.
32

4x
or eq. of SO2 produced = (w.r. to v.f. = 4)
32

4x
= (w.r. to v.f. = 1)
32  4

4x
= × 2(w.r. to v.f. = 2).
32  4
 eq. of SO2 consumed in reaction (2)
4x x
= × 2 eq. = eq.
32  4 16

x
 eq. of SO42– produced = eq.
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
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)

x 3x
mole mole
M M
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
two reaction.
For Ex.

.....(1)

.....(2)

This problem can be solved by mole concept after balance the equation:
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:
( 1) (–2 ) (0 ) 2 (–2 ) 4 (–2 )
Ex. Cu2 S  2 O 2  2 Cu O  SO 2
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
by 10 ml of MnSO4 in neutral medium simultaneously forming a dark brown precipitate of hydrated
MnO2. The brown precipitate is dissolved in 10 ml of 0.2 M sodium oxalate under boiling condition
in the presence of dilute H2SO4. Write the balanced equations involved in the reaction and calculate
the molarity of H2O2.
Sol. Method 1 : (Equivalent concept) :
H
H2O2 + KMnO4  Products ... (1)
v.f. = 2 v.f. = 5
20 ml 20 ml

( 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

 Meq. of MnO2 used in reaction (3) = 10 × 0.2 × 2 (w.r. to v.f. = 2)

10  0.2  2 6
 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
10  0.2  2 6
or M × 20 × 3 =  or M = 0.04
2 5
Let Molarity of H2O2 = M`
 Eq. of H2O2 = Eq. of KMnO4
20 × M’ × 2 = 0.04 × 20 × 5
M` = 0.1 Molar

Balanced reactions are :

2KMnO4 + 5H2O2 + 3H2SO4  K2SO4 + 2MnSO4 + 8H2O + 5O2
2KMnO4 + 3MnSO4 + 2H2O  5MnO2 + 2H2SO4 + K2SO4
MnO2 + Na2C2O4 + 2H2SO4  MnSO4 + 2CO2 + Na2SO4 + 2H2O
Once balanced reactions are known the problem can be solved easily by mole concept.
Method 2 :
One may think using equivalent concept as follows.
Equivalents of Na2C2O4 = Equivalents of MnO2
= Equivalents of KMnO4 = Equivalents of H2O2
Let the molarity of H2O2 solution is M, then
10 × 10–3 × 0.2 × 2 = M × 20 × 10–3 × 2
 M = 0.1
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
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.
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
0.25 M NaOH. Find the atomic weight of X.
Sol. Method 1 : (Mole concept)
0 +5 +2 –3
4X + 7NaOH + NaNO3  4Na2XO2 + NH3 + 2H2O
v.f. = 2 v.f. = 8 v.f. = 8
2NH3 + H2SO4  (NH4)2SO4
(v.f. = 1) (v.f. = 2)

2NaOH + H2SO4  Na2SO4 + 2H2O

(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
 0.04 =
M
2.616
 Atomic weight of X = M = = 65.4
0.04

Method 2 : (Equivalent concept)

100  0.11 2 48  0.5 
Equivalent of H2SO4 consumed by NH3 =  
 1000 1000 
= 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
= Equivalents of X reacted
2.616  2
 0.08 =
M
 Atomic weight of X = M = 65.4

Page # 25
 CHEMISTRY LECTURE NOTES

COURSE : VIKAAS & VIPUL

(LECTURE No. 1 TO 11)

TOPIC : EQUIVALENT CONCEPTS

(2012-13)
 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
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.
2Mg + O2 
48g 32g
12g 8g
 32 g of O2 reacts with 48 g of Mg
48  8
 8 g of O2 = = 12 g
32
 Equivalent weight of Mg = 12
Similarly, Zn + H2SO4  ZnSO4 + H2
65.5 g 32.75
65.5
 Equivalent weight of Zn = = 32.75 g
2
3
Al + Cl  AlCl3
2 2
3
27 g × 71 g
2
 111.5 g chlorine reacts with 27 g of Al.
27  35.5
 35.5 chlorine reacts with = 9.0 g of Al
111 .5
27
 Equivalent weight of aluminium = = 9.0
3
As we can see from the above examples that equivalent weight is the ratio of atomic weight and
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

M
For acid/base, E Where M = Molar mass
Basicity / Acidity

M
For O.A/R.A, E
no. of moles of e – gained / lost
Therefore, in general, we can write.
Atomic or moleculear weight
Equivalent weight (E) = (v.f. = valency factor)
v.f.

CALCULATION OF VALENCY FACTOR :

For Acid-Base Reaction :
n-factor of acid = basicity = no. of H+ ion(s) furnished per molecule of the acid.
n-factor of base = acidity = no. of OH– ion(s) furnised by the base per molecule.
Some Examples :
HCl  H+ + Cl–
(v.f. = 1)

Page # 2
 H2SO4  H+ + HSO4–
(v.f. = 1)

H2SO4  2H+ + SO42–

(v.f. = 1)

H3PO4  H+ + H2PO4–

(v.f. = 1)

H3PO4  2H+ + HPO4–

(v.f. = 2)

H3PO4  3H+ + PO43–

(v.f. = 3)

H3PO3  H+ + H2PO3–

(v.f. = 1)

H3PO3  2H+ + HPO3–

(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.
..
:O:
||
HO – P – OH
|
H
Similarly, CH3COOH  CH3COO– + H+
(v.f. = 1)

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–
(v.f. = 1)

Ba(OH)2  [Ba(OH)]– + OH–

(v.f. = 1)

Ba(OH)2  Ba2+ + 2OH–

(v.f. = 2)

Al(OH)3  Al3+ + 3OH–

(v.f. = 3)

Similarly, valency factor of Al(OH)3 can also be 1 or 2 or 3, depending upon the number of OH–
released.

For Precipitation /Double Decomposition Reactions :

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
BaCl2 + Na2SO4  BaSO  + 2NaCl
v.f = 2 v.f = 2

Concept of number of equivalents :

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
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.
Weight of solute w
Number of equivalents of solute = 
Equivalent mass of solute E

W 1000
 N = E  V( in ml)

W
 Number of equivalents of solute = = N × V (in litre)
E
Normality = Molarity × v.f.
Dilution Law N1V1 = N2V2
For two solution, of same solute when mixed, new normality is given as :
N1V1  N 2 V2
N
V1  V2

Ex. Calculate normality and molarity of the following :

(a) 0.74 g of Ca(OH)2 in 5 mL of solution.
(b) 3.65 g of HCl in 200 mL of solution.
(c) 1/10 mole of H2SO4 in 500 mL of solution.
0.74  1000  2
Sol. (a) N=
74  5

N 4
N=4  M=  =2
v.f . 2
3.65  1000
(b)  N= = 0.5
36.5  200

N 0 .5
and M= = = 0.5
v.f. 1
1
(c) Eq. of H2SO4 = ×2 (  Eq. = mole × v.f.)
10

2  1000 0 .4
 N= = 0.4 and M = = 0.2
10  500 2

Lecture - 02
Equivalent weight, n-factor and Normality for Oxidant and Reductant
Concept of Equivalent weight / Mass : for Redox Reactions :
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

6 3
Cr 2O 72   2Cr 3  valency factor = 2(6 – 3) = 6

Ex. Calculate the valency factor of the reactant (oxidant or reductant) in the following cases.
(i) IO3–  I2
(ii) Zn  ZnO22–
(iii) NO3–  NH3
(iv) NH4+  NH2OH
5 0
Sol. (i)  O 3   valency factor = 1(5 – 0) = 5

0 2 2 
(ii) ZnO 3  ZnO valency factor = 1(2 – 0) = 2
5 –3 1
(iii) NO 3  NH 3 valency factor = 1(5 + 3) = 8

3 1
(iv) N H4  NH2OH valency factor = 1(–1– (– 3)) = 2
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
(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.
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
Cr2 O 72   Cr 3   Cr 3 
In this example, oxidation state of Cr changes from +6 to +3 in both the products.
So v.f. = 2(6 – 3)= 6
(iii) Salts which react in such react in such a way that only one atom undergoes change in oxidation
state but goes in two products with different oxidation state as a result of either only oxidation or
only reduction.
7 2 6
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
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
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
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

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
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
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
states as a result of either oxidation or reduction.
Let us consider the following example,
3 4
FeC2O 4  Fe 3  2 CO2
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–.
Total change in oxidation state = 1(3 – 2) + 2(4 – 3) = 3
 v.f. = 3
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

(ii) [Fe(CN)6]4–  Fe3+ + CO2 + NO3–

(iii) Cu2S  Cu2+ + SO2

(iv) Fe2(SO4)3  Fe2+ + SO2
Sol. (i) v.f. = 1(3 – 2) + 2(4 – (–1)) = 1 + 10 = 11
(ii) v.f. = 1(3 – 2) + 6(4 – 2) + 6(5–(–3)) = 61
(iii) v.f. = 2(2 – 1) + 1(4 – (–2)) = 2 + 6 = 8
(iv) v.f. = 2(3 – 2) + 3(6 – 4) = 8
(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
oxidized or the atom being reduced. For example.
3 6 0 3
(NH4 )2Cr2O 7  N2  Cr2O 3  4H2O .
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
factor and it will be the same.
v.f. of (NH4)2 Cr2O7 considering oxidation 2(0–(–3)) = 6
v.f. of (NH4)2 Cr2O7 considering reduction 2(6 –3) = 6

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

Out of 2 moles of H 2O 2 consumed in the reaction, one mole of H 2O 2 is being oxidized

(H2O2  O2) and one mole of H2O2 is being reduced
(H2O2  2H2O). First consider the oxidation reaction
1 0
H2O 2  O 2
v.f. = 2(0–(–1) = 2
Again, considering reduction reaction
1 2
H2O 2  H2O
v.f = 2(–1– (–2)) = 2
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.
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,
to get the number of moles of electrons exchanged by one mole of the substance, which is the
valency factor of that substance.
For example,
12 OH – + 6Br2  10Br– + 2BrO3– + 6H2O.
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.
Br2  2Br+5 + 10e–
5Br2 + 10e–  10Br–
–––––––––––––––––––––––
6Br2  10Br– + 2Br+5

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.

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 :
Common Oxidising Agents
2–
Cr2O 7
 Cr3+
v.f. = 2(6 – 3) = 6

MnO4¯  Mn2+ (acid)

v.f. = 1(7 – 2) = 5

MnO4¯  MnO2 (basic/neutral)

v.f. = 1(7 – 4) = 3

MnO4¯  MnO42– (highly basic)

v.f. = 1(7 – 6) = 1

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

ClO¯  Cl¯ (basic)

v.f. = 1(1 – (–1)) = 2

H2O2  H2O

v.f. = 2(–1 – (–2)) = 2

NO3¯  NO2¯

v.f. = 1(5 – 3) = 2

NO3¯  NO2

v.f. = 1(5 – 4) = 1

NO3¯  NO
v.f. = 1(5 – 2) = 3

NO3¯  N2O

v.f. = 1(5 – 1) = 4

NO3¯  NH4+

v.f. = 1(5 – (–3)) = 8
2–
O3  O2 + O
v.f. = 1(0 – (–2)) = 2

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
CrO42– and will hinder in titration.
In basic medium many cationic radicals gets precipitated as hydroxides and hence the titrations will
not be that effective.

Common reducing agents and their valency factor :

Fe2+  Fe3+ ; NO2¯  NO3¯
v.f. = 1(3 – 2) = 1 v.f. = 1(5 – 3) = 2

Sn2+  Sn4+ ; H2O2  O2

v.f. = 1(4 – 2) = 2 v.f. = 2(0 – (–1) = 2.

S2O32–  S4O62– ; C2O42–  CO2

v.f. = 2(2.5 –2) = 1 v.f. = 2(4 – 3) = 2

S2–  S ; Zn  ZnO22– (basic)

v.f. = 1(0 –(–2)) = 2 v.f. = 1(2 – 0) = 2

Lecture - 03
Equivalent Concept for Acid Base Titration and Precipitation 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
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
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
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.
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
alkali when sulphate and dihydrogen orthophosphate are formed respectively. Find the ratio of
the masses of H2SO4 and H3PO4.
Sol. H2SO4  2H+ + SO42–
v.f. = 2

H2PO4  H+ + H2PO4–

v.f. = 1

Eq. of alkali = Eq. of H2SO4 = Eq. of H3PO4

Wt. of H2SO 4 Wt. of H3PO 4
 
Eq. wt. of H2SO 4 Eq. wt. of H3PO 4
49 1
 Wt. of H2SO4/Wt. of H3PO4 = 
98 2
TITRATIONS :
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
Titrant.
There are two type of titrants :
(a) Primary titrants/standard : Reagents which can be accurately weighed and their solutions are not to
be standardised before use :
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
standardised before use
Ex - NaOH, KOH, HCl, H2SO4, 2, KMnO4 etc.
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
colour change on completion of titration.

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.

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.
Sol. For complete neutralization
H3PO4 + 3NaOH  Na3PO4 + 3H2O
n=3 n=1
eq. of H3PO4 = eq. of NaOH
20 50  3
or  = 50 × M × 1 × 10–3
1000 98
or M = 0.612
For single stage neutralization
H3PO4 + NaOH  NaH2PO4 + H2O
n=1 n=1
eq. of H3PO4 = eq. of NaOH
20 50  1
 = V × 0.612 × 1 × 10–3  V = 16.67 ml
1000 98

Lecture - 04
Equivalent Concept for Redox reactions, KMnO4 / K2Cr2O7 v/s Reducing
Agents & their Redox Titration
LAW OF EQUIVALENCE (FOR A REDOX REACTION ) :
At equivalence point, equivalent of oxidising agent = equivalent of reducing agent.
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
carbon which can reduce 1.6 kg Fe2O3.
Sol. Method 1 : (Mole concept)
160 328
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
16
O2 required to produce 840 g CO =  840 = 480 g.
28
Method 2 : (Equivalent concept)
Eq. of O2 = eq. of Fe2O3
W 1600 ( 3 ) 0
  Fe 2O 3  Fe
8 160 / 6
v.f = 2(3 – 0) = 6

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

From law of equivalence

equivalents of Cu2S = equivalents of KMnO4
or, moles of Cu2S × v.f = moles of KMnO4 × v.f
or, 1 × 8 = moles of KMnO4 × 5
 moles of KMnO4 = 8/5

Ex. The number of moles of oxalate ions oxidized by one mole of MnO4– ion in acidic medium .
5 2 3 5
(A*) (B) (C) (D)
2 5 5 3
Sol. (A)
H
C2O42– + MnO4– 
 CO2 + Mn2+
v.f. = 2 v.f. = 5

Equivalents of C2O42– = equivalents of MnO4–

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
4 5 3 5
(A*) (B) (C) (D)
5 4 4 3
Sol. (A)
KMnO4 + FeSO4  Fe3+ + Mn2+
v.f. = 5 v.f. = 1

KMnO4 + FeC2O4  Mn2+ + Fe3+ + CO2

v.f. = 5 v.f. = 3

Equivalents of KMnO4 = equivalent of FeSO4 + equivalent of FeC2O4

x×5=1×1+1×3
4
x= mole.
5

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

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.
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
and in volume V (in milliliters of the MnO4¯)
Millimoles of MnO4¯ – V (0.02)
The balanced reaction is :
MnO4¯ + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O

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¯
Normality of MnO4¯ = 5 x molarity of MnO4¯
For Fe2+, moles and equivalents are equal,
At the equivalence point,
Equivalents of MnO4¯ = Equivalents of Fe2+
2
or VMnO 4 X Normality of MnO4¯ = VFe 2  x normality of Fe
For our 0.02000 M MnO4¯ solution
Normality of MnO4¯ = (5) (0.02000) = 0.1 N
and for Our 0.2000 M Fe2+ solution
Normality of Fe2+ = 0.2000 N
 0.2000 
VMnO  = (25.00 mL)   = 50.00 mL
4
 0.1000 

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 ?

 
 
Sol. AO
   A O
2 3   2.198 gm.
 xg   
 ( 2.198 – x ) g 

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

eq. of AO + eq. of A2O3 = eq. of K2CrO4 .

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.

Redox Titration :
Estimation By titrating Reactions
of with
1. Fe2+ MnO4¯ Fe2+  Fe3+ + e–
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O
2. Fe2+ Cr2O72– Fe2+  Fe3+ + e–
Cr2O72– + 14H+ + 6e–  2Cr3+ + 7H2O
3. C2O42– MnO4¯ C2O42–  2CO2 + 2e–
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O

Page # 12
4. H2O2 MnO4¯ H2O2  2H+ + O2 + 2e–
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O

5. As2O3 MnO4– As2O3 + 5H2O  2AsO43– + 10H+ + 4e–

MnO4– + 8H+ + 5e–  Mn2+ + 4H2O

(a) Permanganate Titrations : KMnO4 as O.A. in acidic medium (generally) dil H2SO4 is used not HNO3
or HCl to make medium acidic because :
HNO3 = O.A. HCl = R.A.
KMnO4 as self indicator - persistent pink color is indication of end point used mainly for Fe2+ , oxalic
acid ,oxalates, H2O2 etc.

Ex. KMnO4 vs oxalic acid

Reaction : 2KMnO4 + 3H2SO4 + 5H2C2O4  K2SO4 + 2MnSO4 + 8H2O + 10CO2

 M
Redox Changes : C23+  2C4+ +2e–  E H2C 2O 4  
 2

 M
5e– + Mn7+  Mn2+  E KMnO 4  
 5
Indicator : KMnO4 acts as a self indicator.

Ex. KMnO4 vs ferrous ammonium sulphate.

Reaction : 2KMnO4 + 10[FeSO4(NH4)2SO4. 6H2O] + 8H2SO4 
5Fe2(SO4)3 + 10(NH4)2SO4 + K2SO4 + 2MnSO4 + 68H2O
 M
Redox Changes : Fe2+  Fe3+ + e–  EFeSO 4  
 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.
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 = 6.5 g.
50 4 10

(b) Dichromatic Titrations : K2Cr2O7 in acidic medium, mainly for Fe2+, ¯ etc. Diphenylamine is taken as
the indicator. After oxidation it becomes blue in colour.
Ex. K2Cr2O7 Vs Ferrous ammonium sulphate.
The reaction : 6[FeSO4(NH4)2 SO4 . 6H2O] + K2Cr2O7 + 7H2SO4 
3Fe2(SO4)3 + Cr2(SO4)3 + K2SO4 + 6(NH4)2SO4 + 43H2O.
Redox Changes :
 M
Fe2+  Fe3+ + e–  EFeSO 4  
 1

 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
1. H2O2  H2O + O2
v.f. = 2

2. X2 + OH–(dil.)  X¯ + XO¯

v.f. = 2

3. 6X2 + 12OH–(conc.)  10X¯ + 2XO3¯ + 6H2O.

v.f. = 5/3

F2 does not undergo disproportionation as it is the most electronegative element

4. P4 + 3OH– + 2H2O  PH3 + 3H2PO2¯ (basic)
v.f. = 3

5. S8 + 12OH–  4S2– + 2S2O32– + 6H2O.

v.f. = 16

6. 3MnO42–  2MnO4¯ + MnO2 + 2H2O. (acid)

v.f. = 2/3

7. Oxyacids of Phosphorus ( +1, +3 oxidation number)

3H3PO2  PH3 + 2H3PO3
v.f. = 4/3

2H3PO2  PH3 + H3PO4 (hot)

v.f. = 4

8. Oxyacids of Chlorine( Halogens)( +1, +3, +5 Oxidation number)

2ClO–  Cl– + ClO2–
v.f. = 2

3ClO2–  Cl– + 2ClO3–

v.f. = 4/3

4ClO3–  Cl– + 3ClO4–

v.f. = 3/2

Redox Titration :
Estimation By titrating Reactions
of with

AsO33– BrO3– AsO33– + H2O  AsO43– + 2H+ + 2e–

BrO3– + 6H+ + 6e–  Br– + 3H2O

Titrations involving iodine :

Compound contains iodine are widely used in titrations.
(i) Iodide ions can be oxidised to 2 by suitable oxidising agent
2¯ (aq)  2(s) + 2e¯

(ii) Iodine (V) ions, O3¯ , will oxidise ¯ to 2

O¯ (aq) 5¯ (aq) + 6H+ (aq)  32(s) + 3H2O ()

(iii) Thiosulphate ions, S2O32– , can reduce iodine to iodide ions.

2S2O (aq) (s)  S4 O62– + 2–
colourless black colourless

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,
As2O3, etc. are taken in flask.
 + 2Na2S2O3  Na2S4O6 + 2Na
2I  + As2O3 + 5H2O  2AsO43– + 4H+
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.
 + 2OH¯   H2O
Weakly acidic medium is preferred since
 starch used for the end-point detection tends to hydrolyse or decompose in strong acid.
 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.
4¯ + O2 + 4H+  22 + 2H2O
 The pH for the titration of arsenic () with 2 can be maintained neutral by adding NaHCO3,
Indicator - Starch
Iodimetric titrations have been summarised in Table.
S.No. Estimation of Reaction
1. H2S H2 S +  2  S + 2¯ + 2H+
(in acidic medium)
2. SO32– SO32– + 2 + H2O  SO42– + 2¯ + 2H+
(in acidic medium)
3. Sn2+ Sn2+ + 2  Sn4+ + 2¯
(in acidic medium)
4. As(III) (at pH 8) H2AsO3¯ + 2 + H2O  HAsO42– + 2¯ + 2H+
5. N2H4 N2H4 + 22  N2 + 4H+ + 4¯
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
wt of sulfur = 1.28.

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.
Na 2 S 2 O 3
O.A. + K  2    Na + Na2S4O6 .
Iodometric titrations have been summarised in table.

S.No. Estimation of Reaction

1. 2 2 + 2Na2S2O3  2Na + Na2S4O6
or, 2 + 2S2O32–  2¯ + S4O62–
2. CuSO4 2CuSO4 + 4K  Cu22 + 2K2SO4 + 2
or, Cu2+ + 4¯  Cu22 + 2
white ppt

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¯
5. O3¯ O3¯ + 5¯ + 6H+  32 + 3H2O
6. H2O2 H2O2 + 2¯ + 2H+  2 + 2H2O
7. Cl2 Cl2 + 2¯  2Cl¯ + 2
8. O3 O3 + 6¯ + 6H+  32 + 3H2O
9. ClO¯ ClO¯ + 2¯ + 2H+  H2O + Cl¯ + 2
10. Cr2O72– Cr2O72– + 14H+ + 6¯  32 + 2Cr3+ + 7H2O
11. MnO4– 2MnO4– + 10¯+ 16H+  2Mn2+ + 52 + 8H2O
12. BrO3– BrO3– + 6¯ + 6H+  Br– + 32 + 3H2O
13. As(V) H2AsO4¯ + 2¯+ 3H+  H3AsO3 + H2O + 2
14. HNO2 2HNO2 + 2¯ + 2H+  2 + 2NO + 2H2O
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
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

0.1 0.3
mole (excess) mole
214 214

I2 + 2Na2S2O3 
v.f. = 2 v.f. = 1, 45 ml, M(say)

0.3 2  0.3
mole = 45 × M × 10–3  M = 0.0623 M.
214 214

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
M Na2S2O3 for complete reduction. Find mole ratio of Cu2+ and C2O42– in compound.
H
Sol. 5C2O42– + 2KMnO4   Mn2+ + CO2
v.f. = 2 v.f. = 5

5
× 22.6 × 0.02 m mole 22.6 × 0.02 m mole
2

I2 + 2Na2S2O3  products

v.f. = 2 v.f. = 1

11.3  0.05
m mole 11.3 × 0.05 m mole
2
–
2Cu2+ + 4I  Cu22 + 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

CALCULATION OF AVAILABLE CHLORINE FROM A SAMPLE OF

BLEACHNG POWDER–
The weight % of available Cl2 from the given sample of bleaching powder on reaction with dil acids or
CO2 is called available chlorine.
CaOCl 2  H2SO 4  CaSO 4  H2 O  Cl 2
CaOCl 2  2HCl  CaCl 2  H2 O  Cl2
CaOCl 2  2CH3 COOH  CaCH 3 Coo 2  H2 O  Cl 2

CaOCl 2  CO 2  CaCO 3  Cl 2

Method of determination of available chlorine :

CaOCl2 + 2CH3COOH  Ca(CH3COO)2 + H2O + Cl2
(Sample of bleaching powder)

Cl2 + 2KI  2KCl + I2

Starch as indicator
I2 + 2Na2S2O3    Na2S4O6 + 2Nal
v.f. = 2 v.f. = 1
End point is indicated by disappearance of blue colour.
Let M = Molarity of hypo (Na2S2O3) solution
 millimoles of Cl2 produced = moles of I2 used by hypo
M V
= where V = vol of hypo solution used in ml.
2

M  V  10 3
mass of Cl2 produced = × 71
2
= 35.5 × M × V × 10–3

35.5  M  V  10 3
 % of available chlorine = × 100
W
where W = amount of belaching powder taken in gm.
3.55  M  V
or % of available Cl2 =
W

Ex. 3.55 gm sample of bleaching powder suspended in H2O was treated with enough acetic acid and K
solution. Iodine thus liberated required 80 ml of 0.2 M hypo for titration. Calculate the % of available
chlorine.
3.55  0.2  80
Sol. % of available Cl2 = = 16%
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.
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
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
x 2z
From charge balance x + y – 2z = 0 or 1
y y
x 4 1 x 1
 1 
y 3 3 or y 3
 x:y:z = 1:3:2
 x = 1, y = 3, z = 2.
Here we are assuming that x, y, & z are smallest possible integer.
From (1) M = 254
 KH3(C2O4)2 .nH2O
M = 39 + 3 + 176 + 18 n
or 254 = 218 + 18 n or n = 2.

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’
(Normality = N1) andY (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.
(b) ‘X’ and pure ‘Z’ also reacts with reach other but the impurity present in ‘Z’ does not react with
‘X’.
Z + X (excess)  Product 1 .... (1)
X + Y  Product 2 .... (2)
(Remaining)

(c) Product 1 should not react with Y.

 eq. of Z = eq. of X – eq. of Y ... (3)

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)

equivalent of Ca(OH)2 = eq. of HCl – eq. of NaOH

x2
= 50 × 0.5 × 10–3 – 10 × 0.3 × 10–3
74
or x = 0.814 g
0.814
% purity = × 100 = 16.28%.
5
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.

NaOH + HCl  NaCl + H 2O .... (1)

v.f. = 1
Na2CO3 + HCl  NaHCO3 + NaCl .... (2)
v.f. = 1
NaHCO3 + HCl  NaCl + H2CO3 .... (3)
v.f. = 1
Note that phenolphthalein changes colour only when the weakly basic NaHCO3 is present
& 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
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),
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,
methyl orange changes colour since it requires weakly acidic solution to do so. This point is
called methyl orange end point.
At this point.
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,
Total eq. of HCl used = eq. of NaOH + 2 × eq. of Na2CO3 (v.f. = 1) + eq. of NaHCO3. .. (6)
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.
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
orange is used as indicator from the very beginning. Calculate % composition of the mixture.
Sol. Let NaOH = x g
Na2CO3 = y g
& NaHCO3 = 3 – (x + y) gm.
At phenolphthalein end point
x y
1 × 34.4 × 10–3 =  ... (1)
40 106

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

1
 % of NaHCO3 = × 100 = 33.33%
1 1 1
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

15.8 1 5 1
 mole  mole
158 10 2 10

FeS2  2SO2

1 5 1 5 1
  mole  mole
2 2 10 2 10

1
= mole
8

1
= (56 + 64)g = 15 g.
8

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 KO3 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
requires 30 mL of M/10 KIO3 under similar conditions. Calculate % of AgNO3 in sample. The reaction
is : KIO3 + 2KI + 6HCl  3ICl + 3KCl + 3H2O
Sol. AgNO3 + KI  AgI + KNO3 .... (1)
1g(impure) 50ml

2KI + KIO3 + 6HCl  3Cl + 3KCl + 3H2O .... (2)

(left over)

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
= m mole of AgNO3 in the sample
 AgNO3 = 5 m mole
= 5 × 10–3 × 170 g = 0.85 g
% of pure AgNO3 = 85%

MODIFICATION IN LAW OF EQUIVALENCE :

Case i : – A + B  C .....(1)
C + D
 E .....(2)
eq. of A reacted = eq. of B reacted = eq. of C = eq. of D reacted = eq. of E produced. .....(3)
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).

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

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.

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)
S + O2  SO2
x x
Mole mole mole
32 32

SO2 + Cl2 + 2H2O  4H+ + SO42– + 2Cl–

x x
mole mole
32 32

x
= × 96 = 3x gm.
32
2nd Method : (By Equivalent Concept)
0 ( 4 )
S  SO 2 .....(1)
v.f.= 4
xg v.f.=4
( 4 ) (  6)
SO 2  SO 24– .....(2)
v.f.=2 v.f.=2
x
eq. of SO2 produced = eq. of S consume = × 4.
32

4x
or eq. of SO2 produced = (w.r. to v.f. = 4)
32

4x
= (w.r. to v.f. = 1)
32  4

4x
= × 2(w.r. to v.f. = 2).
32  4
 eq. of SO2 consumed in reaction (2)
4x x
= × 2 eq. = eq.
32  4 16

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
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
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)
x 3x
mole mole
M M
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
two reaction.
For Ex.

.....(1)

.....(2)

This problem can be solved by mole concept after balance the equation:
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:
( 1) (–2 ) (0 ) 2 (–2 ) 4 (–2 )
Ex. Cu2 S  2 O 2  2 Cu O  SO 2
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
by 10 ml of MnSO4 in neutral medium simultaneously forming a dark brown precipitate of hydrated
MnO2. The brown precipitate is dissolved in 10 ml of 0.2 M sodium oxalate under boiling condition
in the presence of dilute H2SO4. Write the balanced equations involved in the reaction and calculate
the molarity of H2O2.
Sol. Method 1 : (Equivalent concept) :
H
H2O2 + KMnO4  Products ... (1)
v.f. = 2 v.f. = 5
20 ml 20 ml
( 7 ) ( 2) ( 4 )
+ Neutal ... (2)
K Mn O 4 MnS O 4   Mn O 2
20 ml
v.f. = 3 v.f. = 2 v.f. = 6/5 (  For 5 mole of MnO2, 6 mole of e– is transferred )

Page # 22
 ( 4 ) 
H 2+
Mn O 2 + Na2C2O4 
 Mn + CO2 ... (3)
10 ml, 0.2 M
v.f. = 2 v.f. = 2

 Meq. of MnO2 used in reaction (3) = 10 × 0.2 × 2 (w.r. to v.f. = 2)

10  0.2  2 6
 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
10  0.2  2 6
or M × 20 × 3 =  or M = 0.04
2 5
Let Molarity of H2O2 = M`
 Eq. of H2O2 = Eq. of KMnO4
20 × M’ × 2 = 0.04 × 20 × 5
M` = 0.1 Molar

Balanced reactions are :

2KMnO4 + 5H2O2 + 3H2SO4  K2SO4 + 2MnSO4 + 8H2O + 5O2
2KMnO4 + 3MnSO4 + 2H2O  5MnO2 + 2H2SO4 + K2SO4
MnO2 + Na2C2O4 + 2H2SO4  MnSO4 + 2CO2 + Na2SO4 + 2H2O
Once balanced reactions are known the problem can be solved easily by mole concept.
Method 2 :
One may think using equivalent concept as follows.
Equivalents of Na2C2O4 = Equivalents of MnO2
= Equivalents of KMnO4 = Equivalents of H2O2
Let the molarity of H2O2 solution is M, then
10 × 10–3 × 0.2 × 2 = M × 20 × 10–3 × 2
 M = 0.1
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
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.
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
0.25 M NaOH. Find the atomic weight of X.
Sol. Method 1 : (Mole concept)
0 +5 +2 –3
4X + 7NaOH + NaNO3  4Na2XO2 + NH3 + 2H2O
v.f. = 2 v.f. = 8 v.f. = 8
2NH3 + H2SO4  (NH4)2SO4
(v.f. = 1) (v.f. = 2)

2NaOH + H2SO4  Na2SO4 + 2H2O

(v.f. = 1) (v.f. = 2)
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

Page # 23
 2.616
 0.04 =
M
2.616
 Atomic weight of X = M = = 65.4
0.04

Method 2 : (Equivalent concept)

100  0.11 2 48  0.5 
Equivalent of H2SO4 consumed by NH3 =  
 1000 1000 
= 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
= Equivalents of X reacted
2.616  2
 0.08 =
M
 Atomic weight of X = M = 65.4

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