Vidyamandir Classes Stoichiometry - 1

Stoichiometry - 1
BASIC IDEAS Section - 1
In this chapter, we are going to build the basics of solving the numerical problems in chemistry. The concepts
here involve, understanding of mole concept, gram equivalents and their applications in various chemical
processes.

Concept of Gram Atom :

One gram-atom of an element means collection of 6.023 × 1023 atoms. This concept applies only to the
elements, which exist in poly-atomic states (e.g. O as O2, Cl as Cl2, S as S8, P as P4 etc.).

Mass of 1 atom of an element

Atomic mass 
1 / 12 th the weight of C12

(in a.m.u. where 1 a.m.u. = Atomic Mass Unit = 1.66 × 1027 kg)

(a) The number of gmatoms in ‘g’ gm of an element whose atomic mass is A is :

g
gm - atoms 
A

Illustrating the Concept :

g 142
 
gm-atoms in 142 grams of chlorine = 4
A 35.5
g 16
 gm-atoms in 16 grams of Oxygen =   1
A 16
(b) The number of atoms in ‘g’ gms of an element is given by :

g
No. of atoms =  N0 (N0 = Avogadro number = 6.023 × 1023)
A

Note : The concept of gm-atom is useful in Radioactivity as it gives us number of nuclei i.e.
g
No. of nuclei = Number of atoms = gm-atoms  N0 =  N0
A
Illustrating the Concept :
56
Number of atoms in 56 grams of Nitrogen =  6.023 1023  2.4092  1024
14

Note : Atomic masses of some common elements are given at the end of this chapter.

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Concept of Gram Mole :

The collection of 6.023  1023 molecules of an element or ions or a compound constitute 1 mole of that
element or of ions or of compound. This magical number 6.023  1023 is known as Avogadro Number (N0).

 The number of moles (n) in ‘g’ grams of a substance, whose molecular weight is M0 is given by :
g
Number of moles = n 
M0
 The number of molecules in n moles :
g
Number of molecules = nN0   N0
M0
 The number of millimoles :
g
Millimoles (m.moles) =  1000
M0

Illustrating the Concept :

 Number of moles in 46 grams of sodium (Na)

g 46
moles   2 (Atomic Mass of Na = 23 = molecular mass as Na is monoatomic)
M 0 23

 Number of moles in 100 gm of Chlorine (Cl2)

g 100
moles    1.4 (Mol. Mass Cl2 = 2  35.5 = 71)
M 0 71

 Number of moles in 54 grams of phosphorus (P4)

g 54
moles    0.4355 (Mol. Mass of P4 = 4  Atomic weight = 4  31 = 124)
M 0 124

 Number of moles in 49 grams of sulphuric acid (H2SO4)

49 1
moles    0.5 (Mol. Mass = 2  1 + 32 + 16  4 = 98)
98 2
 Number of moles in 25 gm of CaCO3 (calcium carbonate)

25
moles   0.25 (Mol. Mass = 40 + 12 + 16 × 3 = 100)
100

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Concept of Gram Equivalents :

We can define gram-equivalent (gm eq) in ‘g’ gms of a substance whose equivalent weight is E as follows :

grams g
gram equivalents (gm.eq)  
Equivalent weight E

To understand the concept of gram equivalent, one must know the meaning of equivalent weight (E) of an
element or a compound.
Theoretically, Equivalent weight (E) of an element or a compound is defined as the weight of an element
or a compound which would combine with or displace (by weight) 1 part of hydrogen or 8 parts of
oxygen or 35.5 parts of chlorine.
Analytically, Equivalent weight (E) is defined for elements/ions/compounds as :
Molecular Weight
E 
x

where x is known as Valence factor or ‘n’factor and its value varies depending upon the compound being
considered.

(i) Equivalent Weight (E) of an Element :

Atomic weight of an element

E
Valency of element

27 24
E(Aluminium) = 9 E(magnesium) =  12
3 2
16 35.5
E(oxygen) = 8 E(chlorine) =  35.5
2 1

(ii) Equivalent Weight (E) of an Acid :

Molecular weight of acid
E=
Basicity

Acid : A species capable of giving H+ ions (protons) in its aqueous solution is an acid. It is generally represented
as HA. The number of H+ ions furnished by an acid determines the basicity of acid.
 Basicity of HCl (Hydrochloric acid) = 1 (As it furnishes only 1 H+ ion)
 Basicity of H2SO4 (Sulphuric acid) = 2
 Basicity of H3PO4 (Phosphoric acid) = 3  Basicity of H2C2O4 (Oxalic acid) = 2

Note : It is not necessary that basicity of an acid is equal to the number of H+ ions contained in its formula.
It is the number of furnishable H+ ions which determines the basicity of an acid.

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Basicity of CH3COOH (Acetic acid) = 1

Basicity of H3PO3 (Phosphorus acid) = 2

This can be deduced from its structure shown ( 

):

As it can be seen that number of –OH groups are 2, the number of

furnishable H+ ions will also be 2.

Note that bond between P and –OH will not break as it is a stronger bond compared to the bond strength
between H and O in –OH group. So, H3PO3 is not a base although it contains 2 –OH groups. The H
attached directly to P atom will not be able to furnish in the solution as this bond is quite strong.
On the similar grounds, try to calculate the basicity of H3PO2 (Hypophosphorus acid).
Its structure is shown on right..

(Ans: Basicity of H3PO2 = 1)

Also, note the structure of H3PO4 (Phosphoric acid) and its basicity (= 3).

36.5 98 90
E HCl   36.5 E H 2SO4   49.0 E H 2C2O 4   45.0
1 2 2
(oxalic acid)
98 82 60
E H3PO4   32.6 E H3PO3   41.0 E CH3COOH   60
3 2 1

(iii) Equivalent Weight (E) of a Base:

Molecular weight of base

E=
Acidity
Base:A species capable of giving OH ions (hydroxyl) in its aqueous solution. It is generally represented as
BOH. The number of OH ions furnished by a base determines the acidity of base.
 Acidity of NaOH (Sodium hydroxide) = 1
 Acidity of Mg(OH)2 (Magnesium hydroxide) = 2
 Acidity of Al(OH)3 (Aluminium hydroxide) = 3
40 58 74
E NaOH   40.0 E Mg(OH)2   29 E Ca(OH)   37.0
1 2 2 2

(iv) Equivalent Weight (E) of an Ion :

E of an ion is determined by the charge on an ion irrespective of anion and cation.
Molecular weight of ion
E of an ion =
Magnitude of charge on ion

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35.5 16 27
E    35.5 E 2  8 E 3   9.0
Cl 1 O 2 Al 3

60 95 88
E   30.0 E   31.66 E 2   44.0
CO32 2 PO34 3 C2O 4 2
(oxalate)

(v) Equivalent Weight (E) of a Compound :

Equivalent of a compound (E) depends upon how a given compound reacts in a particular reaction.
It means that equivalent weight can be variable. However, there are certain compounds for which
equivalent weight remains constant. The equivalent weight of alkali metal salts (Na, K etc) and alkaline-
earth metals salts (Mg, Ca etc) is constant. It depends upon the magnitude of total charge on cation or
anion.
Molecular weight
E=
Magnitude of total charge on cation or anion
106
E Na 2 CO3   53 (Magnitude of total charge on cation or anion = 2)
2
234
E Al  CO    39 (Magnitude of total charge on cation or anion = 6)
2 3 3 6

(vi) Equivalent weight (E) of an Oxidising and Reducing Agent :

For the compounds taking part in redox reactions, the calculation of E becomes rather complex and
one has to be very cautious. First, one should make sure which compound is acting as oxidising agent
(O.A) and which is acting as reducing agent (R.A). Then find the number of electrons transferred by
one mole of O. A or R.A in the reaction.
Molecular weight
E of compound =
Electron transfer per mole of O.A or R.A

Note : We will discuss this concept in the study of Redox Reactions in more detail in upcoming modules.

Illustrating the Concept :

71
 gm. eq. in 71 gms of Chlorine atoms : gmeq.  2 (E Cl  35.5)
35.5
g 16
 gm. eq in 16 gms. of Oxygen atoms : gm.eq   2 (EO = 8)
E 8
g 500 M0
 gm. eq in 500 gms of H3PO4 : gm.eq    15.3 (Ea  )
E 32.67 basicity

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g 150 M0
 gm. eq in 150 gms of Mg(OH)2 : gm.eq    5.17 (Eb  )
E 29 acidity

Note : In practical cases, a smaller unit of moles and gram equivalent is used and is given by :

g
 The number of milli moles (m.moles) in g grams =  1000
M0
g
 The number of milli equivalents (meq) in g grams =  1000
E

Relationship between Moles and Gram Equivalents :

g g g
 x 
Gram equivalents = = x × moles
E M0 / x M0
NOW ATTEMPT IN-CHAPTER EXERCISE-A BEFORE PROCEEDING AHEAD IN THIS EBOOK
Expressing Concentration of Solutions :

Solution is a homogenous mixture of two or more components in which intermingling particles are of atomic
or molecular dimensions. A solution consists of a dissolved substance known as solute and the substance in
which the solute is dissolved is known as solvent. The concentration of a solution means the quantity of
solute dissolved per unit volume of solution, or per unit quantity of solvent.

Concentration of solute  Amount of solute

Amount of solution (or solvent)

Note : While discussing various methods for expressing concentration, we have taken solute as B dissolved in
solvent as A and gB as grams of solute and gA as grams of solvent.

1. Mass fraction is the fractional part of a component that is contributed by it to the total mass of solution.
gB gA
mass fraction of (WB ) B = mass fraction (WA ) A =
gA  gB gA  gB

Note : WB  WB  1

2. Mole fraction is the fractional part of the moles that is contributed by each component to the total number
of moles that comprises the solution. In a solution containing nA moles of solvent and nB moles of solute ;
nB nA
mole fraction of B B = mole fraction of A A =
n A  nB n A  nB

Note :  A   B  1.

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Illustrating the Concept :

A given solution consists of 230 gm of C2H5OH (ethyl alcohol) and 720 gm of H2O (water). How to
determine the mole fraction of each component.
First, calculate moles of ethyl alcohol and water.
230 720
moles of C2H5OH =  5.0 and moles of H2O =  40.0
46 18
Now let A = mole fraction of H2O and B = mole fraction of C2H5OH
40
A   0.88 and  B  1   A  0.12
40  5

3. Molality (m) is expressed as number of moles of solute dissolved in 1000 gms (1.0 Kg) of solvent. It is
denoted by m. The unit is mol/kg. It can also be denoted by m.
moles of solute
i.e. m 
kg of solvent
nB
If nB represent moles of solute and gA represent gms of solvent, then, m =  1000
gA

Illustrating the Concept :

How to determine the molality of solution containing 87.7 gm of NaCl (sodium chloride) dissolved
in 1500 gm of water ?
g 87.7
First, calculate moles of NaCl : moles 
  1.5
M 58.5
n B  1000 1.5  1000
Now, molality (m) =   1.0 m
gA 1500

4. Molarity (M) is expressed as moles of solute contained in one litre of solution or it is also taken as millimoles
of solute in 1 cc (ml) of solution. Its unit is mol/t. It is also denoted by M.
moles of solute millimoles of solute
Molarity (M) = =
litres of solution millilitres of solution

If nB represents number of moles of solute and VL be volume of solution in litres.

nB g MB
M=  B
VL VL

Note : moles of solute = Molarity  Volume in litres  nB = MVL (M : molarity).

or m.moles of solute = Molarity  Volume in cm3 (ml) = MVcc

1 mL = 1 millilitre, 1 cc = 1 ml = 1 cubic centimetres

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Illustrating the Concept :

How to determine the molarity of a solution containing 149 gram of KCl (potassium chloride)
dissolved in sufficient water to make 1500mL of a solution.
moles of KCl  g 
Molarity   where moles  
litres of solution  M0 
149 2.0
moles of KCl   2.0  Molarity   1.33 molar or written as 1.33 M
74.5 1500 /1000

How to calculate grams of solute (solid NaOH) in a 500 cc of 0.25M solution of NaOH ?
Moles = MVL M : molarity of solution;VL : volume of solution in litres.
500
Moles  0.25   0.125  gram of NaOH = 0.125  40 = 5 gm (mass = nM0).
1000

5. Normality (N) is expressed as the number of gram equivalents (gmeq) of solute contained in one litre of
solution or it can also be taken as number of mill equivalents (meq) in 1cc (mL) of solution. It is denoted by N.
gmeq of solute meq of solute
Normality of solution (N) = 
litres of solution millilitres of solution
If gB represents grams of solute, E represents Equivalent weight of solute and VL be volume of solution in
litres,
gmeq g B / E
Normality  
VL VL

Important Concepts in Stoichiometric Calculations :

[A] (a) gm.eq. of solute = normality  volume in litres = NVL
or meq of solute = normality  volume in cm3 (mL) = NVcc
(b) moles of solute = Molarity VL = MVL
or m.mol of solute = Molarity  VmL = MVmL
gm.eq x  moles
[B] Normality    x  Molarity
VL VL
For acidic solutions : N = x M [x : basicity of acid ; M : molarity of acid]
For basic solutions : N = x M [x : acidity of base ; M : molarity of base]
For a mono acidic base (acidity =1) and mono basic acid (Basicity = 1) Normality = Molarity
[C] Relation between molality(m), molarity (M), density(d) of solution and molar mass of solute (M0) :
Molarity (M) means M moles of the solute in 1 L of the solution. If density is in g/mL and M0 is molar
mass in g mol1 , then

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mass of solute = MM0 grams ; mass of solution = 1000 × d grams

 mass of solvent = 1000d  MM 0
M
 Molality (m) =  1000
1000d  MM 0
[D] Relationship between molality (m) and mole fraction (B) of the solute :
nB n nB
B  ; m  B  1000   1000
nA  nB g n M
A A A
m nA MA m n A M A / 1000
 nB  or B 
1000 n A  m n A M A / 1000
m MA B 1000 1   A 1000
 B   m   
1000  m M A 1  B M A A MA

Illustrating the Concept :

A solution was prepared by adding sufficient water to 100g of NaOH to make 0.50 L of solution.
Calculate molarity and normality of solution.
gmeq 100 / 40  g M0 
Normality    5N  gmeq  , E  
VL 0.5  E acidity 
Now using N = x M ;
5
 M  5 M solution [x = 1 for NaOH (Mono-acidic base)]
1

A solution was prepared containing 14.80 gm of Ca(OH)2 in 3000 ml of solution. Calculate:

(a) molarity of solution (b) normality of solution
(c) moles in a 2.5 L of same solution (d) gmeq contained in 1.5L of solution.
moles of Ca(OH) 2 14.8 / 74
(a) Molarity    0.067M
VL 3000 / 1000

gm eq of Ca(OH) 2 14.8 / E 14.8 / 37  M0 74 

(b) Normality     0.133N  E  acidity  2 
VL 3 3  
(c) moles in 2.5 L of sample = MVL = 0.067  2.5= 0.167 moles (in 2.5 L sample).
(d) gmeq in 1.5 L of sample = NVL = 0.133  1.5 = 0.2 gmeq (in 1.5 L).

6. Strength of a solution : It is expressed as grams of solute in 1 L of a solution.

grams of solute
Strength 
VL
g
We know, NVL   gmeq
E

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g
Strength   NE
VL
g
Similarly, Strength   MM 0
VL

Illustrating the Concept :

How to calculate normality when Strength is given ?
(i) HNO3 containing 6.3 g/L of acid
(ii) KOH solution containing 11.2 g/L of base
63 6.3  strength 
(i) EHNO3   63  N  0.1N  N  
1 63  E 
56 11.2
(ii) E KOH   56  N  0.2N
1 56

How to calculate E when Strength is given ?

(i) 10N HCl acid solution containing 3.65 g/10 ml
(ii) N/3.5 H2SO4 acid solution containing 14 g/L.
Strength
Eq. wt 
Normality
(i) E HCl  ? Strength = 3.65 g /10 ml = 365 g /L
365
E HCl   36.5
10
14
(ii) Similarly, E H 2SO4   49
1 / 3.5

Important Concepts in Stoichiometric Calculations :

1. If molarity of a solute Ax By in a solution is ‘M’, assuming the solute to have complete dissociation (100%)
 x Ay+ + y Bx–
Ax By   1mole A x B y gives 
 
Then, molarity of Ay+ ions = x  M ; molarity of Bx– ions = y  M  x moles of A y  and 
 x

 y moles of B 
But, same is not applicable to normality.
If normality of solute Ax By is ‘N’, assuming the solute to have complete dissociation (100%) :
 x Ay+ + y Bx–
Ax By 
gmeq.of A x B y  gmeq.of A y  
Then, normality of A ions = N ; normality of B ions = N 
y+ x– 
  gmeq.of Bx  
(Correlate the above results, with the definitions of molarity and normality respectively).

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Illustrating the Concept :

0.1 M H2SO4  0.2 M H+  0.1 M SO 24  0.1 N H2SO4  0.1 N H+  0.1 N SO 24 

2. When Solute is Solid :

(a) x% by mass of solute (B) in the solution (A): It means x gm of solute (B) are present in 100 gm
of solution (A)
(b) x% by volume of solute (B) in the solution (A): It means x gm of solute (B) are present in
100 cm3 of solution (A).
3. When Solute is also a Liquid :
(a) x% by mass of solute (B) in the solution (A): It means x gm of solute (B) are present in 100 gm
of solution (A)
(b) x% by volume of solute (B) in the solution (A): It means x cm3 of solute are present in 100 cm3
of solution (A).

Illustrating the Concept :

The molarity and normality of solution of H 2SO 4 containing x% H 2 SO 4 by weight.
(dsolution = d gm/cc.)
First, you must understand meaning of x% H2SO4 by weight.
This means x gms of actual amount of H2SO4 in 100 gms of solution or if W (in gms) be the total
x
mass of solution, then the mass of solute (H2SO4) contained =  W gms .
100
Now coming back to original problem ;
Let us consider 1 L or 1000 cc of solution
 mass 
Mass of solution in 1 L = 1000 d d  
 volume 
x
Mass of actual H2SO4 in 1 L   1000 d   10 xd
100
10 xd  g 
moles of H2SO4 in 1 L =  moles  
M0  M0 
10 x d
 Molarity   M   M
0
For normality, M0 is replaced by E
10 xd
 normality   N  
E

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Illustration -1 (a) Concentrated acid H2SO4 has a density of 1.8 g/ml and contains 49% acid by weight.
Compute molarity of the solution. Also calculate the number of gmeq of H2SO4 contained in 1 L solution.
(b) What is the normality of a solution which is prepared by dissolving 100 ml of conc. H 2SO4 in
part (a) in sufficient water to make 500 ml of solution?
(c) If we take 50 ml sample of above solution [in part (b)], find number of milli moles and milli
equivalents in the sample.
10 xd
Solution : (a) We have : Molarity 
M0
10  49  1.8
molarity(M)   9.0M (x = 49, d = 1.8 g/mL = 1.8 g/cc, M0 = 98)
98
To calculate gmeq, it is better to calculate normality first.
N = x M = 2  9 = 18 N x : Basicity of H2SO4 = 2
gm.eq. = NVcc = 1 × 18 = 18 gmeq are contained in 1 L of given solution.

(b) N of H2SO4 = 18 [calculated above in part (a)]

18.0  100
gmeq in 100 cc of conc. H2SO4   1.8
1000
So, 1.8 gmeq of concentrated acid are to be added in water to make 500mL solution.
gmeq 1.8
Normality of required solution = N    3.6
VL 500 / 1000
(c) Milli equivalents = Normality x Volume (in ml) = NVCC
= 3.6 × 50 = 180 meq.
Millimoles = Molarity × Volume (in ml) = MVCC
3.6
=  50  90 m.moles [N = x M and x = 2 for H2SO4, a dibasic acid]
2
Note : If a naturally occurring atom exists in the form of isotopes (say of molecular masses A1, A2, . . . . . etc) with
their percentages as (x1 %, x2 % . . . . . . . etc), then average atomic mass, Aavg of the atom is given as :

x1 x
Aavg   A1  2  A 2  ............
100 100

Illustrating the Concept :

The mass spectrum of carbon shows that 98.892% of carbon atom are C-12 with a mass of 12.000
amu and 1.108% are C-13 with a mass of 13.000335 amu. Calculate the atomic weight of naturally
occurring carbon.
98.892 1.108
Atomic weight of carbon =  12.000   13.00335 = 12.011 amu
100 100

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If isotopic distribution of isotopes (relative abundance) C-12 and C-14 is 98% and 2% respec
tively then the number of C-14 atoms in 12g of carbon is :
(A) 1.20 × 1022 (B) 3.01 × 1022 (C) 5.55 × 1023 (D) 6.023 × 1023
 98   2 
Average atomic mass =   12     14   12
 100   100 
12
 Total No. of C atoms in 12g of C   6.023  1023  6.023  1023
12
2
And Total No. of C-14 atoms in 12g of C =  6.023  1023 = 12.046  1021  1.20  10 22 (A)
100

There are two isotopes of an element with atomic mass z. Heavier one has atomic mass z + 2 and
lighter one has z – 1, then abundance of lighter one is :
(A) 66.6% (B) 96.7% (C) 6.67% (D) 33.3%
(100  x) x
Let x% be abundance of lighter one. Then  (z  2)   (z  1)  z So, x=66.6
100 100
NOW ATTEMPT IN-CHAPTER EXERCISE-B BEFORE PROCEEDING AHEAD IN THIS EBOOK

Important Concepts in Stoichiometric Calculations :

1. Dilution : Whenever a given solution of known concentration i.e. normality and molarity (known as standard
solution) is diluted (adding solvent), the number of millimoles (or milli equivalents) of solute remain unchanged.
The concentration of solution however changes.
In such a case if :
N1 = normality of original solution ; V1 = volume of original solution
and N2 = normality of diluted solution ; V2 = total volume of diluted solution
Since the number of milli equivalents remains same,
 N1V1 = N2V2 (This also called equation of normality)
Also, M1V1 = M2V2 (This also called equation of molarity)

2. Whenever a small sample (volume) is taken from a standard solution, the concentration of sample is same as
that of standard solution. However number of millimoles (or milli equivalents) in sample differs from that of
standard solution.
From a 3.5 L of 0.5 N H2SO4 solution, a sample of 500mL is taken, then normality of a 500 mL solution is
also 0.5N.
But meq in standard solution = 0.5  3500 = 1750 meq
and meq in small sample = 0.5  500 = 250 meq

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Illustration - 2 What volume of water must be added to a 0.5 litre of 10 N acid solution to make it
exactly 0.5 N solution?
Solution : Let Vcc of water is added to given solution of acid.
Apply equation of normality (for dilution) i.e. N1V1 = N2V2

V1  vol.of original solution  0.5L  500 cc ; N1  normality of solution

V2  final volume of solution ; N 2  normality of finalsolution

 10  500 = 0.5  (500 + Vcc)  Vcc = 9500 cc = 9.5 L.

 9.5 L of H2O will have to be added.

Illustration - 3 A commercial sample of oxalic acid is labelled as 22.5% H2C2O4 by weight (density =
1.5 g/cc). Calculate (a) molarity (b) volume of acid having same amount of solute as in 1 L of
0.2 M H2C2O4.
Solution :
10 xd
(a) Using standard formula : molarity =
M0
10  22.5  1.5
M  3.75 M
90
(b) Let Vcc of acid is required.
m.moles of concentrated sample = m.moles of desired sample
Using M1V1 = M2V2 ; 3.75 × Vcc = 0.2 × 1000  Vcc = 53.34 cc

Illustration - 4 A 0.25 molar aqueous solution of NaOH is found to have a density of 1.26 g/cc.
Determine its molality with respect to NaOH. Also determine its mole fraction.
Solution : = 1000  1.26 = 1260 gm
0.25 M NaOH  0.25 moles/litre of NaOH Now mass of NaOH = (moles  M0)
 0.25 moles of NaOH in 1 L of solution = 0.25  40 = 10 gm

 moles of solute   Mass of H2O = 1260  10 = 1250 gms

Use : m   1000 
 gms of solvent  0.25
Hence molality (m) =  1000 = 0.2 m
1250
First find the mass of water.
For conversion of molality into mole fraction, use the
Mass of solution = Volume  density following relation.
Mass of solution in 1.0 litre solution

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B 1000 In given case : m = 0.202, MA = M H 2O  18

m 
1  B MA
 NaOH 1000
 0.2  
B = mole fraction of solute 1   NaOH 18
MA = molecular mass of solvent.
Solve to get: NaOH = 0.00358
Note : TRY to derive the above relation yourself.

Illustration - 5 An aqueous solution of ethyl alcohol (C2H5OH) is found to be 10/9 molal. If the density
of the alcohol solution is 0.8 g/cc, find mole fraction and molarity of solution with respect to ethyl alcohol.

Solution : Mass of solution

= mass of solute (C2H5OH) + mass of water.
   1000
Use m =  B  = (10/9  46) + 1000
 1  B  M A
( = mole fraction of alcohol) = 51.1 + 1000 = 1051.1

10  B  1000 Volume (in cc)

     = 0.0196
9  1  B  18 mass 1051.1
   1313.89cc  1.314 L
density 0.8
10 10
molal solution  mol of C2H5OH in = 1.314 L
9 9
1000 gms of H2O. moles 1019 10
 Molarity     0.845 M
For molarity, find volume of solution and for VL 1.382 11.825
volume of solution, first calculate mass of
solution.
Illustration - 6 One litre solution of 0.5N is heated. The volume of the solution is reduced to 750cc
and 2.675 gm of HCl is lost. Calculate :
(i) normality of the resultant solution.
(ii) number of meq of HCl in 100 cc of the original solution.
Solution :
(i) First calculate grams of HCl in original solution  wt. of HCl in resultant solution
g = 18.25  2.675 = 15.575 gm
Use: NVL 
E Now normality of new solution, N :
g
 0.5  1  g / E 15.575 / 36.5
 36.5 /1 N   0.57N
VL 750 / 1000
 g = 18.25 gm
(ii) meq in 100 cc of original sample
Now wt. of HCl lost due to heating = 2.675 gm meq = NVcc = 0.5  100  50 meq

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STOICHIOMETRIC CALCULATIONS Section - 2

In this section, we will discuss the problems based on balanced chemical equations and application of mole
concept.
The analysis of a chemical reaction is generally carried out in the form of mass of reacting species taking part
in a given reaction (gravimetric analysis) or in terms of concentrations of reacting species taking part in a
given reaction (volumetric analysis).
In Gravimetric Analysis, we generally analyse reactions such as : decomposition of compounds under heat to
produce a residue and a gas, or displacement reactions, action of acids on metals, or simple balanced
chemical equations involving Weight (solid)  Volume (gas) relationships.
In Volumetric Analysis, we generally analyse Neutralisation and Redox Titrations involving aqueous solutions
in general.

Neutralisation :
A reaction in which an acid (or a base) completely reacts with a base (or an acid) to form salt and water is
called as Neutralisation. If HA be the acid, BOH be the base and BA be the salt, then neutralisation
reaction can be represented as follows :
HA + BOH  BA + H2O

Redox Reactions :
A reaction in which both oxidation and reduction takes place simultaneously is called as Redox reaction. A
redox reaction always involves a pair of oxidising agent and a reducing agent.

Note : We will deal with Redox Reactions in the next chapter.

Before we move on to study the balanced chemical equations, let us first analyse meaning of some terms.

Moles of NaCl : NaCl  Na+ + Cl

1 mole 1 mole 1 mole
 1 mole of NaCl contains 1 mole of Na+ (ion) & 1 mole of Cl ion
 2 moles of NaCl contains 2 moles of Na+ ion & 2 moles of Cl ion

Moles of CaCl2 : CaCl2  Ca2+ + 2Cl

1 mole 1 mole 2 mole
 4 moles 4 moles 8 moles

x-moles of H2SO4 : H2SO4  2H+ + SO42

1 mole 2 moles 1 mole
x moles 2x moles x moles

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Application of Mole Concept on Balanced Chemical Equations :

Consider a general balanced chemical reaction or equation :

mA + nB  pC + qD

where A and B are reactants; C and D are products; m, n, p, q are the stoichiometric coefficients.
The above balanced reaction is analysed as :

m moles of A react with n moles of B to produce p moles of C plus q moles of D.

This can be represented (written) as :

m moles of A  n moles of B  p moles of C  q moles of D

Illustrating the mole concept :

What weight of KCl (Potassium Chloride) will be formed on heating 12.25 gm of KClO3 ?
Also calculate weight of O2 will be liberated.

First write a balanced chemical equation for decomposition of KClO3.

2KClO3 
 2KCl  3O2
(2 moles) (2moles) (3 moles)

From Stoichiometry, we have :

2 moles of KClO3  2 moles of KCl  3 moles of O2

 M (KClO )  122.5
 0 3

12.25  g 
moles of KClO3 =  0.1
122.5  moles  M 
 0 
 M 0(KCl)  74.5 

Now, 2 moles of KClO3  2 moles of KCl

 0.1 moles of KClO3 0.1 moles of KCl

 0.1  74.5 gm of KCl [ g  moles  M 0 ]

 7.45 gms of KCl are formed.

Similarly, 2 moles of KClO3  3 moles of O2

3 3
 0.1 moles of KClO 3   0.1moles of O 2   0.1  32 gms of O 2
2 2
= 4.8 gm of O2.

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1. Some Important Anions used in Stoichiometry

X   halides  Cl :Chloride, Br  : Bromide I : Iodide
O2  Oxide S2  Sulphide
N3 Nitride P3  Phosphide
CO32  Carbonate HCO3 Bicarbonate

NO3 Nitrate NO 2 Nitrite

SO 24  Sulphate HSO 4 Bisulphate

SO 32  Sulphite PO34 Phosphate

C2 O 42  Oxalate HC 2 O 4 Bioxalate

S2 O 32  Thiosulphate S4 O 62  Tetrathionate

ClO3 : Chlorate ; BrO3 : Bromate ; IO3 : Iodate

MnO 4 Permanganate Cr2 O72  Dichromate

2. Action of Heat on Some Important Compounds :

Alkali Metals Alkaline Earth Metals
Carbonate Stable Unstable
 
Na 2CO3 
 No Re action CaCO3 
 CaO  CO2
Bicarbonates Unstable Unstable
 
2NaHCO3 
 Na 2CO3  CO2  H2O Ca  HCO 3 2 
 CaO  H 2O  2CO 2

Sulphates Stable Stable


Na 2SO4 
 No Re action
3. Some Basic Chemical Equations :
(i) 2 KClO3   
(ii) 2 NaHCO3 
 2 KCl  3 O 2  Na 2CO3  CO2  H 2O
 1 
(iii) NaNO3   NaNO 2  O 2 (iv) 2 Pb  NO3 2 
 2 PbO  4 NO 2  O 2
2

(v) 2 Na 2S2O3  I2  
(vi) Na 2C2O 4 
 Na 2S4O6  2 NaI  Na 2CO3  CO

(vii) 2 FeSO4  
(viii) 2 AgNO3 
 Fe2O3  SO2  SO3  2 Ag  2 NO 2  O 2
 2 Mg  O 
 2 MgO 
 NH NO   N 2O  2H 2O
2 4 3
(ix)  (x) 
3 Mg  N  Mg3 N 2 
 NH NO   N 2  2H 2O
 2  4 2
 Calcium behaves similarly 
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-1

PROBLEM SOLVING TECHNIQUE (Using Mole Concept)

Follow the given sequence :
1. First write a balanced chemical equation.
2. Analyse the reactants and products according to their respective stoichiometric coefficients i.e.
i.e. m mole of A  n moles of B  p moles of C  q moles of D
3. According to data given, proceed as explained in the above illustration
4. In stoichiometric problems involving gases, we will assume all the gases to be ideal and apply
Gas Equation : PV = nRT.
(P : Pressure of gas in atm units, V : Volume of gas in L and T : Temperature in Kelvin and R : Universal gas
constants = 0.0821 atm L mol1 K1)
(a) At S.T.P., the volume occupied by 1 mole of a gaseous compound is equal to 22.4 L (or 22400 mL). This
is also called as Molar volume.
(b) At room temperature, T = 298 K, P = 1.0 atm., volume of 1 mole of gas is 24.48 L.
(c) N.T.P. (Normal temperature and pressure) condition is same as S.T.P. condition.

Illustration - 7 A flash bulb used for taking photograph in poor light contains 30 mL of O 2 at 780 mm
pressure at 27C. Suppose that metal wire flashed in the bulb is pure Aluminium (Al) and it is oxidised to
Al2O3 in the process of flashing, calculate the minimum weight of Al-wire that is to be used for maximum
efficiency.
Solution : From stoichiometry of the reaction :
Al is oxidised to Al2O3 as follows. 3 mole of O2  4 mole of Al
4 Al + 3 O2  2 Al2O3 4
1.25 × 103 mole of O2  (1.25 × 103) mole of Al
First, calculate the moles (n) of O2. 3
Use PV = nRT 4
gram of Al = (1.25 × 103)  27 = 0.045 gm
PV (780 / 760) (30 /1000) 3
 n   = 1.25  103
RT 0.082  300
Illustration - 8 A mixture of NaCl and Na2CO3 is given. On heating 12 gm of the mixture with dilute
HCl, 2.24 gm of CO2 is evolved at normal temperature. Calculate the amounts of two components in the
mixture.
Solution : From stoichiometry, we have :
Consider the effect of heat on the mixture. 1 mole of Na2CO3  1 mole of CO2
NaCl + HCl  nothing happens x x
moles of Na2CO3 = mol of CO2
106 106
Na2CO3 + 2 HCl  2 NaCl + CO2 + H2O x 2.24
  or x = 5.4 gm.
Let x grams of Na2CO3 are there in the mixture. 106 44
g x Hence grams of NaCl in the mixture
 moles of Na2CO3 = M  106 = 12  x = 6.60 gm
0

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Illustration - 9 A mixture of FeO and Fe3O4 when heated in air to a constant weight, gains 5% of its
weight. Find the composition of the initial mixture.

Solution : 4 moles of Fe3O4  6 moles of Fe2O3

In such type of problems, in order to simplify the 100 – x 6  100 – x 
calculations, let us assume that the initial weight of the  232 moles  4  232  moles of Fe2O3
mixture is 100 gm.
x 6  100 – x 
Then the final weight of the mixture after heating in air will Total moles of Fe O =   
2 3 144 4  232 
be 105 gm.
Let x be the weight of FeO in the initial mixture, then the  x 6  100 – x  
Weight of Fe2O3 =      160 = 105
weight of Fe3O4 = 100  x 144 4  232  
When the mixture is heated in air (O2): Solving for x, we get ;
4 FeO + O2  2 Fe2O3
x = 20.25 gm = weight of FeO
4 Fe3O4 + O2  6 Fe2O3
 weight of Fe3O4 = 100 – x = 79.75 gm.
 4 moles FeO  2 moles of Fe2O3
x x % FeO = 20.25 and % Fe3O4 = 79.75
 moles  moles of Fe2O3
72 144
Illustration -10 Brass is an alloy of Cu-Zn. A sample of brass weighing 6.0 g, when treated with excess
of dil. H2SO4 gives 328 mL of dry H2 at 27oC and 760 mm pressure. What is the percentage of Cu by weight
in the alloy? (Atomic mass of Zn = 65.4 gm)
Solution : 760 / 760  0.328
n  = 0.0133
Only Zn reacts with dil. H2SO4 and produces H2, 0.082  300
whereas Cu does not.
Zn(s) + H2SO4  ZnSO4 + H2 (g) The amount of Zn in the alloy
1 mol of Zn  1 mol of H2
= 0.0133  65.4 = 0.87 g
PV 5.13
 moles of H2 evolved = n  or % Cu =  100  85.5%
RT 6.0
Illustration -11 Calculate the weight of iron which will be converted into its oxide by the action of 18g
of steam.
Solution :
18
Remember that iron reacts with steam, it Moles H 2 O  1
18
forms Fe3O4
3 3
Moles Fe  1 
3Fe  4H2O 
 Fe3O4  4H 2 4 4
From stoichiometry of the reaction : 3
Weight of Fe   56  42g
3 moles of Fe  4 moles H 2 O 4

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Important Concepts in Stoichiometric Calculations :

1. (a) Finding the Equivalent Weight of Basic Compounds :
Oxides, Carbonates and Bicarbonates of alkali metals and alkaline earth metal are basic in nature e.g.
MgO, Na2CO3 and NaHCO3 are basic.
The n-factor (acidity of carbonates, bicarbonates & oxides) is equal to the magnitude of total charge on
cations or anions. It can also be confirmed by visualizing the neutralisation reaction as follows:
Na2CO3 + 2 HCl 
 2 NaCl + H2O + CO2
The above reaction shows that 1 mole of Na2CO3 requires two moles of H+ ions. Thus, its equivalent weight
106
is i.e. 53 gm/mol. [Note: Acidity also refers to the number of H+ ions required to react with the base.]
2
(b) Finding the Equivalent Weight of Acidic Compounds :
The oxides of non-metals are acidic in nature, such as SO2 & SO3 are popular acidic oxides used in
neutralisation. The n-factor (basicity) can be determined as follows:
SO3 + 2 NaOH 
 Na2SO4 + H2O
The above reaction shows that 1 mole of SO3 requires two moles of ions. Thus, its equivalent weight is
80/2 = 40 gm/mol. Note : Basicity also refers to the number of OH- ions required to react with the acid.
2. Concept of Limiting Reagent :
Whenever, the amount of two reacting species (reagents) is given, very rarely they react completely (unless
calculated beforehand). In such cases, one of reagent reacts completely (as per Stoichiometry of the reaction)
leaving behind the other in excess. The reagent which reacts completely is known as Limiting Reagent.
Read the following example carefully to understand the concept.
Illustrating the Concept:
A closed vessel is found to certain 192 gm of Mg and 96 gm of O2 . This mixture is burnt.
(a) Which is the limiting reagent ?
(b) Find the weight of reagent in excess (the other one) ?
2 Mg  O 2  2 MgO 2
 3moles of O 2   3  6 moles of Mg
1
2 moles of Mg  1 mole of O 2
 2 moles of MgO  Mg is in excess.
192 Hence O2 is the limiting reagent as it is consumed fully.
Initial moles of Mg  8 Excess of Mg = 8 – 6 = 2 moles
24
96  Grams of excess Mg = 2  24 = 48 gm
Initial moles of O 2  3 moles of MgO formed
32
= moles of Mg consumed = 6
1 mole of O 2  2 moles of Mg
 Grams of MgO formed = 6  40 =240 gm
Read the following Illustrations carefully to understand the concept of limiting reagent.

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Illustration -12 Consider the reaction : 2A + 3B   4C + 5D

In the above reaction A and B are reactants and C and D are products. If one mole of each of A and B
are reacted. Then:
I. 2.25 mole of of D is formed II. 1.6 mole of D is formed
III. 0.33 mole of A are left after complete reaction IV. 1.33 mole of C is formed
The correct choice is :
(A) I, II (B) II, III, IV (C) I, III, IV (D) I, II, IV
Solution : (B)

2A  3B   4C  5D
2 moles of A  3 moles of B  4 moles of C  5 moles of D [From Stoichiometry]
Initial n A  n B  1.
[For 1 mole of A,1.5 moles of B are needed. But only 1 mole of B is given. Hence, B is the limiting reagent]
2 1 4 5
n A  1    0.33 ; n B  1  1  0 ; n C   1.33 ; n D   1.66
3 3 3 3
Illustration -13 In the following reaction : MnO2 + 4HCl 
 MnCl 2 + 2H 2O + Cl 2 .When 2 moles
of MnO2 reacted with 4 moles of HCl, 11.2 L Cl 2 was collected at STP. Find the percent yield of Cl 2 .
(A) 25% (B) 50% (C) 100% (D) 75%
Solution : (B)
MnO2 + 4HCl   MnCl2 + 2H 2 O + Cl2
From Stoichiometry 1 mole 4 moles 1 mole 2 moles 1 mole
Initial (Given) 2 moles 4 moles [For 2 moles of MnO 2 , 8 moles of HCl are needed,
but only 4 moles of HCl are given. Hence, HCl is the limiting reagent]
Finally 1 mole 0 mole 1 mole 2 moles 1 mole = 22.4 L at STP (Theoretical yield)
11.2
% yield of Cl2   100 %  50%
22.4
Illustration -14 What is the number of moles of Fe  OH  3  s  that can be produced by allowing 1 mole

of Fe2 S 3 , 2 moles of H 2 O and 3 moles of O2 to react as : 2Fe2 S 3 + 6H 2O + 3O2   4Fe  OH  3 + 6S ?

(A) 1 mol (B) 1.84 mol (C) 1.34 mol (D) 1.29 mol
Solution : (C)
 4Fe  OH 3  6S
2Fe2S3  6H 2 O  3O 2 
From Stoichiometry 2 moles 6 moles 3 moles 4 moles 6 moles
Initial 1 moles 2 moles 3 moles
[For 1 mole of Fe 2S3 , 3 moles of H 2O are needed & 1.5 mole of O 2 . But only 2 moles of H 2O are
given and 3 moles of O 2 are given. Hence, H 2 O is the limiting reagent.]
Finally 1/3 mole 0 moles 2 moles 4/3 moles 2 moles

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NEUTRALISATION Section - 3

As we know that an acid may be monobasic (HCl, HNO3 etc.), dibasic (H2SO4, H2C2O4 etc.) or tribasic
(H3PO4 etc.) and similarly a base may be monoacidic (NaOH, NaHCO3 etc.), diacidic [Ca(OH)2, Na2CO3
etc.] or triacidic [Al(OH)3 etc.], so it is better to define the neutralisation reaction in the following manner:
A reaction in which 1 gram equivalent (or 1 meq) of an acid (or a base) completely reacts with 1 gram
equivalent (or 1 meq) of a base (or an acid) to form 1 gram equivalent (or 1 meq) of corresponding salt.
A stage at which the process of neutralisation is complete is known as end point or neutral point and the
process carried out to study neutralisation of acids and base is called as Titration.
At equivalence point :
gm eq. (or meq) of acid = gm eq. (or meq) of base

Na Va = Nb Vb (N : normality, V : volume in mL or L, a: acid, b : base)

This relation can be used in two ways (modified form) :

1. If ga grams of acid are neutralised by a base whose normality is Nb and volume required for neutralisation of
given acid is Vb (in cc), then
ga M0
 1000  N b Vb Ea 
Ea basicity
2. If gb grams of a base are neutralised by an acid of normality Na and volume Va (in cc), then
gb M0
 1000  N a Va Eb 
Eb acidity

Illustrating the Concept :

 How many grams of borax (Na2B4O7.10H2O) are required to neutralize 25 ml of 0.2 M of HCl and
H2SO4 separately.

Borax in water gives : B4 O72  7H 2O 

 4H3BO3  2OH  (Remember it as fact)
 1 mol of borax  2 mol OH  acidity = 2

(i) meq of borax = meq of HCl

g
 1000   0.2  1  25 [ HCl is monobasic acid]
382 / 2
 g = 0.955 gm = mass of Borax
(ii) meq of borax = meq of H2SO4
g
 1000   0.2  2   25 [ H2SO4 is diabasic acid] g = 1.91 gm = mass of Borax
382 / 2

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 How many mL of 0.5 N HCl acid will be required to completely neutralise 500 ml of a 0.1 N NaOH
solution?
Let VmL of acid is required for neutralisation. Using equation of neutralisation we have : NaVa = NbVb
 0.5  Vcc = 0.1  500  Vcc = 100 cc = 100 mL
 0.5 gm of fuming H2SO4 (oleum) is dilute with water. This solution is completely neutralised by
30.0 mL of 0.4 N NaOH. Find the % age of free SO3 in the sample.
Oleum is (H2SO4 + SO3 = H2S2O7)
Note that SO3 is acidic oxide and hence reacts  x 0.5  x 
     1000 = 0.4  30
with NaOH.
 ESO3 E H 2SO 4 
2 NaOH + SO3  Na2SO4 + H2O ;
 x 0.5  x 
i.e., it acts as a dibasic acid.   80 / 2  98 / 2   1000 = 0.4  30
 
Let gms. of SO3 in 0.5 gm = x ;  x  0.4 gm = mass of SO3
Then, gms of H2SO4 = 0.5  x 0.4
 % age of SO3 =  100  80%
At neutralisation stage : meq of sample 0.5
= meq of NaOH

Important Concepts in Stoichiometric Calculations :

1. Salts formed by the reactions between a strong acid (like HCl, H2SO4, HNO3, H3PO4 etc. . . ) and a
strong base like NaOH, KOH, Mg(OH)2, Ca(OH)2) when dissolved in water does not effect the acidity
or basicity of the solution. For example : A solution having Na2SO4 (formed by the reaction between
NaOH and H2SO4) as its solute is neutral as Na2SO4 is a salt of strong acid and strong base.
2. Back Titration : This concept comes into picture while analyzing the Neutralization in case any of the acid
or base is found to be in excess (Over stepping of the end point).
Both of the above concepts can be clearly understood on careful examination of the following
illustrations :

Illustration -15 M
What volume of H3 PO4 solution will completely react with 200 ml of a solution of
6
M
aluminium carbonate ?
2
(A) 600 mL (B) 900 mL (C) 1200 mL (D) 1800 mL

Solution : (C) [Total charge on all cations or on all anions]

Applying equation of neutralisation : 1  1 
 3    VmL   6    200 
meq.of H3PO4 (acid) = meq of Al2(CO3)3 (base) 6  2 
[Meq. = n-factor  mmoles]
n-factor of Al2 (CO3)3 as base = 6
VmL = 1200 mL

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Illustration -16 100 mL of mixture of NaOH and Na2SO4 is neutralised by 10 mL of 0.5 M H2SO4.
Hence, and mass of NaOH in 100 mL solution is :
(A) 0.2 g (B) 0.4 g (C) 0.6 g (D) None of these
Solution : (B)
As Na2SO4 , neutral being a salt of strong acid and strong base, only NaOH will be neutralised by H2SO4.
Applying equation of neutralisation : meq. of H2SO4 (acid) = meq of NaOH (base)
 
2  0.5  10  103  1  n NaOH   n(moles)  0.01
 Mass of NaOH = 0.01  40 = 0.4 g
Illustration -17 1.0 g of the carbonate of a metal was dissolved in 25 mL of 1.0 N HCl. The resulting
liquid required 5 mL of 1.0N NaOH for neutralization. The equivalent weight of the metal carbonate is :
(A) 50 (B) 30 (C) 20 (D) None of these
Solution : (A)
Meq. of acid (HCl) used = 25  1  25 [Meq = n-factor  mmoles]
Excess of meq. of acid (HCl) = Meq. of NaOH = 5  1  5 [Back titration]
Meq. of acid used for metal carbonate = 25 – 5 = 20 = Meq. of carbonate
1  g 
 Meq of carbonate = 20   1000  E  50  Meq.   1000 
E  E 
Illustration -18 5.3g of M2CO3 is dissolved in 150 ml of 1 N HCl. Unused acid required 100 ml of 0.5 N
NaOH. Hence equivalent weight of M is :
(A) 53 (B) 46 (C) 2 (D) 23
SOLUTION : (D)
gmeq of Acid (HCl) = gmeq of M2CO3 + gmeq of NaOH
 gmeq of M2CO3 = gmeq of Acid  gmeq of NaOH = (150  1  10–3) – (100  0.5  10–3)
 n M 2CO3  2  0.1 ;  n M 2CO3  0.05
g M 2CO3
 0.05 5.3
 M M 2CO3  M M 2CO3  2M  60   2M + 60 = 106 M = 23
0.05
Illustration -19 100 ml solution of 0.1N HCl was titrated with 0.2 M NaOH solution. The titration was
discontinued after adding 30 ml of NaOH solution. The remaining titration was completed by adding 0.5
M KOH solution. The volume of KOH required for completing the titration is:
(A) 8ml (B) 16ml (C) 32ml (D) 64ml
SOLUTION : (A) For excess of HCl, now KOH is used.
meq of HCl  0.1100  10  meq of KOH=meq of HCl remaining
meq of NaOH soln  30  0.2  6
0.5  VmL  4  VmL ( KOH )  8mL
meq of HCl remaining  10  6  4

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Illustration -20 5 mL of 8 N HNO3 , 4.8 mL of 5 N HCl and a certain volume of 17 M H2 SO4 are mixed
together and made upto 2 L. 30 mL of the acid mixture exactly neutralises 42.9 mL of Na2CO3 solution
containing 0.1 gm of Na2CO3 .10H 2O in 10 mL of water. Calculate : (a) the volume of H2 SO4 added to
the mixture (b) the amount (in gm) of the sulphate ions in the solution.
Solution :
meq. of acid mixture = meq of HNO3 + meq of HCl + meq of H 2SO 4
Let N be the normality of the acid mixture and VCC be the volume of H 2SO 4 added.
N  2000  8  5  5  4.8  2 17   VCC ......(I)
strength
Now find N of carbonate as follows : N 
E
Strength = 0.1 g/10 ml  10 g/L ; E= M 0 /2 = 286/2 = 143 ;( M 0  106  180 ; adding the mass of 10 H 2 O )
10
N
143
Now meq of acid mixture = meq of Na 2 CO3 solution
10
N  30  42.9   N  0.1  normality of acid mixture
143
Substituting in equation (I), we get : 0.1 2000  40  24  34  VCC   VCC  4 cc
For gms of sulphate ions :
meq of H 2SO4  2 17  VCC  136  VCC  4 

Now, meq of SO 24   meq of H 2SO 4

g g
  1000  136  1000  136  g  grams of SO 24 ions  6.53gm
E 96 / 2
So24

Illustration -21 A sample of chalk  CaCO3  is contaminated with calcium sulphate  CaSO4  ; 1 gm of
the solid mixture is dissolved in 230 mL of N/10 HCl ; 40 mL of N/10 NaOH is required to neutralise the
excess of acid. Find the percentage of chalk in the mixture.
Solution :
Here, note that CaSO 4 does not react with HCl as it gives a netural solution in aqueous medium (a salt of strong
acid and strong base) whereas, CaCO3 being basic reacts with HCl.

So now it is a simple problem of neutralisation, First find the meq of NaOH used for excess
Note that volume of HCl used against CaCO3 is not of HCl.

given. To calculate the volume of HCl for CaCO3 , meq of NaOH  1/10   40  4
proceed as follows : meq of excess of HCl =
Excess of HCl is neutralised by NaOH 4 (def. of neutralisation)
meq of excess of HCl = meq. of NaOH Now Find the initial meq of HCl taken.

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Initial meq of HCl = (1/10)  230 = 23 meq of g

HCl used for neutralisation of carbonate   1000  19
E
= 23 – 4 = 19
 g  0.95 gm  95%
 meq of CaCO3  19

Illustration -22 1 gm of impure Na 2CO3 is dissolved in water and the solution is made upto 250 mL. Too
50 mL of this solution, 50 mL of 0.1N HCl is added and the mixture after shaking well, required 10 mL of
0.16 N NaOH solution for complete neutralization. Calculate % purity of the sample of Na 2CO3.
Solution :
1.0 gm of (impure)
So meq of Na 2CO3 (pure) in 50 mL = 3.4
Na 2CO3  H 2O  250 mL
 meq of pure Na 2CO3 is 250 mL
 50 mL Na 2CO3  50mL of 0.1N HCl 
250 g
 10mL of 0.16 N NaOH  3.4   17 or  1000  17
50 E
In this question, HCl is in excess.
 excess meq of HCl = meq of NaOH 17  106 / 2 
 g  0.901gm
 0.16 10  1.6 1000

meq of HCl added to Na 2CO3  0.1 50  5 Na 2CO3 is a diacidic base  E = 106/2

So mass of pure
 meq of HCl used to neutralised Na 2CO3
0.901
 5  1.6  3.4 Na 2CO3  100  90.1%
1

 Yield of a Chemical Reaction:

In general, in any chemical reaction, the amount of product formed is always less than the calculated
amount due to reversibilities in the chemical reaction. Therefore, yield of a chemical reaction (Y) comes
into picture and is given by :

Actual yield of the product

Y  100  Actual yield  % yield   Theoretical value 
Theoretical yield of the product

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Illustration -23 NH 3 is formed in the following steps :

I. Ca  2C 
 CaC2 50 % yield

II. CaC2  N 2 
 CaCN2  C 100% yield

III. CaCN2  3H2O 

 2NH3  CaCO3 50% yield
Find the moles of calcium needed to produce 2 moles of ammonia

Solution :
Actual yield = % yield  (Theoretical value) ; Let x mole of Ca are needed.
From I : Yield of CaC 2  50%  x  x / 2

From II : Yield of CaCN 2  100%   x / 2   x / 2

From III : Yield of NH3  50%  2   x / 2   x / 2

Given : Moles of ammonia  2  x / 2  x  4 moles

USE OF DOUBLE INDICATORS IN NEUTRALISATION Section - 4

For studying the titrations of alkali mixtures such as NaOH and Na2 CO3 ; NaOH and NaHCO3 ;
Na2CO3 and NaHCO3, two indicators phenolphthalein and methyl orange are used.
 Phenolphthalein is a weak orange acid and gives end point between pH range of 8-10, while methyl
orange, a weak base gives end point between pH range of 3-4.4.
 When methyl orange is used as an indicator for studying the neutralisation titrations for above
mixtures, it indicates complete neutralisation for these, i.e. at the end point (colour change for
indicator) the above mixtures are fully neutralised.
 When phenolphthalein is used as an indicator for the above mixtures:
(a) it indicates complete neutralisation of NaOH (or KOH, i.e. strong alkali).
(b) it indicates half neutralisation of Na2CO3 (at the end point NaHCO3 is formed).
Note: It fails to indicate the neutralisation of NaHCO3 at all. Why? Because CO2 is the product of final
neutralisation of NaHCO3.CO2 is acidic oxide and in acidic medium phenolphthalein fails.
So, in an analysis of such alkali mixtures, both the indicators are used:
 one after the other in the same volumetric mixture
or
 two indicators are used seperately in two different titrations.

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FOR EXAMPLE :
1. In the Neutralisation mixture of NaOH and Na2CO3 :
(a) Use of methyl orange:
NaOH and Na2CO3, both are fully neutralised. i.e.
milliequivalent (meq or gmeq) of acid used = meq of NaOH + meq of Na2CO3
(b) Use of Phenolphthalein :
NaOH is fully neutralised and Na2CO3 is half neutralised
l
milliequivalent (meq. or gm.eq) of acid used = meq of NaOH + meq of Na2CO3
2
2. In the Neutralisation mixture of NaHCO3 and Na2CO3 :
(a) Use of Methyl Orange :
NaHCO3 and Na2CO3, both are fully neutralised, i.e.
milliequivalent (meq or gmeq) of acid used = meq of NaHCO3 + meq of Na2CO3
(b) Use of Phenolphthalein :
Na2CO3 is half neutralised and NaHCO3 is not neutralised at all.
1
milliequivalent (meq or gmeq) of acid used = meq of Na2CO3
2
Illustration -24 A solution of NaOH and Na2CO3 is prepared. 25 ml of this solution required for
neutralisation:
(a) 25.0 mL of 0.10 N HCl when phenolphthalein is used as indicator.
(b) 35.0 mL of 0.10 N HCl when methyl orange is used as indicator.
Find the strength of NaOH and Na2CO3.
Solution :

NaOH 25mL, 0.1 N HCl

 Experiment - I
 (Phenolphthalein)

Na 2CO3 
35 mL, 0.1 N HCl
 Experiment - II
(Methyl Orange)
(25 mL)

Let m moles of NaOH be x and that of Na2CO3 be [Note: Na2CO3 is half neutralised with phenolphtha-
y in 25 ml  3.5 = x + 2y ...(ii) lein as indicator]
Experiment - I :  25  x  y .....(i)
Meq. of Acid = Meq. of Base (For complete Experiment - II:
neutralisation)
Meq of Acids = Meq. of Base (For complete
1 neutralisation)
25  0.1  1 x  2  y 
2 35  0.1  1 x  2  y
[ meq = n-factor  m moles]

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Solving.....(i) and ....(ii), we get: y = 1 and x = 1.5 1 106

 g Na 2CO3   0.106 gm
g NaOH 1000
x  1000 (in 25 ml )
M NaOH
1000
1.5  40 Thus, strength of NaOH  0.06   2.4 g / L
 g NaOH   0.06 gm 25
( in 25 ml ) 1000
1000
and strength of Na2CO3  0.106   4.24 g / L
g Na 2CO3 25
y  1000
M Na 2CO3

Illustration -25 8 gm of a mixture of anhydrous Na CO and NaHCO was dissolved in water and
2 3 3
made upto 1000 mL, 25 mL of this solution required for neutralisation:
(a) 32.0 mL of N/10 HCl using methyl orange and
(b) 12.0 mL of N/10 HCl using phenolphthalein.
Find the strength of NaHCO3 and Na2CO3.
Solution :

Na 2CO3
 25 mL 12 mL, N/ 10 HCl
Experiment  I
NaHCO3 sample phenolphthalein
8gm

32 mL, N / 10 HCl
Experiment  II
Methyl Orange
Let m moles of Na2CO3 be x and that of NaHCO3 be y in 25 ml sample.
Experiment - I : Meq. of Acid = Meq. of Base (For complete Neutralisation)
1 1
12   2  x   1 y  0  1.2 = x + 0  x = 1.2 ....(i)
10 2
Experiment - II : Meq. of Acids = Meq of Base (For complete neutralization)
1
32   2  x  1  1 y  1  3.2 = 2x + y
10
Solving (i) and (ii), we get : x = 1.2 and y = 0.8
g Na 2 CO3 1.2  106
x 1000  g Na 2 CO3   0.127 gm
Thus, M Na 2CO3 1000
(in 25 ml)

g NaHCO3 0.8  84
y  1000  g NaHCO3   0.0672 gm
and M NaHCO3 1000
(in 25 ml)

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1000
Thus, strength of Na2CO3 in the sample  0.127   5.28gm / L
25
1000
and strength of NaHCO3 in the sample  0.0672   2.69 gm / L
25
NOW ATTEMPT IN-CHAPTER EXERCISE-D

THEN ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK

THINGS TO REMEMBER

1. Atomic Weights of Most Commonly used Elements :

ELEMENT SYMBOL ATOMIC WEIGHT ELEMENT SYMBOL ATOMIC WEIGHT

Hydrogen H 1.0 Helium He 4.0

Carbon C 12.0 Nitrogen N 14.0
Oxygen O 16.0 Fluorine F 19.0
Sodium Na 23.0 Magnesium Mg 24.0
Aluminium Al 27.0 Phosphorus P 31.0
Sulphur S 32.0 Chlorine Cl 35.5
Potassium K 39.0 Calcium Ca 40.0
Chromium Cr 52.0 Manganese Mn 55.0
Iron Fe 56.0 Copper Cu 63.5
Zinc Zn 65.4 Arsenic As 75.0
Bromine Br 80.0 Silver Ag 108.0
Tin Sn 119.7 Iodine I 127.0
Barium Ba 137.4 Gold Au 197.0
Mercury Hg 200.0 Lead Pb 207.0

2. Recapitulating and Summarizing:

 g
 gmeq   NVL
 g E

 moles  M  MVL  meq  g  1000  NV
 0 mL
 E
 g
 mmoles  M  1000  MVmL
 0

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 gmeq  x  moles
 meq  x  m.moles x = n - factor

 N  x  M
 n B  1000 1000 B
 molality(m)  gA

MA A

 m
B  1000
 m
 MA
 10 xd
M  M gB
 0 Strength = = N E = M M0
 10 xd litres of solution
 N  E

Note : (i) In experiments involving neutralisation, we should use concept of gmeq (or meq) i.e.,

gmeq of acid = gmeq of base

(ii) In experiments (usually gravimetric analysis) we should use mole concept i.e. first balance the chemical
equation and then correlate the reactants and products as per their stoichiometric coefficient.

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My Chapter Notes

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Illustration - 1

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