CHEMISTRY LECTURE NOTES

COURSE - VIJAY (R)

(LECTURE No. 1 TO 6)

TOPIC : Mole Concept-2

STUDY THE LECTURE NOTES BEFORE

GOING INTO THE CLASS AND IF THERE IS
ANY DOUBT, DO MAKE IT CLEAR AFTER
DISCUSSING IT WITH YOUR SENIORS
 Lecture - 01
CONCEPT OF OXIDATION NUMBER :
Real or imaginary charge present on an element when it goes from its elemental free state to
combined state.

Rules governing oxidation number :

The following rules are helpful in calculating oxidation number of the elements in their different compounds.
It is remembered that the basis of these rule is the electronegativity of the element .

1. Fluorine atom :
Flurine is most electronegative atom yet known and it has always oxidation number equal to –1 in any
compound

2. Oxygen atom :
In general and in the case of its oxide oxygen atom has oxidation number equal to –2. In case of
peroxide (e.g. H2O2, , Na2O2 ) it is –1, In case of super oxide (e.g KO2) and ozonide (KO3) it is –1/2 and
–1/3 , In case of oxgyen Flouride OF2 it is + 2 & in O2F2 it is +1

3. Hydrogen atom :
In general H atom has oxidation number equal to +1 in all its compounds but in case of metallic
hydride e.g. NaH, KH it is –1

4. Halogen atom :
In general all halogen atom (Cl,Br ,I) has oxidation number equal to –1 But if halogen atom is attached
with an atom which is more electronegative than halogen atom then it will show positive oxidation
number

5 5 7 5
e.g. K ClO , HI O , HCIO , KBrO
3 3 4 3

5. Metals :
(a) Alkali metal (Li , Na, K, Rb, .......) always have oxidation number +1 in all its compound.
(b) Alkaline earth metal (Be , Mg , Ca .......) always have oxidation number +2 in all its compound.
Note :- Metal may have negative or zero oxidation number

6. Oxidation number of an element in free state or in allotropic forms is always zero

0 0 0 0
e.g. O , S , P , O
2 8 4 3

7. Sum of the charges of all elements in a molecule is zero.

8. Sum of the charges of all elements in an ion is equal to the charge on the Ion .
9. If the group no. of an element in periodic table is n then its oxidation number may vary from
n to n – 8 (but it is mainly applicable in p-block elements )
e.g. N- atom belongs to v group in the periodic table therefore as per rule its oxidation number may
vary from

3 2 3 4 5
–3 to +5 ( N H ,NO , N 2 O , N O , N 2 O )
3 3 2 5

Page # 24
Calculation of average oxidation number :
Q. Calculate oxidation number of underlined element
1. Na2 S2O3 :
Let oxidation number of S-atom is x. now work accordinly with the rules given before .
(+1) × 2 + (x) × 2 + (–2) ×3 =0
x=+2
2. Na2 S 4O6 :
Let oxidation number of s-atom is x
(+1) × 2 + (x) × 2 + (–2) × 6 = 0
x = + 2.5
It’s important to note here that Na2S2O3 have two s-atom and there are four s-atom in Na2S4O6 but none
sulphur atom in both the compound have + 2 or + 2.5 oxidation number it is the average charge (O.No.)
which reside on each sulphur atom therefore we should work to calculate the individual oxidation
number of each sulphur atom in these compound.

Calculation of individual oxidation number :

It is important to note that to calculate individual oxidation number of the element in its compound one
should know the structure of the compound and use the following guidelines.
Formula:
Oxidation Number = number of electrons in the valence shell – number of electrons left
after bonding

Guidelines :
These guidelines to calculate oxidation number is given on the basis of electronegativity.

1. If there is a bond between similar type of atom and each atom has same type of hybridisation then
bonded pair electrons are equally shared by each element

Ex. Calculate oxidation number of each Cl– atom in Cl2 molecule

Structure :

 : No. of electrons in the valence shell = 7.

No. of electrons left after bonding = 7.
oxidation number = 7 – 7 = 0.

 : similarly oxidation number = 7 – 7 = 0.

2. It there in a bond between differnt type of atoms

e.g. A – B (B is more electronegative than A)
Then after bonding bonded pair electrons are counted with B - atom .

Ex. Calculate oxidation number of each atom in HCl molecule

Structure :

Page # 25
Note : Electron of H-atom is now counted with Cl-atom, because Cl-atom is more E.N. than H-atom
H : number of electrons in the valence shell = 1
number of electrons left after bonding = 0
oxidation number = 1 – 0 = + 1
Cl : Number of electrons in the valence shell = 7
Number of electrons left affer bonding = 8
Oxidation number = 7– 8 = – 1
Ex. Calculate individual oxidation number of each s -atom in Na2S2O3 (sodium thio sulphate) with the help
of its structure .

Sol. Structure :

 (central S-atom) is sp3 hybridised (25% s-character) and  (terminal S-atom) is sp2 hybridised
(33% S-character). Therefore terminal sulphur atom is more electronegative than central sulphur
atom. Now the shared pair electrons are counted with terminal S-atom.
 , S-atom : No. of electrons in the valence snell = 6
: No. of electrons left affer bonding = 0
Oxidation No. = 6 – 0 = + 6
, S-atom : No. of electrons in the valence shell = 6
No. of electrons left affrer bonding = 8
Oxidation No. = 6 – 8 = – 2
62
Now you can also calculate Average Oxidation No. = = + 2 ( as we have calculated before )
2

1. Calculate individual oxidation number of each s -atom in Na2S4O6 (sodium tetrathionate) with
the help of its structure .

Miscellaneous Examples :
In order to determine the exact or individual oxidation number we need to take help from
the structures of the molecules.Some special cases are discussed as follows:
O O
 The structure of CrO5 is Cr
||
O O O

From the structure it is evident that in CrO5 there are two peroxide linkages and one double
bond. The contribution of each peroxide linkage is –2. Let the O.N. of Cr is x.
 x + (–2)2 + (–2) = 0 or x = 6
 O.N. of Cr = +6
O
 The structure of H2SO5 is H O O S
O
H O
Page # 26
 From the structure, it is evident that in H2SO5. there are one peroxide linkage, two sulphur-oxygen
double bond and one OH group. Let the O.N. of S = x.
 +1 – 2 + x + (–2) 2+ (–2) + 1 = 0
or x + 2 – 8 = 0
or x – 6 = 0
or x = 6
 O.N. of S in H2SO5 is + 6.

Paradox of fractional oxidation number :

Fractional oxidation state is the average oxidation state of the element under examination and
the structural parameters reveal that the element for whom fractional oxidation state is realised
is actually present in different oxidation states. Structure of the species C3O2, Br3O8 and
S4O62– reveal the following bonding situations :

 The element marked with asterisk in each species is exhibiting the different oxidation state
(oxidation number) from rest of the atoms of the same element in each of the species. This
reveals that in C3O2, two carbon atoms are present in +2 oxidation state each whereas the
third one is present in zero oxidation state and the average is 4/3. However the realistic
picture is +2 for two terminal carbons and zero for the middle carbon.
2 0 2
O  C  C*  C  O
Structure of C3O2
(Carbon suboxide)
 Likewise in Br3O8, each of the two terminal bromine atoms are present in +6 oxidation state
and the middle bromine is present in +4 oxidation state. Once again the average, that is
different from reality is 16/3.

O O O
+6 +4 || +6
O = Br Br* Br = O
||
O O O
Structure of Br3O8 (tribromooctaoxide)

 In the same fashion, in the species S4O62–, is 2.5, whereas the reality being +5,0,0 and +5
oxidation number respectively for each sulphur.

O O
||+5 0 ||
- 0
O S S* S* S O¯
|| ||
O O
Structure of S4 O62- (tetrathionate ion)

In general, conclude that the idea of fractional oxidation state should be taken with care and
the reality is revealed by the structures only.

1. Find the average and individual oxidation number of Fe3O4, MnO4, Pb3O4 , which are mixed oxides.
2. Calculate oxidation number of each atom in the following compounds.
(a) H2S2O8 (b) CrO5 (c) Rb4Na[HV10O28] (d) Na2S2O3
(e) K2FeO4 (f) Ba2XeO4 (g) HCN (h) HNC
(i) C3O2 (j) S4O62– (k) Br3O8 (l) Fe3O4

Page # 27
OXIDATION & REDUCTION :
Let us do a comparative study of oxidation and Reduction :
Oxidation Reduction
1. Addition of oxygen 1. Removal of oxygen
e.g. 2Mg + O2  2MgO e.g. CuO + C  Cu + CO
2. Removal of Hydrogen 2. Addition of Hydrogen
e.g. H2S + Cl2  2HCl + S e.g. S + H2  H2S
3. Increase in positive charge 3. Decrease in positive charge
e.g. Fe2+  Fe3+ + e– e.g. Fe3+ +e  Fe2+
4. Increase in oxidation number 4. Decrease in oxidation number
(+2) (+4) (+7) (+2)
SnCl2  SnCl4 MnO4–  Mn2+
5. Removal of electron 5. Addition of electron
e.g. Sn2+  Sn4+ + 2e– e.g. Fe3+ + e  Fe2+

Oxidation and reduction always take place simultaneously. Such overall reactions which involves
simultaneous oxidation and reduction are called Redox Reaction.

Oxidizing and reducing agents :

Substances that oxidized is called reducing agent and substances that reduced is called oxidizing
agent.
For Example :

( 5 ) ( 2) ( 2 )
(0)
2 HNO 3 + 3 H2 S  2 NO + 3S + 4H2O
O.A. R.A.

Important oxidizing agents :

O2, O3, X2 (halogens), KMnO4, K2Cr2O7, Na2Cr2O7, CrO3, H2SO4, HNO3, NaNO3, FeCl3, HgCl2, KClO3,
MgO, CuO, CrO3, CO2, P4O10, H2O2, CO2, SO3 etc.
Important reducing agents :
All metals, (ex. Na, Zn, Fe, Al etc), a few nonmetals (ex. C, H2, S, P etc.) Hydra acids (HCl, HBr, HI,
H2S etc), Metallic hydrides (NaH, LiH, CaH2 etc). Organic compounds like HCOOH, (COOH)2 and
tartaric acid and their salts, aldehydes, alkanes etc.
Lithium (Li) is the strongest reducing agent in solution, Cesium is the strongest reducing agent in
absence of water.
Substances which act as oxidising as well as reducing agents are :
H2O2, SO2, H2SO3, HNO2, NaNO2, Na2SO3, O3 etc. Such a molecule is said to autooxidise and the
process (reaction) as autooxidation or disproportionation.
1 1 1 1 1 2 0
Ex. H 2 O 2  H2 O 2  2 H 2 O  O 2

Note : (i) If an element is in it’s highest possible oxidation state in a compound, it can function as an
oxidizing agent.
Ex. KMnO4, K2Cr2O7, HNO3, H2SO4, HClO4 etc.
(ii) If an element is in its lowest possible oxidation state in a compound, it can function as a
reducing agent.
Ex. H2S, H2C2O4, FeSO4, Na2S2O3, SnCl2 etc.
(iii) If an element is in its intermediate oxidation state in a compound it can function both as an
oxidizing agent as well as reducing agent
Ex. H2O2, H2SO4, HNO2, SO2 etc.
Page # 28
Types of Redox Reactions :
1. Combination reactions :
A combination reaction may be denoted in the manner:
A + B  C
Either A and B or both A and B must be in the elemental form for such a reaction to be a redox reaction.
All combustion reactions, which make use of elemental dioxygen, as well as other reactions involving
elements other than dioxygen, are redox reactions. Some important examples of this category are:
0 0 4 2
C(s)  O 2 (g) 

C O 2 (g)
0 0 2 3
3Mg(s)  N2 (g) 

Mg3 N 2 (s)
4 1 0 4  2 1  2
CH4 (g)  2 O 2 (g) 

CO 2 (g)  2H2O()
2. Decomposition reactions : Decomposition reactions are the opposite of combination reactions.
Precisely, a decomposition reaction leads to the breakdown of a compound into two or more components
at least one of which must be in the elemental state. Examples of this class of reactions are:
1 2 0 0
2H2O() 

2H2 (g)  O 2 (g)
1 1 0 0
2NaH(s) 

2Na(s)  H2 (g)
1  5  2 1 1 0
2KClO3 (s) 

2KCl(s)  3O 2 (g)
3. Displacement reactions : In a displacement reaction, an ion (or an atom) in a compound is replaced
by an ion (or an atom) of another element. It may be denoted as:
X + YZ  XZ + Y
Displacement reactions fit into two categories: metal displacement and non-metal displacement.
(a) Metal displacement: A metal in a compound can be displaced by another metal in the uncombined
state. Metal displacement reactions find many applications in metallurgical processes in which pure
metals are obtained from their compounds in ores. A few such examples are:
2  6  2 0 0 2  6  2
CuSO 4 (aq)  Zn(s)  Cu(s)  ZnSO 4 (aq)
5  2 0 0 2  2
V2O 5 (s)  5 Ca(s) 

2V(s)  5CaO(s)
4 1 0 0 2 1
TiCl4 ()  2 Mg(s) 

Ti (s)  2MgCl2 (s)
3 2 0 3 2 0
Cr2O3 (s)  2 Al(s) 

Al 2O3 (s)  2Cr(s)
In each case, the reducing metal is a better reducing agent than the one that is being reduced which
evidently shows more capability to lose electrons as compared to the one that is reduced.
(b) Non-metal displacement: The non-metal displacement redox reactions include hydrogen displacement
and a rarely occurring reaction involving oxygen displacement.
All alkali metals and some alkaline earth metals (Ca, Sr, and Ba) which are very good reductants, will
displace hydrogen from cold water.
0 1  2 1  2 1 0
2Na(s)  2H2O()  2NaOH(aq)  H2 (g)
0 1  2 2  2 1 0
Ca(s)  2H2O( )  Ca(OH)2 (aq)  H2 (g)
Less active metals such as magnesium and iron react with steam to produce dihydrogen gas.
0 1 2 2  2 1 0
Mg(s)  2H2O() 

Mg(OH)2 (s)  H2 (g)
0 1 2 3 2 0
2Fe(s)  3H2O() 

Fe 2O3 (s)  3H2 (g)

Page # 29
 Many metals, including those which do not react with cold water, are capable of displacing hydrogen
from acids. Dihydrogen from acids may even be produced by such metals which do not react with
steam. Cadmium and tin are the examples of such metals. A few examples for the displacement of
hydrogen from acids are :
0 1 1 2 1 0
Zn(s)  2HCl(aq)  ZnCl2 (aq)  H2 (g)
0 1 1 2 1 0
Mg(s)  2HCl(aq)  MgCl2 (aq)  H2 (g)
0 1 1 2 1 0
Fe(s)  2HCl(aq)  FeCl2 (aq)  H2 (g)
Above three reactions are used to prepare dihydrogen gas in the laboratory. Here, the reactivity of
metals is reflected in the rate of hydrogen gas evolution, which is the slowest for the least active metal
Fe, and the fastest for the most reactive metal, Mg. Very less active metals, which may occur in the
native state such as silver (Ag), and gold (Au) do not react even with hydrochloric acid.
We already know that the metals - zinc (Zn), copper (Cu) and silver (Ag) through tendency to lose
electrons show their reducing activity in the order Zn> Cu>Ag. Like metals, activity series also exists
for the halogens. The power of these elements as oxidising agents decreases as we move down from
fluorine to iodine in group 17 of the periodic table. This implies that fluorine is so reactive that it can
replace chloride, bromide and iodide ions in solution. In fact, fluorine is so reactive that it attacks water
and displaces the oxygen of water:
1  2 0 1 1 0
2H2O()  2F2 (g)  4HF(aq)  O 2 (g)
It is for this reason that the displacement reactions of chlorine, bromine and iodine using fluorine are
not generally carried out in aqueous solution. On the other hand, chlorine can displace bromide and
iodide ions in an aqueous solution as shown below:
0 1 1 1 1 0
Cl2 (g)  2KBr(g)  2KCl(aq)  Br2 ( )
0 1 1 1 1 0
Cl2 (g)  2K (aq)  2KCl (aq)   2 (s)
As Br2 and I2 are coloured and dissolve in CCI4, can easily be identified from the colour of the solution.
The above reactions can be written in ionic form as:
0 1 1 0
Cl2 (g)  2Br  (aq)  2Cl  (aq)  Br2 ( )

0 1 1 0
Cl2 ( g)  2  (aq)  2Cl  (aq)   2 ( s)
Above two reactions form the basis of identifying Br– and I– in the laboratory through the test popularly
known as ‘Laye!’ Test’. It may not be out of place to mention here that bromine likewise can displace
iodide ion in solution:
0 1 1 0
Br2 (  )  2  (aq)  2Br  (aq)   2 ( s)
The halogen displacement reactions have a direct industrial application. The recovery of halogens from
their halides requires an oxidation process, which is represented by:
2X–  X2 + 2e
–

here X denotes a halogen element. Whereas chemical means are available to oxidise Cl , Br and I ,
– – –

as fluorine is the strongest oxidising agent; there is no way to convert F ions to F2 by chemical
–

means. The only way to achieve F2 from F is to oxidise electrolytically, the details of which you will
–

study at a later stage.

4. Disproportionation reactions :
Disproportionation reactions are a special type of redox reactions. In a disproportionation reaction an
element in one oxidation state is simultaneously oxidised and reduced. One of the reacting substances
in a disproportionation reaction always contains an element that can exist in at least three oxidation
states. The element in the form of reacting substance is in the intermediate oxidation state; and both
higher and lower oxidation states of that element are formed in the reaction. The decomposition of
hydrogen peroxide is a familiar example of the reaction, where oxygen experiences disproportionation.
1 1 1 2 0
2H2O 2 (aq)  2H2O ()  O 2 (g)

Page # 30
 Here the oxygen of peroxide, which is present in -1 state, is converted to zero oxidation state in O2 and
decreases to -2 oxidation state in H2O. Phosphorous, sulphur and chlorine undergo disproportionation
in the alkaline medium as shown below:
0 3 1
P4 (s)  3OH  (aq)  3H2 O( )  PH3 (g)  3H2PO 2 (aq)

0 2 2
S 8 (s)  12OH (aq)  4S
 2
(aq)  2S 2 O 23  (aq)  6H2 O( )
0 1 2
Cl2 ( g)  2OH  (aq)  ClO  (aq)  Cl  (aq)  H2 O(  )

The last reaction describes the formation of household bleaching agents. The hypochlorite ion (CIO-)
formed in the reaction oxidises the colour-bearing stains of the substances to colourless compounds.

It is of interest to mention here that whereas bromine and iodine follow the same trend as exhibited by
chlorine in the last reaction, fluorine shows deviation from this behaviour when it reacts with alkali. The
reaction that takes place in the case of fluorine is as follows:
2F2(g) + 2OH–(aq)  2F– (aq) + OF2(g) + H2O()
(It is to be noted with care that fluorine in reaction above will undoubtedly attack water to produce
some oxygen also). This departure shown by fluorine is not surprising for us as we know the limitation
of fluorine that, being the most electronegative element, it cannot exhibit any positive oxidation state.
This means that among halogens, fluorine does not show a disproportionation tendency.
5. Comproportionation reactions : Reverse of disproportionation is called comproportionation
For Ex. I + IO3 + H  I2 + H2O.
– – +

Ex. Which of the following species, do not show disproportionation reaction and why?
CIO–, CIO2–, CIO3– and ClO4–
Also write reaction for each of the species that disproportionates.
Sol. Among the oxoanions of chlorine listed above, CIO4– does not disproportionate because in this oxoanion
chlorine is present in its highest oxidation state that is, +7. The disproportionation reactions for the
other three oxoanions of chlorine are as follows:
1 1 5
3ClO   2Cl   ClO 3
3 5 1
6ClO 2 
h
 4ClO 3  2Cl
5 1 7
4ClO 3  Cl   3ClO 4

Ex. Suggest a scheme of classiflcation of the following redox reactions.

(a) N2(g) + O2(g)  2NO(g)
1
(b) Pb(NO3)2(s)  PbO(s) + 2NO2(g) + O (g)
2 2
(c) NaH(s) + H2O()  NaOH(aq) + H2(g)
(d) 2NO2(g) + 2OH (aq)  NO2 (aq) + NO3 (aq) + H2O()
– – –

Sol. In reaction (a), the compound nitric oxide is formed by the combination of the elemental substances,
nitrogen and oxygen ; therefore, this is an example of combination redox reaction. The reaction (b)
involves the breaking down of lead nitrate into three components ; therefore, this is categorised under
decomposition redox reaction. In reaction (c), hydrogen of water has been displaced by hydride ion
into dihydrogen gas. Therefore, this may be called as displacement redox reaction. The reaction (d)
involves disproportionation of NO2 (+4 state) into NO2 (+3 state) and NO3 (+5 state). Therefore
– –

reaction (d) is an example of disproportionation redox reaction.

Page # 31
Ex. Why do the following reactions proceed differently?
Pb3O4 + 8HCl  3PbCl2 + Cl2 + 4H2O
and Pb3O4 + 4HNO3  2Pb(NO3)2 + PbO2 + 2H2O
Sol. Pb3O4 is actually a stoichiometric mixture of 2 mol of PbO and 1 mol of PbO2. In PbO2, lead is present
in +4 oxidation state. whereas the stable oxidation state of lead in PbO is +2. PbO2 thus can act as an
oxidant (oxidising agent) and, therefore, can oxidise Cl ion of HCI into chlorine. We may also keep in
–

mind that PbO is a basic oxide. Therefore, the reaction

Pb3O4 + 8HCl  3PbCl2 + Cl2 + 4H2O
can be splitted into two reactions namely:
2PbO + 4HCl  2PbCl2 + 2H2O (acid-base reaction)
4 1 2 0
Pb O 2  4H Cl  Pb Cl2  Cl2  2H2O (redox reaction)
Since HNO3 itself is an oxidising agent therefore, it is unlikely that the reaction may occur between
PbO2 and HNO3. However, the acid-base reaction occurs between PbO and HNO3 as:
2PbO + 4HNO3  2Pb(NO3)2 + 2H2O
It is the passive nature of PbO2 against HNO3 that makes the reaction different from the one that
follows with HCl.

Lecture - 02
Balancing of redox reactions :
All balanced equations must satisfy two criteria
1. Atom balance (mass balance) :
That is there should be the same number of atoms of each kind in reactant and products side.
2. Charge balance :
That is the sums of actual charges on both sides of the equation must be equal

Two methods are used to balance chemical equations for redox processes. One of these methods is
based on the change in the oxidation number of reducing agent and the oxidising agent and the other
method is based on splitting the redox reaction into two half reactions - one involving oxidation and the
other involving reduction. Both these methods are in use and the choice of their use rests with the
individual using them.
(a) Oxidation Number Method : In writing equations for oxidation-reduction reactions, just as for other
reactions, the compositions and formulas must be known for the substances that react and for the
products that are formed. The oxidation number method is now best illustrated in the following steps:

Step 1: Write the correct formula for each reactant and product.
Step 2: Identify atoms which undergo change in oxidation number in the reaction by assigning the oxidation
number to all elements in the reaction.
Step 3: Calculate the increase or decrease in the oxidation number per atom and for the entire molecule/ion in
which it occurs. If these are not equal then multiply by suitable coefficients so that these become
equal. (If you realise that two substances are reduced and nothing is oxidised or vice-versa, something
is wrong. Either the formulas of reactants or products are wrong or the oxidation numbers have not
been assigned properly).
Step 4: Ascertain the involvement of ions if the reaction is taking place in water, add H+ or OH– ions to the
expression on the appropriate side so that the total ionic charges of reactants and products are equal.
If the reaction is carried out in acidic solution, use H+ ions in the equation; if in basic solution, use OH–
ions.
Step 5: Make the numbers of hydrogen atoms in the expression on the two sides equal by adding water (H2O)
molecules to the reactants or products. Now, also check the number of oxygen atoms. If there are the
same number of oxygen atoms in reactants and products. the equation then represents the
balanced redox reaction.
Let us now explain the steps involved in this method with the help of a few problems given below:
Page # 32
Ex. Write the net ionic equation for the reaction of potassium dichromate (VI), K2Cr2O7 with sodium sulphite
(Na2SO3) in an acid solution to give chromium(III) ion and the sulphate ion.
Step 1: The skeletal ionic equation is:
Cr2O72–(aq) + SO32–(aq)  Cr3+(aq) + SO42–(aq)
Step 2: Assign oxidation numbers for Cr and S.
6 2 4  2 3 6  2
Cr2 O 72 (aq) SO 32  (aq)  Cr (aq)  SO 24 (aq)
This indicates that the dichromate ion is the oxidant and the sulphite ion is the reductant.
Step 3: Calculate the increase and decrease of oxidation number, and make them equal:
6  2 4  2 3 6  2
Cr2 O 72 (aq)  3SO 32 (aq)  2Cr 3  (aq)  3SO 24 (aq)

Step 4: As the reaction occurs in the acidic medium, and further the ionic charges are not equal on both the
sides, add 8H+ on the left to make ionic charges equal
Cr2O72–(aq) + 3SO32–(aq) + 8H+(aq)  2Cr3+(aq) + 3SO42–(aq) + 4H2O()
Step 5: Finally, count the hydrogen atoms, and add appropriate number of water molecules (i.e., 4H2O) on the
right to achieve balanced redox change.
Cr2O72–(aq) + 3SO32–(aq) + 8H+(aq)  2Cr3+(aq) + 3SO42–(aq) + 4H2O()

Ex. Permanganate ion reacts with bromide ion in basic medium to give manganese dioxide and bromate
ion. Write the balanced ionic equation for the reaction.

Step 1 : The skeleton ionic equation is :

MnO4– (aq) + Br – (aq)  MnO2(s) + BrO3 (aq)
–

Step 2 : Assign oxidation numbers for Mnand Br

7 1 4 5
MnO 4 (aq)  Br  (aq)  MnO 2 ( s)  BrO 3 (aq)
this indicates that permanganate ion is the oxidant and bromide ion is the reductant.

Step 3: Calculate the increase and decrease of oxidation number, and make the increase equal to the decrease.
7 1 4 5
2MnO 4 (aq)  Br  (aq)  2MnO 2 ( s)  BrO 3 (aq)

Step 4: As the reaction occurs in the basic medium, and the ionic charges are not equal on both sides, add 2
OH- ions on the right to make ionic charges equal.
2MnO4–(aq) + Br –(aq)  2MnO2(s) + BrO3–(aq) + 2OH–(aq)

Step 5: Finally, count the hydrogen atoms and add appropriate number of water molecules (I.e. one H20
molecule) on the left side to achieve balanced redox change.
2MnO4 (aq) + Br (aq) + H2O()  2MnO2(s) + BrO3–(aq) + 2OH–(aq)
– –

(b) Half Reaction Method (Ion electron method): In this method, the two half equations are balanced separately
and then added together to give balanced equation.
Suppose we are to balance the equation showing the oxidation of Fe2+ ions to Fe3+ ions by dichromate
ions Cr2O72– in acidic medium, wherein, Cr2O72– ions are reduced to Cr3+ ions. The following steps are
involved in this task.
Step 1: Produce unbalanced equation for the reaction in ionic form :
Fe2+(aq) + Cr2O72– (aq)  Fe3+(aq) + Cr3+(aq)
Step 2: Separate the equation into half reactions :
2 3
Oxidation half : Fe 2  (aq)  Fe 3  (aq)
6  2 3
Reduction half : Cr2O 27  (aq)  Cr 3  (aq)

Page # 33
Step 3: Balance the atoms other than and H in each half reaction individually. Here the oxidation half reaction
is already balanced with respect to Fe atoms. For the reduction half reaction, we multiply the Cr3+ by
2 to balance Cr atoms.
Cr O (aq)  2Cr3+(aq)
2–

2 7

Step 4: For reactions occurring in acidic medium, add H2O to balance O atoms and H to balance H atoms.
+

Thus, we get:
Cr2O72–(aq) + 14H+ (aq)  2Cr3+(aq) + 7H2O()
Step 5: Add electrons to one side of the half reaction to balance the charges. It need to, make the number of
electrons equal in the two half reactions by multiplying one or both half reactions by appropriate
coefficients.
The oxidation half reaction is thus rewritten to balance the charge:
Fe2+ (aq)  Fe3+ (aq) + e
–

Now in the reduction half reaction there are net twelve positive charges on the left hand side and only
six positive charges on the right hand side. Therefore. we add six electrons on the left side.
Cr2O72–(aq) + 14H+(aq) + 6e–  2Cr3+(aq) + 7H2O()
To equalise the number of electrons in both the half reactions. we multiply the oxidation half reaction
by 6 and write as : Fe2+(aq)  Fe3+(aq) + 6e–

Step 6: We add the two half reactions to achieve the overall reaction and cancel the electrons on each side.
This gives the net ionic equation as :
6Fe2+(aq) + Cr2O72–(aq) + 14H+(aq)  6Fe3+(aq) + 2Cr3+(aq) + 7H2O()

Step 7: Verify that the equation contains the same type and number of atoms and the same charges on both
sides of the equation. This last check reveals that the equation is fully balanced with respect to
number of atoms and the charges.
For the reaction in a basic medium, first balance the atoms as is done in acidic medium. Then for each
H+ ion, add an equal number of OH- ions to both sides of the equation. Where H+ and OH- appear on
the same side of the equation, combine these to give H2O.
Ex. Permanganate (VII) ion. MnO4– in basic solution oxidises iodide ion, I– to produce molecular iodine (I2)
and manganese (IV) oxide (MnO2). Write a balanced ionic equation to represent this redox reaction.

Step 1: First we write the skeleton ionic equation, which is

MnO4–(aq) + I– (aq)  MnO2(s) + I2(s)
Step 2: The two half-reactions are:
1 0
Oxidation half :   (aq)   2 ( s)

7 4
Reduction half : MnO 4 (aq)  MnO 2 ( s)

Step 3: To balance the 1 atoms in the oxidation half reaction, we rewrite it as:
2I–(aq)  I2(s)
Step 4: To balance the atoms in the reduction half reaction. we add two water molecules on the right:
MnO4–(aq)  MnO2(s) + 2H2O()
To balance the H atoms. we add four H+ ions on the left:
MnO4–(aq) + 4H+(aq)  MnO2(s) + 2H2O()
As the reaction takes place in a basic solution, therefore, for four H+ ions, we add four OH– ions to both
sides of the equation :
MnO4–(aq) + 4H (aq) + 4OH (aq)  MnO2(s) + 2H2O() + 4OH–(aq)
+ –

Replacing the H+ and OH- ions with water, the resultant equation is:
MnO4–(aq) + 2H2O()  MnO2(s) + 4OH–(aq)
Page # 34
Step 5 : In this step we balance the charges of the two half-reactions in the manner depicted as:
2I(aq)  I2(s) + 2e
–

MnO4 (aq) + 2H2O() + 3e  MnO2(s) + 4OH (aq)

– – –

Now to equalise the number of electrons, we multiply the oxidation half-reaction by 3 and the reduction
half-reaction by 2.
6I(aq)  3I2(s) + 6e–
2MnO4–(aq) + 4H2O() + 6e–  2MnO2(s) + 8OH–(aq)

Step 6: Add two half-reactions to obtain net reactions after cancelling electrons on both sides.
6I– (aq) + 2MnO4– (aq) + 4H2O()  3I2(s) + 2MnO2(s) +8OH (aq)
–

Step 7: A final verification shows that equation is balanced in respect of the number of atoms and charges on
both sides.

Ex. FeSO4 + KMnO4 + H2SO4  Fe2(SO4)3 + MnSO4 + H2O

Sol.
Step 1: Assign the oxidation No. to each elements present in the reaction.
2 6 2 1  7 – 2  1  6 2 3 6 2 2 6 2 1 2
Fe S O 4 + K MnO 4 + H 2 S O 4  Fe 2 (S O 4 )3 + Mn S O 4 + H 2 O
Step 2: Now convert the reaction in ionic form by eleminating the elements or species which are not going
either oxidation or reduction
7
Fe2+ + Mn O 4  Fe3+ + Mn2+
Step 3: Now Identify the oxidation / reduction occuring in the reaction

Step 4: Spilt the ionic reaction in two half one for oxidation and other for reduction

Fe2+    Fe3+ MnO 4    Mn2 

oxidation  Re duction

Step 5: Balance the atom other than oxygen and hydrogen atom in both half reactions

Fe2+  Fe3+ MnO4 – Mn2+

Fe & Mn atom are balanced in both side.

Step 6: Now balance O & H atom by H2O & H+ respectively by the following way. For one excess oxygen
atom add one H2O on the other side and two H+ on the same side.
Fe2+  Fe3+ (no oxygen atom ) .................(i)
8H+ + MnO4–  Mn2+ + 4H2O ................(ii)
Step 7: Now see equation (i) & (ii) is balanced atomwise. Now balance both equations chargewise To balence
the charge add electrons to the electrically positive side .
Fe2+ oxidation
  Fe3+ + e– ............(1)
Re
5e– + 8H+ + MnO4–  duction
  Mn + 4H2O ............(2)
2+

Page # 35
Step 8: The number of electrons gained and lost in each half -reaction are equalised by multipling suitable
factor in both the half reaction and finaly the half reactions are added to give the over all balanced
reaction
Here we multiply equation (1) by 5 and (2) by one
Fe2+  Fe3+ + e– ..........(1) × 5

5e   8H  MnO 4  Mn 2   4H2O .........( 2)  1



5Fe  8H  MnO 4  5Fe  Mn  4H2 O

2   3 2

Here at this stage you will get balanced redox reaction in ionic form

Step 9: Now convert the Ionic reaction into molecular form by adding the elements or species which are
removed in step (2).
Now by some manipulation you will get
5
5 FeSO4 + KMnO4 + 4H2SO4  Fe2 (SO4)3 + MnSO4 + 4H2O or
2
10FeSO4 + 2KMnO4 + 8H2SO4  5Fe2(SO4)3 + 2MnSO4 + 8H2O + K2SO4.

Ex. Balance the redox reaction in basic medium

ClO– + CrO2– + OH–  Cl– + CrO42– + H2O
Sol. By using up to step V we will get

1 3 6
Cl O     Cl –
Re duction
Cr O 2    Cr O 24
Oxidation

Now student are advised to follow step VI to balance ‘O’ and H– atom

2H+ + ClO–  Cl– + H2O | 2H2O+ CrO2–  CrO42– + 4H+

 Now since we are doing balancing in basic medium therefore add as many as OH– on both side of
equation as there are H+ ions in the equation
2OH– + 2H+ + ClO–  Cl– + H2O +2OH– 4OH– + 2H2O + CrO2–  CrO42– + 4H+ + 4OH–
Finally you will get Finally you will get
H2O + ClO–  Cl– + 2OH– ...........(i) 4OH– + CrO2–  CrO42– + 2H2O ........... (ii)

Now see equation (i) and (ii) in which O and H atoms are balanced by OH– and H2O
Now From step VIII
2e– + H2O + ClO–  Cl– + 2OH– ............. (i) ×3
4OH + CrO2
– –
 CrO4 + 2H2O + 3e
2– –
............. (ii) ×2
–––––––––––––––––––––––––––––––––––––––––––––––––––
Adding : 3ClO– + 2CrO2– + 2OH–  3Cl– + 2CrO42– + H2O

Ex. Balance the following reactions

(a) FeC2O4 + KMnO4 + H2SO4  Fe2(SO4)3 + CO2 + MnSO4 + K2SO4 + H2O
(b) V  [HV6O17]3– + H2
Do tell the students that whenever oxygen or hydrogen is coming out from the redox reaction(in
aqeous medium) then the water is taken as source of these.
(c) As2S3 + HNO3  H3AsO4 + H2SO4 + NO ; (d) FeS2 + O2  Fe2O3 + SO2

Page # 36
 Lecture - 03
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 + O 2 
48g 32g
12g 8g
 32 g of O2 reacts with 48 g of Mg
48  8
 8 g of O 2 = = 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.
So,
Atomic weight
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.

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

Page # 37
 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.

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


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.

Page # 38
Some Examples :
HCl  H+ + Cl–
(v.f. = 1)

H2SO4  H+ + HSO 4–

(v.f. = 1)

H2SO4  2H+ + SO 42–

(v.f. = 1)

H3PO 4  H+ + H2PO 4–

(v.f. = 1)

H3PO4  2H+ + HPO 4–

(v.f. = 2)

H3PO4  3H+ + PO 43–

(v.f. = 3)

H3PO 3  H+ + H2PO 3–

(v.f. = 1)

H3PO3  2H+ + HPO 3–

(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 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
M nO 4 
 M n2

H

(v.f = 5)

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
Page # 39
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
changes to Mn+6. So total decrease in oxidation state of Mn = 
3 3
11
So, v.f.= .
3
Ex. Calculate the n-factor of the reactant (oxidant or reductant) in following cases.
(i) 3MnO4–  2Mn2+ + Mn4+
(ii) 2MnO 4–  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

(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.

Page # 40
 For example.
K2Cr2O 7 + 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 FeC2O 4
contains one mole of Fe2+ and one mole of C2O 42– (i.e. 2 carbon atoms per mole of C2O 42–.
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 2O3  SO 2

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

(iii) Cu2S  Cu2+ + SO 2

(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 3
(NH4 )2Cr2O 7  N2  Cr2O 3  4H2O .
0

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
(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 + O 2

Page # 41
 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 H2O 2 is being reduced
(H2O 2  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  2H2O 2
v.f = 2(–1– (–2)) = 2
So, valency factor of H2O 2 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 – + 6Br 2  10Br – + 2BrO 3– + 6H2O.
In this reaction, the electrons released by the oxidation of some of the Br 2 are the sameones 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 Br 2 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.

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

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
Cr2O 7
2–
 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 # 42
 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

O3  O2 + O
2–

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

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

Page # 43
 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

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.

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.

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.

Page # 44
Ex. Calculate the amount of oxygen required to produce enough carbon mono oxide on reaction with
carbon which can reduce 1.6 kg Fe2O 3.
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 Fe2O 3 =  1600 = 3 × 28 × 10 = 840 g
160

1 16 28
C O 2  CO
2
16
O 2 required to produce 840 g CO =  840 = 480 g.
28
Method 2 : (Equivalent concept)
Eq. of O 2 = eq. of Fe2O 3
W 1600

( 3 ) 0
8 160 / 6
 Fe 2O 3  Fe
v.f = 2(3 – 0) = 6

8  1600  6
W= = 480 g
160

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+ + SO 42–
v.f. = 2

H2PO 4  H+ + H2PO 4–

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
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 .
vEyh;ek/;eesaMnO4– vk;uds,deksy}kjkvkWDlhd`rfd;sx;svkWDlsysVvk;uksadseksyksadhla[;kfuEugS&
5 2 3 5
(A*) (B) (C) (D)
2 5 5 3
Sol. (A)
C2O42– + MnO4– 
 CO2 + Mn2+
H

v.f. = 2 v.f. = 5

Equivalents of C2O42– = equivalents of MnO4–

5
x(mole) × 2 = 1 × 5 ; x=
2
Page # 45
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

Lecture - 04
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.

Page # 46
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 .

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.

Page # 47
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

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  Na3PO 4 + 3H 2O
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

Page # 48
Double Titration :
Purpose : To find the % composition of an alkali mixture.
Consider a mixture NaOH, Na2CO 3 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 NaHCO 3.

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 NaHCO 3 produced in reaction (2) = eq. of Na2CO 3 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 NaHCO 3 present in the original mixture. or,
Total eq. of HCl used = eq. of NaOH + 2 × eq. of Na2CO3 (v.f. = 1) + eq. of NaHCO 3. .. (6)
Also,
eq. of HCl used after phenolphthalein end point = eq. of Na2CO3 (v.f. = 1) + eq. of NaHCO 3. .. (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
& NaHCO 3 = 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
Similarly % of NaOH = 33.33%
% of Na2CO3 = 33.33%
Page # 49
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
Redox Titration (Excluding Iodometric / Iodimetric)
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

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

BrO3– + 6H+ + 6e–  Br– + 3H2O

Page # 50
(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.
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+  EF2Cr2O7  
 6

Page # 51
 Lecture - 05
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
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 storng 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 matintained neutral by adding NaHCO3,
Indicator - Starch
Iodimetric titrations have been summarised in Table.
S.No. Estimation of Reaction
1. H2S H2S + 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 # 52
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.
O.A. + K  2    Na + Na2S4O6 .
Na 2S 2 O 3

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 # 53
Ex. One litre of acidified KMnO4 containing 15.8 g KMnO4 is decolorized by passing sufficient SO 2.
If SO2 is produced by FeS2, what is the amount of FeS2 to give desired SO2?
Sol. 2KMnO4 + 5SO2 
 Mn2+ + S+6

H

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. 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. The molarity of sodium thiosulphate
solution is
O3– + – + H+ 2 + H 2O
(A*) 0.063M (B) 0.0313M (C) 0.126M (D) 0.252M
Sol. KIO3 + 5KI  3I2
HCl

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
214 214
 M = 0.0623 M.

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%

Page # 54
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 our mole ratio of Cu2+ and C2O42– in compound.8

2KMnO4 
 Mn2+ + CO2H
Sol. 5C2O42– +
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 mlole
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 =  = 0.5.
C 2O 4 5  22.6  0.02 2
2–

MODIFICATION IN LAW OF EQUIVLAEUCE :

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

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  SO 2
x x
Mole mole mole
32 32

Page # 55
 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 SO 2 produced = eq. of S consume = × 4.
32

4x
or eq. of SO 2 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 SO 2 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.

Ex. KIO3 + KI   I2
HCl

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 KIO 3 = 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

Page # 56
 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 H2O 2.
Sol. Method 1 : (Equivalent concept) :

KMnO 4 
 Products
H
H2O2 + ... (1)
v.f. = 2 v.f. = 5
20 ml 20 ml

( 7 ) ( 2) ( 4 )
K Mn O 4 + MnS O 4   Mn O 2
Neutal ... (2)
20 ml
v.f. = 3 v.f. = 2 v.f. = 6/5 (  For 5 mole of MnO 2, 6 mole of e– is transferred )

( 4 )
Mn O2 + Na2C2O4 
 Mn + CO2 ... (3)

H 2+

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 MnO 2 produced in reaction (2) =  (w.r. to v.f. = 6/5)
2 5
Let Molarity of KMnO4 = 4
 Meq. of KMnO4 = meq. of MnO 2
10  0.2  2 6
or M × 20 × 3 =  or M = 0.04
2 5
Let Molarity of H2O 2 = M`
 Eq. of H2O 2 = Eq. of KMnO4
20 × M’ × 2 = 0.04 × 20 × 5
M` = 0.1 Molar

Page # 57
 Balanced reactions are :
2KMnO4 + 5H2O 2 + 3H2SO4  K2SO4 + 2MnSO 4 + 8H2O + 5O2
2KMnO4 + 3MnSO 4 + 2H2O  5MnO 2 + 2H2SO4 + K2SO4
MnO 2 + Na2C2O 4 + 2H2SO4  MnSO 4 + 2CO 2 + 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 Na2C2O 4 = Equivalents of MnO2
= Equivalents of KMnO 4 = Equivalents of H2O 2
Let the molarity of H2O 2 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 H2SO 4. 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 + NaNO 3  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
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 # 58
 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  Cl2
CaOCl 2  2HCl  CaCl 2  H2 O  Cl2
CaOCl 2  2CH3 COOH  CaCH3 Coo 2  H2 O  Cl2
CaOCl 2  CO 2  CaCO 3  Cl2

Method of determination of available chlorine :

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

Cl2 + 2KI  2KCl + I2

I2 + 2Na2S2O3    Na2S4O6 + 2Nal

Starch as indicator

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 soqlution.
3.55  20  0.125
Sol. % of available Cl2 = = 10%
3.55
 25
100

Page # 59
 Lecture - 06
HYDROGEN PEROXIDE (H 2O 2 ) :
H2O2 can behave both like oxidising and reducing agents in both the medium (acidic and basic).

1. Oxidising agent : (H 2 O 2  H 2O)

(a) Acidic medium : 2e– + 2H+ + H2O2  2H2O v.f. = 2
(b) Basic medium : 2e– + H2O2  2OH– v.f. = 2
2. Reducing agent : (H 2 O 2  O 2 )
(a) Acidic medium : H2O2  O2 + 2H+ + 2e– v.f = 2
(b) Basic medium : 2OH– + H2O2 O2 + 2H2O + 2e– v.f = 2
Note : Valency factor of H2O2 is always equal to 2.

Volume strength of H 2O2 : Volume strength of H2O2 is represented as 10V , 20 V , 30 V etc.

20V H2O2 means one litre of this sample of H2O2 on decomposition gives 20 litre of O2 gas at S.T.P.
Decomposition of H2O2 is given as
1
H2O2  H2O + O
2 2
1
1 mole × 22.4 lt O2 at S.T.P
2
= 34g = 11.2 lt O2 at S.T.P.

 To obtain 11.2 litre O2 at S.T.P. at least 34 gm H2O2 must be decomposed.

34
 for 20 lt O2 , we should decompose atleast ×20 gm H2O2
11.2
34
 1 lt solution of H2O2 contains ×20 gm H2O2
11.2
34 20 M 34
 1 lt solution of H2O2 contains × equivalents of H2O2 ( EH2O 2   = 17)
11.2 17 2 2

34 20 20
 Normality of H2O2 = × =
11.2 17 5 .6

Volume strength of H2 O 2
Normality of H2O2 (N) =
5. 6

NH2O2 NH2O2 Volume strength of H2 O 2

MH2O2 = = Molarity of H2O2 (M) =
v.f 2 11.2


Strength (in g/) :

Strength = molarity × mol.wt.= molarity × 34
Strength = Normality × Eq. weight. = Normality × 17

Page # 60
Ex. A fresh H2O2 solution is labeled as 11.2 V. Calculate its concentration in wt/vol percent.
Sol. v.s. = N × 5.6
or 11.2 = N × 5.6
or N = 2eq/L
= 2 × 17 g/L
= 34 g/L
34g
= 1000 ml × 100 = 3.4% (wt/vol)

Ex. 100 ml each of 1 N H2O2 and 11.2 V H2O 2 solution are mixed then find the strength of final solution
in g/L.
Sol. v.s. = N × 5.6
11.2 = N × 5.6 or N=2
V1 = 100 ml, N1 = 1
N1V1  N2 V2 1 100  2  100 300
V2 = 100 ml N2 = 2 N=  =
V1  V2 200 200
 Strength = 1.5 eq/L = 1.5 × 17 = 25.5 g/L
N
Ex. 20 ml of H2O2 after acidification with dil H2SO4 required 30 ml of KMnO4 for complete oxidation.
12
The strength of H2O2 solution is [Molar mass of H2O2 = 34]
1
Sol. 30 × = 20 × N
12
30 1
N = =
12  20 8

1
 strength = N × equivalent mass = × 17 = 2.12 g/L.
8

STRENGTH OF OLEUM :
Oleum is SO3 dissolved in 100% H2SO4. Sometimes, oleum is reported as more than 100% by weight,
say y% (where y > 100). This means that (y  100) grams of water, when added to 100 g of given
oleum sample, will combine with all the free SO3 in the oleum to give 100% sulphuric acid.

 H2SO4
80 18
SO3 + H2 O
80
× (y – 100) (y – 100)
18

Hence weight % of free SO3 in oleum = 80(y 100)/18

It means if an oleum is labelled as 109% it means 100 g oleum (SO3 + H2SO4) when dissolved in
(109 – 100) = 9g of H2O will produce 109 g pure H2SO4.

Ex. An oleum sample is labeled as 118%. Calculate % of free SO3

80
Sol. % of free SO3 = × 18 = 80%
18

PARTS PER MILLION (PPM) :

When the solute is present in very less amount then this concentration term is used. It is defined as
the number of parts of the solute present in every 1 million parts of the solution. ppm can both be in
terms of mass or in terms of moles. If nothing has been specified we take ppm to be in terms of mass.
Hence a 100 ppm solution means that 100 g of soulte are present in every 1000000 g of solution.
mass of A
ppm of A in solution = 10 6 = mass fraction × 106
Total mass of solution

Page # 61
HARDNESS OF WATER :
Hard water does not give lather with soap.
A water is said to be soft water if it gives enough lather with the soap .
The water sample is said to be hard if it forms a insoluble scum and gives very little lather with soap.
Generally , all salts ( except the salts of alkali metals Viz Na,K, Li etc) containing Mg2+, Ca2+,Al3+ etc
makes water hard.
Hardness can be grouped primarily under two heads:
I) Temporary hardness II) Permanent Hardness
I) Temporary Hardness : It is due to presence of bicarbonates of calcium and magnesium.
It is easily removed by boiling which decomposes bicarbonates readily and the insoluble
carbonates settle down.So its named as temporary hardness.

II) Permanent hardness : It is due to chlorides or sulphates of Ca , Mg, Al, Fe etc.

Its permanent hardness because this cannot be removed just by boiling the sample. Although special
methods can be employed to remove the hardness .

There are some method by which we can Softening the water

(a) by boiling : 2HCO3–  H2O + CO2 + CO32–
or, Ca(HCO3)2  CaCO3  + H2O + CO2
(b) by slaked lime : Ca(HCO3)2 + Ca(OH)2  2CaCO3 + 2H2O
(c) By Washing Soda : CaCl2 + Na2CO3  CaCO3 + 2NaCl
(d) By ion exchange resins : Na2R + Ca2+  CaR + 2Na+ (R = resin)
(e) By adding chelating agents like (PO3–)3 etc.

Degree of hardness :
The degree of hardness of water is defined as the number of parts of calcium carbonate or equivalent
to various calcium and magnesium salts present in a million parts of water. ( ppm in terms of CaCO3)
A sample labeled as “ Hardness 180 ppm in terms of MgSO4 “.
It means that the sample contains 180 g of MgSO4 in a 106 g of given water sample.
If this is expressed in terms of CaCO3 ( which is the normal practice ) , we can convert it as follows,
Equiv.mass of CaCO3 = 100/2 = 50
Equiv.mass of MgSO4 = 120/2 = 60
50 g of CaCO3 = 60 g of MgSO4
if any sample that contain 150 ppm of MgSO4 ,then in terms of CaCO3 ,
degree of hardness = 50/60 X180 = 150 ppm
So hardness of water is expressed in terms of ppm of CaCO3 although hard water does not contain
CaCO3 .
So we can say that
1 mole CaCl2  1 mole CaCO3 1 mole MgCl2  1 mole CaCO3

1 mole CaSO4  1 mole CaCO3 1 mole MgSO4  1 mole CaCO3

mass of CaCO3
Hardness in ppm = 10 6
Total mass of water
Ex. 0.00012% MgSO 4 and 0.000111% CaCl2 is present in water. what is the measured hardness of
water and millimoles of washing soda requires to purify water 1000 lt water.
Sol. Basis of calculation = 100 g hard water
0.00012
MgSO4 = 0.00012g = Mole
120

0.000111
CaCl2 = 0.000111g = mole
111

 0.00012 0.000111 
 equivalent moles of CaCO3 =    mole
 120 111 

Page # 62
  0.00012 0.000111 
 mass of CaCO3 =    × 100 = 2 × 10–4 g
 120 111 

2  10 4
Hardness (in terms of ppm of CaCO3) =  10 6 = 2 ppm
100

CaCl2 + Na2CO3  CaCO3 + 2NaCl

NaSO4 + Na2CO3  MgCO3 + Na2SO4

0.00012 0.000111
 Required Na2CO3 for 100g of water =  mole
120 111
= 2 × 10–6 mole

2  10 6 2
 Required NaCO3 for 1000 litre water =  10 6  mole ( d = 1g/ml)
100 100

20
= mole = 20 m mole
1000

Ex. Calculate the weight of CaO required to remove the hardness of 1m3 of water containing 1.62 g of
calcium bicarbonate per liter.
56 162
Sol. CaO + Ca(HCO3 )2  CaCO3 + H2O
56
 1.62  10 3 g 1.62 × 103g
162

= 560 g.

Ex. A sample of hard water contains 96 ppm of SO42– and 183 ppm of HCO3– with Ca2+ as the only cation.
How many mole of CaO will be required to remove HCO3– from 1000 kg of this water ? If 1000 kg of this
water is treated with the amount of CaO calculated above, what will be the concentration ( in ppm ) of
residual Ca2+ ions (Assume CaCO3 to be completely insoluble in water) ? If the Ca2+ ions in one litre of
the treated water are completely exchanged with hydrogen ions, what will be its pH.
Sol. 2
Sample of hard water contains 96 ppm SO42– and 40 ppm Ca as CaSO4. Also it contains 183 ppm
HCO3– and 60 ppm Ca2+ as Ca(HCO3)2.
To remove Ca(HCO3)2 from 103 kg or 106 g sample of hard water which contains 243 g Ca(HCO3)2 or
3/2 mole of Ca(HCO3)2, CaO required is 3/2 mole.
Ca(HCO3)2 + CaO  2CaCO2 + H2O
Thus, mole of CaO required = 3/2 or 1.5
Also Ca2+ ions left in solution are fo CaSO4 i.e., 40 ppm
40  10 3
Now 1 litre water contains Ca2+ after removal of Ca(HCO3)2 =  40  10 3 g
10 6
40  10 3
or [Ca 2  ]   10 3
40
If these Ca2+ are exchanged with H+ then [H+] in solution = 2 × 10–3
 pH = – log 2 × 10–3 = 2.6989.

Page # 63