VMC Modules PDF

VIDYAMANDIR MODULES
INDEX
1. Stoichiometry I
2. Stoichiometry II
3. Atomic Structure
4. Periodicity of elements
5. States of Matter
6. Chemical Bonding I
7. Chemical Bonding II
8. Chemical Equilibrium
9. Ionic Equilibrium
10. Chemical Thermodynamics I
11. Chemical Thermodynamics II
12. Thermochemistry
13. Solid State
14. Theory of solutions
15. Chemical Kinetics
16. Electrochemistry
17. Coordination Compounds
18. Introduction to organic chemistry
19. Organic Concepts – Reaction mechanisms
20. Hydrocarbon
21. Halogen containing organic compounds
22. Oxygen containing organic compounds
23. Surface chemistry
24. Basic principles of extraction – Metallurgy
25. S Block elements
26. P Block elements I
27. P Block elements II
28. D Block elements
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
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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Stoichiometry - 1 Vidyamandir Classes
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
 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.

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

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.

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

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.


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

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


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

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

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

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

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

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).


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).

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

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

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

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

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

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

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

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

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.

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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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.

Stoichiometry -1
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
 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

 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

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

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
Section
Stoichiometry -1
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

Stoichiometry -1
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]
Section
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)

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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Stoichiometry - II
Analysis of Redox Reaction
There are two ways of analysing and solving the stoichiometric problems based on redox reactions :
(a) One is to balance the redox reaction and then approach the problem like a simple balanced chemical
equation using the concept of moles (Application of mole concept as done earlier).
(b) Second, use the concept of gram equivalents (or milli equivalents) as used in neutralisation.
Here gmeq. (or meq) of oxidising agent = gmeq. (or meq) of reducing agent.
First we will learn how to analyse a given redox reaction and different methods used for
balancing it. Then as the chapter progress, you will learn how to proceed while solving
numerical problems based on the redox analysis.
OXIDATION - REDUCTION Section - 1
Oxidation is a process that involves the loss of electrons by the atoms or ions.
Reduction is a process that involves the gain of electrons by the atoms or ions.
Any reaction, in which the electrons are exchanged between atoms or ions, represents simultaneous pro-
cess of oxidation and reduction and is called as a Redox Reaction.
In a Redox Reaction, the species that loses electron (i.e., gets oxidised) is known as reducing agent or
reductant, (since it causes reduction of other species), the species which accepts electrons from reductant
(i.e., gets reduced) is known as oxidising agent or oxidant (as it causes oxidation of other species).
Illustrating the concept :
Mg + Zn2+ 
 Mg2+ + Zn is a redox reaction.
Oxidation : Mg0  Mg2+ + 2e


Reduction : Zn2+ + 2e  Zn0


Mg causes reduction of Zn2+, so it is Reductant.
Zn2+ causes oxidation of Mg, so it is Oxidant.
Note : A redox reaction involves two half reactions: Oxidation half reaction and Reduction half reaction

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Now, a new concept of Oxidation Number and Oxidation State is being introduced in order to study
oxidation and reduction reactions (redox reactions) in a much better way.
Oxidation Number (O.N.) : It refers to the total charge on all atoms of same kind in a compound.
Oxidation State (O.S.) : It refers to the charge per atom of all atoms of same kind in a compoun.
Oxidation state, many a times, is alos referred to as Oxidation Number (Refer to NCERT Book).
This means, oxidation number of an element in a compound is equal to oxidation state of that element
multiplied by total atoms of that element in particular compound.
(i) In ionic compounds, it is simply the charge on corresponding cation and anion which is expressed as
oxidation state of that partiular element. For example, oxidation state of potassium and chlorine in
potassium chloride (KCl) is simply +1 and –1 respectively as KCl is treated as K+ Cl–.
Refer to following examples where oxidation states are written above the atoms : .
+2 –1 +2 –2 +3 –1 +2 –2 +1 –1 +1+6 –2
MgCl2 CaS AlCl3 CaO NaF K2SO4
Note : (a) In MgCl2 and AlCl3, -1 is the oxidation state of Cl atom and its oxidation number is -2 and -3
respectively.
(b) In each of the cases, the sum of oxidation number of all atoms of all kinds is equal to zero (as the
compound is neutral).
(ii) In Covalent Compounds, it is not so easy to assign oxidation state of an atom. In order to simplify
the concept, we are going to define a set of rules which would enable us to assign oxidation state to
every element in any compound.
Rules for Assigning Oxidation State (O.S.) and Oxidation Number (O.N.) :
1. Any element in free state is assigned an oxidation state of zero (0). For example: O.S. of H, P, S, O,
Fe, Br, in H2, P4, S8, O2, Fe, Br2 is equal to 0.
2. The oxidation state of any cation or anion (of form A+ or B ) is equal to the magnitude of its charge.
For example: O.S. of Ca in Ca2+ = +2, O.S. of Al in Al3+ = +3, O.S. of Cl in Cl = 1 and so on.
3. (a) The algebraic sum of the oxidation number of all atoms in a neutral compound is equal to 0.
(b) The algebraic sum of the oxidation numbers of all atoms in an ion (like PO34 etc.) is equal to
the charge on the ion.

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4. The oxidation states of Alkali Metals (Group IA) is +1 in all of their compounds and that of Alkaline
Earth elements (Group IIA) is +2 in all of their compounds.
5. Hydrogen in almost all of its compounds is assigned an oxidation state of +1. The exception occurs
when hydrogen forms compounds with strong metals (metallic hydrides). For example : KH, NaH,
MgH2, CaH2 etc. In all of these, the oxidation state of hydrogen is 1.
6. Oxygen in almost all of its compounds is assigned an oxidation state of 2. In a class of compounds,
Peroxides, oxidation state of oxygen is 1, for example : H2O2, Na2O2 etc. Another exception is
1
OF2, where O.S. is +2. O2F2, where O.S. is +1 and KO2 in which O.S. is  .
2
7. Fluorine is most electronegative element and is assigned an O.S. of 1, in all its compounds. For
other halogens, O.S. is generally 1 except when they are bonded to a more electronegative halo-
gen or oxygen. O.S. of iodine in IF7 is +7, O.S. of chlorine in KClO3 is +5.
Concept of Fractional Oxidation States :

Fractional oxidation state is the average oxidation state of the element under examination and it means
that the element for which fractional oxidation state is realised is present in different oxidation states.
Structure of the species C3O2, Br3O8 and S4O62 reveal the following bonding situations :
The elements marked with asterisk in the above examples are exhibiting different oxidation state from the
rest of the atoms of the same element in each of the species. This means 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. 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 and the average is 16/3. In the same manner, in the species
S 4 O 62  is 2.5, whereas the reality being +5, 0, 0 and +5 oxidation number respectively for each sulphur..
Fe3O4, Mn3O4, Pb3O4 are some of the other examples of the compounds, which are mixed oxides having
the metal in fractional oxidation state. However, the oxidation states may be in fraction as in O 2 and O 2
where it is +1/2 and 1/ 2 respectively..
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Using all these rules, we can now assign oxidatizon states to almost all the elements in various compounds
and ions.
Try Yourself : Find the oxidation state of atoms (written in bold) in the following compounds.
SiO2, OF2, KClO3, HClO4, NH4+, Hg2O, Pb3O4, MnO2, C3H6Cl2, BO33, K2MnO4, Cr2O3,
CrO2Cl2, Mg3N2, N2O5, MgSiO3, Na2S2O3, S4O62, CaC2, H2C2O4, NH4NO3
Analysis of a Redox Reaction

Consider the following Redox Reaction :
CuSO4 + Pb  
 PbSO4 + Cu
1. Assign oxidation state to each atom.

+2 +6 2 0 +2 +6 2 0
Cu S O4 + Pb 
 Pb S O4 + Cu
Note : (i) O.S. of S, O remains same, i.e., neither of the two is oxidised or reduced (by inspection).
(ii) O.S of Pb and Cu2+ has changed from left to right.
Rewriting the equation as two equations (oxidation and reduction) as follows :
Reduction : Cu2+ + 2e 

 Cu0 (gaining 2e)
Oxidation :  Pb2+ + 2e
Pb0  (losing 2e)
Note : (i) O.S of Pb has increased from 0 to +2.

(ii) O.S of Cu2+ has decreased from +2 to 0.
We can now re-define oxidation and reduction as follows :

Oxidation is an increase in oxidation state and Reduction is a decrease in oxidation state.
Note : Pb is oxidised and causes the reduction of Cu2+. Pb is called as reductant. Cu2+ is reduced and causes the
oxidation of Pb. Cu2+ is called as oxidant.
Now an important aspect at this stage is to learn “How to balance the redox reactions”. So first we will learn
balancing the Redox Reactions.
4 Section
Section 11 Self Study Course for IITJEE with Online Support
Balancing of Redox Reactions

For balancing of Redox Reactions, two methods are generally adopted :
(A) Oxidation Number Method
(B) Ion Electron (Half-Reaction) Method
(A) Oxidation Number Method :

While balancing a given reaction by this method, following steps are to be followed :
1. Assign oxidation state to each element (atom) on both sides of the equation and identify which
element has been oxidised and which reduced.
2. Write two oxidation and reduction reactions (two half reactions) separately involving only atoms.
Now balance the atoms on both sides of equation in each half reaction.
3. Balance charge on both sides by adding electrons to whichever side is deficient in electrons. (i.e.,
negative charge)
4. Add two half reactions together. How ? In doing this we want electrons to cancel from both sides. For
this, multiply the equations by appropriate coefficients so that number of electrons produced in oxidation
reaction equals to that used up in reduction reaction.
5. Now compare this balanced equation with original unbalanced equation. Here, notice whether the
given equation is a molecular equation or an ionic equation.
6. For molecular equation, to balance Oxygen (O) and Hydrogen (H), add required water to the side
deficient in H and check for Oxygen atoms on both sides. (They will be equal on both sides)
7. For ionic equation, apart from balancing O and H atoms, charge needs to be balanced. It depends
upon the medium in which the reaction is taking place : Acidic (containing H+ ions or any acid) or
Alkaline (containing OH ions or any base).
(a) In Acidic medium, count total charge on both sides and balance it by adding H+ ions to the
required side (i.e., to the side deficient in +ve charge). Finally add enough water molecules to
balance H and O atoms to the required side.
(b) In Basic medium, balance the charge by adding OH ions to the side with excess of +ve charge
and finally add required number of H2O molecules to the appropriate side to balance O and H.
(B) Ion Electron (Half-Reaction) Method

1. Identify the oxidation and reduction half reactions and write them separately in ionic form. Note that,
write whole of ion in half reaction (unlike the oxidation number method where only atoms undergoing
the change of state were taken).

Stoichiometry-
Stoichiometry-IIII Vidyamandir Classes
For example : Mn in MnO4 in acidic medium generally goes to MnSO4 or Mn2+
Write it like this : MnO4 

 Mn2+ (and not as Mn7+ 
 Mn2+ )
2. Balance each half reaction separately. This is done accordingly to the following procedure.
3. Balance all the atoms of both reactions except O and H.
4. Now first balance O and H atoms (unlike in first method) depending upon the medium of reaction.
Acidic Medium :
To balance O atoms add same number of water (H2O) molecules to the side deficient in O atoms.
MnO4 
 Mn2+ (acidic medium)
Illustration - 1 MnO4 
 Mn2+ + 4 H2O
Now to balance H atoms, add as many H+ ions required to the side deficient in H atoms (generally it is
equal to double the number of water molecules added to the other side while balancing O atoms).
MnO4 + 8 H+ 
 Mn2+ + 4 H2O
Basic Medium :
To balance O atoms, add same number of H2O molecules to the side having excess of O atoms and add the
double the number of OH ions to the other side (i.e., to the side deficient in O atoms).
NO3  
 NH4+ (basic medium)
NO3 + 3 H2O   NH4+ + 6 OH


Now to balance H atoms (if required), add same number of OH ions to the side in excess of H atoms and
then add same number of water molecules to the other side (i.e., the side deficient in H atoms).
NO3 + 3 H2O + 4 H2O 

 NH4+ + 6 OH + 4 OH
NO3 + 7 H2O 
 NH4+ + 10 OH
5. Now add electrons to the side deficient in negative charge in order to balance the charge on both
sides.
MnO4 + 8 H+ + 5e  
 Mn2+ + 4 H2O
NO3 + 7 H2O + 8e 

 NH4+ + 10 OH
These are balanced half reactions in acidic and basic medium respectively.
6 Section
Vidyamandir Classes Stoichiometry- IIII
Stoichiometry-
6. Now add two half reactions together in such a manner that electrons from both sides cancel. So
multiply by coefficients so that number of electrons produced in oxidation equals the number of electrons
used in reduction (as done in oxidation number method step – 4).
Note : In this method we don’t have to calculate oxidation states as done in first method.
Illustration - 1 Balance the following reaction by Oxidation number and Ion electron method.
KMnO4 + H2SO4 + K2C2O4 

 MnSO4 + CO2 + K2SO4
SOLUTION :
Oxidation Number Method :
Follow the steps given below to balance the 2 Mn7+ + 5 C23+ 
 2 Mn2+ + 10 C4+
reaction given above :
Now compare this balanced equation with the
Assign O.S. to the atoms which are oxidised or molecular unbalanced equation as follows.
reduced. Note that O.S of O, K, H, S are same
on both sides. This is done by oral inspection. 2 KMnO4+ 5 K2C2O4 
 2 MnSO4+10 CO2
We’ll consider O.S of Mn and C on both sides. As the charge is balanced, now balance ‘K’ atoms
+7 +3 on both sides by adding 6 K2SO4 on right.
KMnO4 + H2SO4 + K2C2O4
2 KMnO4 + 5 K2C2O4 

 +2 +4
2 MnSO4 + 10CO2 + 6K2SO4

 MnSO4 + CO2
Now to balance SO42 ions on both sides, add
Write two half reactions and balance the atoms as 8H2SO4 on left.
follows.
2 KMnO4 + 5 K2C2O4 + 8 H2SO4 

(a) Mn7+ 
 Mn2+ (reduction)
2 MnSO4 + 10 CO2 + 6 K2SO4
(b) C23+ 
 2 C4+ (oxidation)
Finally add 8 H2O on right to balance O and H
Balance the charge by adding 5e to left of (a) and atoms to get balanced equation.
2e to the right of (b).
2 KMnO4 + 5 K2C2O4 + 8 H2SO4  
(a) Mn7+ + 5e 
 Mn2+ (reduction) 2 MnSO4 + 10 CO2 + 6 K2SO4 + 8 H2O
(b)  2 C4+ + 2 e
C23+  (oxidation)
Note : You can always make a final check by counting O
atoms on both sides.
Add two half reactions after multiplying (a) by 2
and (b) by 5 in order that electrons cancel from
both sides.

Stoichiometry-
Stoichiometry- IIII Vidyamandir Classes
Ion Electron Method :

First write the given equation in Ionic form having Add 5e in LHS (Note : each e is equivalent to a
ions with Central atom (which has undergone a charge of –1).
change in Oxidation State).
MnO4 + 8H+ + 5e 
 Mn2+ + 4H2O . . . .(i)
 2 2+
MnO4 + C2O4  Mn + CO2

Oxidation :
Note that O and H atoms attached to the Central
atom (shown in bold), have to be retained. C2O42 
 CO2
Now, write the Oxidation and Reduction half and Following the same procedure as above, we have
balance them as shown : :
Reduction :
(i) Balance C atoms : C2O42  
  2 CO2
MnO4 
 Mn
2+
(ii) Balance O atoms : Already balanced.
(i) First, make sure that the element (iii) Balance H atoms : No H atom.
undergone a change in Oxidation State is
balanced. (iv)   2 CO2 + 2e . . . .(ii)
C2O42  
(ii) Balance O atoms by adding 4 H2O on Multiply equation (i) by 2 and (ii) by 5 to balance
right hand side (RHS). the electrons transfer and add to get :
MnO4 
 Mn2+ + 4H2O 2 MnO4+ 5 C2O42 + 16 H+  

(iii) Now, RHS has excess of 8 H atoms. Add 2 Mn2+ + 10 CO2 + 8 H2O
8H+ on left hand side (LHS). Note, the Using the above balanced equation, convert it to
medium is acidic due to the presence of its corresponding given Neutral equation to get :
H2SO4.
2 KMnO4 +5 K2C2O4+ 8H2SO4 
 + 2+
MnO4 + 8H  
 Mn + 4H2O 2MnSO4 + 10 CO2 + 8H2O
(iv) Note, now O and H is balanced. Balance Now, K (12 atoms on LHS) and SO42 (6 atoms
the charge on both sides. on LHS) is unbalanced. Add 6 K2SO4 on RHS to
On LHS : Charge is 1  (1) + 8  (+1) get the final equation as :
= +7
2 KMnO4 + 5 K2C2O4 + 8 H2SO4  
On RHS : Charge is 1  (+2) + 4  (0) 2 MnSO4 + 10 CO2 + 6 K2SO4 + 8H2O
= +2
Note : At the later stages, you will find that it is Ion electron method which is more important.

Illustration - 2 Balance the following reaction by oxidation number method.
CrO42 + I 
 Cr3+ + IO3 (in alkaline or basic medium)
SOLUTION :
Proceeding on the pattern of last illustration On adding (a) and (b) we get :
+6 1 +3 +5
2 Cr6+ + I 
 2 Cr3+ + I5+
(i) CrO42 + I 
 Cr3+ + IO3 On comparing with given reaction
(ii) (a) Cr6+ 
 Cr3+
2 CrO42 + I 
 2 Cr3+ + IO3
(Reduction : decrease in O.S.) Note that the given reaction is ionic, so first of all
charge needs to be balanced. Balance charge by
(b) I 
  I5+
adding OH ions (in basic medium).
(Oxidation : increase in O.S.) A charge of 5 on left and +5 on right side means
add 10 OH ions to the right side of the equation.
(iii) (a) Cr6+ + 3e 
 Cr3+
2 CrO42 + I 
 2 Cr3+ + IO3 + 10 OH
 
 5+ 
(b) I I + 6e
Finally add 5 H2O molecules on the left to bal-
(iv) (a) [ Cr + 3e6+  
 Cr ] × 2 3+ ance H and O and get the balanced equation.
(b) [ I 
 I5+ + 6e ] × 1 2 CrO42 + I + 5 H2O 

2 Cr3+ + IO3 + 10 OH
Illustration - 3
Balance the following reaction in acidic medium.
CuS + NO3 
 Cu2+ + S8 + NO
SOLUTION :
Proceeding on the same pattern of last illustration (b) N5+ + 3e 
 N2+
2 +5 0 +2
(iv) 24 CuS + 16 NO3 
 3 S8 + 16 NO
 2+
(i) CuS + NO3  
 Cu + S8 + NO
Add 24 Cu2+ ions on right side to balance Cu
before balancing the charge.
(ii) (a) 8 S2 
 S80 (Oxidation)
24 CuS + 16 NO3  

(b) N5+  
 N2+ (Reduction)
24 Cu2+ + 3 S8 + 16 NO
(iii) (a) 8 S2 
 S80 + 16e

Stoichiometry-
Stoichiometry- IIII Vidyamandir Classes
A charge of 16 on left and +48 on right means,

24 CuS + 16 NO3 + 64 H+ 

add 64 H+ ions to the left (acidic). Finally add 32
H2O on right to balance H and O atom s. 24 Cu2+ + 3 S8 + 16 NO + 32 H2O
Illustration - 4 Complete and balance the following in acidic medium.
Ag+ + AsH3 
 H3AsO3
SOLUTION :
+1 3 +3 (b) Ag + 1e  
 Ag
Ag+ + AsH3 
 H3AsO3 As3 + 6 Ag  
 As3 + 6 Ag
(a) As3 
 As3 (Oxidation) AsH3 + 6 Ag 
 6 Ag + H3AsO3
Now balance charge by adding 6 H on right
(b)  Agx
Ag  x=?
side and finally add 3 H2O on left side.
Clearly, (b) must be a reduction, so x must be 0,
as x can’t be ve for Ag (Silver being metal). AsH3 + 6 Ag + 3 H2O 

(a)  As3 + 6e

As3  6 Ag + H3AsO3 + 6 H+
Illustration - 5 Balance the following by ion-electron method in basic medium.
NO3 + Zn 
 Zn2 + NH +
4
SOLUTION :
Two half reactions are : NH4+ + 6 OH + 4OH
Balancing the charge :
(a) NO3 
 NH4+
NO3 + 8e + 7 H2O 


(b) Zn 
 Zn2+
NH4 + 10 OH
+
First balance ‘O’ atoms in basic medium.

(b)  Zn2+ + 2e
Zn 
(a) NO3 + 3 H2O 
 NH4+ + 6 OH
Now overall reaction is :
Balancing H atoms in basic medium
4 Zn + NO3 + 7 H2O 

NO3 + 3H2O + 4 H2O 
 4 Zn2+ + NH4+ + 10 OH
10 Section
Stoichiometry-
Illustration - 6 Balance the following by ion-electron in acidic medium.
 IO3 + Cl
ClO3 + I2 
SOLUTION :
Two half reactions are : 5 ClO3 + 3 I2 + 3 H2O  
5 Cl + 6 IO3 + 6 H+
(a) ClO3 
 Cl
(b) I2 
 IO3
Balancing them separately :
 IO3
I2 
ClO3 
 Cl
 2 IO3+ 12 H+
I2 + 6 H2O 
ClO3 + 6 H+ 
 Cl + 3 H2O
 2 IO3 + 10e + 12
I2 + 6 H2O 
ClO3 + 6 e + 6 H+ 
 Cl + 3 H2O +
H
Balancing electrons in two half reactions, and
adding we get :
Illustration - 7 Balance the following by ion-electron method. (Acidic medium)
Mn2+ + S2O8 2 
 MnO4 + HSO4
SOLUTION :
Two half reactions are :  2 MnO4
2 Mn2+ + 5 S2O82 + 8 H2O 
+ 
+ 6 H + 10 HSO4
(a)  MnO4
Mn2+ 
(b) S2O82 
 HSO4
Balancing these two half reactions :
S2O82 + 2 H+ + 2e 
 2 HSO4
 MnO4 + 5e + 8 H+
Mn2+ + 4 H2O 
Adding the two equations, we have the balanced
equation.
Illustration - 8 Balance the following by ion-electron method. (Basic medium)
 I + CrO42
Cr(OH)3 + IO3 
SOLUTION :
Two half reactions are : (b) IO3 
 I
Balancing O atoms
(a) Cr(OH)3 
 CrO42

(a) Cr(OH)3 + 2 OH 

 CrO42 + H2O Balancing the charge
(b) IO3 + 3 H2O 

 I + 6 OH (a) Cr(OH)3 + 5 OH 
CrO42 + 4 H2O + 3e
Balancing H atoms
(b) IO3 + 3 H2O + 6e 
 I + 6 OH
  

(a) Cr(OH)3 + 2 OH + 3 OH
Adding (a) and (b), we get :’
CrO42 + H2O + 3 H2O
2 Cr(OH)3 + IO3 + 4 OH  
(b) IO3 + 3 H2O  
 I + 6 OH
2 CrO4 + I+ 5 H2O
2
Illustration - 9 Which of the following are examples of disproportionation reactions ?
(a) Ag(NH3)2+ + 2H+ 

 Ag+ + 2NH4+ (b) Cl2 + 2OH 
 ClO + Cl + H2O
(c) CaCO3 
 CaO + CO2 (d) 2HgO 
 2Hg + O2
(e) Cu2O + 2H+ 

 Cu + Cu2+ + H2O (f) CuS + O2 
 Cu + SO2
(g)  Cu + Cu2+ + 4Cl + 2H+

2HCuCl2 + dilute with H2O 
(h) 2H2O2 
 2H2O + O2
SOLUTION :
What is the criteria for a disproportionation reaction ?
A reaction in which same atom is oxidised and reduced at the same time is called as a disproportionation
reaction. Observing very carefully among the above reactions, we note that (b), (e), (g) and (h) are
disproportionation reactions.
Illustration - 10 H SO acts as an oxidising agent, a dehydrating agent and an acid. Among the each of
2 4
following reactions, which behaviour is shown by H2SO4 ?
(a) C6H12O6 + H2SO4(conc.) 

 6C + 6H2O
(b) 5 H2SO4 (conc.) + 4 Zn 

 H2S + 4 Zn2+ + 4 SO42 + 4H2O
(c)  Zn2+ + H2 + SO42

H2SO4 (dil) + Zn 
(d)  Zn2+ + CO2 + SO42 + H2O

H2SO4 (dil) + ZnCO3 

SOLUTION :
(a) As a dehydrating agent since it simply removes water from glucose.
(b) H2SO4 (S in +6 state)   H S (S in 2 state), i.e., acid is reduced. So it acts as an oxidising agent.
2
(c) All strong acids liberate H2 with an active metals like Zn (i.e., it is reduced) unless SO42 is reduced. In this
case, H+ is reduced to H2. So it acts as an oxidising agent. We can also call it as an acidic property.
(d) Simply an acid.
Illustration - 11 Balance the following reaction by ion-electron method. (Acidic medium)
As2S3 + NO3 
 S + NO2 + AsO43
SOLUTION :
This is a very special case of redox reac-  3 S + 6e
(ii) 3 S2 
tion.
Now add the two equations to get :
Note that, the given reaction involves two oxi-
dations and one reduction. Proceed carefully as
follows. (a) 2As3+ + 3S2 + 8H2O 
 2AsO43 + 3S +
16H+ + 10e
(a) Two half reactions (oxidation) are :
Now balance oxidation half reaction and pro-
(i) As3+ 
 AsO43 ceed as usual.
(ii) S2 
 S (b) NO3 + 2H+ + 1e 
  NO2 + H2O
Adding the two reactions
(b) Reduction half reaction : NO3  
  NO2
First balancing these two half reductions : As2S3 + 10 NO3 + 4H+ 
3
2 AsO4 + 10 NO2 + 3S + 2H2O
(i) 2As3+ + 8H2O 
 2AsO43 + 16
H+ + 4e
Note : In above type of cases, take total change in oxidation number (increase or decrease) for cross multi plica-
tion while adding oxidation and reduction half reactions. For example, in the given case, 10e1s are lost per
mole of As2S3.

IN - CHAPTER EXERCISE - A
1. Indicate the species which are oxidized and reduced in the following reactions.
(i) CN  + OCl   N 2 + HCO3 + Cl 
(ii) C6 H5OH + O3  CO 2 + H 2O + O 2
(iii) I  + O3  O 2 + I 2
(iv) S2 O32   Cl2  HSO 4  Cl 

(v) C ZnO  Zn  CO
2. Write balanced ionic half equations ( oxidation and reduction) for each of the following reactions.
(i) Te(s)  NO3 (aq)  TeO 2 (s)  NO(g)
(ii) H 2 O 2 (aq)  Fe 2+ (aq)  Fe 3+ (aq)  H 2O(l )
(iii) Mn(s)  NO3 (aq)  Mn 2+ (aq)  NO 2 (g)
(iv) Mn 3+ (aq)  MnO 2 (s)  Mn 2+ (aq)

3. Balance the following half-reactions in acidic medium.
(i) VO2+ (aq)  V 3+ (aq)
(ii) NO3 (aq)  NO 2 (g)
(iii) IO 3 (aq)  I3 (aq)

4. Balance the following half-reactions in basic medium.
(i) CrO 24  (aq)  Cr(OH) 4 (aq)
(ii) Bi3+ (aq)  BiO3 (aq)
(iii) ClO (aq)  Cl (aq)

5. Write balanced net ionic equations for the following reaction in basic solution.
(i) MnO 4 (aq)  IO3 (aq)  MnO 2 (s)  IO 4 (aq)
(ii) Cu(OH)2 (s)  N 2H 4 (aq)  Cu(s)  N 2 (g)
(iii) Fe(OH) 2 (s)  CrO 42  (aq)  Fe(OH)3 (s)  Cr(OH) 4 (aq)
(iv) H 2 O 2 (aq)  ClO 4 (aq)  ClO 2 (aq)  O 2 (g)

6. Write balanced redox reactions for each of the following reactions.

(i) H 2O 2 (aq) reduces Cr2O 72  (aq) to green coloured Cr3+ (aq) in acidic medium
(ii) H 2O 2 (aq) Oxidises Mn 2+ (aq) to MnO 2 in basic medium
(iii) Sn 2+ (aq) reduces IO 4 ( aq ) to I (aq) and is oxidized to Sn 4+

(iv) A purple solution of aqueous potassium permanganate (KMnO 4 ) reacts with aqueous
2
sodium sulphite (Na 2SO3 ) in basic solution to yield the green manganate ion MnO 4 and  

2
sulphate ion SO4 . 
(v) Potassium dichromate (K 2Cr2O7 ) reacts with hydroiodic acid (HI ) to produce potassium iodide,
chromium (III) iodide and solid iodine, I2 (s).
7. Balance the following chemical reactions. ( It is better to use ion electron method )
(i) CuO + NH3  Cu+ N 2 + H 2O (ii) HI + HNO3  I2 + NO  H 2O
(iii) P4 + H 2 O  PH 3 + H 2PO 2  H + (iv) H 2S SO 2  S + H 2O
(v) CN   MnO 4  H 2O  MnO 2  CNO   OH 
(vi) [Fe(CN) 6 ]3  + N 2 H 4 + OH   [Fe(CN) 6 ]4   N 2 + H 2O
(vii) C2 H 5 OH+ MnO 4  CH 3COO  + MnO 2 + H 2O+ OH 
(viii) P + H + + NO  + H O  H PO  + NO
4 3 2 2 4
(dil)
(ix) HS + HSO3  S2 O 32  + H 2 O
(x) Fe3+ + NH 2 OH  Fe2+ + N 2O+ H  (xi) O2 + H 2O  OH  + O2

(superoxide ion)
(xii) IO 3 + HSO3  I  + H + + SO 42  (xiii) I  + IO3 + H +  H 2 O+ I 2

(xiv) Fe2S3 + H 2O + O2  Fe(OH)3 +S
(xv) IBr+ BrO 3 + H 2 O  IO 3 + Br  + H +
(xvi) CrI3 + H 2O 2 + OH   CrO 42  + IO 4 + H 2O
(xviii) H 2 O 2 + H + + Fe2+  H 2O+ Fe3+
(xviii) As 2S3 + MnO 4 + H +  H 3AsO 4 + Mn 2+ + S
FOR REMAINING QUESTIONS IN EXERCISE-A ATTAMPT IN-CHAPTER EXERCISE-A

ANALYSIS BASED ON MOLE CONCEPT Section - 2
Let us now solve some numerical problems based on the analysis of redox reactions. In such type of applications
based problems, first we have to create a chemical equation and then balance it. And then proceed as per the given
problem, using Mole concept.
Illustration - 12 Find the amount of Iron pyrites (FeS ) which is sufficient to produces enough SO on
2 2
roasting (heating in excess of O2) such that (SO2) completely decolourises a 1L solution KMnO4 containing
15.8 g/L of it.
The equation are : FeS2  O2 

 Fe2O3  SO2 and KMnO4  SO2 
 MnSO4  H 2 SO4  K 2 SO4
SOLUTION :
 1.0 L of KMnO4 contains 0.1 moles
First calculate the amount of SO2 required to
declourise 15.8 g/L of KMnO4 solution. For this 5
you need to balance the following chemical Hence moles of So2 required = (0.1)
2
reaction.
= 0.25
KMnO 4  SO2 
 To calculate the amount of pyrites, we have to
MnSO 4  H 2SO4  K 2SO 4 balance the reaction :
Proceeding in the manner as given in above FeS2  O2 

 Fe2 O3  SO2
illustrations, we have balanced equation as :
Balancing the reaction (using Hit and Trial
2 KMnO 4  5SO 2  2H 2 O 
 Method) we have
2 MnSO 4  2H 2SO 4  K 2SO 4
4FeS2  11O2 
 2Fe2 O3  8SO2
Now, using our understanding to solve a
From stoichiometry of roasting, we have :
typical stoichiometric problems, we can solve
this problem as follows : 8 moles of SO2  4 moles of FeS2
From stoichiometry of balanced equation, we 4
have: 0.25 moles of SO2  (0.25) moles of FeS2
8
2 moles of KMnO4  5 moles of SO2
= 0.125 moles of FeS2
Calculate moles in 15.8 g/L of KMnO4 :
 mass of FeS2 = 0.125  120 = 15 gm
Using : Strength (g/L) = M M0
15.8
Molarity = = 0.1 M
158

Illustration - 13 20 mL of a solution containing 0.2 gm of impure sample of H O reacts with 0.316 gm of

2 2
KMnO4 in presence of H2SO4 as per following reaction.
KMnO4  H2O2  H 2SO4 

 MnSO4  O2  H2O
(a) Find the purity of H2O2 solution (b) Calculate the volume of dry oxygen evolved at 27C and at 750
mm Hg.
SOLUTION :
0.17
First write a complete balanced the reaction :  % age purity of H2O2 = 100
0.2
2 KMnO4 + 5 H2O2 + 3H2SO4 
 = 85 %
2 MnSO4 + K2SO4 + 5 O2 + 8 H2O Now : 2 moles of KMnO4  5 moles of O2
From the balanced reaction, we have : 5 0.316
Moles of O2 produced = 
5 moles of H2O2  2 moles of KMnO4 2 158
0.316 = 5  103
Moles of KMnO4 =
158 Using PV = nRT we have :
5 0.316
 Moles of H2O2 required =  nRT 5×103 ×0.0821×300
2 158 V= =
P 760 / 760
5 0.316
Grams of H2O2 =  34 = 0.17 gm = 0.123 L = 123 mL
2 158
Illustration - 14
Calculate the amount of SeO32  in a solution on the basis of given analysis. 20 mL of M/
60 KBrO3 was added to a sample of SeO32  . The bromine evolved was removed and the excess of KBrO3 was
titrated with 5.1 mL of M/25 solution of NaAsO2 . The reactions involved are : [ASe = 79 gm/mol]
 SeO42   Br2  H 2O and BrO3  AsO2  H 2O 

SeO32   BrO3  H    Br   AsO43  H 
SOLUTION :
In this problem, find the exact amount of KBrO3 Balancing the two equations
used for SeO32- (in the first equation) by
calculating the excess of KBrO3 with the help (i) 5 SeO32   2BrO3  2H  

of second equation.
5 SeO 24   Br2  H 2O

(ii) BrO3  3AsO 2  3H 2O 

  1 
   20   0.068  0.265 m.moles
Br   3AsO34  6H   60 
From equation (i) :
From the equation (ii) :
2 m.moles of K BrO3  5 m.moles of SeO32 
3 m.moles of AsO 2  1 m.moles of excess of
KBrO3 0.265 m.moles of KBrO3  5/2 (0.265)
m.moles
1 
  5.1 m.moles of AsO 2  5/2 (0.265)  127 mg
25
Mass of SeO32  = 84.13 mg = 0.08413 g
1 5.1
  (= 0.0628) m.moles of excess of
3 25
KBrO3 m.moles of KBrO3 used in equation (i)
Illustration - 15 1.0 gms of AgNO is dissolved in 50 mL of water. It is titrated with 50 mL of KI solution.

3
The Agl precipitated is filtered off. The excess of KI in the filtrate is titrated with M/10 KIO3 in presence of 6
M HCl till all I- is converted to ICl. It requires 50 ml of M/10 KIO3 solution. 20 mL of same KI solution requires
30 mL of M/10 KIO3 under same conditions. Determine the percentage of AgNO3 in the sample.
The reaction involved is : KIO3  KI  HCl 

 ICl  KCl  H 2O
SOLUTION :
The problem considers three experiments : First of all you must balance the equation
involved in experiments 2 and 3. (Note that the
(i) 1.0 gm AgNO3 (50 mL) + 50 mL of KI
reaction is same in both cases)
(M = ?)
I  
 I   2e 
AgNO3 + KI 
 AgI + KNO3
(ii) Excess of KI + 50 mL of M/10 KIO3 in IO3  6H   4e 
 I  3H 2O
6M HCl
 The overall balanced equation is :
KI  KIO3  HCl 
 ICl  KCl  H 2O.
2I   IO3-  6H  
 3I  3H 2O
(iii) Tod determine the molarity of KI (say M)
20 mL KI (original) + 30 mL of M/10  2 m.moles of KI  1 m.moles of KIO3
KIO3
18 Section
Using the above stoichiometry, first find the This gives us initial m.moles of KI in 50 mL
excess of KI and then molarity of KI volume taken initially.
 m.moles of KIO3 used  1/10  50  Initial m.moles of KI = (6/20)  50 = 15
=5
 m. moles of KI used for AgNO3
1 m mole of KIO3  2 m. moles of
= 15 – 10 = 5
KI
Now, 1 m.mole of KI  1 m.mole of AgNO3
 5 m.moles of KIO3  10 m.moles of
KI (excess)  m.moles of AgNO3 = 5
 m.moles of KIO3 used for titrating 20 g
mL KI  1000  5  g  0.85 gram
170
= 1/10  30 = 3
or % AgNO3 = 85%
 m.moles of KI = 6 = M  20
(mass of sample = 1gm)
 M = 6/20
IMP. Not n-factro of KBrO3 in illustration-14 and that of KI in illustration-15 is different in two redox reactions.
It is advised to use concept of mole in such case as done above

Vidyamandir Classes
CONCEPT OF GRAM EQUIVALENTS Section - 3
In the method of gram-equivalents (milli-equivalents), there is no need to balance a redox reaction. For
example, let us consider a typical redox reaction (consisting of two reactants and two main products):
X + Y 
 A + B
Reducing Oxidising
agent agent
According to concept of gram equivalent (or meq) ;
1 gm.eq. of X  1 gm. eq. of Y  1 gm eq. of A  1 gm eq. of B
or meq. of an oxidising agent = meq. of a reducing agent
g g
Note : gm.eq. = and meq = meq   1000
E E
Now to understand the method of gram-equivalents more clearly, let us understand the following illustrations
very carefully.

What volume of a deci-normal solution of K2Cr2O7 is required to oxidise 1.0 gm of Tin (Sn) in pres-
ence of HCl to its highest oxidation state ?
The involved reaction is :
K2Cr2O7 + Sn + H+ 
 Sn4+ + Cr3+(The highest oxidation state of Sn is +4, so SnCl4 will be formed here)
Here, Sn is a reducing agent (RA) and K2Cr2O7 is an oxidant (OA).
So applying the concept of gram-equivalent, we have : gm.eq of OA (K2Cr2O7) = gm.eq of RA (Sn)
g
Using the definition : N VL  , we get :
E
1 1 119
 VL  ; ESn  where x = electron transfer / mol (also known as valence or n-factor)
10 ESn x
 Sn4+ + 4e
Sn   x=4
V 1 40
   V= = 0.336 L = 336 mL
10 119 / 4 119
20 Section
Vidyamandir Classes Stoichiometry-
Stoichiometry- IIII
 g 
Note : From definition of gram-equivalents  gmeq.   N VL  , it is very clear that, we must be very confident
 E 
about the concept of equivalent weight (E), for an oxidising or reducing agent. So first let us learn intricacies
of the concept of equivalent weight for an oxidant(s) and reductant(s) in detail.
Equivalent Weight (E) of Oxidant and Reductant :

The equivalent weight of an oxidising or reducing agent is defined as :
M0
Equivalent weight = E 
x
where M0 = molecular mass ; x = number of electrons transferred (loss or gain) by one mole of oxidising or
reducing agent as given by their balanced ionic half reaction.

 FeSO4 (Ferrous Sulphate)
As reducing agent : As an oxidising agent :
Fe2+ 
 Fe3+ + 1e Fe2+ + 2e 
 Fe + le–
1 mole of e’s are transferred/ mole of FeSO4, so x = 1  x=2
M 152 M 152
 E FeSO   = 152  E FeSO  
4 x 1 4 x 2
Note : FeSO4 (ferrous sulphate) acts both as an oxidant and as a reductant
 H2C2O4 (Oxalic acid) or C2O42 (Oxalate ion)
As reducing agent only
 2 CO2 + 2e or H2C2O4 

C2O42   2 CO2 + 2 H+ + 2 e
90
x = 2 or E H 2C 2O4 
2
134 128
Note : E Na C O  ; E CaC 2O 4  as nfactor for C2O42 is always 2
2 2 4 2 2
Sodium oxalate Calcium oxalate

 SO2 (Sulphur Dioxide)

As reducing agent
 SO42 + 4H+ + 2e

SO2 + 2H2O 
64
x=2  ESO 2 
2
 HI (Hydrogen Iodide)
As reducing agent only
2HI 
 I2 + 2H+ + 2e  2 mole of e’s / 2 mole of HI
2 128
x= = 1 (for 1 mole of HI)  EHI =
2 1
 Fe2(SO4)3 (Ferric sulphate)  Na2S2O3 (Sodium Thiosulphate)

As oxidising agent only As reducing agent in acidic medium
Fe3+ + 1e  
  Fe2+
 S4O62 + 2e
2 S2O32 
Since 1 mole of Fe2(SO4)3  2 moles of x = 2/2 = 1 for 1 mole of Na2S2O3
Fe3+
 x = 2 for 1 mole of Fe2(SO4)3 158
 E 
Na 2S2 O3 / H  1
400
 E Fe SO    K2Cr2O7 (Potassium Dichromate)
2 4 3 2
As oxidising agent only
 KMnO4 (Potassium Permanganate)
Cr2O72 + 6e + 14 H+  

As oxidising agent in acidic medium
2 Cr3+ + 7 H2O
MnO4 + 8H+ + 5e 
 Mn2+ +
4H2O 294
x = 6  E K 2Cr2O7 
6
158
x=5  E  
KMnO 4 / H 5  MnO2 (Managanese dioxide)
As oxidising agent in strong alkaline As oxidising agent in acidic medium
medium
MnO2 + 4H+ + 2e 
 Mn2+ + 2 H2O
MnO4 + 1e 
 MnO42
158 87
x = 1  E KMnO4  x = 2  E MnO2 
1 2
22 Section
As oxidising agent in dilute alkaline As reducing agent in alkaline medium

medium
S2O32 + 10OH 
 2SO42 + 5H2O + 8e
 
MnO4 + 2H2O + 3e 
 MnO2 + x=8

4 OH
158
 E Na 
x = 3  158 2S2O3 /OH

8
E 
KMnO 4 /OH  3
Note : From the above case, you should observe carefully that the equivalent weight depends upon medium.
 HNO3 (Nitric Acid) As oxidising agent (dil. HNO3)

As oxidising agent (conc. HNO3)
NO3 + 4 H+ + 3e 
 NO + 2 H2O
NO3 + 2H+ + 1e 
  NO2 + H2O x=3
x=1
63
 E HNO3 (dil)   21
63 3
 E HNO3 (conc.)   63
1
Note : Equivalent weight depends on dilution for HNO3.
Try to Calculate ‘E’
(a)  NH4+
HNO3 (very dilute)  (b) HNO3 (cold dilute) 
 NH2OH
Note : Some substance act both as OA (oxidants) and reductans (RA) in different reactions. Like FeSO4, H2O2,
HNO2 etc
H2O2 (Hydrogen Peroxide) as OA : H2O2 + 2H+ + 2e 

 2H2O
as RA :   O2 + 2H+ + 2e
H2O2 
FeSO4(Ferrous Sulphate) as OA : Fe2+ + 2e  

 Fe
as RA :   Fe3+ + 1e
Fe2+  
HNO2(Nitrous Acid) as OA : HNO2 + H+ e 

 NO + H2O
as RA :   NO3 + 3H+ + 2e

HNO2 + H2O 
Some other type of oxidants and reductants are also given below.

 (NH4)2 Cr2O7 
 N2 + Cr2O3
(Ammonium Dichormate)
RA : NH 4 
 N2 OA : Cr2O72  
 Cr2O3
 FeC 2O 4  Fe3+ + CO 2
 Ferrous Oxalate 
RA : Fe2+ 
 Fe3+ + 1e– ; C2O42  
  2CO2 + 2e–  x = 3
Note : In FeC2O4 both cations and anions are oxidised.
  I– + IO3–
I2  (disproportionation reaction)
OA :  2I– ;
I2  RA :   IO3–
I2 
(same compound as OA/RA)
Note : Some compounds act as Acids and RA or OA in separate experiments.

 as acid  x  2  as acid  x  1
  as acid  x  1

H2C2O4 ; HNO3 ; NaHC2O4

 as RA  x  2  as OA  x  1, 3, 6, 8
  as RA  x  2 

Illustration - 16 Complete and balance the following.
(a) H2O2 + I2  
 I + ?? (b) H2O2 + Sn2+ 
 Sn4+ + ??
(c) MnO42 + H+ 
 Mn2+ + ?? (d) NO2 + H2O 
 NO + ??
SOLUTION :
(a) I2 is reduced to I, so H2O2 must be  I + O2
H2O2 + I2 
oxidised, i.e., it acts as a reducing agent.
Hence final product will be O2 gas. The balanced equation will be :
The complete chemical equation is :  2I+ O2 + 2H+

H2O2 + I2 
24 Section
Stoichiometry-
(b) Sn2+   Sn4+, i.e., Sn2+ is oxidised. (c) MnO42 is reduced to Mn2+, i.e it is act-
So H2O2 acts as an oxidising agent, which ing as an oxidising agent. Now H+ is al-
means it must be reduced to H2O. ready in the maximum oxidation state, so
MnO42 must also be reduced to Mn7+
H2O2 + Sn2+ 
 Sn4+ + H2O state i.e. MnO4 will be formed. Hence it
The balanced equation will be : is a case of disproportionation reaction.
 Mn2+ + MnO4
MnO42 + H+ 
2+
H2O2 + Sn + 2H + 
 Sn4+ + 2H2O
The balanced equation will be :
Important Note :
5 MnO42 + 8H+
H2O2 is chemical species acting both as a re-
ducing agent and as an oxidising agent.  Mn2+ + 4MnO4 + 4H2O
 
as oxidant
H 2O 2  H 2O (d) NO2 (+4 state) disproportionate (like in
as reductant last case) to NO (+2 state) and NO3
 O2
(+5 state).
NO2 + H2O  NO + NO3
The balanced equation will be :
 NO + 2NO 3 
3 NO 2 +H 2 O 
+2 H+
Equivalent weight of a compound undergoing disproportion :

Let a compound ‘A’ contains an ion ‘X’ undergoing disproportionation.
Effective molecular weight of A

Then, EA = Equivalent weight of A =
Number of e transfer
 Total weight of A in   Total weight of A in 

where Effective molecular weight of A =   
 Oxidation half reaction   Re duction half reaction 
1. When number of e- transfer are in oxidation and reduction half reactions
Illustration the concept :

H2O2 undergoes disproportionation in ocidic medium given by the following reaction :
H 2O2 
 H 2O  O 2

Stoichiometry-
Stoichiometry - IIII Vidyamandir Classes
Oxidation half reaction : H2O2 

 O2 + 2H+ + 2e- [2e- transfer] …(i)
Reduction half reaction : H2O2 + 2H+ + 2e- 

 2H2O [2- transfer] …(ii)
Thus, Effective molecular mass of H2O2 = M H 2O2  M H 2O 2  2M H 2O2

from  i  from  ii 
2M H 2O2
 E H 2 O2   34
2
2. When number of e- transfer are different in oxidation and reduction half reaction
Br2 undergoes disproportionation in basic medium given by the following reaction:
Br2  OH  
 Br   BrO3  H 2O
Oxidation half reaction : Br2 + 12OH– 

 2BrO3– + 6H2O + 10e– [10e– transfer] …(i)
Reduction half reaction : Br2 + 2e– 

 2Br– [2e– transfer] …(ii)
Now, Effective molecular mass of Br2 = M Br2  5M Br2  6M Br2

from  i  from ii 
Note : 5M Br2 is taken because we have to equalize the number of electrons in both oxidation reduction.
6M Br2
Thus, E Br2   0.6 M Br2  96
10
10
This means n-factor of Br2 is
6
Note : However, we should use “Mole concept” while solving problems based on such ractions.
Illustration - 17 1.0 gram of a sample of H O solution containing y% H O by weight requires y mL of

2 2 2 2
KMnO4 solution for complete titration under acidic condition. Find the molarity of KMnO4 solution.

SOLUTION :  y 
1  
This question involves a redox reaction between  100   1000
meq of H2O2 =
EH O
H2O2 (RA) and KMnO4 (OA). Let us apply 2 2
the concept of gram (milli) equivalents to solve
 34 
this problem.  E H 2 O2  2 
 
i.e., meq of H2O2 = meq of KMnO4
meq of KMnO4 = N (y)
Let us find n-factor (valence factor) of H2O2
and KMnO4 as follows.  y 
1  
 100   1000  N(y) 10
 N =
MnO4 + 8H+ + 5e  
  Mn2+ + 4H2O 17 17
 O2 + 2H+ + 2e
and H2O2   N
And Molarity = ; x = 5 for KMnO4/H+
x = 5 for KMnO4 and x = 2 for H2O2 x
10 / 17 2
 M =  = 0.117
5 17
Illustration - 18 A solution of KMnO /H+ containing 3 gm/L is used to titrate H O solution containing 2
4 2 2
gm/L. What volume of KMnO4 will be required to react with 20 mL of H2O2 solution ? Also find the strength
of H2O2 in terms of available oxygen.
SOLUTION :
It is also called as volume strength of H2O2.
This redox reaction is a typical one.
Volume strength is the volume of O2 given out
strength 3 15 at S.T.P. by 1 volume solution of H2O2.
N KMnO 4   
E 158 / 5 158
2H2O2  
  2H2O + O2
strength 2
N H 2O2  
E 17 2 mol H2O2  1 mol of O2  22.4 L of O2
Now using equation of titration 1 mol H2O2  1/2 mol of O2  11.2 L of O2

per 1.0 L
meq. of OA = meq of RA
 1 M H2O2  11.2 vol of O2 at STP
 NOAVOA = NRAVRA (meq = NVcc)
or 1N H2O2  5.6 vol of O2
15 2
V  20 In the present question :
158 17
2 2
 V = 24.8 mL N H2O2   5.6 = 0.66 L of O2
17 17
What is strength in terms of available
oxygen ? It is written as : 0.66 vol H2O2

Stoichiometry
Stoichiometry-- IIII Vidyamandir Classes
Try yourself : Express the volume strength of H2O2 sample if 100 cc of H2O2 solution were diluted with
100 cc of water. 10 cc of this diluted solution required 20 cc of M/50 KMnO4 in presence
of H2SO4 for complete titration. [Ans : 2.24 vol H2O2]
Illustration - 19 1.25 gm of a sample of bleaching power (CaOCl2) is dissolved in 100 mL of water. 25 mL

of it are treated with KI solution. The iodine so liberated required 12.5 mL of M/25 hypo solution (Na2S2O3 /
H+) for complete titration. Find the percentage of available chlorine from the sample of bleaching powder.
SOLUTION :
CaOCl2 
 Cl2  meq of Cl2 in 100 mL = (0.5  4)
g
Cl2 + 2 KI 
 I2 + 2 KCl   1000 = 2
E
I2 + 2 Na2S2O3  
 2 NaI + Na2S4O6 (Cl2 + 2e  
 2Cl ; E = 71/2)
2 71
  S4O62 + 2e ; x = 1)
(2 S2O32  g  = 0.071 gms
1000 2
In 25 ml sample : % available chlorine
meq of Cl2 in bleaching powder g Cl 2 0.071
=  100   100  5.68 %
= meq of I2 liberated = meq of hypo solution g CaOCl2 1.25
 1 
meq of Hypo = NVcc  1    12.5  0.5
 25 
 meq of Cl2/ 25ml. = 0.5
Try yourself : 5.0 gm of CaOCl2 is dissolved in water to make 500 mL solution. 20 mL of it is acidified
with acetic acid and treated with KI solution. The iodine liberated required 20 mL of M/
10 Na2S2O3 solution. Find the percentage of available chlorine. [Ans: 35.5%]
Illustration - 20
50 ml of an aqueous solution of H2O2 was titrated with an excess of KI solution in dilute
H2SO4, the liberated iodine required 20 ml of 0.1 N Na2S2O3 solution for complete reaction.Calculate volume
strength of H2O2 solution.
SOLUTION :
Both the chemcial equations involved in the H2O2 + KI + H2SO4 

problem are typical redox reactions.
I2 + H2O + K2SO4 . . . (i)

Stoichiometry- IIII
and I2 + 2 Na2S2O3 
 2 NaI + Now, 1 N H2O2 solution = 5.6 vol. of O2
Na2S4O6 . . . (ii)
1 1
Now : meq. of I2 = meq. of Na2S2O3 (in eq (ii))  N H 2O 2 solution  5.6 
25 25
 meq. of I2 = 20  0.1 = 2 = 0.224 vol of O2
and meq. of H2O2 = meq. of I2 (in eq (i))  Volume Strength of H2O2 solution
2 1 = 0.224 vol.
N H 2O2  VH  2  N H2O2  
2O 2 50 25
Note : In above two problems, Na2S2O3 is used as reducing agent (very common and important reductant). You
must remember its action in acidic and basic both, though acidic medium (hypo solution) is more important.
H OH 
 S4 O 6 2 
Na 2S2O3  ; Na 2S2O3  SO 42 
SUBJECTIVE SOLVED EXAMPLES
Example - 1 A polyvalent metal weighing 0.1 gm and having atomic weight of 50 reacted with dilute
H2SO4 to give 44.8 mL of hydrogen at STP. The solution containing the metal in this Lower oxidation state,
was found to require 60 mL of 0.1 N KMnO4 solution for complete oxidation. What are valencies of metal ?
SOLUTION :
 Mx+ + xe, i.e., oxidation sate
Thus, M 
Metal (M) + H2SO4 
 H2 is +2
Now M2+ will acquire higher oxidation state
44.8 when oxidized by KMnO4
44.8 mL H2 at STP  moles of H2
22400
M2+ 
 M2 + n + ne-
Now, meq of M = meq of H2
meq of M2+ = meq of KMnO4
+ 
Note : For Hydrogen 2H + 2e 
 H2
0.1
Meq of H2 = 2  m.moles of H2 1000  0.1 60  n 3
50 / n
0.1  44.8  So oxidation state of M is M 2  n  M 5
  2  x 2
50 / x  22400 
Hence the possible valencies are + 2, + 5.
Self Study Course for IITJEE with Online Support Subjective Solved Examples 29
Stoichiometry
Example - 2 Hydroxylamine (NH2OH) reduces Fe3+ as per following reaction :
NH 2OH  Fe3 
 N2O  H 2O  Fe2 
Fe2+ produced is estimated by titration with KMnO4. A 10 mL sample of NH2OH is diluted to 1000 mL, 50 mL
of this diluted sample is boiled with excess of Fe3+ solution. The resulting solution required 12 mL of 0.02 M
KMnO4 for complete oxidation. Determine the strength of NH2OH.
SOLUTION :
Consider 50 mL sample : Now meq. of NH2OH in original 10 mL = 24
(meq. remain same on dilution)
NH 2OH  Fe3 
 Fe 2   N 2O
Now find grams of NH 2 OH using
meq of NH2OH  meq of Fe3+  meq of Fe2+
g
2+ 1000  24
Now meq of Fe ions are calculated by titrating E
it against KMnO4.
meq of Fe2+ = meq of KMnO4  N 2O  H 2O  4H   4e
2 NH 2OH 
Now for calculating meq. of KMnO4, convert
4
molarity (M) into normality (N). Now, x  for 1 mole of NH2OH
2
N = xM = 5  0.02 = 0.10 N
33
 E NH 2OH 
x  5; MnO4 
 5e 
 Mn 2
 2
meq of Fe2+ in 50 mL sample = 0.10  12 24   33 / 2 

 g  0.396
= 1.2 = meq of NH2OH 1000
meq of NH2OH in 1000 mL sample 10 mL sample  0.396 grams
= 1.2  20 = 24  1000 mL  39.6 grams

 Strength of NH2OH = 39.6 g/L
30 Subjective Solved Examples Self Study Course for IITJEE with Online Support
Stoichiometry- IIII
Example - 3 A sample of Pyrolusite (MnO2) weighs 0.5 gm. To this solution 0.594 gm of As2O3 and a
dil. acid are added. After the reaction has ceased, As3+ in As2O3 is titrated with 45 mL of M/50 KMnO4
solution. Calculate the % age of MnO2 in pyrolusite.
SOLUTION :
 Mn2+ + AsO43
MnO2 + As2O3  meq of excess As2O3 = meq of KMnO4
0.5 gm 0.594 gm = 45 [1/50  5 ] = 4.5
For excess of As2O3 :

MnO4 + 5e + 8H+  
  Mn2+ + 4 H2O
(x = 5)
As2O3 + MnO4 
 Mn2+ + AsO43
Note that the number of electron transfer for
E AS2O3 = ? As2O3  As2O3 in two reactions is same.
 AsO43
so meq. of As2O3 used for MnO2 = 12  4.5
 2AsO43 + 10 H+ +
(As2O3 + 5H2O  = 7.5

4e ) meq of MnO2 = 7.5
For 1 mole of As2O3, x = 4 g
  1000 = 7.5
87 / 2
198
 E AS2O3 =
4 (MnO2 + 4H+ 
 Mn2+ + 2H2O ; x = 2)
0.594  g = 0.326
meq of As2O3 taken = 1000  12
198 / 4
0.326
% MnO2 =  100  65.25%
0.5
Example - 4 1 gm of Fe2O3 solid of 55.2 % purity is dissolved in acid and reduced by heating the
solution with Zn dust. The resultant solution is cooled and made upto 100 mL. An aliquot of 25 mL of this
solution, requires 17 mL of 0.0167 M solution of an oxidant. Calculate the number of electrons taken up by
the oxidant in the above reaction.
SOLUTION :
 Fe2+ 
Fe2O3 + Zn   100 mL solution Now meq of Fe2+ in 25 mL = meq of oxidant
25 mL sample 17 mL of 0.0167 M of an = [ 0.0167  n]  17 [N = xM]
oxidant.
meq of Fe2+ in 100 mL = [ 0.0167  n  17 ]  4
Let ‘n’ be the number of electrons taken up by
Also meq of Fe2O3 = meq of Fe2+ in 100 mL
oxidant
Stoichiometry
 x = 2 for 1 mole of Fe2O3

0.552
meq of Fe2O3 =  1000
E 160
 E Fe2 O3   80
= (0.0167  68 ) n 2
EFe2O3 = ?  0.552 
 n =   1000   (0.0167 × 68) = 6
 80 
1 mole of Fe2O3  2Fe3+ ; Fe3+ + 1e–  Fe2+
 Electrons taken by oxidant = 6
Example - 5 An equal volume of a reducing agent is titrated separately with 1 M KMnO4 in acid,
neutral and alkaline media. The volumes of KMnO4 required are 20 mL in acid, 33.4 mL in neutral and 100
mL in alkaline media. Find out he oxidation state of manganese in each reduction product. Give the balanced
equations for all three half reactions. Find out the volume of 1 M K2 Cr2O7 consumed, if the same volume of
the reducing agent is titrated in an acid medium.
SOLUTION :
Let meq of RA = P (Since equal volume of RA Balanced half reaction are :
is used in all cases, meq in each case are
same.) (a) MnO4  5e 
 Mn 2 
1 M KMnO4 (in acidic medium)
7
(a) Mn O 4  xe  H  
 Mn 7  x (b) MnO4 1e 
 Mn 6
volume of KMnO4 = 20 mL (in alkaline medium)
7 (c) MnO 4  3e  
 Mn 4
(b) Mn O4  ye   OH  
 Mn 7 y
(in neutral medium)

volume of KMnO4 = 100 mL
Now this mean P = 100
7
(c) Mn O4  ze  
 Mn 7  z meq of RA = meq of K 2Cr2O7
volume of KMnO4 = 33.4 mL
meq of KMnO4 = meq of Ra in each case  Cr O
2 7
2
 14 H   6e 
 2Cr 3  7H 2O 
(a) P = x 1 20 [N = xM] 100  6 1 V
(b) P = y 1100 100

 V = 16.67
6
(c) P = z 1 33.4
 20 x = 100 y = 33.4 z Note : Dil. Alkaline KMnO 4 should be

considered as neutral KMnO4
 x : y : z  5: 1 : 3
Stoichiometry- IIII
Example - 6 20 mL of a solution containing oxalic acid and sulphuric acid on titration with 0.05 N
NaOH required 40 mL of the base. 20 mL of same solution on titration with 0.02 N KMnO4 required 50 mL of
KMnO4. Determine the strength of oxalic acid and H2SO4.
SOLUTION :
In this problem, two type of titrations viz :  2  x  2  y  meqof NaOH= 40  0.05  2
Neutralisation and Redox are involved. Note that
in both cases, the volume of sample is same,  x+y=1
i.e., mmoles of two constituent are same in both. In second titration, only H2C2O4 (being reducing
Let x = mmoles of H2C2O4 and y = mmoles of agent) reacts with KMnO4.
H2SO4 in first titration, both H2C2O4 and H2SO4
 2  x = meq of KMnO4 = 50  0.02  1
react with base (as acids). [n-factor of both
being 2 due to 2H+ per mole in each].
 H C O 
 CO 2  2H   2e  
 2 2 4 
Note : In the above reaction H2SO4 also reacts with KMnO4 but in the same reaction with H2C2O4 so the meq. of
H2SO4 should not be added separately.  H C O  KMnO  H SO 

 Mn 2   CO 2 
 2 2 4 4 2 4

Hence x = y = 0.5 mmoles
g H 2 C2 O 4 g H 2SO 4
 1000  0.05 Similarly, 1000  0.05
M H 2 C2 O 4 M H 2SO 4
 g  0.045 gm  g  0.049 gm
0.045 0.049
Strenght of H2C2O4 =  2.25 g / L Strengh of H2SO4 =  2.45 g / L
20 / 1000 20 / 1000
Stoichiometry
Example - 7 The neutralization of a solution of 1.2 gm of mixture of H2C2O4. 2H2O and KHC2O4.H2O
and same impurities which are neutral, consumed 40.0 mL of 0.25 N NaOH. On the other hand on titration
with KMnO4 in acidic medium, 0.4 gm of mixture required 40.0 mL of 0.125 N KMnO4. Find the molar ratio
of the components.
SOLUTION :
Note that the mass of two samples is different in 2. Rdox reaction with KMnO4 :
tow titrations.
meq of H2C2O4.2H2O + meq of KHC2O4. H2O
Let x = mmoles of H2C2O4. 2H2O
= meq of KMnO4
and y = mmoles of KHC2O4. H2O in 0.4 g
sample 2  x  2  y  0.125  40
So mmoles of oxalic acid in 1.2gm sample = 3x

 HC 2O4 
 2 CO 2  H   2e ; x  2 
and mmoles of bioxalate in 1.2 gm sample = 3y  
 and C O 2   
 2CO2  2e ; x  2 
 2 4 
1. Neutralisation with NaOH :
meq of H2C2O4. 2H2O + meq of KHC2O4. H2O  x + y = 2.5 ... (ii)
= meq of NaOH 5 5
Solve for x and y to get : x  and y 
6 3
2  3 x  1 3y  0.25  40
 x:y=1:2
[oxalic acid has 2 H+ ions while bioxalate has only
1 H+]
10
 2x  y  ...(i)
3
Example - 8 A sample of Fe2(SO4)3 and FeC2O4 was dissolved in H2SO4 . 40 mL of N/16 KMnO4 were
required for complete oxidation. After oxidation, the mixture was reduced by Zn/H2SO4 . On again oxidation
by same KMnO4, 60 mL of it were required. Calculate the ratio of millimoles of Fe2(SO4)3 and FeC2O4.
SOLUTION :
Let m.moles of Fe2(SO4)3 = x Fe2+ 
 Fe3+ + 1e-
and m.moles of FeC2O4 = y y mmol FeC2O4  y mmol Fe2+  y meq Fe2+
Fe3+ + 1e- 
 Fe2+
C2O 42  
 2CO 2  2e
x mmole Fe2 (SO4)  2x mmol meq Fe3
y mmol C2O 42   2y meq C2O 42 
meq Fe3
Stoichiometry- IIII
In the first titration In the second titration

meq of KMnO4 = meq of Fe2+ + meq of So total meq of Fe2+ = 2x + y
C2O 42  meq of KMnO4 = meq of Fe2+
1/16  60 = (2x + y)
1/16  40 = y + 2y (Fe3+ will not be oxidised
further) 60 70
 2x  y   x
 y = 40/48 16 48
Zn reduces whole of Fe3+ (Fe3+ : original and Ratio of millimoles = x : y = 7 : 4
Fe3+ from FeC2O4) to Fe2+
Example - 9 A 4:3 molar mixture of Cu2S and CuS was titrated with 200 mL of 0.75 M KMnO4 in acidic
medium producing SO2, Cu2+ . The SO2 was boiled off and the excess of MnO4 was titrated with 175 mL of
1 M Fe2+ solution. Find the moles of CuS and Cu2S in the original mixture.
SOLUTION :
Note that in Cu2S, both Cu2+ and S2- will get  meq of Cu2S + meq of CuS = 575 ….(ii)
oxidize
Oxidation of Cu2S
Let x = mmoles of Cu2S ; y = mmoles of CuS
Cu 2 
 2Cu 2   2e
x 4
   3 x  4 y …(i)
y 3
S2  
 SO 2  6e
Now, first find excess of KMnO4
1 mole of Cu2S  8e  n- factor = 8
2 3 
Fe 
 Fe  1e  x 1
Oxidation of Cus
and MnO 4  5e  
 Mn 2   x  5
S2  
 SO 2  6e
meq of Fe2   11 175 175 1 mole of CuS  6e   n – factor = 6

 excess meq. of KMnO4 = 175
Using (ii), x  8  y  6  575
Now, meq of KMnO4 taken
= 200  (0.75  5) = 750 4 
  . y   8  y  6  575 [Using (i)]
3 
 meq of KMnO4 used for Cu2S and CuS
 x = 46 mmoles and y = 34.5 mmoles
= 750 – 175 = 575 meq.
Stoichiometry
Example - 10 25 mL of a solution of ferric alum Fe2(SO4)3. (NH4)2SO4.24 H2O containing 2.41 gm of

salt was boiled with iron then the reaction Fe + Fe2(SO4)3   3Fe(SO4) take place. The un-reacted iron
was filtered off and the solution was treated with 0.1 N KMnO4 in acidic medium. What is the titre value (vol.
of KMnO4) of KMnO4 ? If Cu had been used in place of iron, what would have been titre value ?
SOLUTION :
Fe  Fe 2  SO4  3 
 3FeSO 4  V = 75 mL
 Titre value = 75 mL
1 mole of Fe 2  SO4 3  3 moles of FeSO 4
If Cu were used in place of Fe
1 mole of Fe 2  SO4 3 .  NH 4 2 SO 4 .24H 2O
Cu  Fe2  SO 4 3 
 2FeSO 4  CuSO4
1 mole 2 mole
 1 mole of Fe 2  SO4 3
(only FeSO4 react with KMnO4)
2.41
moles of salt  2.41 mole of Fe 2  SO4 3
9.64 964 2.41 2.41
mol Fe 2  SO4 3  2  mole FeSO4
964 964
3  2.41
 moles of FeSO4 . meq of FeSO4  meq of KMnO4
964
Now, meq of FeSO 4  meq of KMnO 4 .  2  2.41 

   11000  0.1 V
 964 
 3  2.41 
  1000  0.1 V  V = 50 mL
 964 
 Titre value = 50 mL
 Fe 2
 Fe3  1e ; x 1
 
Example - 11 A solution of 0.2 gm of a compound containing cupric and oxalate ions or titration with
0.02 M potassium permanganate in presence of sulphuric acid consumes 22.6 mL of the oxidant. The resultant
solution is neutralised with sodium carbonate, acidified with dil. acetic acid and treated with excess of KI.
The iodine liberated required 11.3 mL of 0.05 M sodium thiosulphate solution for reduction. Find the mole
rate of two ions. Also write down the balanced redox reactions involved in the above titrations.
SOLUTION :
Cu2+ ion can not be oxidised, so only C2O42- 5C 2O42   2MnO 4 16H  

will be oxidised by KMnO4.
2Mn 2   10C O 2  8H 2
Stoichiometry- IIII
2 millimoles of MnO 4  5 millimoles of 2 millimoles of S2O32   1 millimoles of I2
C2 O42  ions (0.05  11.3)mmole S2O32  
0.02  22.6 m . m o l e s o f MnO 4  5 / 2 1 / 2(0.05  11.3) mmol of I2

 0.02  22.6 m.moles = 1.13 m.moles of
= 0.2825 mmole I2
oxalate ions
Also, 1 mmol I 2  2 mmol Cu 2 
Important :
Cu 2   KI 
 Cu  (not Cu 0 ) 0.2825 m.mol I 2  2  0.2825 mmol Cu 2 
2Cu 2   2I 
 I2  2Cu  = 0.565 mmol Cu2+
2
and I2  2S2O32  
 2I   S4O62  C2 O 4 1.13
So, mole ratio of  2
Cu 2  0.565
Example - 12 25 ml solution containing 6.35 g/L of K H3(C2O4)2 .2H2O required V1 ml of 0.1 N NaOH
and V2 ml of 0.1 N KMnO4 in two separate titrations. Calculate V1 and V2
SOLUTION :
KH3(C2O4)2 . 2H2O : M0 = 254 gm/mol (b) meq of compound (as RA) = meq of
KMnO4
(a) meq of compound (as acid)  meq of
NaOH 25  NRA = V2  0.1
25  Na = V1  0.1 S 6.35
where N RA    0.10
E 254 / 4
S 6.35
 where Na    0.075
E 254 / 3 25  0.1
 V2   25ml
[Note : 3 acidic Hydrogens] 0.1
25  0.075 [Note : n - factor = 4 due to 2 mole of C2 O 42  ]

 V1   18.75 ml
0.1
Stoichiometry-- IIII
Stoichiometry Vidyamandir Classes
Example - 13 Three solution, each 100 ml containing 0.3 M Ag2S2, 4.5M NaOH and 4.5M H2O2 respectiley
were mixed to form AsO43- and SO42- as products.
(i) Give a balanced redox equation.
(ii) Calculate the molarity of each species left at the end of the reaction.
(iii) If the above solution is allowed to stand for sometime, what volume of O2 will be collected at STP ?
SOLUTION :
(i)  AsO43  H 2O  SO42 

Given: As 2S3  NaOH  H 2O2 
Oxidation : As32 16OH  

 2AsO34  8H 2O  4e  ...(i)
S32   24OH  
 3SO42   12H 2O  24e ...(ii)
Adding (i) and (ii), we ger : As32  S32   40OH  

 2AsO34  3SO42   20H 2O  28e ...(iii)
  As2S3 
Reduction : H 2O 2  2e  
 2OH  ...(iv)
Multiply (iii) by 1 and (iv) by 14 and add to get :
As2S3  12OH   14 H 2O2 

 2 AsO34  3SO42   20 H 2O
(ii) Initial mmoles of As 2S3  0.3100  30; Initial mmole of NaOH  4.5 100  450
Initial mmoles of H 2O2  4.5 100  450;
It is clear form the balanced equation and mmoles of reactants that As 2S3 is the limiting regent.
90
moles of NaOH left = 450  12  30  90  M NaOH   0.3M
300
30
mmoles of H 2O 2 left  450 14  30  30  M H 2O2   0.1M
300
60
mmoles of AsO 34 formed  2  30  60  M   0.2 M
AsO34 300
Stoichiometry- IIII
90
mmoles of SO 24  formed  3  30  90  M   0.3M
SO24  300
600
mmoles of H 2O formed  20  30  60  MH2O  2M
300
(iii) If a H 2O 2 solution is allowed to stand, it decomposes to give O2 and H 2O 2 .
1
H 2O 2 
 H 2O  O 2
2
1
Thus, mmoles of O2 formed  30   15
2
or, volume of O2 at STP 15  22.4 103 L  0.336 L [ 1 mole of O2 at STP  22.4 L]
NOW ATTEMPT OBJECTIVE WORKSHEET TO COMPLETE THIS EBOOK
Stoichiometry
Stoichiometry-- IIII Classes
Vidyamandir Classes
THINGS TO REMEMBER
1. In a typical redox reaction : X  Y 

AB
meq. of an oxidising agent = meq. of a reducing agent
 g 
2. From definition of gram-equivalents  gmeq.   N VL  , it is very clear that, we must be very confident
 E 
about the concept of equivalent weight (E), for an oxidising or reducing agent.
 The equivalent weight of an oxidising or reducing agent is defined as :
M0
Equivalent weight = E 
x
where M0 = molecular mass ; x = number of electrons transferred (loss or gain) by one mole of
oxidising or reducing agent as given by their balanced ionic half reaction.
3. Variable equivalent weight : Equivalent weight may be variable in many cases. It may depend upon the
medium (acidic/basic) ; dilute/concentrated solution ; whether a reagent is acting as an oxidant or reductant ;
whether a reagent is acting as an oxidant or an acid ; whether a reagent is acting reductant or an acid.
4. A reaction in which same atom is oxidised and reduced at the same time is called as a disproportion-
ation reaction. And the equivalent weight of a compound undergoing disproportionation is :
Effective molecular weight of compound

E 
Number of e  transfer
 Total weight in   Total weight in 

where Effective molecular weight =    
 Oxidation half reaction   Re duction half reaction 
5. Volume strength is the volume of O2 given out at S.T.P. by 1 volume solution of H2O2.
1 M H2O2  11.2 vol of O2 at STP or 1N H2O2  5.6 vol of O2
6. Avoid use of concept of meq in following cases. (Non-typiccal Redox reactions).

H
(a) KMnO4  HCl 
 Cl2  MnCl2  KCl (b) KIO3  KI 
 I2
(c) KMnO4 
 KMnO4  MnO2
7. If a reagent (oxidant or reductant) shows different equivalent weights in two different redox reactions in
a given problem then apply concept of meq carefully. In fact it is advised to use the mole concept in such
cases. (Refer to Illustration 14 & 15)
40 Things
Things to
to Remember
Remember Self Study Course for IITJEE with Online Support
SOLUTION - IN-CHAPTER EXERCISE - A
1. (i) CN  
 N 2  HCO3 and OCl 
 Cl
(Both C and N areoxidised) (Re duced)
(ii) O3 
 O2 and C6 H5OH 
 CO 2
Reduced Oxidised
(iii) I 
 I2 and O3 
 O2
Oxidised Re duced
(iv) S2O32  
 HSO4 and Cl2 
 Cl
Oxidised Re duced
(v) C 
 CO and ZnO 
 Zn
Oxidised Re duced
2. (i) Te(s)  NO3 (aq.) 

 TeO 2 (s)  NO(g)
 TeO 2 (s)  4H   4e

Oxidation : Te(s)  2H 2O  ; Reduct ion :
NO3 (aq.)  4H   3e 

 NO(g)  2H 2O
(ii) H 2O 2 (aq.)  Fe 2 (aq.) 

 Fe3 (aq.)  H 2O()
Oxidation : Fe 2  (aq.) 
 Fe3 (aq.)  e  ; Reduct ion :
H 2O 2 (aq.)  2H   2e 
 2H 2O()
(iii) Mn(s)  NO3 (aq.) 

 Mn 2  (aq.)  NO 2 (g)
 Mn 2  (aq.)  2e 
Oxidation : Mn(s)  ; Reduct ion :
NO3 (aq.)  2H   1e  
 NO 2 (g)  H 2O()
(iv) Mn 3 (aq.) 
 MnO2 (s)  Mn 2  (aq.) (Disproportionation Rxn.)
Oxidation : Mn 3 (aq.)  2H 2O 
 MnO 2 (s)  4H   e  ; Reduction :
Mn 3  (aq.)  e  
 Mn 2  (aq.)
Self Study Course for IITJEE with Online Support Solution-INE 41

3. (i) VO2  (aq.) 

 V3 (aq.)  VO2  (aq.)  2H   e 
 V3 (aq.)  H 2O
(ii) NO3 (aq.) 

 NO2 (g)  NO3 (aq.)  2H   e 
 NO2  H 2O
(iii) IO3 (aq.) 

 I3 (aq.)  3IO3  18H  18e 
 I3  9H 2O
4. (i) CrO24  (aq.) 

 Cr(OH)4 (aq.)  CrO24  (aq.)  4H 2O  3e 
 Cr(OH)4  4OH
(ii) Bi3 (aq.) 

 BiO3 (aq.)  Bi3 (aq.)  6OH 
 BiO3 (aq.)  3H 2O  2e
(iii) ClO (aq.) 

 Cl (aq.)  ClO (aq.)  H 2O  2e 
 Cl (aq.)  2OH 
5. (i) MnO4 (aq.)  IO3 (aq.) 

 MnO 2 (s)  IO 4 (aq.)
Re duction : MnO 4 (aq)  2H 2O  3e   MnO2 (s)  4OH 

Oxidation : IO3 (aq.)  2OH    IO 4 (aq.)  H 2O  2e 
________________________________________________
2MnO4  3IO3  H 2O 
 2MnO 2  3IO 4  2OH 
(ii) Cu(OH) 2 (s)  N 2H 4 (aq.) 

 Cu(s)  N 2 (g)
Oxidation : N 2 H 4 (aq.)  4OH   N 2 (g)  4H 2O  4e

Re duction : Cu(OH) 2 (s)  2H 2O  2OH   2e   Cu(s)  4OH   2H 2O
_________________________________________________________
2Cu(OH)2 (s)  N 2H 4 (aq.) 
 2Cu(s)  N 2 (g)  4H 2O
(iii) Fe(OH)2 (s)  CrO 42  (aq.) 

 Fe(OH)3 (s)  Cr(OH)4 (aq.)
Oxidation : Fe(OH) 2 (s)  OH    Fe(OH)3 (s)  e

Re duction : CrO 24  (aq.)  4H 2O  3e  
 Cr(OH) 4  4OH 
_________________________________________________________
3Fe(OH)2  CrO 42  (aq.)  4H 2O 
 3Fe(OH)3  Cr(OH) 4  OH 
(iv) H 2O 2 (aq.)  ClO4 (aq.) 

 ClO2 (aq.)  O2 (g)
Oxidation : H 2O2 (aq.)  2OH    O 2 (g)  2H 2O  2e 

Re duction : ClO4 (aq.)  2H 2O  4e   ClO2 (aq.)  4OH 
____________________________________________________
2H 2O2 (aq.)  ClO 4 (aq.) 
 2O2 (g)  ClO 2 (aq.)  2H 2O
42 Solution-INE Self Study Course for IITJEE with Online Support

6. (i) H 2O 2 (aq.)  Cr2O72  (aq.) 

 Cr 3 (aq.)  O2 (g)
Oxidation: H 2O2 (aq.)   O2 (g)  2H   2e 

Re duction : Cr2O72  (aq.)  14H   6e  
 2Cr 3 (aq.)  7H 2O
________________________________________________
Cr2O72  (aq.)  3H 2O2  8H  
 2Cr 3  3O2  7H 2O
(ii) H 2O 2 (aq.)  Mn 2  (aq.) 

 MnO 2 (s)  H 2O
Oxidation : Mn 2  (aq.)  4OH  

 MnO 2 (s)  2H 2O  2e
Re duction : H 2O2 (aq.)  2e  
  2OH 
_______________________________________________
Mn 2  (aq.)  H 2O2 (aq.)  2OH  
 MnO 2  2H 2O
(iii) Sn 2  (aq.)  IO4 (aq.) 

 I (aq.)  Sn 4  (aq.)
Oxidation : Sn 2  (aq.) 
 Sn 4  (aq.)  2e
Re duction : IO 4 (aq.)  8H   8e  
 I (aq.)  4H 2O
_____________________________________________________
4Sn 2  (aq.)  IO4 (aq.)  8H  
 4Sn 4  (aq.)  I   4H 2O
(iv) MnO4 (aq.)  SO32  (aq.) 

 MnO42  (aq)  SO42  (aq.)
Oxidation : SO32  (aq.)  2OH   SO 42  (aq.)  H 2O  2e 

Re duction : MnO 4 (aq.)  e   MnO42  (aq.)
_______________________________________________________________
SO32 (aq.)  2MnO4 (aq.)  2OH  
 SO 42  (aq.)  2MnO 42  (aq.)  H 2O
(v) Cr2O72  (aq.)  HI (aq.) 

 CrI3 (aq.)  I2 (g)  KI
Oxidation : 2HI(aq.)   I 2 (aq)  2H   2e 

Re duction : Cr2O72  (aq.)  14H   6e    2Cr 3  7H 2O
______________________________________________________
Cr2O72  (aq.)  6HI(aq.)  8H  
 2Cr 3 (aq.)  3I 2 (g)  7H 2O

7. (i) CuO  NH3 

 N 2  Cu  H 2O
Oxidation : 2NH3   N 2  6H   6e

Re duction:CuO  2H   2e    Cu  H 2 O
________________________________
3CuO  2NH3 
 3Cu  N 2  3H 2O
(ii) HI  HNO3 
 I2  NO  H 2O
Oxidation : 2HI   I 2  2H   2e

Re duction : HNO3  3H   3e    NO  2H 2O
__________________________________
6HI  2HNO3 
 3I 2  2NO  4H 2O
(iii)  PH3  H 2 PO2  H 

P4  H 2O 
Oxidation : P4  8H 2O   4H 2PO 2  8H   4e

Re duction :P4  12H   12e   4PH 3
_______________________________________
 4PH3  12H 2 PO 2  12H 
4P4  24H 2O 
(iv) H 2S  SO 2 
 S  H 2O
 S  2H   2e
Oxidation : H 2S 
Re duction : SO 2  4H   4e 
 S  2H 2O
_____________________________
2H 2S  SO 2 
 3S  2H 2O
(v) CN   MnO4  H 2O 
 MnO 2  CNO   OH 
Oxidation : CN   2OH  
 CNO  H 2O  2e
Re duction : MnO 4  2H 2O  3e 
 MnO2  4OH 
_______________________________________________
3CN   2MnO 4  H 2O 
 3CNO  2MnO 2  2OH 
(vi) [Fe(CN)6 ]3  N 2 H 4  OH  

 [Fe(CN)6 ]4   N 2  H 2O

Re duction :[Fe(CN)6 ]3  e  

 [Fe(CN) 6 ]4 
Oxidation : N 2 H 4  4OH  
 N 2  4H 2O  4e 
______________________________________________________
4[Fe(CN)6 ]3  N 2 H 4  4OH  
 4[Fe(CN) 6 ]4  N 2  4H 2O
(vii) C2 H5OH  MnO 4 

 CH3COO  MnO2  H 2O  OH 
Oxidation : C2 H5OH  5OH    CH3COO  4H 2O  4e 

Re duction : MnO4  2H 2O  3e 
 MnO 2  4OH 
_______________________________________________________
3C 2H5OH  4MnO4 
 3CH3COO  4MnO2  4H 2O  OH 
(viii) P4  H   NO3 (dil)  H 2O 

 H 2PO 4  NO
Oxidation : P4  16H 2O   4H 2PO4  24H   20 e

Re duction : NO3  4H   3e  NO  2H 2O
______________________________________________
3P4  20NO3  8H 2O  8H  
 12H 2 PO 4  20NO
(ix) HS  HSO3 

 S2O32   H2O
Oxidation : HS  3H 2O   S2O32   8H   8e 

Re duction : 2HSO3  4H   4e   S2O32  3H 2O
____________________________________
2HS  4HSO3 
 3S2O32   3H 2O
(x) Fe3  NH2OH 

 Fe2   N 2O  H 
Oxidation : 2NH 2OH   N 2O  H 2O  4H   4e 

Re duction : Fe3  e 
 Fe 2
_____________________________________________
4Fe3  2NH 2OH 
 4Fe 2   N 2O  H 2O  4H 
(xi) O2  H 2O 
 OH   O2

Oxidation : O 2 
 O 2  e
Re duction:O2  2H 2O  3e 
 4OH 
___________________________
4O 2  2H 2O 
 3O 2  4OH 
(xii) IO3  HSO3 

 I  H  SO42 
Oxidation : HSO3  H 2O   SO42   3H   2e 

Re duction: IO3  6H   6e   I  3H 2O
_________________________________
IO3  3HSO3   3SO 42   I  3H 
(xiii) I  IO3  H  
 I 2  H 2O
Oxidation : 2I   I 2  2e 
Re duction : 2IO3  12H   10e  
 I 2  6H 2O
________________________________
IO3  5I  6H  
 3I2  3H 2O
(xiv) Fe2S3  H2O  O2 

 Fe(OH)3  S
Oxidation : S2 
 S  2e 
Re duction :O 2  2H 2O  4e  
 4OH 
_______________________________
O2  2S2   2H 2O 
 2S  4OH 
 2Fe2S3  3O2  6H 2O 

 4Fe(OH)3  6S
(xv) IBr  BrO3  H 2O 

 IO3  Br   H 
Oxidation : I  3H 2O   IO3  6H   4e

Re duction : BrO3  6H   6e  Br   3H 2O
_______________________________________
3I  2BrO3  3H 2 O 
 3IO3  2Br   6H 
 3IBr  2BrO3  3H 2O 
 3IO3  5Br   6H 
(xvi) CrI3  H 2O 2  OH  
 CrO42  IO4  H 2O

Oxidation : CrI3  32OH    CrO 42   3IO 4  16H 2O  27e

Re duction : H 2O 2  2e  
 2OH 
_________________________________________________
2CrI3  27H 2O2  10 OH  
 2CrO 42  6IO4  32H 2O
(xvii) H 2O 2  Fe2   H  
 H 2O  Fe3
Oxidation : Fe 2  
 Fe3  e 
Re duction: H 2O 2  2H   2e  
 2H 2O
___________________________________
2Fe 2   H 2O2  2H  
 2Fe3  2H 2O
(xviii) As2S3  MnO4  H 2O  H  

 H3AsO 4  Mn 2   S
Oxidation : As 2S3  8H 2O   2H3AsO 4  3S  10H   10e 

Re duction : MnO 4  8H   5e   Mn 2   4H 2O
______________________________________________
As 2S3  2MnO 4  6H  
 2H3AsO4  3S  2Mn 2 

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Atomic Structure
Atomic Structure
DALTON’S THEORY OF ATOM SECTION - 1A
John Dalton developed his famous theory of atom in 1803. The main postulates of his theory were :
 Atom was considered as a hard, dense and smallest indivisible particle of matter.
 Each element consists of a particular kind of atoms.
 The properties of elements differ because of differences in the kinds of atoms contained in them.
 This theory provides a satisfactory basis for the law of chemical combination.
 Atom is indestructible, i.e., it cannot be destroyed or created.
Drawbacks
 It fails to explain why atoms of different kinds should differ in mass and valency etc.
 The discovery of isotopes and isobars showed that atoms of same elements may have different
atomic masses (isotopes) and atoms of different kinds may have same atomic masses (isobars).
 The discovery of various sub-atomic particles like X-rays, electrons, protons etc. during late 19th
century lead to the idea that the atom was no longer an indivisible and smallest particle of the matter.
DISCOVERY OF CATHODE RAYS & POSITIVE RAYS SECTION - 1B

Cathode Rays
Sir William Crooks studied various gases in a gas discharge tube (a glass tube with a very high potential
applied to its ends) at low pressures. If the pressure in the tube is lowered to about 104 atm, glass begins to
fluoresce (glow) faintly. It was established that the glow was due to bombardment of the glass by a certain
kind of rays emerging from cathode (negative electrode) which travel in a straight line until they strike the
anode (positive electrode). These rays were called as cathode rays.
Sir J. J. Thomson demonstrated that when cathode rays were deflected on to an electrometer, it acquired
negative charge. He also showed that the rays were deflected on application of an electric field. The
cathode ray beam was deflected away from the negatively charged plate. These results were found to be
identical, irrespective of the gas taken in the discharge tube. He concluded that the cathode rays were a
stream of fast moving negatively charged particles called electrons (named by Stoney). He also calculated
the velocity and specific charge for an electron. The specific charge is the ratio of charge to the mass of
an electron, denoted as e/m ratio. The e/m ratio was found to be same for all gases. This led to the
conclusion that the electron must be a fundamental or universal particle common to all kinds of the atoms.
The e/m ratio (for an electron) = 1.758 x 1011 C/Kg.

Atomic Structure Vidyamandir Classes
Note : (i) J. Millikan determined the value of the charge on an electron with the help of famous Oil drop
experiment. The magnitude of the charge on an electron = 1.60206  1019 C and the mass of an
electron = 9.1  1031 kg.
(ii) You will be studying the details of Thomson’s calculations of e/m ratio and Millikan’s oil drop experiment
for the determination of electronic charge later in Modern Physics in the Module of Physics.
Positive Rays
Since the atom as a whole is neutral, it means that an equal amount of positive charged particle should also
be there in the atom. Goldstein, by carefully experimenting with the discharge tube consisting of perforated
cathode, showed the presence of another type of rays. These rays emanating from anode passed through
the perforations in the cathode. These carried positive charge and were called as positive or anode rays.
It was established that these rays consist of positively charged particles called as protons. The magnitude
of charge on a proton is same as that on an electron, but its mass was found to be 1837 times the mass of
an electron. The mass of a proton = 1.6735  1027 kg.
Since the electron has negligible mass (as compared to the proton), so it was assumed that whole mass of
an atom is associated with the protons. Later in 1932, with the discovery of neutron as IIIrd fundamental
particle (Ist and IInd being electron and proton), it was established that the mass of an atom is the total
mass of protons and neutrons taken together.
MODELS OF ATOM SECTION - 2A
Thomson’s Model
Putting together all the facts known at that time, Thomson assumed that an atom is a sphere of positive
charges uniformly distributed, with the electrons scattered as points throughout the sphere. This was
known as plum-pudding model at that time. However this idea was dropped due to the success of
scattering experiments studied by Rutherford and Mardson.
Rutherford’s Model
Rutherford studied the scattering of  particles (doubly ionised Helium atom) by the thin metallic foils (of
gold, platinum etc.). A narrow pencil beam of fast moving  - particles were struck on a thin metal foil
( 104 atoms thick). The angular deflections of scattered  particles were studied with the help of a moving
microscope.
Observations of the Rutherford’s experiment :

 Most of the particles passed through the foil undeflected, i.e., went straight through the foil.
 Some of them were deflected, but only at small angles.
 A very few (1 in 20,000) were deflected at large angles (180 ).

Conclusions :
 As most of the -particles passed undeflected, it was concluded by Rutherford that the atom must be
predominantly empty.
 -Particles are positively charged with appreciable mass (4 amu) and were moving high kinetic
energy. In order to produce deflections, there must be some enormous positively charged body inside
the atom.
 Only a few received large deflections. This led to the conclusion that enormous charge must be con-
fined to a very small region. This small region was given the name nucleus.
 Rutherford then proposed that an atom is composed of a dense positive nucleus, thinly surrounded by
the electrons. The mass and the positive charge of the nucleus are confined in a very small region of
space. The electrons are outside the nucleus, so that an atom is almost entirely empty space.
 From stability point of view, the electrons cannot be stationary otherwise they would be drawn into
the nucleus. So Rutherford assumed that electrons were moving in circles around the nucleus; the
necessary centripetal force being provided by the electrostatic attraction between nucleus and the
electrons. He gave no further justification for this assumption.
Note :  From experiments, it was confirmed that with in the nucleus, the distribution of positive charge is
uniform and atomic nuclei are spherical in shape.
 Later with the discovery of the neutrons (In 1932 by Chadwick), it was established that these also
occupy the place in the nucleus bonded along with the protons by a very complex type of forces
called as Nuclear Forces.
 Now the constituents of the nucleus, i.e., Protons and Neutrons are called as Nucleons and the
number of nucleons in a particular atom is called as Mass Number denoted by A. The number of
protons is known as Atomic Number denoted by Z.
 The order of the diameter of an atom is 1010 m or 1 Å (1 Å = 1010 m) and the order of the diameter
of the nucleus is 1015 m or 1 fm (fm is called as Fermi and 1 fm = 1015 m).
 Radius of the nucleus of an atom is proportional to the cube root of the mass number of an atom (i.e.,
the number of nucleons in the atom). If r0 denotes the radius of the nucleus then,
r0 = (1.2  1015) A1/3 m. (A = mass number)
Failure of Rutherford’s Model

According to Classical Theory of Electromagnetism, whenever a charge is subjected to acceleration
around an opposite charge, it emits radiation continuously. Hence the electron in Rutherford’s atom will
loose energy and will not be able to stay in a circular path around the nucleus and should ultimately go into
a spiral motion. Such an electron will fall into the nucleus. This, of course, does not happen for electrons in
an atom and the discrepancy could not be explained at that time.
Note : Later Niel Bohr, a student of Rutherford analysed atomic spectra of Hydrogen atom in terms of Quantum
Theory of Radiation and applied the results of Photoelectric Effect to it and developed a model of atom
which was widely accepted at that time.

NATURE OF CHARACTERISTICS OF RADIANT ENERGY SECTION - 2B
Newton was first person to comment on the nature of light in terms of Corpuscular Theory of Light.
According to this theory, light is a stream of particles commonly known as corpuscles of light. He was able
to explain reflection and refraction, the most common phenomenon of light. But the other phenomenon
like diffraction and interference could not be explained on the basis of this theory.
Maxwell, in 1870 proposed that radiant energy (light) has wave characteristics. Light according to him is
Electromagnetic Wave arising due to the disturbance created by electric and magnetic fields oscillating
perpendicular to each other in space. Like all other mechanical waves, it is characterised by velocity, c ;
frequency,  and wavelength,  which are related as :
c=  [value of c is constant and equal to 3  108 m/s]
Electromagnetic Spectrum
 Electromagnetic wave or radiation is not a single wavelength radiation, but a mixture of various wave
length or frequencies. All the frequencies have same speed (= c).
 If all the components of Electromagnetic Radiation (EMR) are arranged in order of decreasing or
increasing wavelengths or frequencies, the pattern obtained is known as Electromagnetic Spectrum.
The following table shows all the components of light.
Continuous Spectrum :
When sunlight (white light) is passed through a prism, it is dispersed or resolved into continuous spectra of
colours. It extends from Red (7600 Å) at one end to the Violet (3800 Å) at other end. In this region, all the
intermediate frequencies between red and violet are present. This type of spectrum is known as Continuous
Spectrum. Hence continuous spectrum is one, which contains radiation of all the frequencies.
Note : A similar spectrum is produced when a rainbow forms in the sky.
Discontinuous Spectrum :
Light emitted from atoms heated in a flame or excited electrically in gas discharge tube, does not contain a
continuous spread of wavelengths (or frequencies). It contains only certain well-defined wavelengths (or
frequencies). The spectrum pattern appears as a series of bright lines (separated by gaps of darkness) and
hence called as Line Spectrum.
One notable feature observed is, that each element emits a characteristic spectrum, suggesting that there is
direct relation between the spectrum characteristics and the internal atomic structure of an atom.

The Quantum Theory of Radiation

In 1901, Max Planck studied the distribution of the frequencies of radiations emitted from the hot bodies.
He proposed a bold hypothesis that the radiant energy such as heat or light, is not emitted continuously but
discontinuously in the form of small packets called as quanta. According to him, the energy of the
electromagnetic radiation is directly proportional to the frequency of the radiation. The proportionality
constant is called as Planck’s constant (h). If energy of the radiation is E, and the frequency of the radiation
is , then we have :
E=h (The value of h is 6.626  1034 Js)
If n is the number of quanta of a particular frequency and TE be the total energy, then :
TE = n (h)
Illustration - 1 Find the ratio of frequencies of violet light (1 = 4.10  105cm) to that of red light
(2 = 6.56  105 cm). Also determine the ratio of energies carried by them.
SOLUTION :
Using c =  
where c: speed of light;  : frequency; Now the energy associated with electromagnetic
 : wavelength radiation is given by E = h
E1 v1  2
ν1  2  E  v    1.6 :1
 [1 : violet and 2 : red] 2 2 1
ν2 1
Hence the ratio of energies is same as that of frequencies.
1 6.56  105
   1.6 : 1
2 4.10  105
Illustration - 2 A 100 W power source emits green light at a wavelength  = 5000 Å. How many photons
per minute are emitted by the source ?
SOLUTION :
Energy given out by the source per sec
Using P = 100 J/s,  = 5000  1010 m and t = 60 s
= Power (P)
 Energy given by source in t sec = P  t  Number of photons (n) :
As  = 5000 Å, the energy per photon of green
hc 

100  60  5000  10 10   1.5  1022
light is given by : h 


Number of photons (n) emitted in time
 6.626  10  3  10 
34 8
Pt Pt
t sec is given by : n 
 hc /   hc
Photoelectric Effect
It was observed by Hertz and Lenard around 1880 that when a clean metallic surface is irradiated by
monochromatic light of proper frequency, electrons are emitted from it. This phenomenon of ejection of the
electrons from metal surface was called as Photoelectric Effect.
 It was observed that if the frequency of incident radiation is below a certain minimum value (threshold
frequency), no emission takes place however high the intensity of light may be.
 Another important feature observed was that the kinetic energy of the electrons emitted was indepen-
dent of the intensity of the light. The kinetic energy of the electrons increase linearly with the frequency
of incident light radiation. This was highly contrary to the laws of Physics at that time i.e. the energy of
the electrons should have been proportional to the intensity of the light, not to the frequency.
These features could not be properly explained on the basis of Maxwell’s concept of light i.e.
light as electromagnetic wave.
In 1905, Einstein applied Planck’s quantum theory of light to account for the extraordinary features of the
photoelectric effect. He introduced a new concept that light shows dual nature. In phenomenon like
reflection, refraction and diffraction, it shows wave nature and in phenomenon like photoelectric
effects, it shows particle nature. According to the particle nature, the energy of the light is carried in
discrete units whose magnitude is proportional to the frequency of the light wave. These units were called as
photons (or quanta).
According to Einstein, when a quantum of light (photon) strikes a metal surface, it imparts its energy to the
electrons in the metal. In order for an electron to escape from the surface of the metal, it must overcome the
attractive force of the positive ions in the metal. So a part of the photon’s energy is absorbed by the metal
surface to release the electron, this is known as work function of the surface and is denoted by W0. The
remaining part of the energy of the photon goes into the kinetic energy of the electron emitted. If Ei is the
energy of the photon, KE is the kinetic energy of the electron and W0 be the work function of the metal then
we have ;
Ei = KE + W0 (This is known as Einstein’s photoelectric equation)
For each metal, there is a characteristic minimum frequency
known as the threshold frequency (0) below which the
photoelectric effect does not occur. Electrons are emitted only
after the frequency of light is equal to or above the threshold
frequency. The threshold frequency is proportional to the work
function of the metal. If 0 be the threshold frequency and  the
frequency of incident light, E is energy of incident light, then we
have :
W0 = h 0 and Ei = h 
 KE = Ei  W0 or KE = h   h 0 = h (  0)

Also, if m be the mass and v be the velocity of the electron ejected then
1
KE  mv 2  h  ν  ν 0 
2
Note :
 The Electromagnetic radiation (or wave) now emerges as an entity which
shows dual nature i.e. sometimes as Wave and sometimes as Particle
(quantum aspect).
 The energy of an individual photon depends only on its frequency and
not on the intensity of the light beam. The intensity of a light beam is a
measure of the number of photons in the beam and not of the energies
of those photons. A low-intensity beam of high-energy photons might
easily knock out electrons from a metal but a high intensity beam of low
energy photons might not be able to knock out a single electron.
 Sometimes, it is convenient to calcualte energy (in eV) of a photon in short form using:
hc 12400 1240
EP   eV  eV
λ λ  in Å  λ  in nm 
Illustration - 3
Illustration - 3 Calculate the velocity of electron ejected from platinum surface when radiation of 200 nm
19
falls on it. Work function of platinum is 5 eV. (1eV  1.6  10 J )
SOLUTION :
Using Einstein’s photoelectric equation :  KE = Ei  W0 = (6.2 – 5) eV = 1.2 eV
Ei = KE + W0 = 1.2 × 1.6 × 10–19 J = 1.94 × 10–19
where Ei : energy of incident radiation ; 1 2 2KE
Now, KE = mv  v =
KE : kinetic energy of ejected electron 2 m
W0 : work function of metal 2(1.94 1019 )
 v= = 6.52  105 m/s
1240 (9.11031 )
Ei  eV  6.2 eV; and W0  5 eV
200

Illustration - -4 4
Illustration A photon of light with  = 400 nm falls on a metal surface. As a result, photoelectrons are
ejected with a velocity of 6.4  105 m/s. Find :
(a) the kinetic energy of emitted photoelectrons, (b) the work function (in eV) of the metal surface.
SOLUTION :
1
(a) Kinetic energy of electron = mv 2 (b) From Einstein’s photoelectric equation :
2
Ei = KE + W0  W0 = Ei  KE
1
 KE = (9.1  1031) (6.4  105)2 1240
2  W0   KE  3.1  1.16  1.94eV
= 1.86  1019 J = 1.16 eV 400
 W0  1.94eV
ATOMIC SPECTRA OF HYDROGEN AND BOHR’S MODEL SECTION - 3
It is observed that the atoms of hydrogen in gas discharge tube emit radiations whose spectrum shows line
characteristics (line spectra). The line spectra of hydrogen lies in three regions of Electromagnetic Spectrum:
Infra-red, Visible and UV region. In all there are five sets of discrete lines.
The set of lines in the Visible region are known as Balmer Series, those in Ultra-Violet as Lyman series
and there are three sets of lines in Infra-red region : Paschen, Brackett and Pfund series. Balmer and
Rydberg gave an empirical relation to define the wavelength of the lines in each series in terms of a param-
eter called as Wave Number denoted by  . The wave number is defined as reciprocal of the wavelength
1 2
 1 1 
i.e.,   ;   RZ   
  n 2 m2 
 
where n and m are whole numbers;  : wavelength of spectral line ;  : wave number of spectral line
R : Rydberg constant. The values of n and m for different spectral lines for each series are listed below.
Region Spectral line n m

UV Lyman Series 1 2, 3, 4, . . .
Visible Balmer Series 2 3, 4, 5, . . .
Infra-red Paschen Series 3 4, 5, 6, . . .
Infra-red Brackett Series 4 5, 6, . . . .
Infra-red Pfund Series 5 6, 7, . . . .
Humphry Series 6 8, 7, 8 . . .

In Hydrogen atom spectra :

 Intermediate frequencies were emitted i.e. only specific spectral lines are there in the spectrum
(Planck’s quantum theory).
 Lines observed were characteristic of Hydrogen atom only.
These observations led Bohr to conclude that electrons in an atom are not randomly distributed, but were
arranged in definite energy states. The energy of each state (or level) was fixed or quantised (from charac-
teristic nature of H-atom spectra). The complete theory developed by him is organised in his postulates.
Bohr’s Postulates
Bohr’s theory was based on the application of Planck’s Quantum theory on the atomic spectra of Hydrogen
atom. The fundamental postulates of his theory are discussed below :
 The electron in an atom has only certain definite stationary states of motion allowed to it, called as
energy levels. Each energy level has a definite energy associated with it. In each of these energy
levels, electrons move in circular orbit around the positive nucleus. The necessary centripetal force is
provided by the electrostatic attraction of the protons in the nucleus. As one moves away from the
nucleus, the energy of the states increases.
 These states of allowed electronic motion are those in which the angular momentum of an electron
h
is an integral multiple of or one can say that the angular momentum of an electron is quantised.
2
 h 
 Angular momentum = mvr  n   Angular momentum = moment of Inertia  angular velocity
 2 
v
= mr 2 × = mvr
r
where m is the mass of the electron, v is the velocity of the electron, r is the radius of the orbit, h is Planck’s
constant and n is a positive integer.
 When an atom is in one of these states, it does not radiate any energy but whenever there is a
transition from one state to other, energy is emitted or absorbed depending upon the nature of
transition.
When an electron jumps from higher energy state to the lower energy state, it emits radiations in form of
photons or quanta. However, when an electron moves from lower energy state to a higher state, energy is
absorbed, again in form of photons.
The energy of a photon emitted or absorbed is given by using Planck’s relation (E = h ). If E1 be the energy
of any lower energy state and E2 be the energy of any higher energy state, then the energy of the photon
(emitted or absorbed) is given as E (i.e., the difference in the energies of two states) :
c
E = E2  E1 = h  h

where h : Planck’s constant and  : frequency of radiation emitted or absorbed.

Additional Information :
Coulomb’s Law of Electrostatic force of attraction or repulsion (F) between two charges q1 and q2
K | q1 | | q 2 |
separated by a distance ‘r’ is given by : Force (F) 
r2
1
where K  = 9  109 Nm2 C–2
4 0
Note that charge on any particle can only be an integral multiple of charge on an electron (e).
Electrostatic Potential energy (E.P.E.) of a system of two charges separated by a distance ‘r’ is
given by :
Kq1q 2
E.P.E. 
r
Note : E.P.E. is +ve when charges are like and ve when charges are opposite.
Electrostatic force (F) is repulsive when both q1 and q2 are of same sign (i.e. either both are positive or both
are negative) and is attractive when q1 and q2 are of different signs.
Bohr Model :
Consider a species of atomic number (Z) containing single electron
revolving around its nucleus at a distance of ‘r’ as shown in the figure.
Note : Atomic number  Number of protons on the nucleus = Z

 Charge on the nucleus = + Ze
[As charge on each proton is +e and neutrons don’t have any charge]
Electrostatic force of attraction (F) between the nucleus of charge + Ze and electron (e) is given by :
K Ze  e K Ze2
F  . . . (i)
r2 r2
me v2
The centrifugal forces acting on the electron is . . . (ii)
r
[Assuming uniform circular motion]
This centrifugal force must be provided by the electrostatic force of attraction (F).
 From (i) and (ii), we have :
K Ze2 me v 2
 . . . (iii)
r2 r
10Section Section
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Also, according to Bohr’s postulate of quantization of angular momentum, we have :

nh
Angular momentum of electron about the nucleus = m e vr  . . . (iv)
2
where ‘n’ is a positive integer
(n = 1, 2, 3, . . . . )
Solve (iii) and (iv) to get :
2  K Ze 2 n 2h2
v and r 
nh 4 2 K me e 2 Z
Put K = 9  109 Nm2C–2, e = 1.6  10–19 C and h = 6.626  10–34 Js in the above expressions to get :
Z
Velocity of an electron in nth Bohr orbit  vn  2.18  10
6
ms 1
n
and Radius of the nth Bohr orbit
n2 n2 n2
 rn  0.529  1010 m  0.529 Å  52.9 pm 1pm  1012 m 
Z Z Z
Now, the Total Energy of the electron moving in nth orbit  K.E.n + E.P.E.n
1 K  Ze   e   Kq1q 2 
T.E.n  mv n2    E.P.E.  r 
2 r  
1  KZe 2  K  Ze    e 
 T.E n    [Using (iii)]
2  rn  rn
 KZe2
 E n  T.E. n 
2rn
It can be shown from the above expressions that :
1 KZe2  KZe2  KZe2
K.E.n  , P.E.n  and En 
2 rn rn 2rn
or K.E.n =  En and E.P.E.n = 2En
Using the value of rn in the expression of En, we get :
2  2 K 2 m e e 4 Z2
En 
n2h 2
Z2 Z2
E n  2.18  1018 J / atom  13.6 eV / atom  1eV  1.6  10 19 J 
n 2
n 2  

Z2 Z2
 2.18  1018  6.02  1023 J / mole  1312 kJ / mole
n2 n2
Note :  Bohr’s Model is applicable only to one-electron atoms like : He+, Li2+, Be3+ apart from H-atom.
Illustration - 5 Determine the frequency of revolution of the electron in 2nd Bohr’s orbit in hydrogen
atom.
SOLUTION :
The frequency of revolution of electron is given by : Calculate velocity (v2) and radius (r2) for electron in 2nd
Bohr orbit in H-atom (Z = 1)
1 Z = 1 for H-atom.
Frequency = time period
n2
Using rn  0.529 Å
Time period Z
Total distance covered in 1 revolution 10  22
 r2  0.529  10 m  1.12  1010 m
velocity 1
vn = 2.18  106 (1/n) m/s

2 r

v
v2 = 2.18  106 (1/2) = 1.09  106 m/s
v
Hence frequency =
2 r
v2 1.09  106

Hence frequency 2 r 
2 2(  )(2.12  1010 )
 = 8.18 × 1014 Hz.
2 r n3  n2 Z
Note : Frequency of revolution (f) = 1/T where T    r  and v  
v Z2  Z n
Z2
 f 
n3
What does the negative electron energy (En) means ?

The energy of the electron in a hydrogen atom has a negative sign for all possible orbits. What do this
negative sign convey ? This negative sign means that the energy of the electron in the atom is lower than the
energy of a free electron at rest. An electron in an atom is because of attractive force due to protons in the
nucleus. A free electron at rest is an electron that is infinitely far away from the nucleus and is assigned the
energy value of zero. Mathematically, this corresponds to setting n equal to infinity in the equation so that
E= 0. As electron gets closer to the nucleus, En becomes larger in absolute value and more and more nega-
tive. The most negative energy value is given by n = 1 which corresponds to the most stable orbit.

When an electron jumps from an outer orbit (higher energy) n2 to an inner orbit (lower energy) n1, then the
energy emitted in form of radiation is given by :
2 2 K 2 me 4 Z2  1 1   1 1 
E = E n 2  E n      E  2.18  1018  Z2   
1 h2  n 2 n2   n2 n 2 
 1 2   1 2
 1 1 
Also, E  13.6  Z2    eV/atom
 n2 n2 
 1 2
1 E 2 2 K 2 me4 Z2  1 1 
As we know that : E  h ;        
 hc c h3  n2 n 2 
 1 2
The above equation can be represented as :
 1 1  2 2 4
  RZ2    where R  2  K me
 n2 n2 
 1 2 c h3
R is known as Rydberg constant. Its value to be used is = 109677 cm–1 = 10967700 m–1
1
Note : (i) The value of  911.5 Å is sometimes useful.
R
(ii) This relation exactly matches with the empirical relation given by Balmer and Rydberg to account
for the spectral lines in H-atom spectra. In fact the value of Rydberg constant in the empirical
relation is approximately the same as calculated from the above relation (Bohr’s Theory). This
was the main success of Bohr’s Theory i.e. to account for the experimental observations by postu-
lating a theory.
(iii) The maximum number of lines that can be emitted when an electron in an excited state n = n2
(n 2  n1  1)(n 2  n1 )
de-excites to a state n = n1 (n2 > n1) is given by :
2
Illustration - 6 Determine the maximum number of lines that can be emitted when an electron in H atom
in n = 6 state drops to the ground sate. Also find the transitions corresponding to the lines emitted.
SOLUTION :
The maximum number of lines can be calculated by using the above formula with n2 = 6 and n1 = 1 are 15.
The distinct transitions corresponding to these lines are:
6 1
6 2, 2 1
6 3, 3 2, 3 1
6 4, 4 3, 4 2, 4 1
6 5, 5 4, 5 3, 5 2, 5 1

Note : Each line (in emission spectra) corresponds to a particular photon emitted. The photon with shortest
wavelength is corresponding to the largest energy difference (6  1) and with longest wave length is
corresponding to minimum energy difference (6  5).
ENERGY LEVELS OF HYDROGEN ATOM SECTION - 4
The spectrum of H-atom studied by Lyman, Balmer, Paschen, Brackett and Pfund can now be explained
on the basis of Bohr’s Model.
It is now clear that when an electron jumps from a higher energy state to a lower energy state, the radiation is
emitted in form of photons. The radiation emitted in such a transition corresponds to the spectral line in the
atomic spectra of H-atom.
Lyman Series
When an electron jumps from any of the higher states to the ground state or Ist state (n = 1), the series of
spectral lines emitted lies in ultra-violet region and are called as Lyman Series. The wavelength (or wave
number) of any line of the series can be given by using the relation :
1 1 
  R Z2    n2 = 2, 3, 4, 5, . . . .
 12 n 2 
 2
Note : For H-atom, Z = 1 ; He+ ion, Z = 2 and Li2+, Z = 3

Balmer Series
When an electron jumps from any of the higher states to the state with n = 2 (IInd state), the series of
spectral lines emitted lies in visible region and are called as Balmer Series. The wave number of any
spectral line can be given by using the relation :
 1 1 
  R Z2    n2 = 3, 4, 5, . . . .
 22 n 2 
 2
Paschen Series
When an electron jumps from any of the higher states to the state with n = 3 (IIIrd state), the series of
spectral lines emitted lies in near infra-red region and are called as Paschen Series. The wave number of
any spectral line can be given by using the relation :
 1 1 
  R Z2    n2 = 4, 5, 6. . . . .
 32 n 2 
 2
Brackett Series
When an electron jumps from any of the higher states to the state with n = 4 (IVth state), the series of
spectral lines emitted lies in far infra-red region and called as Brackett Series. The wave number of any
 1 1 
  R Z2    n2 = 5, 6, 7. . . .
 42 n 2 
 2
Pfund Series
When an electron jumps from any of the higher states to the state with n = 5 (Vth state), the series of
spectral lines emitted lies in far infra-red region and are called as Pfund Series. The wave number of any
 1 1 
  RZ2    n2 = 6, 7 . . . .
 52 n 2 
 2 
Note that Lyman series in UV region, Balmer series in visible region and Paschen, Brackett & Pfund series
in Infra-red region are only for H-atom (Z = 1).
Note : In a particular series, First [(n1 + 1)  n1], second [(n1 + 2)  n1], third [(n1 + 3)  n1] . . . . lines are called
as, , , . . . .lines respectively. For example line in Balmer series corresponds to (2 + 2)  2 i.e.,
4  2. In Lyman series :   line  2  1 ;   line  3  1 ;   line  4  1.
The energy required to remove the electron from the outermost orbit of the atom in gaseous phase is called
as Ionisation energy. Here, since we are considering only one electron species, Ionisation energy
(IE) = E1 = +13.6 Z2 eV.

Illustration - 7 The Lyman series of Hydrogen spectrum can be represented by the equation :
1 1  1
v  3.28  1015    s . Calculate the maximum and minimum frequency in this series.
2
1 n2 
SOLUTION :
Lyman frequency will be maximum corresponding to maximum energy transition. i.e. 1  
1 1  1
  max  3.28 1015    s = 3.28  10 s
15 1
2
1 2 
Note that corresponding wavelength will be shortest wavelength.
And Lyman frequency will be minimum corresponding to minimum energy transition. i.e. 1  2
1 1  1
  min  3.28  1015   s = 2.46  1015 s1
2 2
1 2 
Note that corresponding wavelength will be longest wavelength.
Illustration - 8 The wavelength of second line (also called as line) in Balmer series of hydrogen atom
is :
(A) 656.28 Å (B) 4872 Å (C) 6562.8 Å (D) 486.2 Å
SOLUTION :
The transition responsible for second Balmer (line) line is 4  2. In H-atom, n1 = 2 for Balmer series.
 1 1 
 E = 13.6 (1)2  2  2  = 2.55 eV
2 4 
hc 6.626  1034  3  108
Now   
E 2.55  1.6  1019
  = 4.872  107 m = 4872 Å

Hence correct option is (B).

Illustration - 9 A spectral line in the spectrum of H-atom has a wave number of 15222.22 cm1. The
transition responsible for this radiation is : (Rydberg constant R = 109677 cm1).
(A) 2 1 (B) 42 (C) 32 (D) 23
SOLUTION :
  1 / v  1 /15222.22  6.569  10 5 cm  6569 Å

Clearly, it lies in Visible region i.e, in Balmer series.
Hence n1 = 2
Using the relation for wave number for H-atom:
 1 1 
  1 /   RZ2   
 n2 n2 
 1 2
 1 1 
15222.22  109677   
 22 n 2 
 2
 n2 = 3
 the required transition is 3  2
Hence (C) is correct.+
Note : (D) is wrong, since 2  3 will absorb radiation.
Drawbacks of Bohr model :

Bohr’s model was successful in explaining the spectra and hence the structure of Hydrogen atom; still many
questions were not answered.
 His postulates combined two different concepts : one from classical physics and second from modern
theory of quantization.
 It could not explain the spectrum of atoms or ions having two or more electrons. It accounted only for
the spectra of H-atom, He+ ion and Li++ ion.
 There was no justification for the quantization of angular momentum of an electron, though this was a
correct assumption.
 His model could not provide a satisfactory picture of Chemical Bond.
 It also failed to account for the brightness of the spectral lines, splitting spectral lines in electric field
(Stark Effect) and in magnetic field (Zeeman Effect).

Illustration - 10 Calculate the wavelength of light radiation that would be emitted, when an electron in the
fourth Bohr’s orbit of He+ ion falls to the second Bohr’s orbit. To what transition does this light radiation
correspond in the H-atom ?
SOLUTION :
First calculate the energy difference (E) between 4th and 2nd Bohr orbit using :
 1 1 
E 4 2   13.6 Z2    eV
 n2 n 2 
 1 2
Substituting n1 = 2 and n2 = 4, Z = 2 we get ;
E = 10.2 eV
This energy difference (energy lost by the electron) will be equal to the energy of the emitted photon.
12400 12400
Using :   Å Å = 1215.7Å
E Photon  eV  10.2
Note : The emitted radiation is in UV region which implies that, in H-atom this transition would lie in Lyman
Series (n1 = 1). Hence our aim is now to find the transition : n2  1
1 1 
Use : E(n 2 1)  13.6  12    eV
 12 n 2 
 2
 1 
 10.2 = 13.6  1  2  eV
 n 
 2 
 n2 = 2
Hence the corresponding transition in H-atom is 2  1
Note : This concept can be applied only for H-atom.
Alternate Approach :
hc  1 1 
As discussed above : E(4  2) (in He  )   13.6  22     eV . . . .(i)
 Photon  22 42 
hc  1 1 
E (n 2  n1 ) (in H)   13.6  12   eV
 Photon 2 2 . . . .(ii)
n
 1 n 2
Try to convert equation (ii) in the form given in equation (i) and compare it with equation (i) as below :
hc 1 1 
 E(4  2) (in He  )   13.6  12     eV [22 shifted inside]
 Photon  12 22 
On comparing the above equation with equation (i), we get :
n1 = 1 and n2 = 2
Note : This concept can be applied for any H-like species.

Illustration - 11 Find the wavelength of radiation required to excite the electron in ground level of Li ++
(Z = 3) to third energy level. Also find the ionisation energy of Li2+. (R = 109, 677 cm1)
SOLUTION :
Ground level : n = 1
1  1 1 
Use :  RZ2   
2
  n1 n 22 
Putting the values : n1 = 1, n2 = 3, Z = 3
1 2  1 1 
We get :   109677  3   2  2 
1 3 
1 1
  877416cm1   = 113.97 Å
 v
Ionisation energy is the energy required to remove the electron from ground state to infinity i.e. corresponding
transition responsible is 1  .
1 1 
i.e. E (1   )  13.6  32    eV
 12 2 
Ionisation energy = E (1   )  122.4 eV  1.95  10 17 J  1eV  1.6  10 19 J 
Note : Ionisation Energy (IE) = –E1 = + 13.6 Z2 eV
Illustration - 12 Find the energy released (in ergs) when 2.0 gm atom of Hydrogen atoms undergo transi-
tion giving spectral line of lowest energy in visible region of its atomic spectra.
SOLUTION :
For Hatom, the spectral lines in visible region correspond to Balmer Lines (n1 = 2). Now for lowest energy
photon, the required transition will be from 3  2.
Using the relation for E :
 1 1 
E  2.18  1018 (1) 2    J / atom
 2
2 32 
= 3.03  1019 J
Now for 2.0 gmatoms, the energy released will be
E  (2  6.023  10 23 )  3.03 10 19 J

= 3.65  105 J  3.65  1012 [1J 107 ergs]

WAVE NATURE OF PARTICLES SECTION - 5
We have studied that light shows dual nature i.e. wave nature (Electromagnetic Radiation) and particle
nature (photons). In the following article we will see that not only light but matter also shows dual nature.
In 1923, de Broglie suggested that, since light is dualistic in nature: behaving in some aspects as waves and in
others like particles, the same might be true of matter. According to him, every form of matter (electron or
proton or any other particle) behaves like waves in some circumstances. These were called as matter waves
or de Broglie waves. de Broglie postulated that a particle of mass m moving with a velocity v should have a
wavelength  given by :
h h
  (p = linear momentum = mv)
p mv
Now we can think of a model of atom where moving electrons (obviously around the nucleus) should behave
like waves. The wave hypothesis of de Broglie was later developed by Heisenberg, Schrödinger, Fermi and
many others in modern atomic theory and is known as wave mechanics or quantum mechanics.
In new theory, electrons in an atom are visualised as diffused clouds surrounding the nucleus. The idea that the
electrons in an atom move in definite orbits (Bohr’s model) is now abandoned. The new theory assigns
definite energy states to an atom but discards a definite path for movement of an electron.
Due to wave nature of electron in an atom, it is now highly impossible to ascertain the exact whereabouts of an
electron. This idea is defined by Heisenberg’s Uncertainty Principle as :
“ It is impossible to specify at any given instant, both the momentum and the position of a sub-atomic
particle like electron.”
Whenever there is an attempt to specify the position of electron precisely, an uncertainty is introduced in its
momentum and vice-versa. If x is the uncertainty in position and p be the uncertainty in its momentum, then
according to Heisenberg, these quantities are related as follows :
h
x . p 
4
In other words, it can be defined as :
An expression of limits set by the wave nature of matter (electron) on finding the position and the state
of motion of moving body (momentum) such that the product of uncertainties in simultaneous mea-
surements of the position and momentum of a sub-atomic particle cannot be less than h/4 .
Hence, in new atomic theory, an electron can not be regarded as having a fixed (definite) path around the
nucleus, called orbits. It is a matter of probability that an electron is more likely to be found in one place or the
other. So we can now visualise a region in space (diffused cloud) surrounding the nucleus, where the probabil-
ity of finding the electron is maximum. Such a region is called as an orbital. It can be defined as :
“ The electron distribution described by a wave function and associated with a particular energy.”

 The new theory still defines a definite energy to an orbital in an atom

(a remarkable and accepted feature of Bohr’s model). The new theory
abandons the concept of sharply defined paths.
 If we consider an electron moving in a circular orbit around the nucleus, then
the wave train associated with the electron is shown in the figure.
If the two ends of the electron wave meet to give a regular series of crests and
troughs, the electron wave is said to be in phase.
n   2  r
where n is the number of waves made by an electron in that Bohr orbit
 The number of waves made by the electron
circumference of the orbit

=
wavelength
2 r 2 r  h 
Thus, n =    
 h / mv mv 
2 2  nh nh 
  mvr      n 
 mvr  2  
h h  2 
Hence the number of waves ( n ) made by an electron in an orbit is equal to principal quantum number (n)

Find out the number of waves made by a Bohr electron in one complete revolution in its 3rd orbit.
Using the above result, the number of waves made by the electron in 3rd Bohr orbit is 3 (i.e. n = 3).
Illustration - 13 An electron is accelerated through a potential difference of V volts. Find the de Broglie
wavelength associated with the electron.
SOLUTION :
When the electron is accelerated through a po- And de Broglie wavelength ()
tential difference of V volts, it acquires a kinetic h h
= 
energy given by E = qV, where q is the charge on mv 2Em
the electron. Also, if m be its mass and v be the Note :The above result can be used directly, whenever
1 required.
velocity then, E  mv 2 In the given case, E = qV
2
2E h
 v  
m 2 (q V) m

Illustration - 14 Calculate the uncertainty in position assuming uncertainty in momentum within 0.1 %
for :
(a) a tennis ball weighing 0.2 kg and moving with a velocity of 10 m/s.
(b) a electron moving in an atom with a velocity of 2 106 m/s.
SOLUTION :
Using Uncertainty Principle,
h
x . p =
4π
(a) p = mv = 0.2  10 = 2.0 Kg m/s
p = 0.1% of p = 2  103
h 6.626 1034
 x = 
4 p 4  3.14  2 103
= 2.63  1032 m.
(b) For an electron, p = m v

p = 9.1  1031  (2  106)
= 1.82 1024 Kg m/s
p = 0.1 % of p = 1.82  1027 Kg m/s
h 6.626 1034
x = 
4 p 4  3.14  1.82  1027
 x = 2.89  108 m
Note : This shows that for sub-atomic (microscopic) particles, Heisenberg’s Principle is highly meaningful, as x is
greater than their atomic radius.

CONCEPT OF QUANTUM NUMBERS SECTION - 6
Introduction to Quantum Mechanics

Macroscopic Objects :
Motion of these objects can be described/calculated using classical mechanics (based on Newton’s law
of motion).
Microsopic Objects
Motion of these objects can not be described/calculated using classical mechanics (based on Newton’s
law of motion).
(i) Dual nature of matter is not considered in classical mechanics, so there is a need for Quantum
Mechanics (takes into consideration the dual nature of matter).
(ii) Quatum mechanics can also be applied on macroscopic objects (we can ignore their wave like
properties) and still get the same results as Classical Mechanics.
Equation of Quantum Mechanics :

It defines the laws of motion that microscopic objects must obey.
Schrödinger equation is the governing equation of Quantum Mechanics. It is a complex equation and difficult
to understand and solve with the knowledge of mathematics in classes XI and XII.
Schrödinger equation is relatively easier to construct. For a H-atom, when this equation is solved, it gives
the energy levels for the electrons and corresponding wave function (  ) of the electron associated with
each energy level.
What is a wave function (  ) ?

 It is a mathematical function whose value depends upon the coordinates of the electron in the atom.
 It doesn’t have any physical significance.
 It is characterized (represented) by set of three quantum numbers (n : Principal quantum number,
 : Azimuthal quantum number and m: Magnetic quantum number).
Basically, it contains all the information about the electron.
Note :  Schrödinger equation can not be solved exactly for multi-electron atom (but can be solved
approximately).
 In case of single electron atom, energy of the orbital depends only on the principal quantum number
(n) but in case of multi-electron atom, it depends on ‘n’ as well as .

Designation of An Electron in an Orbital

An orbital is basically designated by three quantum numbers n,  and m as defined below :
(i) Principal Quantum Number (n) :

It is a positive integer with values of n = 1, 2, 3, . . . . . In other way, it can also be designated with
letters as K (n = 1), L (n = 2), M (n = 3), . . . . . . .
Significance :
(a) It determines the size and energy of the orbital.
Note : For H and H-like species, orbital size and energy depends only on ‘n’ but for multi electron species, orbital
energy depends on both ‘n’ and ‘’.
(b) It is also used to calculate the number of orbitals given by ‘n2’. Thus, the maximum number of elec-
trons in a shell (i.e. energy level as designated with letters as K, L, M etc.) are given by ‘2n2’, since
one orbital can at the maximum contains two electrons.
 As we have learnt in Bohr Model, increasing ‘n’ increases the energy of the electron, thus, energy of
the orbital increases.
 Also, we have learnt that size of the energy shells increases with increasing ‘n’. Thus, we can expect
the orbital size to increase with ‘n’.
(ii) Azimuthal Quantum Number () : It is an integer having all values between 0 and n – 1. It is also
also known as orbital angular momentum quantum number or subsidiary quantum number.
Significance :
(a) It is used to define the shape of an orbital.
(b) It is used to represent a subshell (Each shell has subshells equal to shell number). A subshell can be
thought of as sub-energy level inside an energy level.
For example : n = 1 (K shell) has only one subshell ( = 0)

n = 2 (L shell) has two subshells (= 0, 1)
And so on . . . . .
Each value of ‘’ can be designated with letters as s ( = 0), p ( = 1), d ( = 2), f ( = 3), g ( = 4)
and so on . . . . .
We can create the following notation :

n = 1,  = 0  1s
n = 2,  = 0, 1  2s, 2p
n = 3,  = 0, 1, 2  3s, 3p, 3d and so on . . . . .
(iii) Magnetic Quantum Number (m) :
It is an integer having values between – to + including zero.

Significance :
(a) It gives information about the orientation of an orbital with respect to coordinate axis.
 For example : ‘s’ orbital is spherical in shape. So, it can be oriented only in one way in
space, hence only one orbital is possible.
Note : Number of orbitals in a sub-shell  Number of possible orientations of an orbital.

 ‘p’ orbital has lobes above and below the plane as shown on page 27:
‘p’ subshell can be oriented in three ways (lobes can be along X, Y and Z axes).
Thus, three orbitals are possible in a p-subshell.
In general, number of orbitals in a sub-shell = 2 + 1
Thus, ‘s’ – subshell ( = 0) has 2 (0) + 1 = 1 orbital
‘p’ – subshell ( = 1) has 2 (1) + 1 = 3 orbital
Subshell  No. of orbitals Max. e’s per subshell Possible values of m 
s 0 1 2 0
p 1 3 6 –1, 0, 1
d 2 5 10 –2, –1, 0, 2
f 3 7 14 –3, –2, –1, 0, 1, 2, 3
Note the conventions :

‘s’ – subshell ‘p’ – subshell ‘d’ – subshell
m  0
Note : n, , m are the solutions of Schrödinger equation. There is another quantum number known as spin quantum
number (ms) which has been obtained experimentally.

There is an orbital angular momentum associated with an electron in a subshell given by :

h h
L      1      1  (where   = reduced Planck’s constant)
2 2
Spin Quantum number (ms) : This quantum number accounts for the spin of electron about its axis
similar to earth’s motion about the sun as well as about its own axis.
An orbital can have a maximum of two electrons spinning in opposite directions leading to a spin angular
momentum (vector quantity).
Thus, for two electron in an orbital,
1
ms   (spin anticlockwise)  
2
1
ms   (spin clockwise)  
2
h
Magnitude of spin angular momentum is given by : s  s  1
2
3 h  1 
  s  for an electron 
2 2  2 
3  1 
     reduced planck's constant 
2  2 
1 1
Note :  ms  for any electron. In an orbital, ms   has been taken so as to distinguish the two
2 2
electrons in it.
 spin quantum number has no classical analogue.
Difference between Orbit and Orbital :

Orbit Orbital
1. It is circular path around the nucleus in which 1. It is a quantum mechanical concept and
an electron moves. refers to one electron wave.
2. It is characterized by n. 2. It is characterized by n, , m.
3. It has no real meaning. 3. It represents the probability of finding an
electron at any point (through  2 ).

Hydrogen atom and the Schrodinger Equation:

When Schrodinger equation is solved for hydrogen atom, the solution gives the possible energy levels the
electrons can occupy function(s)  ψ  of the electron associated with each energy level. These quantized
energy sates and corresponding wave functions which are characterized by a set of three quantum numbers
(principal quantum number n, azimuthal quantum number l and magnetic quantum number m1) arise as a
natural consequence in the solution of the Schrodinger equation. When an electron is in any energy state, the
wave function corresponding to that energy state contains all information about the electron. The wave
function is a mathematical function whose value depends upon the coordinates of the electron in the atom
and does not carry any physical meaning. Such wave functions of hydrogen or hydrogen like species with
one electron are called atomic orbitals. Such wave functions pertaining to one-electron species are called
one-electron system. The probability of finding an electron at a point within an atom is proportional to the
2
ψ at that point. The quantum mechanical results of the hydrogen atom successfully predict all aspects of
the hydrogen atom specturm including of the hydrogen atom spectrum including sum phenomena that could
not be explaoned by the Bohr model.
Application of Schrondinger equation of multi-electron atoms presents a difficulty: the Schrodinger equation
cannot be solved exactly for a multi-electron atom. This difficulty can be overcome by using approximate
methods. Such calculations with the aid of modern computers show that orbitals discussed above. The
principal difference lies in the consecuence of increased nuclear charge. Because of this all the orbitals are
somewhat contracted. Further, as you shall see later (in subsections 2.6.3 and 2.6.4), unlike orbitals of
hydrogen or hydrogen only on the quantum number n, the energies of the orbitals in multi-electron atoms
depends on quantum numbers n and l.
Shapes of Atomic Orbitals :

Graph of  for various orbitals as a function of 2 at any point, gives the probability density of
electron at that point.
r (the distance from the nucleus is as shown :
As we see from the above graph, 2 decreases and approaches to zero as r increases. Region where 2
reduces to zero is called nodal surface (nodes). A node is a region of space where probability of finding the
electron is zero. There also angular nodes (nodal plane) which represents plane passing through nucleus and
having probability density function as zero.

For a hydrogen like atom wave function, of principal quantum number n, there are
(i) (n – – 1) radial nodes (ii) angular nodes (iii) (n – 1) total nodes.
Thus :
 2s has one node. 3s has two nodes and so on.
 1s (n = 1,  = 0) subshell is without any node.
 2s (n = 2,  = 0) subshell will have only one radial node, while 2p (n = 2,  = 1) subshell will have
only one angular node.
 3s (n = 3,  = 0) subshell will have two radial nodes, 3p (n = 3,  = 1) subshell will have one radial
and one angular node while 3d (n = 3,  = 2) will have two angular nodes.
Boundary surface diagram : It is surface (contour) which represents a constant ||2. In general, it is the
region where the probability of finding the electron is 90%.
As mentioned earlier, the ‘s’ orbitals are spherical in shape which means that
the probability of finding the electron at a given distance is equal in all the
direction.
Also, the size of these orbitals increases as ‘n’ increases.
Boundary Surface Diagrams of p-orbitals are not spherical as shown :
As we can see, there are two lobes on either side of the plane passing through the nucleus having
probability of finding the electron as zero on it.
 All three orbital have same shapes and energy.
 Here also, energy of these orbitals increases with increasing ‘n’.
 No. of radial nodes (for p-orbitals) are given by n – 2
Boundary Surface Diagrams of d-orbitals are shown below. For d-subshells, there are 5 values of m. Thus,
d has 5 orbitals.

Energy of orbitals :
 For H-atom, energy of an orbital can be solely calculated by using ‘n’
Thus, 1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f < ……
Orbitals having same energy are called degenerate orbitals.
 For an atom containing multi electrons, energy of an electron depends on ‘n’ as well as ‘’.
In this case, each e– is attracted by the nucleus but is repelled by every other electron. The electrons in the
outer shell experiences less attractive force as there is a partial screening of positive change known as
shielding of the outer shell electrons from the nucleus.
 ‘s’ orbitals are more tightly bound to nucleus than p orbitals, p orbitals are more tightly bound to
nucleus than d orbitals and so no. Thus, energy of ‘s’ orbitals is more negative than p-orbitals.
Illustration - 15 In all, how many nodal planes are there in the atomic orbitals for the principal quantum
number n = 3.
SOLUTION :
Shell with n = 3 has 1 ‘s’ (3s), 3 ‘p’ (px, py, pz) and 5
‘d’ (dxy, dxz, dyz, d 2 2 and dz2) orbitals.
(x  y )
 ‘s’ has no nodal plane.
 Each of px, py, pz has one nodal plane, which means a total of 3 nodal planes.
 dz2 has no nodal plane.
Each of dxy, dxz, dyz, d 2 2 has 2 nodal planes, which means a total of 8 nodal planes.
(x  y )
Hence for n = 3, a total of 11 nodal planes are there.

ELECTRONIC CONFIGURATION OF ELEMENTS SECTION - 7
Quantum numbers can now characterise the electrons in an atom. To describe the arrangements and distribution
of electrons for different elements, following rules and selective principles are used. The distribution of electrons
in an atom is known as the electronic configuration of that element.
Aufbau Principle
An atom in its lowest state of energy is said to be in ground state. The ground state is the most stable state in
an atom. According to Aufbau principle:
“ electrons are added progressively to the various orbitals in their order of
increasing energy starting with the orbital of lowest energy.”
The order of increasing energy may be summed up as follows:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d,.....
As a working rule, a new electron enters an empty orbital

for which the value of (n + ) is minimum. If the value of
(n + ) is same for two or more orbitals, the new electron
enters an orbital having lower value of n.
Pauli Exclusion Principle

According to this principle :
“ no two electrons in an atom can have the same set of
all the quantum numbers. or one can say that no two
electrons can have the same quantised states.”
Consider an electronic arrangement in Ist energy level
(n = 1). For n = 1,  = 0, and m = 0. Now ms can have
two values corresponding to each value of m i.e.
ms = +1/2, 1/2. Hence the possible designation of an
electron in a state with n = 1 is (1, 0, 0, +1/2) and
(1, 0, 0, 1/2)  (n, , m, ms) i.e., two quantised states.
This implies that an orbital can accommodate (for n = 1,
m = 0, i.e., one orbital) maximum of two electrons having
opposite spins.
The maximum number of electrons in the different sub-shells
are :
s sub-shell = 2, p sub-shell = 6, d sub-shell = 10 and f sub-shell = 14.

Hund’s Rule Of Maximum Multiplicity

According to this rule : “ electrons never pair until no available empty degenerate orbitals are left to
them.”
This means an electron always occupies a vacant orbital in the same sub-shell (degenerate orbital) and pairing
starts only when all of the degenerate orbitals are filled up. This means that the pairing starts with 2nd electron
in s sub-shell, 4th electron in p sub-shell, 6th electron in d sub-shell and 8th electron in f sub-shell.
By doing this, the electrons stay as far away from each other as possible. This is highly reasonable if we
consider the electron-electron repulsion. Hence electrons obey Hund’s rule as it results in lower energy state
and hence more stability.
Extra Stability of Half And Fully Filled Orbitals

A particularly stable system is obtained when a set of equivalent orbitals (degenerate orbitals) is either fully
filled or half filled, i.e., each containing one or a pair of electrons. This effect is more dominant in d and f sub-
shells.
This means three or six electrons in p sub-shell, five or ten electrons in d sub-shell, and seven or fourteen
electrons in f sub-shell forms a stable arrangement. Note this effect when filling of electrons takes place in d
sub-shells (for atomic numbers Z = 24, 25 and 29, 30).
Electronic configuration of an element is represented by the notation n x :
n : principal quantum number  : denotes the sub-shell x : number of electrons present in an orbital
Illustration - 16 Write down the electronic configuration of following species. Also find the number of
unpaired electrons in each. (a) Fe, Fe2+, Fe3+ (Z of Fe = 26) , (b) Br, Br  (Z of Br = 35) ,
(c) V, V3+ (Z of Fe = 23)
SOLUTION :
Follow the order of increasing energy (Aufbau Rule) :
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d……..
(a) Fe(Z = 26): 1s2 2s2 2p6 3s2 3p6 4s2 3d6
Note that 3d orbital are not fully filled.
3d6 
Orbitals filled as per Hund’s Rule.
Clearly the number of unpaired electrons is 4.
 Fe2+ : (Z = 26) [No. of electrons = 24]

While writing electronic configuration (e.c.) of cations, first write e.c of neutral atom and then “remove desired
number of electrons from outermost orbital”.
In Fe2+, remove 2e from 4s2 since 4s orbital (through lower in energy then 3d) is the outermost. Hence e.c.
of Fe2+ is: 1s2 2s2 2p6 3s2 3p6 3d6 4s0
Note that number of unpaired electrons remains same as that in Fe, i.e. 4.
 Fe3+ (Z = 26) [No. of electrons = 23]
Now remove 2e from 4s2 and 1e from 3d6 to get e.c. as : 1s2 2s2 2p6 3s2 3p6 3d5 4s0

Note that, now all ‘d’ orbits have an odd electron (i.e. are half filled).
Hence number of unpaired electrons in Fe3+ = 5.

(b) Br (Z = 35) [No. of electrons = 35]
Following Aufbau rule, e.c. is : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p5
Clearly one of 4p5 orbitals contains unpaired electrons: 4p5 
Hence Br has only one unpaired electron.
 Br   Z  35  [No. of electrons = 36]
Since anion(s) is(are) formed by adding electron(s), so simply write e.c. as per total number of electrons
finally. For Z = 35, e.c. is : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6
Clearly there are no unpaired electrons.
(c) Following on pattern in (a), we can write e.c. for V as follows.
V(Z = 23) : 1s2 2s2 2p6 3s2 3p6 4s2 3d3
3d3 
 3 unpaired electrons.
 V3+ (Z = 23) [No. of electrons = 20]
Remove 3e  from outermost orbitals successively i.e.,‘2e  ’ from 4s 2 and 1e  from 3d 3 .
Hence e.c. of V3+ is :
1s2 2s2 2p6 3s2 3p6 4s0 3d2
3d 2 

 2 unpaired electrons.

Illustration - 17 A compound of Vanadium has a magnetic moment of 1.73 B.M. Work out the electronic
configuration of vanadium in the compound.
SOLUTION :
The magnitude of magnetic moment () of a compound/species/ion is given by :
  n  n  2 B M
(n = number of unpaired electrons ; BM : unit of magnetic moment in Bohr’s Magneton)
 1.73  n  n  2 
On solving for n, we get n = 1. This means that vanadium ion (Z = 23) in the compound has one unpaired
electron.
3d :
So its electronic configuration (e.c.) must be :
1s2 2s2 2p6 3s2 3p6 3d1
i.e., vanadium exists as V4+ ion in the compound since the ground state e.c. of 23V is :
1s2 2s2 2p6 3s2 3p6 3d3 4s2
3d : 4s :
Note : In these kind of questions, keep on removing e from the outermost orbitals till the required number of unpaired
e is achieved.
MISCELLANEOUS ILLUSTRATINS
Illustration - 18 Find the threshold wavelength for a copper plate, a sodium plate and cesium plate. The
work functions of these plates are : 4.5 eV, 2.3 eV & 1.9 eV respectivley.
SOLUTION :
hc
Use λ 0= E  stopping energy.
E
For copper λ 0 = 1242 ev – nm = 276 nm

4.5eV
1242 ev – nm
For Sodium λ0 = = 540 nm
4.5 eV
For caesium λ 0 = 1242 ev – nm = 654 nm

1.9 eV

Illustration - 19 A UV light of wavelength 280 nm is used an experiment on photoelectric effect with Li

(work function = 2.5 eV) as cathode. Find:
(a) the maximum KE of photoelectrons and (b) the stopping potential
SOLUTION :
(a) The maximum K.E is : (b) Stopping potential V is given by
hc
K max = 
λ K max
V  1.9 V
1242 e
  2.5  1.9 eV
280
Illustration - 20 (a) Find the wavelength of the radiation required to excite the electron in Li++ from
the first to the third Bohr orbit. (b) How many spectral lines are observed in the emission spectrum of the
above excite system ?
SOLUTION :
z2
(a) As we know E = 13.6 eV (b) There are three lines in the spectrum.
n2
So  E = E 3  E1 = 8×13.6 eV = 108eV.
1242 eV  nm
Use λ  108.8 eV
= 11.4 nm
Illustration - 21 A hydrogen sample is prepared in a particular excited state A. Photons of energy 2.55 eV
get absorbed into the sample to take some of the electrons to a further excited state B. Find the quantum
number of the states A and B.
SOLUTION :
Use the energy difference diagram and we can see that 2.55 eV can only be absorbed in transition
n = 2 to n = 4. Hence the quantum number are 2 and 4.

Illustration - 22 Find the wavelengths in a hydrogen spectrum between the range 500 nm to 700 nm.
SOLUTION :
First find energy of the photons having wave Thus the energy difference should be between
length 500 nm and 700 nm. 1.77 eV and 2.44 eV.
1242 eV  nm The desired transition is  2 for
Eλ 500   2.44 eV
500 nm  E = 1.9 eV.
1242 eV  nm hc 1242 eV  nm
Eλ  700   1.77 eV Hence λ  ΔE  1.9 eV
 654 nm
700 nm
Illustration - 23 A beam of ultraviolet radiation having wavelength between 100 nm and 200 nm is inci-
dent on a sample of atomic hydrogen gas. Assuming that the atoms are in ground state, which wavelengths
will have low intensity in the transmitted beam ? If the energy of a photon is equal to the difference between
the energies of an excited state and the ground state, it has large probability of being absorbed by an tom in
the ground state.
SOLUTION :
1242 eV  nm Thus 10.2 eV and 12.1 eV have larger
E λ=100 nm = = 12.42 eV probability.
100 nm
And that corresponding to 1 = 200 nm is 1242 eV  nm
 λ1 = = 122 nm
6.21 eV 10.2 eV
E 2  E1 = 10.2 eV and E 3  E1 = 12.1eV 1242 eV  nm
and λ2 = = 103nm
E 4  E1 = 12.75 eV 12.1eV
Illustration - 24 Light corresponding to the transition n = 4 to n = 2 in hydrogen atoms falls on cosium

metal (work function = 1.9 eV). Find the maximum kinetic energy of the photoelectriosn emitted.
SOLUTION :
The energy of photons emitted in transition
n = 4 to n = 2 is
 1 1 
hv  13.6 eV  2  2   2.55 eV
2 4 
K .Emax  2.55  1.9  0.65 eV

Illustration - 25 Calculate the smallest wavelength of radiation that may be emitted by

(a) hydrogen (b) He+ and (c) Li++
SOLUTION :
Smallest wavelength will be from   1 . 1 1 1  1
For He+ ion Z = 2 = R .Z2  2  2  ; λ=
λ 1   4R
For H-atom
1 1 1  1
1 1 1  For Li2+; 2 = 3 = R .32  2  2  ; λ=
= RZ2  2  2  = R  1 = 911.5 Å λ 1   9R
λ 1  
Illustration - 26 Find the binding energy of a hydrogen atom in the state n = 2.

SOLUTION :
z2
Binding energy will be 13.6 2
n
12
For n = 2; B.E. = 13.6 = 3.4 eV
22
Illustration - 27 Find the radius and eenrgy of a He+ ion in the states
(a) n=1 (b) n = 4 and (c) n = 10
SOLUTION :
n2
Radius = 52.9 pm
z
z = 2, n = 1
12
 r  52.9   26.45 pm
2
42 102
r4  52.9   423.2 pm rn 10  52.9   2645 pm
2 2
Illustration - 28 A positive ion having just one electron ejects it if a photon of wavelength 228 Å or
less is absorbed by it. Identify the ion.
SOLUTION :
First find  E corresponding to this wavelength
1242
E = = 54.47 eV
22.8
 54.47 = 13.6 z 2  z=2
Hence the ion is He+.

Illustration - 29 A hydrogen atom in state n = 6 makes two successive transitions and reaches the ground
state. In the first transition a photon of 1.13 eV is emitted.
(a) Find the energy of the photon emitted in the second transition.
(b) What is the value of n in the intermediate state ?
SOLUTION :
Use the energy diagram 1 1 1 
E6 = – 0.378 = R×12 ×  2  2 
λ 1 5 
E5 = – 0.544
E4 = – 0.85 1 8R
E3 = – 1.51 =
λ 9
By looking at the energy gap vale of 1.13 eV.
9 9
We can see that intumidiate state is 3rd . λ= = ×911.5Å = 1024.4 Å
8R 8
Hence the second transition will be form 3  1.
Illustration - 30 A beam of light having wavelengths distributed uniformly between 450 nm to 550 nm
passes through a sample of hydrogen gas. Which wavelength will have the least intensity in the transmitted
beam ?
SOLUTION :
hc
E1 = = 2.76 eV;
450
1242
E2 = = 2.26 eV Observing from the energy diagram
550
Clearly, the intermediate wavelength absorbed will be corresponding to

energy = 2.55 eV
Hence corresponding wavelength will be 486 nm.
Illustration - 31 A hydrogen atom in ground state absorbs a photon of ultraviolet radiation of wavelength
50 nm. Assuming that the entire photon energy is taken up by the electron, with what kinetic energy will the
electron be ejected ?
SOLUTION :
Illustration - 31the given situation corresponding to a photoelectric effect.
Visualise
1242
Energy corresponding to 50 nm wavelength = = 24.84 eV
50
The ionization energy of hydrogen atom in ground state is 13.6 eV which is equivalent to work function of
hydrogen atom.
Hence, K.E. of electron ejected = 24.84  13.6 = 11.24 eV .

Electronic Configurations of the Elements

Element Z 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
H 1 1
He 2 2
Li 3 2 1
Be 4 2 2
B 5 2 2 1
C 6 2 2 2
N 7 2 2 3
O 8 2 2 4
F 9 2 2 5
Ne 10 2 2 6
Na 11 2 2 6 1
Mg 12 2 2 6 2
Al 13 2 2 6 2 1
Si 14 2 2 6 2 2
P 15 2 2 6 2 3
S 16 2 2 6 2 4
Cl 17 2 2 6 2 5
Ar 18 2 2 6 2 6
K 19 2 2 6 2 6 1
Ca 20 2 2 6 2 6 2
Sc 21 2 2 6 2 6 1 2
Ti 22 2 2 6 2 6 2 2
V 23 2 2 6 2 6 3 2
Cr* 24 2 2 6 2 6 5 1
Mn 25 2 2 6 2 6 5 2
Fe 26 2 2 6 2 6 6 2
Co 27 2 2 6 2 6 7 2
Ni 28 2 2 6 2 6 8 2
Cu* 29 2 2 6 2 6 10 1
Zn 30 2 2 6 2 6 10 2
Ga 31 2 2 6 2 6 10 2 1
Ge 32 2 2 6 2 6 10 2 2
As 33 2 2 6 2 6 10 2 3
Se 34 2 2 6 2 6 10 2 4
Br 35 2 2 6 2 6 10 2 5
Kr 36 2 2 6 2 6 10 2 6
Rb 37 2 2 6 2 6 10 2 6 1
Sr 38 2 2 6 2 6 10 2 6 2
Y 39 2 2 6 2 6 10 2 6 1 2
Zr 40 2 2 6 2 6 10 2 6 2 2
Nb* 41 2 2 6 2 6 10 2 6 4 1
Mo* 42 2 2 6 2 6 10 2 6 5 1
Tc 43 2 2 6 2 6 10 2 6 5 2
Ru* 44 2 2 6 2 6 10 2 6 7 1
Rh* 45 2 2 6 2 6 10 2 6 8 1
Pd* 46 2 2 6 2 6 10 2 6 10
Ag* 47 2 2 6 2 6 10 2 6 10 1
Cd 48 2 2 6 2 6 10 2 6 10 2
In 49 2 2 6 2 6 10 2 6 10 2 1
Sn 50 2 2 6 2 6 10 2 6 10 2 2
Sb 51 2 2 6 2 6 10 2 6 10 2 3
Te 52 2 2 6 2 6 10 2 6 10 2 4
I 53 2 2 6 2 6 10 2 6 10 2 5
Xe 54 2 2 6 2 6 10 2 6 10 2 6
*Elements with exceptional electronic configurations

Example - 1 Calculate the wavelength and wave number of the spectral line when an electron in H-atom
falls from higher energy state n = 3 to a state n = 2. Also determine the energy of a photon to ionize this atom
by removing the electron from 2nd Bohr’s orbit. Compare it with the energy of photon required to ionize the
atom by removing the electron from the ground state.
SOLUTION :
First calculate the energy (E) between the Bohr

orbits n = 3 and n = 2 using :
 1 1 
E = 13.6 Z  2  2
2  eV

 n1 n2 
 To ionize the atom from n = 2, the responsible
 1 1 
 transition will be
E(3  2) = 13.6 (1)2  2  eV = 1.89 eV
2 32  n = 2  n = .
 1 1 
Now this energy difference is the energy of the E(2  ) = 13.6  12   2  2  eV
photon emitted. 2  
= 3.4 eV
12400  To ionize the atom from ground state (n = 1),
 E Photon  eV
  in Å  the transition is 1  .
12400 1 1 
   6560.3 Å E = 13.6 eV 12   2  2  = 13.6 eV
1.89 1  
1
and    1.52  106 m 1

Example - 2 A hydrogen atom in the ground state is hit by a photon exciting the electron to 3rd excited
state. The electron then drops to 2nd Bohr orbit. What is the frequency of radiation emitted and absorbed in
the process ?
SOLUTION :
18  1 1 
Energy is absorbed when electron moves from  E(1  4)  2.18  10  12    J
 22 42 
ground state (n = 1) to 3rd excited state (n = 4).
 4.08  1019 J
First calculate the energy difference between This is the energy of the photon absorbed.
n = 1 and n = 4. Use : E Photon  h  4.08  10 19 J to get :
Use :  14
  6.16  10 Hz
 1 1   Similarly, when electron jumps from n = 4 to
E (1  4)  2.18  1018  Z2    ; n = 2, energy is emitted and is given by the
2 2 ;
n
 1 n 2 same relation.
Put n1 = 2 and n2 = 4 in the expression of E,
to get
 1 1 
E(4  2)  2.18  1018  12    J
 22 42 
 4.08  1019 J
This is the energy of the photon emitted.
Use : E Photon  h  4.08  10 19 J
Here Z = 1, n1 = 1, n2 = 4
   6.16  1014 Hz
Example - 3 A hydrogen like ion, He+ (Z = 2) is exposed to electromagnetic waves of 256.4 Å. The
excited electron gives out induced radiations. Find the wavelength of the induced radiations, when electron
de-excites back to the ground state. R = 109677 cm1.
SOLUTION :
He+ ion contains only one electron, so Bohr’s Substitute for  = 256.4 Å = 256.4  108 cm,
model is applicable here. It absorbs a photon of
R = 109677, Z = 2 for He+ ion, n1 = 1
wavelength  = 256.4 Å. Assume the electron to
be in ground state initially. Let it jumps to an ex- Now, Find n2 .
cited state n2. Use the relation, to find n2.
1
1  1 1  256.4  108
   R Z2   
  n2 n2  1
 1 2 1 
 109677 107  (2) 2   
 12 n 2 
 1 2
 n2 = 3  (3  1) = 256.4 Å,  (3  2) = 1641.3 Å,
From n = 3, the electron can fall back to the  (2  1) = 303.9 Å
ground state in three possible ways (transitions) :
3  1, 3  2, 21
Hence three possible radiations are emitted. Find
the wavelengths corresponding to these transi-
tions.
The wavelength () for transition, 3  1 will be
same i.e., 256.4 Å. Find  for 3  2 and 2  1
using the same relation.
Example - 4 Hydrogen gas when subjected to photo-dissociation, yields one normal atom and one atom
possessing 1.97 eV more energy than normal atom. The bond dissociation energy of hydrogen molecule into
normal atoms is 103 kcals mol1. Compute the wave length of effective photon for photo dissociation of
hydrogen molecule in the given case.
SOLUTION :
H2  H + H* The extra energy possessed by excited atom is
*
where H is normal H-atom and H is excited 1.97 eV
H-atom. So the energy required to dissociate H2 in  1.97  1.6  1019 J = 3.15  1019 J
this manner will be greater than the usual bond E (absorbed) = 7.175  1019 + 3.15  1019 J
energy of H2 molecule. = 1.03  1018 J
E(absorbed) = dissociation energy of Now calculate the wavelength of photon
H2 + extra energy of excited atom corresponding to this energy.
hc
Energy required to dissociate in normal manner E photon   1.03  1018 J

= 103  103 cal per mol (given)   = 1930 Å
103  103  4.18

= = 7. 17  1019 J /molecule
23
6  10
Example - 5 An electron in the first excited state of H-atom absorbs a photon and is further excited.
The de Broglie wavelength of the electron in this state is found to 13.4 Å. Find the wavelength of photon
absorbed by the electron in Å. Also find the longest and shortest wavelength emitted when this electron de-
excites back to ground state.
SOLUTION :
Note : The energy state n = 1 is known as Ground State Using the relation :
The energy state n = 2 is known as First Excited  1 1 
State. E  13.6 Z2    eV
(2  4)  n2 n2 
The energy state n = 3 is known as Second  1 2
excited State and so on. = 2.55 eV [n1 = 2, n2 = 4, Z = 1]
The electron from n = 2 absorbs a photon and is 12400
 E  eV
further excited to a higher energy level (2  4)   in Å 
(let us say n). 12400

 =  Å  4863.1Å
The electron in this energy level (n) has a de 2.55
Broglie wavelength () = 13.4 Å.
The longest wavelength emitted when this
electron (from n = 4) falls back to the ground
state will corresponds to the minimum energy
transition.
The transition corresponding to minimum energy
will be 4  3.
h Note : The transition corresponding to maximum
e 
m e ve energy will be 4  1.
Z hc
and ve  2.18  106 ms 1 E (Energy diff .)  E Photon   h
n 
[ve is the velocity of e in nth Bohr orbit] 1
 E  or E  vPhoton
h  Photon
1
 ve   2.18  106  
m n Using the same relation :
6.626 1034  1
E (4  3)  13.6 Z2  
1 
 2  eV
13.4 1010   9.11031   n1 n 22 
1
 2.18  106  [ n1 = 3, n2 = 4, Z = 2]
n
 n=4  E(4  3)  0.66 eV
Now find the wavelength of the photon respon- 12400

E  E Photon  eV
sible for the excitation from n = 2 to n = 4   in Å 
  = 18752.8 Å 12400
 E (4  1)  E Photon  eV
  in Å 
Shortest wavelength : 4 1
   973.2Å
1
2 1 
E(4  1)  13.6  1     eV
 12 42 
= 12.75 eV
Example - 6 A single electron orbits around a stationary nucleus of charge +Ze, where Z is a constant and
e is the magnitude of electronic charge. It requires 47.2 eV to excite the electron from second Bohr orbit to the
third Bohr. Find :
(a) the value of Z
(b) the energy required to excite the electron from n = 3 to n = 4
(c) the wavelength of radiation required to remove electron from 2nd Bohr’s orbit to infinity
(d) the kinetic energy, potential energy and angular momentum of the electron in the first orbit.
(e) the ionisation energy of above one electron system in eV.
SOLUTION :
Since the nucleus has a charge +Ze, the atomic  DE = 16.53 eV
number of the ion is ‘Z’.
(c) The required transition is n1 = 2  n2 =  by
(a) The transition is n1 = 2  n2 = 3 by absorbing absorbing a photon of energy E.
a photon of energy 47.2 eV. Find E by using the relation :
 E = 47.2 eV
 1 1 
Using the relation : E  13.6 (5) 2   
 2
2 2 
 1 1 
E  13.6 Z2     E = 85 eV
 n 2 n 2  eV
 1 2
Find  of radiation corresponding to energy
 1 1  85 eV.
 47.2  13.6 Z2     Z = 5
2
2 32  12400
  Å = 146.16 Å
(b) The required transition is n1 = 3  n2 = 4 by 85
absorbing a photon of energy E.
(d) If energy of electron be En, then KE = En and
Find E by using the relation : PE = 2En
 1 1 
E  13.6 Z2    13.6 Z 2 13.6  52
 n 2 n 2  eV En   = 340 eV
 1 2 n2 12
 1 1  KE = (340 ev) = 340 eV
 E  13.6(5)2    eV
 32 42  PE = 2 (340 eV) = 680 eV
 h  (e) The ionisation energy (IE) is the energy required

Angular momentum () = n  
 2  to remove the electron from ground state to infin-
 6.626  1034  ity. So the required transition is 1  .
  1  
 2  The ionisation energy
= 1.05 1034 J-s
(IE) =  E1 = 13.6 (Z)2 eV
Note : Angular momentum of e is also equal to
 1E = +13.6  52 = 340 eV.
me v e r .
Example - 7 The hydrogen-like species Li 2 is in a spherically symmetric state S 1 with one radial node.
Upon absorbing light the ion undergoes transition to a state S 2 . The state S2 has one radial node. The ratio
of its energy in state S 1 to the ground state energy of the hydrogen atom.
(i) The state S 1 is : (A) 0.75 (B) 1.50
(A) 1s (B) 2s (C) 2.25 (D) 4.50
(C) 2p (D) 3s (iii) The orbital angular momentum quantum
(ii) Energy of the state S 1 in units of the number of the state S 2 is :
hydrogen atom ground state energy is: (A) 0 (B) 1
(C) 2 (D) 3
SOLUTION : (i)-(B) (ii)-(C) (iii)-(B)

Radial node = n    1 Energy of electron in S1
S 1 2 s (As it is spherically symmetric and has
Z2 32
one radial node) = 13.6× eV = 13.6× eV
n2 22
S2  3 p (As its energy is equal to ground state
Energy of hydrogen in ground state
energy of H-atom hence, its principal quantum
= 13.6 eV
number is 3 and it contains only 1 radial node)
Hence its Orbital angular momentum quantum  Energy of electron in S1 is 2.55 times the
number is 1. (1  3    1  1) energy hydrogen atom in ground state.
Example - 8 Find the energy required to excite 1.10 litre of hydrogen atoms gas at 1.0 atm and 298 K to
the first excited state of atomic hydrogen. The energy required for the dissociation of HH bond is 436
kJ/mol. Also calculate the minimum frequency of a photon to break this bond.
SOLUTION :
Let us, first find the number of moles of hydrogen The energy required to excite the given number
atoms. of Hatoms = 6.02  1022  1.635  10–18 J
= 98.43 kJ
PV 1 1.10
n H2    0.045 So the total energy required
RT 0.0821 298
= 19.62 + 98.43 = 118.05 kJ
Thus the energy required to break 0.045 moles
Now the energy required to break a single
of H2 (HH bond) = 0.045  436 = 19.62 kJ.
Now calculate the energy needed to excite the 436 103
H-H bond =
Hatoms to first excited state i.e., to n = 2 (First 6.023  1023
excited state is referred to n = 2).
 1  7.238  1019 J / atm
18 2 1 
E  2.18  10 (1)    J / atom
12 2
2  = Energy supplied by the photon
= 1.635  1018 J/atom  7.238  1019 = h = 6.626  1034 ()
No. of H atoms = (No. of H2 molecules)  2   = 1.09  1015 Hz.
= (0.05  6.02  1023)  2 = 6.02  1022
Example - 9 Estimate the difference in energy between 1st and 2nd Bohr’s orbit for a Hatom. At what
minimum atomic number (Z), a transition from n = 2 to n = 1 energy level would result in the emission of
radiation with wavelength  = 3.0  108 m ? Which Hydrogen atom like species this atomic number corre-
sponds to ? How much ionisation potential is needed to ionise this species ? (R = 1.097  107 m1)
SOLUTION :
The difference in energy is given by E : Hence the Hlike atom is He+ ion.
18 2 1 1  To ionise, He+ ion, ionisation energy (IE)

E  2.18  10 (1)  2  2  J / atom = (E1)
1 2 
IE = (13.6  22) = + 54.4 eV
= 1.65  1018 J  1.65  1011 ergs  10.2 eV
The ionisation potential (IP) is the voltage dif-
8
For a Hlike atom,  = 3.0 10 m. ference required to generate this much energy.
 IE = qV = e (IP) = 54.4 eV
18 2 1 1 
 E  2.18  10 Z  2  2J  IP (required) = 54.4 Volts
(2  1) 1 2 
hc
 E Photon   Z=2

Example - 10 Math the following :

List 1 List 2
(A) Orbital angular momentum of the electron in a hydrogen-like (p) principal quantum number
atomic orbital
(B) A hydrogen-like one-electron wave function obeying (q) Azimuthal quantum number
Pauli principle
(C) Shape, size and orientation of hydrogen-like atomic orbitals (r) Magnetic quantum number
(D) Probability density of electron at the nucleus in (s) Electron spin quantum number
hydrogen-like atom
SOLUTION : [A-q, r] [B-p, q, r, s] [C-p, q, r]
[D-p, q]
(A) Orbital angular momentum of the (C) Shape, size and orientation of hydrogen-like
electron in a hydrogen like atomic atomic orbital are indicated by , n, m .
orbital depends on type of atomic
(D) Probability density of electron at the nucleus in
orbital ( ) and its orientation (m ) . hydrogen-like atom is obtained by the square
(B) As per Pauli’s principle, every electron
of the wave functions. (ψ 2 ) and it depends on
is unique, hence all four quantum
numbers are required. n and 
Example - 11 A stationary He+ ion emits a photon corresponding to the first line (H) of Lyman series.
The photon thus emitted, strikes a Hatom in the ground state. Find the velocity of the photoelectron ejected
out of the hydrogen atom. The value of R = 1.097  107 m1.
SOLUTION :
1 2
The difference in energy (E) will be equal to the KE = Ei  Wo = m e ve [Ei = Incident energy]
2
energy of the photon emitted.
First line in Lyman series corresponds to the 2 (Ei  Wo )
 ve 
transition 2 1. me
1 1 
E  2.18  1018 (2) 2  
 12 22 
 J / atom
 ve 
2  6.54 1018  2.18 1018 
= 6.54  1018 J 9.11031
The photon of this much energy strikes a Hatom in  ve = 3.09  106 m/s
the ground state. Note that the ionisation energy of
We can also calculate the wavelength of electron
Hatom is +2.18  1018 J. This will be the work
function of Hatom. Using the Einstein’s photoelectric ejected out  2.36  1010 m  2.36 Å
equation :
h 6.626  1034
e   m  2.36 Å
me ve 9.1  1031  3.09  106
Example - 12 An electron in a hydrogen like species, makes a transition from nth Bohr orbit to next
outer Bohr (  n  1) . Find an approximate relation between the dependence of the frequency of the photon
absorbed as a function of ‘n’. Assume ‘n’ to be a large value (n >> 1).
SOLUTION :
 1 1 
E (energy difference)  h  2.18  1018  Z2   J
2 2
(n  n  1) n (n  1) 
2n  1
 h  2.18  1018  Z2  
2 2 J
 n (n  1) 
Since n >> 1 (given)
 n + 1 ~ n ; 2n + 1  2n
2n
 h  2.18  1018 Z2  J
n4
   n 3
NOW ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK
THINGS TO REMEMBER
1. Number of photons (n) emitted in time t sec from a source of radiation with power P is given by :
Pt Pt
n 
 hc /   hc
2. Einstein’s photoelectric equation : Ei = KE + W0 or KE = h   h0 = h (  0) or
1
KE  mv2  h  ν  ν 0 
2
3. Bohr model of Atom : Bohr’s Model is applicable only to one-electron atoms like : He+, Li2+, Be3+ apart
from H-atom.
6 Z
Velocity of an electron in nth Bohr orbit  vn  2.18  10 ms 1
n
Radius of the nth Bohr orbit
n2 n2 n2
 rn  0.529  1010 m  0.529 Å  52.9 pm 1pm  1012 m 
Z Z 2
Energy of electron in nth Bohr orbit
Z2 18 Z
2
 E n  13.6 eV / atom  2.18  10 J / atom 1eV  1.6  1019 J 
n 2 2
n  
K.E.n =  En and E.P.E.n = 2En
Self Study Course for IITJEE with Online Support Things To Remember 47
4. When an electron jumps from an outer orbit (higher energy) n2 to an inner orbit (lower energy) n1, then the
energy is emitted in form of photons, which is given by :
 1 1   1 1 
E  E n 2  E n1  2.18  1018  Z2    J/atom  13.6  Z2   
 n2 n2   n 2 n 2  eV/atom
 1 2  1 2
If an electron is to be moved from lower energy state (n1) to a higher energy state (n2), the same amount of
energy ( E) is needed to absorb in the form of photons
h h
5. de-Broglie wavelength is given as :    (p = linear momentum = mv)
p mv
48 Things To Remember Self Study Course for IITJEE with Online Support
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Periodic Properties of Elements
Classification of Elements & Periodicity in Properties

EARLIER ATTEMPTS OF PERIODIC CLASSIFICATION OF ELEMENTS Section - 1
Certain groups of elements have similar chemical properties; we classify elements as members of the same
chemical family. Such similarity in the properties of elements has led scientists to classify them in such a form
where one can study them in an organized manner. Such an arrangement is called as Periodic Table. Some of
significant earlier attempts are discussed below.
Dobereiner’s Triads
In 1829, J. Dobereiner made an important first step towards a systematic classification by arranging elements
into groups of three (triads). He observed that the atomic weight of the middle element of the group was
midway between the atomic weights of the other two. He also concluded that the same midpoint relation held
true for the physical properties of these elements.
Some of his triads were :
Li, Na, K Cl, Br, I Ca, Sr, Ba
Newland’s law of Octaves

In 1865, Newland proposed that if the elements are arranged according to the increasing atomic weights
(beginning with lightest element, excluding Hydrogen), the chemical and physical properties of a particular
element would be similar to those of the elements seven places before and seven places after it (like the eight
note in an octave of music). This led to the idea of periodicity for the first time in true sense.
For example, Li, the second element in Newland’s list, had properties similar to Na, the ninth element in the
list and K, the sixteenth element. Thus these were similar elements represented by numbers 2, 9, 16 that
show interval of seven.
Mendeleev’s Periodic law and Classification

In 1869, the Russian Chemist Mendeleev was successful in arranging the elements in the form a periodic
table, in such a way that the elements having similar properties were placed in same vertical columns, called
groups.
Mendeleev organized the elements according to a regular increase in the atomic weight. He thus obtained a
pattern where similar chemical properties for element recurred periodically. In fact his observations were
based on a periodic law stating :
“ The physical and chemical properties of the elements are periodic functions of their respective
Atomic weights.”

Periodic Properties of Elements Vidyamandir Classes
His proposal was even backed by the predictions for the undiscovered elements. He took a bold step to
leave the blank places for such elements. He in fact predicted the properties of these elements and called
some of them as eka-sillicon (Germanium), eka-aluminum (Gallium) and eka-boron (Scandium). Later on
when these elements were discovered, Mendeleev’s predictions were found to be amazingly accurate.
Modern Periodic Table
With the establishment of atomic theory in the first quarter of 20th century and work of physicist Henry
Moseley, the chemical behavior of an atom is known to be dependent on its electrical characteristic signified
by its Atomic number (Z). So Mendeleev’s periodic table was modified to include the later developments in
so called Long-form of periodic table. It is based on modern Periodic Law stated as :
“The physical and chemical properties of the elements are periodic functions of their respective Atomic
numbers”
In the long form of periodic, the elements having the same electronic configuration in their outer shell were
grouped together. The electrons in the outer shell are termed as valence electrons. Valence electrons determine
the properties and chemcial reactivity of the elements and participate in chemical bonding (discussed later in
the chapter).
Hence a major modification in the long form of periodic table, is the arrangement of elements in order of
increasing Atomic numbers rather than increasing Atomic weights.
MODERN PERIODIC TABLE Section - 2
In modern periodic table, elements are arranged in horizontal rows (periods) and vertical columns (groups).
In all there are seven periods and eighteen groups. The groups were divided into two categories according to
old convention. Now the groups are numbered from 1 to 18. In old convention group nos.were
IA, IIA, ......... VIIA, IB, IIB ......... VIIIB.
IA, IIA, IIIA,…………VIIIA ; now written as 1, 2, 13, 14, 15, 16, 17, 18
IIIB,…………VIIB ; now written as 3, 4, 5, 6, 7
VIIIB corresponds to 8, 9, 10 and IB, IIB correspond to 11, 12 respectively.
Periods :
Ist Period contains only two elements namely Hydrogen (H), Helium(He). It is called as shortest period.
IInd period starts with Lithium (Li) and contains eight elements.
Li, Be, B, C, N, O, F, Ne.
IIIrd period starts with Sodium (Na) and contains eight elements.
Na, Mg, Al, Si, P, S, Cl, Ar.
Note : II and III periods are called as short-periods.

IVth period contains eighteen elements starting with Potassium (K).

K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Kr.
Vth period contains eighteen elements starting from Rubidium (Rb).
Rb, ………….., Xe (Xenon).
Note : IVth and Vth periods are called as long-periods.

VI period consists of 32 elements, starting from Cesium (Cs) and ending with Radon (Rn). It is called as
longest period. Apart from the representative and transition elements this period also contains Inner
transition elements called as Lanthanides (Ce,………., Lu).
VII period is incomplete period and at present contains 19 elements starting form Fr (Francium). Upto
Uranium (U) all the elements are naturally occurring but rest are radioactive with very short half-lives. These
also include a part of inner transition elements, called as actinides (Th,…Lr).
Groups :
Group 1 consists of H (1s1), Li (2s1), Na (3s1),… The common outermost electronic configuration is ns1.
Elements belonging to this group are called as Alkali Metals.
Group 2 consists of Be (2s2), Mg (3s2), Ca (4s2),… The common electronic configuration is ns2. Elements
of this group are called as Alkaline Earth Metals.
Group 13 consists of B (2s2 2p1), Al (3s2 3p1),… The common electronic configuration is ns2 np1. Elements
of this group are called as Boron Family.
Group 14 contains C (2s2 2p2), Si (3s2 3p2),… The common electronic configuration is ns2 np2. This group
is known as Carbon Family.
Group 15 contains N (2s2 2p3), P (3s2 3p3),… The common electronic configuration is ns2np3. This group
is known as Nitrogen Family. The elements of this group are also called as PNICTOGENS (poisonous
compounds forming elements).
Group 16 contains O (2s2 2p4), S (3s2 3p4),… The common electronic configuration is ns2 np4. This group
is known as Oxygen Family. The elements of this group are also famous as CHALCOGENS (ore-forming
elements).
Group 17 contains F (2s2 2p5), Cl (3s2 3p5),… The common electronic configuration is ns2 np5. Elements of
this group are called as HALOGENS (salt forming elements).
Group 18 (or Zero group) contains He (1s2), Ne (2s2 2p6), Ar (3s2 3p6),… The common electronic
configuration is ns2 np6. Elements of this group are called as Inert Gases or Noble Gases.

Classification of periodic table in different blocks :

PERIODIC TABLE
s-block p-block d-block f-block

 Elements have last  Elements have last electron  Elements have last electron  Elements
electron in s-orbital i.e. in p-orbital i.e. Group 13- in d-orbital i.e. Group 3- have
18. 12.
Group 1 and Group 2. last
 Group No. of any  Group No. of any element
 Group No. of any electron
= no.o f elements in
element = no. of element = no. of in f-orbital.
penultimate d-shell and
elements in valencey electrons in valence shell. valency shell.
shell. + 10.
Features of Groups 1, 2, 13 – 18
 Elements belonging to these groups are in general called as Representative Elements
 General Electronic Configuration for group 1, 2 can be written as: ns1-2 and ns2 nd 1-6, for group 13- 18.
n : here represents the number of period to which a particular elements belongs (principal quantum number).
The total number of electrons i.e., number of electrons in s & p sub-shells gives the number of group to
which a particular elements belongs.
 Elements of 1 and 2 groups are also called as s-block elements, as final electron in these elements (also
called as differentiating electron) enters s sub-shell. Elements of 13 to 18 groups are called as p-block
elements, as differentiating electron in these elements enters p sub-shell.
Features of Groups 3 – 12
 Groups 3 to 12 are known as transition elements or d -block elements, as the differentiating electron
(last electron) in these elements enters d-sub-shell. General electronic configuration of these elements can
be written as
(n – 1) d 1-10 n s0-2.
 Group 3 has a special feature in sense that, it contains elements in which the differentiating electron enters the
f sub-shell, hence these elements are also called as f-block elements apart from being called as Inner
transition elements. These are placed in two horizontal rows below the table and are called as Lanthanides
(also called as Lanthanoides) and Actinides (also called as Actinoids).
General electronic configuration of these elements is :
Lanthanoides : 4 f n 5d 0-1 6s2
Actinoids : 5 f n 6d 0-2 7s2.

Some other features of the periodic table are as follows :

Typical Elements
Elements of third period are also called as Typical Elements. These include Na, Mg, Al, Si, P, S, Cl. The
properties of all the elements belonging to a particular group resemble the properties of the corresponding
typical element of that group. For example, the general properties of Alkali Metal can be predicted from the
behaviour of Na, not Li, the first member of the family.
The typical elements (all having n = 3) can take up 18 electrons. Note that, for these elements 3d sub-shell is
available, but it is not filled i.e., these have vacant d sub-shell. This is not the case with second period elements,
hence they have somewhat different properties than the rest of the group or we can say that it is the typical
element, which in true sense represents a group.
Bridge Elements
Elements of second period are also called as Bridge Elements. The properties of these elements resemble
with the properties of elements belonging to third period placed diagonally. This is illustrated as follows.
2 Period Li Be B C N O F
3 Period Na Mg Al Si P S Cl
Noble or Inert Gases
Elements of group 18 or zero group are called Inert or Noble Gases. They have completely filled (2 or 8
electrons in outermost shell) outermost shells, called as stable configuration. Their valency is zero. They are
almost inert in their chemical behaviour. They have weak intermolecular forces in them and hence are gases and
exist in monatomic states.
Classification of Elements based on their position is the periodic table

1. Metals
This is the largest class of the elements. This includes elements belonging to 1, 2, 3 to 12 (i.e. all transition and
inner-transition elements) and some elements of groups 13 to 15 lying near the bottom of the table. The metals
are characterized by their nature of readily giving up the electron apart from shinning luster. The oxides of
metals are basic in nature.
2. Non-metals
These do not give up electron, in fact like to take up the electron to form negative ion. These include 10
elements lying to the right side of the table. They are C, N, O, F (2nd period), P, S, Cl (3rd period), Se, Br (4th
period) and I (5th period). The oxides of non-metals are acidic in nature.
3. Metalloid
You can have very easily observed that metallic character has decreased when one moves to the right of the
table across a row. It is observed that some elements lying at the border of metallic and non-metallic behaviour,
exhibit both the metallic and non-metallic character, these are called as metalloids. These include 8 elements
namely ; B, Si, Ge, As, Sb, Te, Po and At. The oxides of metalloids are generally amphoteric in nature.

Note :The elements in group 18 do not behave like metals, nor do they behave like non-metals. So they are classified
separately as Noble Gases. Also the element Hydrogen (H) is different from any other element and cannot be
easily classified into a particular group (however it is placed along with the Alkali Metals, though it does
not exhibit metallic character).
PERIODIC PROPERTIES Section - 3

Properties of Elements like valency, atomic and ionic radii, ionization enthalpy, electron gain enthalpy,
electronegativity etc. follow some regular trends as we move down a group or along a period. This is
because all these properties depends on the electronic configuration of the atoms.
Beside there some properties like melting point, boiling point, density, atomic volume etc. which are not
defined for individual atoms but for a bulk (collection) of atoms. These properties are also indirectly related
to electronic configuration of atoms and follow a regular trends along periods and groups.
 As we proceed down a column (group), outer-shell electronic configuration remains the same. The
only difference in the atoms as we go down the table is that the nuclear charge and the number of inner
shells increase. This thing happens in regular manner.
 As we proceed across the periods (from left to right), electronic configuration of each element differ
from that of one before in terms of an additional electron and some nuclear charge being added
successively. Note that the number of shells in a period remains constant.
Let us discuss some of the important periodic properties.

1. Valency
It is defined as combining capacity of an element. It can also be defined in terms of valence electrons (electrons
in the outer most shells). The valency is equal to number of valence electrons (or equal to 8 minus the
number of valence electrons).
For representative elements, in general, valency of elements belonging to a chemical family i.e., in a group is
constant. It is known from its general electronic configuration. To illustrate, for group 1 (Alkali metals), valency
is 1 (ns1), for group 2 (Alkaline earth metals), it is 2 (ns2) and for group 3, it is 3 (ns2 np1).
For transition elements, no general trend is observed in the valency of elements. The reason is that those
elements have variable valencies due to availability of vacant d-subshells in them.
Similar is the case with inner-transition elements ( f-block elements) i.e., no general trend is observed due
to variable valency.
2. Types of atomic radii :

It is impossible to define the size of atoms, as we know that atoms have no sharp boundaries due to delocalized
picture of electron cloud. This is necessary in order to explain a number of chemical properties of different
elements in terms of the size of their atoms of ions. There are four operational concepts which have been widely
used. These are :
(i) Covalent radii (ii) Ionic radii (iii) van der Waals’ radii (iv) Metallic radii

(i) Covalent Radii

One of techniques to define size is to study molecules that are made up of two atoms (for example. H2, Cl2, O2
etc). These are held together by covalent bonds. In a molecule, two nuclei remain at a fixed average distance
(d) from each other.
Atomic Radius is now defined as the average distance between the centres of two nuclei forming the covalent
bond divided by 2. In this case atomic radius is called as covalent radius given by d/2.
1
Thus, for a homonuclear diatomic molecule, rcovalent  [Internuclear distance between two bonded atoms]
2
Since the internuclear distance between two bonded atoms is called the bond length. Therefore,
1
rcovalent  [bond length]
2
For atoms which do not form such molecules 3s, same technique can be applied to their molecules with other
atoms For example. C-Cl bond in CCl4 etc.
Down the group : The sizes of atoms increases as we go down a column (group) of a periodic table. Each
time we go down one step, the outer shell configuration is same, but there is an additional inner shell being
added continuously. Consequently, the atomic size increases.
Increasing order of sizes in some families is shown below.
Li (1.33) Be (0.90) …………… O (0.74) F (0.71)
Na (1.54) Mg (1.36) …………… S (1.02) Cl (0.99)
K (1.96) Ca (1.74) …………… Se (1.16) Br (1.14)
Rb (2.16) Sr (1.92) …………… Te (1.35) I (1.33)
(Sizes given in brackets are in Å)
Along the period : In general, the sizes of the atoms decrease as we go down from left to right along the
horizontal rows (periods) except group 18 (Noble Gases). All the electrons in an atom are under two influences.
One is attraction of the electrons for the positive nucleus and other is mutual repulsion of the electrons for each
other. It is important to note that both the forces are inversely proportional to the square of the distance
between the electrons and the protons. Now as we go across the period, number of shells remains the same
and electrons and protons are continuously added. This leads to considerable force of attraction between
electrons and protons and consequently atoms become smaller. You can observe in above illustration that
rLi > rBe > rO > rF ,where r denotes atomic radii. Some Exceptions occur in case of d-block elements i.e.
Ni < Cu < Zn, Pd < Ag < Cd.
(ii) Ionic Radii
It is defined as the distance between the nucleus and outermost shell of an ion. Losing an electron or two from
the neutral atom forms a cation.
A positive ion is formed when the electrons are lost from the outer most shell. This ion is always smaller than the
corresponding neutral atom. because it contains smaller number of electrons compared to neutral atom, while

both contain same number of protons. The electrons in positive ions therefore experience a stronger pull
towards nucleus as compared to neutral atoms and hence ion becomes smaller.
A negative ion is formed when an extra electron is added to a neutral atom.This ion is always larger than the
corresponding neutral atom. because it has more electrons than neutral atom. Additional electron in negative
ion creates more repulsion in the outer most shell and thus outer shell expands.
 The sizes of ions increase as we go down a group provided that we are comparing ions of same charge.
For example Li+ < Na+ < K+ < Rb+
Be2+ < Mg2+ < Ca2+ < Sr2+
F¯ < Cl¯ < Br¯ < I¯
 Atoms or ions with the same electronic configuration are called as isoelectronic. If we consider a series of
iso-electronic species (atoms or ions), the size decreases with the increasing atomic number. This is beacuse
the number of electrons and shell remain constant while positive charge of nucleus increase which pull the
electrons more strongly. To illustrate the concept, Consider the following iso-electronic species all having
10 electrons.
Iso-electronic species O2– (1.401) F– (1.36) Ne (1.31) Na+ (0.95) Mg2+ (0.65)
Atomic number (Z) 8 9 10 11 12
(sizes given in the bracket are in Å)
 The size of cations of same element decreases with the increase in the magnitude of positive charge. For
example. Cu2+ is smaller than Cu+ , Fe3+ is smaller than Fe2+ , Sn4+ is smaller than Sn2+.
(iii) Van der Waals’ radius

It is defined as one-half the distance between the nuclei of two identical non-bonded isolated atoms or two
adjacent identical atoms belonging to two neighbouring molecules of an element in the solid state.
The magnitude of the van der Waals’ radii depends upon the packing of the atoms when the element is in the
solid state.
(iv) Metallic radius

It is defined as one-half the inter-nuclear distance between the two adjacent metal ions in the metallic lattice.
According to Electron-sea model, a metal lattice or crystal consists of positive kernels or metal ions (left after
the removal of valence electrons) arranged in a definite pattern in a sea of mobile valence electrons. Thus, each
kernel (i.e., metal ion) is simultaneously attracted by a number of mobile electrons and each mobile electron is
attracted by a number of metal ions. This simultaneous force of attraction between the mobile electrons and the
positive kernels is called the metallic bond.
The inter-nuclear distance is determined by X-ray studies and the metallic radius is usually expressed in angstrom
units or picometers.

Since in a metallic lattice, the valence electrons are mobile, therefore, they are only weakly attracted by the
metal ions or kernels. In contrast to covalent bond, a pair of electrons is strongly attracted by the nuclei of two
atoms. Thus, a metallic radius is always longer than its covalent radius.
Comparison of covalent radius and van der Waal’s radius

Van der Waal’s radius of an element is always larger than its covalent
radius because of the following two reasons :
(i) Since the van der Waal’s forces of attraction are weak, therefore the
inter-nuclear distances in case of atoms held by van der Waal’s forces
are much larger than those between covalently bonded atoms.
Therefore, van der Waal’s radii are always larger than covalent
radii.
(ii) Since a covalent bond is formed by overlap of two half-filled atomic orbitals, a part of the electron cloud
becomes common. Therefore, covalent radii are always smaller than the van der Waals’ radii.
A comparison of three types of atomic radii discussed above reveals that van der Waal’s radius is the longest
while covalent radius of an atom is the shortest, i.e., vander Waal’s radius > metallic radius > covalent
radius.
3. Ionisation energy
First ionization energy is defined as the energy required to remove a single electron from the outer shell of
a neutral gaseous atom. Consequently the atom changes to a mono-valent cation
M(g) + IE1 
 M+ (g) + e–
Down the Group: First ionization energy decreases as we go down a group in the table. It measures the ease
of removing an electron from the outer shell. As we go down a group, this shell is farther away from the nucleus.
It is true that the positive charge of nucleus increases, but its effect is weakened due to the shielding supplied by
the inner shells to the outer most shell. As a result nuclear attraction decreases. Some exception occurs in
group 13 where the ionisation energy of Ga is more than that of Al. It is due to the fact that Ga has electrons
filled in d-shell and shielding of d shell to nucleus is compratively small. So increased nuclear charge effect
dominates here.
Along the period: As we go from left to right across a period, the atomic size decreases. As the number of
shells in a particular period remains same and new electrons are being continuously introduced in the outer
shell, the outer electrons are greatly attracted to the nucleus. Hence it becomes difficult to remove them and
consequently first ionization energy increases.

In the following table, I ionization energies (in eV) of II period are shown :
Li Be B C N O F Ne
5.39 9.32 8.3 11.26 14.53 13.62 17.42 21.56
You should have clearly noted two irregularities as we move from left to right in the above table.
 I.E. of B < I.E. of Be. When Be loses an electron, it is removed from a fully filled 2s sub-shell, whereas
B gives its lone 2p electron. Hence extra-stability of fully filled sub-shell is the cause of this irregularity.
 I.E. of O < I.E. of N. Here half filled (2p3) outer most sub-shell of N is highly stable and hence it becomes
difficult to remove the electron. Thus extra-stability of half filled sub-shells is the cause of irregularity.
Second ionization energy is defined as the amount of energy required to remove the second electron from an
atom that has already lost an electron, i.e. to remove an electron from a mono-valent cation. Third and higher
I.E.(s) are analogously defined.
M+ + IE2 
 M+ + e–
M2+ + IE2 
 M3+ + e–
In general : IE1 < IE2 < IE3 < ………..
This happens because, as the number of electrons decreases regularly, the attraction of the nucleus for the
remaining electrons increases considerably (which are now less in number), and hence subsequent I.E.(s)
increase.
 Whenever all the outer-shell electrons are removed, the next I.E. is much greater than the previous value of
I.E. for the same element. Note that first I.E. of Li is 5.39 eV and the second I.E. for the same is 75.64 eV.
 If we compare first I.E.s of the elements in a period (e.g., Li……Ne), the noble gas (Ne in present case)
had the highest I.E. A noble gas configuration (ns2 np6) is completely filled and hence highly stable.
 The electrons in different orbitals (s, p, d or f) belonging to the same energy level (i.e., same value of n)
experience different pull of the nucleus. The I.E. for pulling out an s-electron is maximum and it decreases
in pulling out p-electron, a d-electron or a f-electron of the same principal energy shell in the order of their
mention. Hence we can say that I.E. for pulling out an electron from a given energy level decreases in the
order s > p > d > f orbitals. For example first I.E. of AI is lower than that of Mg. Here two factors govern
the first I.E. the extra stability of fully filled sub-shells apart from the above mentioned factor.
Factors affecting the ionisation energy

1. The charge on the nucleus 2. The size of the aotm
3. Presence of half filled or fully filled orbitals 4. Shielding of s, p, d or f orbitals.
4. Electron Affinity
It is defined as the energy given out when a neutral gaseous atom takes up an extra electron.
X(g) + e– 
 X– (g) where X represents a neutral gaseous atom.

Electron affinity of an atom measures the tightness with an atom bonds an extra electron to it. The value of
electron affinity shows the same trend as atomic size and ionization energy. It is also known as Electron Gain
Enthalpy.
 It decreases down a group, because as the atom gets larger (due to increasing atomic size), the attraction
of positive nucleus for an outside electron decreases. Exception: in halogens, Fluorine (F) has lower electron
affinity than Chlorine (Cl). It is mainly due to extremely small size of F atom as compared to that of Cl. The
addition of an extra electron creates a high electron density and hence strong electron-electron repulsion is
not highly favoured. Due to the same reason oxygen has smaller affinity than sulphur.
 It in general increases when one moves from left to right across a period. It is due to decreasing atomic size
(across a period) that the nuclear attraction for an additional electron increases. Hence the electron affinity
and I.E. of metals is low while that of non-metals is high.
 The electronic configuration of elements also affects their electron affinities. Electron affinities of Noble
gases are zero. It is attributed to their fully filled stable configuration (ns2 np6). Also the electron affinity of
N and Be atoms are quite low due to extra stability of half filled orbitals and fully-filled orbitals (p3 in N
and s2 in Be).
 The concept of higher electron affinities is rather interesting. After taking up an extra electron an atom
becomes negatively charged (anion) and now a second electron is to be added to it. The anion will repel
the incoming of an electron and an additional energy will be required to add it to the anion. This means first
E.A is the energy released while the second E.A. is the energy required. If one considers the energy
released as negative and that required as positive then first E.A of O is – 141 KJ/mol and second E.A.
is +770 KJ/mol.
Factors on which the Electron Gain Enthalpy depends

Some important factors on which electron affinity depend are discussed below:
(i) Atomic size : As the size of the atom increases, the distance between the nucleus and the last shell which
receives the incoming electron, increases. As a result, the force of attraction between the nucleus and the
incoming electron decreases and hence the electron gain enthalpy becomes less negative.
(ii) Nuclear charge : As the nuclear charge increases, the force of attraction between the nucleus and the incoming
electron increases and hence the electron gain enthalpy becomes more negative.
(iii) Electronic configuration : Elements having exactly half-filled or completely filled orbitals are very stable. As
a result, energy has to be supplied to add an electron. Hence their electron gain enthalpies have large positive
values the additional electron so easily and easily and hence their electron affinities are either very low or are
almost zero.
5. Electronegativity
It is the measure of the ability of an atom in a combined state (i.e. in a molecule) to attract to itself the electrons
within a chemical bond. In general in the covalent bond both the atoms don’t share the electron pair equally. It
depends upon the pulling power (electronegativity) of the atom for electrons that which atom will share the
electron pair dominetly. More the electronegativity of the atom, more dominently it will share the electron pair.

Electron pair will get slightly shifted towards the more electronegative atom and this atom will aquire a δ
charge resulting in δ charge on the other atom.
In general, non-metals have high value of electronegativity while the metals have a quite low value. For example
F, O, N and Cl (non-metals) are highly electronegative whereas K, Rb and Cs (metals) are non-electronegative,
in fact they are electropositive.
 It follows the same trends as shown by electron affinity or ionization energy. This means that higher I.E.
and greater E.A., both results in high electronegativity.
 Across a period from left to right the electronegativity increases due to increase in the nuclear charge and
decrease in atomic size. Down the group electronegativity decreases due to the increase in effective nuclear
attraction force. Fluorine has the highest electronegativity of any element.
 The difference in electronegative values of two atoms in a compound predicts the nature of chemical bond
formed between two atoms. More the difference between the electronegativity of two atoms involved in a
bond more will be the ionic character. There is no direct method to measure the value of electronegativity,
however there are some scales to measure its value.
Pauling scale
According to Pauling, electronegativity difference (XA – XB) in between two atoms A & B is given by :
XA – XB = 0.208  where  = EA-B – E A  A  E B B where EA-B, EA-A and EB-B are bond energy of
molecules AB, A2 and B2 respectively in kcal/mole. This scale is the most popular scale.
Mulliken scale
According to Mulliken, the electronegativity of an atom is the average of the two values i.e.. electron affinity
and ionization energy.
IE  EA
Electronegativity = where I.E. and E.A. are in kJ/mol. Note : X Mulliken  X Pauling  2.8
2
Allred - Rechow scale

According to this concept, electronegativity of an atom is simple electrostatic force of attraction between
0.359 Zeff
atoms and an electron separated from the nucleus by the covalent radius. i.e. electronegativity = +
r2
0.744, where Zeff is the effective nuclear charge and r is covalent radius of atom in Å.
6. Atomic Volume
Atomic volume of an element is the ratio of its gram-atomic weight to its density. In a group, atomic volume
generally increases from top to the bottom. Actually it is not a very good periodic property as different elements
have different packing arrangements in solid states, so a general trend is not observed. This is particularly true

in right side of the periodic table where in halogens and Fe-Pt sub-groups it becomes nearly constant. Note
that atomic volume is a bulk property. It depends on the packing of atoms as well.
7. Metallic Character
Metallic character or the electropositive character of an element is defined as its tandency to loose electrons
and form positive ions. Metallic character increases down the group and decreases along the period (from left
to right). There is a series of metallic (electropositive) character that is good to remember.
K > Na > Ba > Ca > Mg > Al > Zn > Fe > Ni > Sn > Pb > H > Cu > Hg > Ag > Au > Pt
The trick to remeber this series is to remember the name PSBC MAZINTL CHAAP
In PSBC P = Potassium, S = Sodium, B = Barium, C = Calsssium. In MAZINTL, M = Mg, A = Al, Z = Zn,

I = Iron, N = Nickel, T = Tin, L = Lead. In chaap C = Cu, A = Ag, A = Au, P = Pt. Also note that Hydrogen
(not a metal) comes between Mazintl and Chaap.
Summary of the trends in the Periodic Properties of Elements in the Periodic Table
Note: Direction of arrow represents the increase in property.
Note that Electronegativity, Ionisation Enthalpy, electron gain Enthalpy follow the same trends because they
all represent the same character - attraction of nucleus for the outermost shell electron. While Atomic radius
follows trends opposite the three.

There are some effects which sometimes affect the periodic properties.
(i) Penetration effect of the electrons
Ionization enthalpy increases as the penetration effect of the electrons increases. It is a well known fact that in
case of multi-electron atoms, the electrons of the s-orbital has the maximum probability of being found near the
nucleus and this probability goes on decreasing in case of p, d and f-orbitals of the same shell. In other words,
s-electrons of any shell are more penetrating towards the nucleus than p-electrons of the same shell. Thus,
within the same shell, the penetration effect decreases in the order : s > p > d > f
Obviously, if the penetration effect of the electron is more, it will be closer to the nucleus and hence will be held
more firmly by the nucleus. Consequently, the ionization enthalpy will be high. In other words, ionization
enthalpy increases with the increase in the penetration effect of electrons. Thus, the ionization enthalpy will
be more to knock out a s-electron of the same shell, which in turn, will be more than that required to
remove a d-electron and so on.
(ii) Screening (shielding) Effect

The electrons in the valence shell experience an attractive force from the nucleus and a repulsive force from the
electrons in the inner shells. The overall effect of these two opposing forces is that the attractive force exerted
by the nucleus on the valence shell electrons is somewhat reduced by the repulsive force exerted by the
electrons present in the inner shells. This affects the nuclear attraction of the positive nucleus for the outer
electrons. In d-block elements (transition elements), while writing electronic configuration of elements, it is
seen that the new electrons are being added to the inner shell i.e., penultimate shell (3d after 4s, 4d after 5s and
so on). As the differentiating electron enters the inner shells, they tend to screen or shield the outer shell
electrons from the nucleus and hence offset the nuclear attractive force.
The actual charge felt by the valence shell electrons is called effective nuclear charge and the repulsive
force felt by the valence shell electrons from the electrons present in the inner shells is called the shielding effect
or screening effect. Shielding effect of shells closer to nucleus is higher and it follows the trends s > p > d >
f. Due to this effect, the atomic size of transition elements (which should have been decreasing across a
period) remains nearly same or constant. The same is the case with ionisation energy, electron affinity and
other periodic properties when one moves across a period.
(iii) Inert Pair Effect

Inert pair effect occurs when electrons are pulled closer to nucleus making them stabler and more difficult to
ionise. It is basically the tendency of outermost (or valence) ‘s’ electrons to remain non-ionised (and not
participate in bonding ). It occurs because of the poor shielding of the nucleus by the inner ‘d’ -electrons due
to which the outer ‘s’ electrons are more tightly bound to the nucleus and become less able to participate in
bond formation. This effect is espcially seen in group 13 and 14 of the periodic table, in which the heavier
elements in the group tend to form compounds with valency two lower than the expected group valency. For
e.g. the lighter elements in Group IV tend to have a valency of +4 whereas the heavier elements from 2+ ions
that are more stable than 4+ ions. For example, PbO is much more stable than PbO2 which decomposes
readily to PbO.

Magnetic Properties
Each element has some kind of magnetics properties associated with it. These magnetics properties are direct
consequence of the electronic configuration of the atom. An electron in an atom has two kind of motions. One
is its motion about the nucleus and the other is its spin about its own axis. A single electron spinning about its
own axis generates a magnetic field. For two electrons in an orbital the spins are opposite and hence the fields
cancel each other. Thus on the basis of magnetic properties substances can be classified broadly into three
categaries (i) Paramagnetic (ii) Diamagnetic (iii) Ferromagnetic.
(i) Paramagnetism: Some substances has one or more unpaired electrons in their atoms. These
substances are called as paramagnetic substances. There substance are weekly attracted by magnetics
field. Cu2+, Fe3+, Cr3+ and O2 are some examples of these kind of substances.
(ii) Diamagnetism: Some substances have all the electrons paired in their atoms. There substances are
called as diamagnetic substances. Thus substances are weekly repelled by magnetic field. NaCl and
H2O are some examples of diamagnetic substances.
(iii) Ferromagnetism: Beside paragnetic and diamagnetic substances there are some kind of substances
which are strongly attracted by magnetic field. These substances are called Ferromagnetic substances.
Ferromagnetism is much stronger than paramagnetism and diamagnetism. Ferromagnetic substances
keep their magnetism even after the field is removed while paramagnetic and diamagnetic substances
fail to do so. Iron, cabalt and Nickel are some examples of these kind of substances.
Some Additional Information

All the elements with Z = 101 – 112 and Z = 114 have recently been identified. Although names and symbols
to many of these elements have been assigned but these are still not universally accepted. Also some of these
elements have been assigned two names/symbols. For example, element with Z = 104 is called either
Kuruchatovium (Ku) or Rutherfordium (Rf) while element with Z = 107 is called Neilsbohrium (Ns) or simply
Bohrium (Bh). To overcome all these difficulties, IUPAC approved the official names for elements with
Z = 104 to Z = 109 and suggested a systematic nomenclature for naming other elements with Z > 100 (also
collectively called as super heavy elements) till their names are officially announced.
The main points of this nomenclature are :
(i) The names are derived directive from the atomic numbers using numerical roots for 0 and numbers from 1 – 9
and adding the suffix ium. A strange mixture of Latin Greek roots has been chosen to ensure that the symbols
are all different. The roots for the numbers 0 – 9 are :
Roots for IUPAC Nomenclature of Elements
Digit 0 1 2 3 4 5 6 7 8 9
Root nil un bi tri quad pent hex sept oct enn
Abbreviation n u b t q p h s o e

(ii) In certain cases, the names are shortened. For example, bi ium and tri ium are shortened to bium and trium
and enn nil is shortened to ennil.
(iii) The symbol of the element is then obtained from the first letters of the roots of numbers which make up the
atomic number of the element. The recommended and official names of some super heavy element are given in
Table.
IUPAC Nomenclature of elements with Atomic Number above 100
Atomic Name Symbol Atomic Symbol

Name
Number Number
101 Un-nil-unnium Unu 110 Un-un-nillium Uun
102 Un-nil-bium Unb 111 Un-un-unnium Uuu
103 Un-nil-trium Unt 112 Un-un-bium Unb
104 Un-nil-quadium Unq 113 Un-un-trium Unt
105 Un-nil-pentium Unp 114 Un-un-quadium Uuq
106 Un-nil-hexium Unh 115 Un-un-pentium Uup
107 Un-nil-septium Uns 116 Un-un-hexium Uuh
108 Un-nil-octium Uno 117 Un-un-septium Uus
109 Un-nil-ennium Une 118 Un-un-octium Uuo

Illustration - 1 The formation of F - (g) from F(g) is exothermic whereas that of O2- (g) from O(g) is
endothermic. Explain.
SOLUTION :
The addition of an electron to a neutral atom is Thus, the addition of an electron to O- requires energy
an exothermic process. to overcome the force of repulsion.
F  e  F  energy O  e   energy  O 2 . . . . (ii)
O  e   O   energy . . . . (i)
The energy absorbed in (ii) step is more than the
The addition of second electron to a
energy in the step(i). Hence, the formation of O2- from
monovalent anion O-, as to make it O2- is
O is endothermic in nature.
difficult because both have the same charge
and experience a lot of repulsion.
Illustration - 2 (a) Why chlorine has higher negative electron gain enthalpy than F ?
(b) Why N has higher 1st ionization enthalpy than O-atom ?
(c) Why Mg has higher 1st ionization enthalpy than Al-atom ?
SOLUTION :
(a) The size of fluorine atom is small and thus (c) The electronic configurations of Mg and Al are
electron density is high. This resists the as follows:
addition of electron, hence electron gain
Mg : 1s 2 , 2s 2 2 p6 ,3s 2
enthalpy of fluorine is less.
Al : 1s 2 , 2s 2 2 p6 ,3s 2 3 p1
(b) The electronic configurations of nitrogen and
oxygen are follows: It is difficult to remove an electron from 3s in
comparison to 3p (3s paired and 3p singly
N : 1s 2 , 2s 2 2 p1x 2 p1y 2 p1z
occupied).
O : 1s 2 , 2s 2 2 px2 2 p1y 2 p1z Hence, IE of Mg is higher than Al.
In, N p-orbitals are half and hence, its structure
is stable. It requires more energy to remove an
electron. Hence, the IE of nitrogen is higher
than oxygen atom which has less stable
structure.

Illustration - 3 Arrange the following in order of increasing radii :

(i) I, I+, I- (ii) C, N, Si, P (iii) O2-, F-, Ne, Mg2+ (iv) Fe, Fe2+, Fe3+
SOLUTION :
(i) I+ < I < I-
53 53 53
z/e values are , , respectively..
52 53 54
Since z/e decreases, hence size increases.
(ii) N<C<P<Si (a) Effective nuclear charge in nitrogen is higher than in carbon, hence N<C.
(b) Effective nuclear charge I phosphorus is higher than in silicon, hence P<Si.
(c) C and Si both belong to same group.
C 1s2, 2s2 2p2 (Two orbits)
Si 1s2, 2s2 2p6, 3s23p2 (Three orbits) C<Si
(iii) Mg2+<Ne<F-<O2- (iv) Fe3+<Fe2+<Fe

12 10 9 8 26 26 26
z/e values are , , , respectively.. z/e values are , , respectively..
10 10 10 10 23 24 26
Since z/e decreases, hence size increases. Since z/e decreases, hence size increases.
Illustration - 4 Give the formula of a species that will be isoelectronic with the following atoms or ions :
(i) Ar (ii) F- (iii) K+ (iv) Sr2+
SOLUTION :
(i) Ar has 18 electrons. Therefore, the species P3-, S2-, Cl-, K+, Ca2+, etc., are isoelectronic to Ar.
(ii) F- has 10 electrons. Therefore, the species N3-, O2-, Ne, Na+, Mg2+, etc., are isoelectronic to F-.
(iii) K+ has 18 electrons. Therefore, the species P3-, S2-, Cl-, Ar, Ca2+, etc., are isoelectronic to K+.
(iv) Sr2+ has 36 electrons. Therefore, the species Br-, Kr, Rb+, etc., are isoelectronic to Sr2+.
Illustration - 5 The ionization enthalpy of lithium is 520 kJ mol-1. Calculate the amount of energy
required to covert 140 mg of lithium atoms in gaseous state into Li+ ion.
SOLUTION :
Mass of lithium  140 mg  140  103 g  14  102 g
14  102
No. of moles of lithium   2  102 mole
7
Energy required to convert 2  102 mole atoms of lithium into Li+ ions = 520  2  102  10.4 kJ

Illustration - 6 The first and second ionization enthalpies (kJ mol- ) of three elements I, II and are given
below.
I II III
i H1 403 549 1142
i H 2 2640 1060 2080
Identify the element which is likely to be :

(a) non-metal (b) an alkali metal (c) an alkaline earth metal.
SOLUTIONS :
(a) Element (III) is a non-metal because its i H1 is highest among the three.
(b) Element (I) is an alkali metal as its first ionization enthalpy is lowest and second ionization enthalpy
is very high.
(c) Element (II) is an alkaline earth metal because its first ionisation enthalpy is near to enthalpy of
element (I) and second ionisation enthalpy is not very high.
NOW ATTEMPT IN-CHAPTER EXERCISE
THEN ATTEMPT OBJECTIVE WORKSHEET TO COMPLETE THIS EBOOK

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes States of Matter
States of Matter
Gases, Liquids and Solids
ANALYSIS OF IDEAL GASES Section - 1

In this section, we are going to study laws governing the behavior of gases. Gases don’t have definite shape
and volume. They tend to fill all the space available to them and take on the shape and volume of the
container. In gases, the molecules are relatively far apart and thus influence each other to a lesser extent
(than they do so in solids and liquids).
Three fundamental measurements that we can perform on any sample of a gas are :
Volume, Pressure and Temperature
Volume :
The volume of any sample of a gas is considered to be the space of the container that it occupies (the space
occupied by the molecules of gas is negligible as compared to the volume of container). The volume is
expressed in liters (or ml) or m3 (or cm3).
1 L  103 ml  103 m3  1 dm3  103 cc
Pressure :
The molecules of gases are in continuous random motion. They frequently collide with each other and with
the walls of the container. The collisions of the molecules with the walls of the container give rise to what is
called as the Pressure. It is measured as force per unit area and is uniform in all the directions. It is measured
by instruments: Manometer and Barometer (for atmospheric pressure). It is expressed in N/m2 or mm of
Hg or atmospheres (atm) or torr.
1 atm  1.013  105 N / m 2  1.013  105 Pa 1Pa  1N / m2 

1 bar = 105 N/m2
1 atm = 760 mm of Hg column = 76 cm of Hg column = 760 torr = 1.013 bar
Temperature :
The temperature can be discussed in terms of hotness or coldness. The measurement is based on the
expansion of certain material (most often it is mercury) with increasing temperature.
One of the scale to measure the temperature is taken as Celsius (C) scale. The freezing point of water is
taken as 0 C and its boiling point as 100 C.
It was observed by Gay Lussac that the rise in volume of a given mass of gas for each degree rise in
temperature is nearly equal to 1/273 time of the volume of gas at 0 C. If Vo is the volume of gas at 0 C and
VT is the volume of gas at T C, then :
 T 
VT  V  1  
 273 

States of Matter Vidyamandir Classes
Thus, VT = 0 if T =  273 C i.e., the volume of a given mass of a gas is zero at constant pressure or we can
say that the gas would completely disappear if T =  273 C.
So T = 273 C (or more precisely 273.15 C) is the lowest possible temperature that can be achieved
(since below  273 C, the volume will be negative, which is impossible). This temperature  273.15 C
is called as absolute zero. Now a new scale called as absolute scale or Kelvin scale is defined where
273 C = 0 K (Kelvin).
Note : 0 K = 273 C or 273 K = 0 C or 373 K = 100 C
 9 
Also, T ( F)  32   T ( C) [F Fahrenheit]
5
Standard Temperature and Pressure conditions (S.T.P.) :
For gases, the S.T.P. conditions are 273 K (0 C) and 1 atm pressure. A gas at this temperature is said
to be at S.T.P. (or N.T.P.  Normal Temperature and Pressure) conditions.
Definition of Ideal Gas :

A gas is said to be an ideal gas if it has the following properties :
(a) There is no intermolecular forces between the gas molecules, i.e., gas molecules don’t exert any kind
of force on each other.
(b) Size of the gas molecules is negligible as compared to the volume occupied by the gas (i.e., container
volume).
Note : The concept of Ideal gas is theoretical and no gas exists which satisfy the above requirements at all the
conditions. Thus, all the gases are Real gases but they may behave as ideal under certain conditions of
Pressure, Volume and Temperature.
Gas Laws (For Ideal gases only) :

Boyle’s Law :
At a constant temperature (T), the pressure (P) of a given mass
(or moles (n)) of any gas varies inversely with the volume (V).
1
Mathematically : P  (for given n and T)
V
 PV = constant
If P1 is the pressure when volume is V1 and P2 is the pressure when volume is V2 (T is same), then :
P1 V1 = P2 V2
Graphically, it can be represented as shown in the figure. Each line is called as Isotherm.
Note : In the P-V curve, as we move away from origin, each isotherm represents a higher temperature.

Boyle’s law can also be represented using following graphs :
Charles Law :
At a constant pressure, the volume of a given mass of any gas varies
directly with the absolute temperature.
Mathematically : V  T (for a given n and P)
V
 = constant
T
If V1 and V2 are volumes of a gas at temperature T1 and T2 respectively and the pressure is kept constant,
then :
V1 V2
 
T1 T2
Graphically it is expressed as shown in the figure.

Each line is called as Isobar.
Note : In the V-T curve, an isobar with lesser slope will have a higher pressure.
The Combined Gas Law :

For any sample of an ideal gas, the pressure times the volume divided by the absolute temperature is a
constant.
PV
Mathematically : = constant
T
If at one condition, for a given mass of a gas P1, V1 and T1 are pressure, volume and temperature
respectively and at some other condition P2, V2 and T2 are new pressure, volume and temperature
respectively then :
P1V1 P2V2

T1 T2

Gay Lussac’s Law :

The pressure of a given mass of any gas is directly proportional to
the absolute temperature at constant volume.
Mathematically : P  T (for constant n and V)
P
 = constant
T
If P1 and P2 are volumes of a gas at temperature T1 and T2 respectively
and the volume is kept constant, then :
P1 P2
 
T1 T2
Graphically it is expressed as follows. Each line is called as Isochor.
Note that slope is greater for lower volume.
Note : In the P-T curve, an isochor with lesser slope will have a higher volume.
Gay Lussac’s Law of Combining Volumes :

When measured at same temperature and pressure, the ratios of volumes of the gases that were reactants
and of gases that were products (in a chemical reaction), were always small whole numbers.
Illustration :
(a) 2 H2 (g) + O2 (g)  2 H2O (g)
2 volumes 1 volume 2 volumes (ratio = 2 : 1 : 2)
(b) N2 (g) + O2 (g)  2 NO (g)
1 volume 1 volume 2 volumes (ratio = 1 : 1 : 2)
(c) CH4 (g) + 2 O2 (g)  CO2 (g) + 2 H2O (g)
1 volume 2 volume 1 volume 2 volume (ratio = 1 : 2 : 1 : 2)
Avogadro’s Law :
It states that equal volume of all gases at same pressure and temperature contain equal number of molecules.
We know that 1 mole contains 6.023 × 1023 molecules (a number called as Avogadro Number). It is
obvious that if two gases contain equal number of molecules, they must also contain the same number of
moles. So, at given temperature and pressure, the volume of any gas is also proportional to the number of
moles.
 V  n (at given T and P) This is also a form of Avogadro’s Law.

At any given temperature and pressure, there must be some volume that will contain 6.023 × 1023 molecules
or 1 mole of a gas. At S.T.P. (0C and 1 atm), this volume is 22.4 L or 22400 mL. This is known as Molar
volume.
Avogadro’s Law can be used in determination of molecular masses of gases. As 1 mole of any gas at S.T.P.
occupies 22.4 L, we can calculate the molecular weight of a gas as follows :
If Mo be the molecular weight of a gas A weighing gA grams and occupying V L of volume at S.T.P., then :
g A  22.4
M 
VL  at S.T.P.
Also, Mo = (density in g/L)  22.4
The Ideal Gas Equation :

PV
We know that = constant = K
T
The constant K depends upon the amount of gas. Now at constant P and T, V depends upon number of
moles of gas (Avogadro Law). This implies that K is directly proportional to the number of moles (n).
 K n  K = nR R : a constant independent of amount of gas.
PV
  K  nR  PV = nRT
T
This is called as ideal gas equation. R is same for all gases and is known as universal gas constant.
Values of R :
PV
Note : R 
nT
L atm
(i) R = 0.0821 mol.K (use this value when P is in atm. and V is in L)
J
(ii) R = 8.31 (use this value when P is in N/m2 and V is in m3) [This is the S.I. unit of R]
mol.K
cal
(iii) R = 2 (4.184 J = 1 cal)
mol.K
Different forms of Ideal Gas Equation :

(i) PV=nRT
g
(ii) PV  RT
M
(iii) PM0 = d R T (density d = g/V)


When 3.2 gm of sulphur is vapourised at 450 C and 723 mm pressure, the vapour occupies a volume
of 780 cm3, what is the formula for the sulphur under these conditions ?
The molecular weight of a poly-atomic element = number of atoms × atomic mass
So let us find the molecular weight of S from the data given.
gRT 3.2  0.0821 723
M  
PV  723 / 760    780 /1000  = 256
256
 Number of atoms = =8
32
Hence, molecular formula of sulphur = S8
Vapour Density :
It is defined as the ratio of the mass of the gas (X) occupying a certain volume at a certain temperature and
pressure to the mass of hydrogen occupying the same volume at the same temperature and pressure.
g PVM 
Now, PV = nRT = M  RT  g X  RT

PV  2
and g H 2 
RT
  M   2 for H 2 gas 
gX MX
 g   vapour density
H2 2
Thus, it can be seen that vapour density of a gas does not depend on pressure or temperature or volume.
Dalton’s Law of Partial Pressures :

Total pressure of a mixture of number of non-reacting gases is equal to the sum of pressures exerted by
individual gases.
PTotal = p1 + p2 + p3 + p4 +..............
where PTotal : Total pressure of the mixture and p1, p2, p3, p4,... are the partial pressures exerted by individual
gases in the mixture.
Assumption : All the gases spread uniformly to occupy the volume of the vessel.
The partial pressure is defined as the pressure a gas would exert if it were alone in the container at the same
temperature of the mixture.
Let p1, p2 be the partial pressures of gases 1 and 2 present in the mixture and n1 and n2 be their respective
moles. Let V be the volume of the container and T be the temperature at which the gases are mixed.

RT RT
Then, using Gas Equation, we have : P1  n1 . . . (i) and P2  n 2 . . . (ii)
V V
Using Dalton’s Law :
PTotal = P1 + P2
RT RT
 PTotal  n1  n2
V V
RT
or PTotal   n1  n 2  . . . (iii)
V
From (i), (ii) and (iii), it can be seen that :
n1 n2
P1  PTotal and P2  PTotal
n1  n 2 n1  n 2
or P1  1 PTotal and P2   2 PTotal
where 1 and  2 are the mole fractions of gases 1 and 2 respectively..

So in general, Partial pressure of a gas = Its mole fraction ×Total pressure exerted by the mixture
in a mixture in the mixture
Its partial pressure

Also, % of a gas in the mixture (by moles) =  100  (mole fraction of that gas)100
Total pressure
A 2.5L flask contains 0.25 mol each of SO2 and CO2 gas at 27C. Calculate the partial pressure
exerted by each gas and total pressure .
RT
Now, Partial pressure of SO2 = nSO 2 V
vessel
RT 0.25  0.0821  300
= 0.25 V   2.46 atm
vessel 2.5
RT
and Partial pressure of CO2 = n CO2 V
vessel
RT 0.25  0.0821  300

= 0.25 V   2.46 atm
vessel 2.5
 PTotal = 2.46 + 2.46 = 4.92 atm

Application of Dalton’s Law of Partial Pressure

Many gases in the laboratory are collected by the downward displacement of water. The gas collected in this
way also contains molecules of water that have been evaporated into the gas. The pressure exerted by these
molecules depends on the temperature of water. The partial pressure of water in the gas mixture collected is
called the aqueous tension and is equal to the vapour pressure of water at that temperature.
 Pressure of the dry gas obtained  Pdry gas = Pobserved  Aqueous tension
Note : Pressure of air decreases with the increase in altitude (height from the sea level).

6.52 gm of a sample of oxygen is collected over water at a total pressure of 735.5 torr measured
5.45L at a temperature of 27 C. Find the vapour pressure of water vapours.
Using gas equation, calculate the pressure of the gas and then subtract it from the pressure of the gas
measured (observed).
gRT 6.52  0.0821 300
P  = 0.92 atm. = 699.8 mm of Hg [ 1atm. 760 mm of Hg]
M0V 32  5.45
Now this is pressure of dry gas, hence
Vapour pressure of water = 735.5  699.8 = 35.7 mm of Hg

Assume that the air is essentially a mixture of nitrogen and oxygen in mole ratio of 4 : 1 by volume.
Calculate the partial pressures of N2 and O2 on a day when the atmospheric pressure is 750 mm of Hg.
Neglect the pressure of other gases.
From Dalton’s Law of partial pressure, we have :
Partial pressure of nitrogen = p N 2   N 2  P and Partial pressure of oxygen = pO2  O2  P
Now,  N 2  4 / 5 , and O 2  1/ 5 ; P = 750 mm of Hg

4
 p N2   750  600 mm of Hg
5
1
and pO2   750  150 mm of Hg
5


One of the best rocket fuels is dimethyl hydrazine (an organic compound with molecular formula :
(CH3)2N2H2 ). When mixed with dinitrogen tetroxide, N2O4, it reacts according to the equation :
 CH 3 2 N 2 H 2 (l ) + 2N 2O 4 (l ) 
 3N 2 (g) + 4H 2O (l ) + 2CO 2 (g)
If 2.5 mol of dimethyl hydrazine reacts completely with N2O4 and if the product gases are collected at
20C in a 250 L vessel, what is the pressure in the vessel?
From stiochiometry of above reaction : 1 mol (CH3)2N2H2 3 mol N2  4 mol H2O  2 mol CO2
Moles of N2 formed = 3  2.5 = 7.5
Moles H2O formed = 4  2.5 = 10 [H2O will not exert any pressure at 20C as it will become a liquid]
Moles CO2 formed = 2  2.5 = 5
n TotalRT  7.5  5.0   0.0821  293
 PTotal =   1.20 atm
V 250
When 2 gm of a gaseous substance A is introduced into an initially evacuated flask at 25 C, the
pressure is found to be 1 atm. 3 gm of another gaseous substance B is then added to it at the same
temperature and pressure. The final pressure is found to be 1.5 atm. Assuming ideal gas behaviour,
calculate the ratio of the molecular weights of A and B.
Let MA and MB be the molecular weights of A and B.
Using PV = nRT for A, we get :
2
RT
MA . . . . . . (i)
1
V
 2 3 
 n A + n B  RT  +  RT
and using Dalton’s Law : PTotal = M
 1.5 =  A M B . . . . . . (ii)
V
V
MA 1
Solving (i) and (ii), we get : M  3
B
Graham’s Law of Diffusion :

A gas expands to fill the entire container even if other gas(es) is (are) already present in the container.
This process of spreading of gas is called as diffusion. A gas confined to a container at high pressure
than the surrounding atmosphere will escape from a small hole which is opened in the container until the
pressure outside and inside have been equalized. This process is called as effusion.
Example of effusion: Escaping of air through a punctured tyre.
Note : The process of effusion is always followed by the process of diffusion.

According to Graham’s Law :

When compared at the same temperature and pressure, the rates of diffusion (or effusion) of any two gases
are inversely proportional to the square roots of their densities.
1
rate 
density
Note : This is why lighter gases diffuse faster than the denser gases.
It t1, t2 are the time required for the passage of the same volume, Vm , of two gases with densities d1 and d2
respectively at the same temperature and pressure, through the same orifice, then:
Volume effused Vm
Rate of effusion (r) = 
Time taken t
Vm Vm
 r1  t and r2  t
1 2
r1 Vm / t1 d2 M2 t2 d2 M2
By Graham’s Law : r  V / t  d  M   
2 m 2 1 1 t1 d1 M1
(Densities of gases at given temperature and pressure are proportional to molecular weights)
It has been found that the rate of diffusion (r) is also proportional to the pressure of a gas (or number of
molecules) at a given temperature. In that case, the rate of diffusion is given as :
P
r
d
If two gases 1 and 2 at different pressures P1 and P2 respectively are allowed to effuse through a small hole
in a container, then the ratio of rates of diffusion of two gases is given by:
r1 P1 d 2 P1 M2
 
r2 P2 d1 P2 M1
Note : Rate of effusion (r) can be defined in the following ways (depending on the analysis of a problem):
Volume effused distance travelled in a tube

(i) r=  (if the cross sectional area is uniform).
time taken time taken
moles effused  n
(ii) r=
time taken =  t
Drop in Pressure due to effusion  P
(iii) r= = t
time taken


As shown in the figure, NH3(g) and HCl (g) are
introduced in a cylindrical container of uniform
crossection. At what distance from NH3 inlet,will
NH4Cl form ?
Using Graham’s law :
rNH3 x/t M HCl 36.5
    1.46
rHCl    x  / t M NH3 17
 M HCl M NH3 
 x   0.59 
1  M HCl M NH 
 3 
Ammonia will diffuse faster than hydrogen chloride gas.
Application of Graham’s Law of diffusion :

 Separation of isotopes and other gaseous mixture is based on this law.
 It provides a method for the determination of molar mass.
Effective molecular weight of the mixture effusing out through a hole:

Let a container A contains 3 moles of He and 2 moles of N2 at some temperature and pressure. Suppose the
container has a hole through which this gaseous mixture is effusing out.
Let us first calculate the effective molecular mass of the mixture present initially in the container.
From the very definition of molecular mass, we have :
Molecular mass is the mass of an element or compound contained in 1 mole of that element or compound.
Now, total mass of 3 moles He and 2 moles N2 (i.e., mass of the gas mixture)
 3  4 + 2  28 = 68 gm.
And the total moles of gas mixture = 3 + 2 = 5
68
Thus, molecular mass of the mixture  M mix   13.6 gm/mole
5
We can generalize the above result as :
n
 M mix   i M i
i  1
where i is the mole fraction of the ith gas in the mixture and Mi is the molar mass of the ith gas in that mixture.

Now, to find the Mmix of the gas mixture effusing out, we have to determine the relative rates of effusion of the
mixture components.
rHe P M N2 n He M N2
  He 
rN 2 PN 2 M He n N2 M He
rHe 3 28
   3.97
rN 2 2 4
 moles He 
   3.97
 In the mixture effusing out :
 moles N 2 at t  0
moles N 2
 Mole fraction of N2 effusing out at t = 0 = moles N  moles He
2
1 1
   0.2
1  3.97 4.97
  N2  0.2 and He  1   N 2  0.8
 M mix  He M He   N 2 M N 2 = 0.8  4  0.2  28  8.8 gm / mole
Illustration - 1 At 30°C and 720 mm of Hg, the density of a gas is 1.5 g/L.Calculate molecular mass of the
gas. Also find the number of molecules in 1 cc of the gas at the same temperature.
SOLUTION :
Assuming ideal behavior and applying ideal gas Now number of molecules = n  NA
equation :
PV 720 / 760  1  103
PV = nRT =  N A   6.023  1023
RT 0.0821  303
Another form of gas equation is PMo = dRT
= 2.29  1019
dRT 1.5  0.0821  303
 M  
P 720 / 760
(T = 30 + 273 K)
 Mo = 39.38 gm/mol
Illustration - 2 The pressure exerted by 12 gm of an ideal gas at temperature T in Kelvin in a vessel of

volume V litre is one atm. When the temperature is increased by 10 K at the same volume, the pressure rises
by 10%. Calculate the temperature T and volume V. (Molecular mass of the gas = 120 gm/mole)

SOLUTION :
Using Gas equation : PV = nRT Putting the value of T in (i), we get :
We have,  1  V = 0.1  0.0821  100
1  V  0.1  R  T . . . . . . . (i) V = 0.821 L
and 1.1  V  0.1  R  (T  10) . . . . . . . (ii)

T 1
Using (i) and (ii), we have : 
T  10 1.1
 T = 100 K
Illustration - 3 An open vessel at 27C is heated until three fifth of the air has been expelled. Assuming
that the volume of the vessel remains constant, find the temperature to which the vessel has been heated.
SOLUTION :
In the given question, volume is constant. Also, as the Now let n1 = initial moles and n2 = final moles
vessel is open to atmosphere, the pressure is constant.  n2 = 2/5 × n1
This means that the gas equation is simply reduced to the
(as 3/5 th of the air has been expelled)
following form:
n1T1 nT 5
 T2   1 1  T1
nT = constant (Use PV = nRT) n2 2 / 5n1 2
or n1 T1 = n2 T2 5
 T2   300  = 750 K = 477 C
2
Illustration - 4 A spherical balloon of 21 cm diameter is to be filled with H2 at NTP from a cylinder con-
taining the gas at 20 atm at 27C. If the cylinder can hold 2.80L of water, calculate the number of balloons
that can be filled up using pumping.
SOLUTION :
(Note: the balloons are being filled at NTP)
The capacity of cylinder = 2.80 L
3
Let n = moles of hydrogen contained in cylinder and no = 4 / 3πr 3 4 / 3× 3.14× 10.5 
no = = = 0.216
moles of hydrogen required to fill one balloon. 22400 22400
PV 20  2.80  Number of balloons that can be filled
n  = 2.273
RT 0.0821 300
n
volume of balloon =  10.50  10
n  n
22400

Illustration - 5 A 672 mL of a mixture of oxygen-ozone at N.T.P. were found to be weigh 1 gm. Calculate
the volume of ozone in the mixture.
SOLUTION :
672  V
Let V mL of ozone are there in the mixture Mass of oxygen at N.T.P. =  32
22400
 volume of oxygen = (672  V) mL
V 672  V
V   48   32  1
Mass of ozone at N.T.P. =  48 22400 22400
22400
 On solving we get : V = 56 ml
Illustration - 6 Two flasks of equal volume connected by a narrow tube (of negligible volume) are at 27C
and contain 0.70 mole of H2 at 0.5 atm pressure. One of the flask is then immersed into a bath kept at 127C,
while the other remains at 27C. Calculate the final pressure and the number of moles of H2 in each flask.
SOLUTION :
Moles of H2 initially = 0.7 = 2no . . . . . (i) and P1Vo = n2RTo (Finally)
 n1 + n2 = 2no . . . . . (ii)
Flask A : PoVo = no RTo (Initially)
P1Vo = n1RT1 (Finally) P n 
  . . . . .(iv)
P1 n2
Solve to get :
P n  T n1 = 0.3 ; n2 = 0.4
   . . . . (iii) Using (iv),
P1 n1 T1
P n 0.4
Flask B : PoVo = noRTo (Initially) P1   2  0.5  atm  0.56 atm
n 0.35
Illustration - 7 1 gm of an alloy of Al and Mg reacts with excess HCl to form AlCl3, MgCl2 and H2. The
evolved H2 collected over mercury at 27C occupied 1200 mL at 684 mm Hg. What is the composition of
alloy?
SOLUTION :
 Mass of Mg will be (1  x) gm
3
Al  3HCl   AlCl3  H 2 . . . . . (i) From stoichiometry of reactions (i) & (ii) ;
2
684
 1.2 Moles H 2 
3

x

1  x   1  0.044
PV 
Also, Moles of H 2   760  0.044 2 27 24
RT 0.0821  300  0.0555 x + 0.0416 + (1  x) = 0.044
 MgCl2  H2 . . . . . (ii)
Mg  2HCl   0.0139x = 2.4  10–3  x = 0.172 gm
Let mass of Al be x gm Thus, % Al = 17.2 % and % Mg = 82.8 %

EUDIOMETRY Section - 2
Application of Gay Lussac’s Law of combining Volumes

It is a method used to analyze the gaseous mixtures of hydrocarbons and to determine their molecular
formulae.
Here, the combustible gases (i.e., hydrocarbons) are exploded in a tube with the excess of O2 so that C and
H in the gas are converted to CO2(g) and H2O(g) respectively. After cooling and contraction, the volume of
contents of the tube are measured (this does not include H2O as it condenses). At this stage, the contents
include CO2 (g), unused O2 (if any left) and N2 (if any in the air).
Now NaOH is used to separate out CO2 (2 NaOH + CO2   Na2CO3 + H2O). As a result a further
contraction in volume takes place. After this, the unused O2 is left which is generally absorbed by the pyro-
gallol solution. In general after cooling, the contraction in volume is given as :
V = VR  VP (VR: volume of reactants, VP: volume of products after cooling)
Note : NaOH also absorbs Cl2, apart from CO2
From the measurements made, and applying Gay Lussac’s Law of combining volumes, we can calculate molecular
formulae and compositions of gaseous mixtures. Please read the given Illustrations on the next page carefully to
understand the application of law.
Illustration - 8 8.4 mL of a gaseous hydrocarbon (A) was burnt with 50 ml of O2 in an eudiometer tube.
The volume of the products after cooling to room temperature was 37.4 mL, when reacted with NaOH, the
volume contracted to 3.8 ml. What is the molecular formula of A?
SOLUTION :
Let CxHy (g) be the hydrocarbon. Contraction in volume
= VR  VP = (8.4 + 50)  (37.4) = 21 ml
 y y
Cx H y(g)   x   O 2(g) 
 x CO2(g)  H 2O(g) From equation, we have, the contraction
 4 2
= 1 + (x + y/4)  (x + 0)
[Remember this balanced combustion equation
for CxHy] (Note: Vol. of water is not taken as it has condensed)
From Gay Lussac’s Law of combining volume, we get :  Contraction = 1 + y/4
 y  For 8.4 mL of CxHy, the contraction
1 vol. of CxHy =  x   vol. of O 2
 4 = 8.4 (1 + y/4)
 x vol. of CO 2  y / 2 vol. of H 2O  8.4 (1 + y/4) = 21  y=6

After treating with NaOH, there is a contraction of Another method to calculate y:

(37.4  3.8) = 33.6 mL, which is equal to the volume After NaOH treatment, the volume is reduced to 3.8 ml,
of CO2 produced. this corresponds to the volume of O2 unused.
Volume of CO2 produced by 8.4 ml of hydrocarbon Volume of O2 unused = 50  8.4 (x + y/4) = 3.8
= 8.4 x Solve to get : y=6
 8.4 x = 33.6  x=4 Hence hydrocarbon is C4H6.
Illustration - 9 15 ml of gaseous hydrocarbon required for complete combustion 357 ml of air (21 % of O
2
by volume) and the gaseous products occupied 327 ml (all volumes being measured at S.T.P.). What is the
formula of hydrocarbon ?
SOLUTION :
Let CxHy (g) be the hydrocarbon. The gaseous products after contraction = 327 ml
This includes volume of CO2 plus volume of N2 in the
 y y
C x H y(g)   x   O 2(g) 
 x CO2(g)  H 2O (g) air (O2 is completely used up). So let us calculate the
 4 2 volume of N2 in the air.
From Gay Lussac’s Law of combining volume, we get :
Vol. of O2 = 0.21 × 357 = 75 ml
1 vol. of Cx Hy
 Vol. of N2 = 357  75 = 282 ml
 y
  x   vol. of O2  x vol. of CO2 Now, Vol. of N2 + Vol. of CO2 = 327 ml
 4
 Vol. of CO2 = 327  282 = 45ml
y
 vol. of H2O The volume of CO2 produced = 15 x
2
From equation, we have, the contraction  15x = 45  x=3
= 1 + (x + y/4)  (x + 0) = 1 + y/4 Hence the hydrocarbon is C3H8
 For 15 mL gas, contraction = 15(1 + y/4)
Also contraction = VR  VP= (15 + 357)  (327) = 45
 y=8
Illustration - 10 60 ml of a mixture of equal volumes of Cl2 and an oxide of chlorine were heated and then
cooled back to the original temperature. The resulting gas mixture was found to have a volume of 75 ml. On
treatment with caustic soda, the volume was contracted to 15 ml. Assuming that all measurements were
made at the same temperature and pressure, deduce the simplest formula of the oxide of Cl 2. (The oxide of
chlorine on heating decomposes quantitative to O2 and Cl2).

SOLUTION :
Let ClxOy be the oxide. NaOH apart from CO2 also absorbs Cl2. So after NaOH
ClxOy 
 x/2 Cl2 + y/2 O2 treatment, the residual volume corresponds to the volume
of O2 = 15 ml
1 vol. x/2 vol. y/2 vol.
 Vol. of Cl2 = 45  15 = 30 ml
 Volume of ClxOy = volume of Cl2 = 30 ml
Now from equation :
After cooling volume = 75 ml
Vol. of Cl2 = 30 (x/2) = 30  x=2
This corresponds to vol. of Cl2 initially plus vol. of Cl2
produced and O2 produced. Vol. of O2 = 30 (y/2) = 15  y=1
 V(Cl2) + V(Cl2 produced) + V(O2) = 75 Hence formula of chloride is Cl2O
 V(Cl2 produced) + V(O2) = 75  30 = 45 ml
(vol. of Cl2 initially = 30 ml)
Illustration - 11 20 ml of a mixture of ethane (C H ), ethylene (C H ) and CO are heated with O . After the
2 6 2 4 2 2
explosion there was a contraction of 28 ml and after treatment with KOH there was a further contraction of
32 ml. What is the composition of the mixture ?
SOLUTION :
Let volume of ethane = a ml  VR = (a + 7/2 a) + (b + 3b) + (20  a  b)
and volume of ethylene = b ml and VP = (2a + 2b) + (20  a  b)
 Volume of CO2 = (20  a  b) mL
 VR  VP = 5/2 a + 2b = 28
Now contraction after cooling = 28
 VR  VP = 28 5a
 + 2b = 28 or 5a + 4b = 56 . . . . . . (i)
2
VR = volume of ethane + volume of ethylene + volume of
Also there is a further contraction of 32 mL on treatment
CO2 + volume of O2 used for combustion
with KOH.
VP = volume of CO2 produced (volume of H2O is not
 Volume of CO2 produced + Vol. of CO2 origi-
taken as it condenses)
Considering combustion of gases : nal = 32
 (2a + 2b) + (20  a  b) = 32
1. C2H6 + 7/2 O2   2 CO2 + 3 H2O
a vol. (7/2)a vol. 2a vol.  a + b = 12 . . . . . . (ii)
On solving (i) and (ii), we get :
2. C2H4 + 3 O2   2 CO2 + 2 H2O
a=8  Vol. of ethane = 8 ml
b vol. 3b vol. 2b vol.
b=4  Vol. of ethylene = 4 ml
3. CO2   CO2 (no reaction)
 Volume of CO2 = 8 ml
(20  a  b) volume

Illustration - 12 9 volumes of gaseous mixture consisting of gaseous organic compound A and just
sufficient amount of O2 required for complete combustion yielded on burning 4 volumes of CO2, 6 volumes of
water vapour and 2 volumes of N2 all volumes measured at the same temperature and pressure. If the
compound A contained only C, H and N,
(a) How many volumes of O2 required for complete combustion ?
(b) What is the molecular formula of the compound A ?
SOLUTION :
Let the molecular formula of A be C x H y N z y
Volume of H2O = a  6
 y y z 2
C x H y N z   x   O2   xCO 2  H 2O  N 2
 4 2 2 1
 y So, 4  12  9a
1vol C x H y N z   x   vol of O 2  x vol CO 2 4
 4  7=9–a  a=2
y z z
 vol of H 2O  vol N 2
2 3 Volume of N2 = a   2
2
Let a volumes of Cx Hy Nz were taken.
Thus, x = 2, y = 6, z = 2
 y
Volume of O2 = a  x    9  a  Molecular formula of A  C2H6N2
 4
and O2 used = 9  a = 7 volumes.
 Volume of CO2 = ax = 4
KINETIC MOLECULAR MODEL OF A GAS Section - 3
In the previous sections, we have studied the macroscopic properties of gases and their relationships in the
form of gas laws. Now, we know that for a given amount of gas, volume is directly proportional to the
absolute temperature but gas laws do not provide any reason for this.
To understand the underlying principles, a theory based on a model is proposed. If the theoretical results on
the basis of this particular model agree with the experimental observations, it indicates that the model is
realistic. The theory that provides an explanation for the various experimental observations about a gas is
based on the Kinetic Molecular Model.
Maxwell proposed the postulates for the behavior of gas molecules known as Kinetic Theory of gases.
The postulates of this model are :
 Each gas is made up of a large number of identical and small (tiny) particles known as molecules (i.e.,
the dimensions of these molecules are very-very small as compared to the space between them).
 The volume of a molecule is so small that it may be neglected in comparison to the total volume
occupied by the gas.

 There are practically no attractive forces between the molecules. Thus, the molecules move indepen
dently.
 The molecules are never in stationary state but are believed to be in random motion in a straight line
motion in all possible directions with altogether different but constant velocities. The direction of motion
is changed only when it collides with the walls of container or with other molecules.
 The molecules are perfectly elastic and bear no change in energy during collisions.
 The effect of gravity on molecular motion is negligible.
 The temperature of gas is the measure of its kinetic energy. K.E. of molecules is proportional to
absolute temperature of the gas.
 The pressure of the gas is due to the continuous collision of molecules on the walls of container.
Consider a container of volume V occupied by a gas.
Let m = mass of the gas in the container and N = number of molecules in the container
If mo is the mass of one molecule  m = moN
If No is the Avogadro number and M is the molecular weight of the gas,
 M = moNo
Root mean Square (Crms) speed :
c12  c22  c32  ..........  c 2N

It is defined as : crms  c2 
N
[where bar   represents average  c2 = Average of c2 values]
2
c dN c
 
3k BT 3RT
Since the distribution is continuous, we can write : c2rms  c2  
N m M
Where Mo = Mol. mass of the gas (in Kg)
3RT
 crms 
M
Note : Derivation of the above integrals is not required.

Illustrating the concept:

The escape velocity, the velocity required by an object to escape from the gravitational field of earth,
is given by ce  2gr where r = 6400 km for earth. At what temperature will the crms of an H2
molecule attain escape velocity ? (g = 10 ms2)
ce  2  10  6400  103  11313.7 ms 1
3RT 3  8.314  T
crms   [Note : M H 2  2  103 kg ]
M 2  103
As crms = ce  T = 10263.8 K
Average speed (cavg) :
c  c  c  .....  c N
This is defined as : cavg  c  1 2 3
N
For a continuous distribution, it can be written as : cavg 

 c dNc 
8RT
N M
Note : This is actually “average speed”. Since, the molecule move randomly, average velocity of the gas is
zero.

The average speed of a gas molecule is 400 m/s. Calculate its rms velocity at the same temperature.
3RT 8RT 3
crms  and cavg   crms   400 ms 1  434.24 ms1
M M 8
Most Probable speed (CMP) :
A very small fraction of molecules occupy either very small or very high speeds. The speed occupied by
majority of molecules is known as most probable speed.
2RT
It is given by : c MP 
M


For a gas consisting of only six molecular having speeds as 2 ms 1 , 3ms 1 , 3ms 1, 3ms 1, 4 ms 1, 5ms 1,
find crms, cavg and cMP.
N
 ci
i 1 c  c2  . . .  c N 2  3  3  3  4  5
cavg.  c   1   3.33ms 1
N N 6
N
 ci 2
i 1 c12  c 22  . . .  c N 2 22  32  32  32  42  52
crms  c2     3.46 ms 1
N N 6
c MP  3ms1 (Since maximum numbers of molecules are having a speed of 3 ms–1)
Note :
(i) cMP < cavg. < crms
8
cMP : cavg : c rms : : 2 : : 3

1 : 1.128 : 1.224
Also, cavg = crms  0.9215
(ii) cavg and crms values lie in the vicinities of cMP values.
(iii) The numerical values of cMP , cavg , crms increases with increase in temperature.
(iv) Also, it is important to note that the average translational kinetic energy of a gas molecule is given by :
1 2 1 2
K.E avg  m  crms  m  cavg
2 2
If in a gas, there are N molecules, their total K.E. is :
1 1 1
K.E Total  K.E1  K.E 2  . . .  K.E N  m c12  m c 22  . . .  m c2N
2 2 2
1 1 1
mc12  mc 22  . . . .  mc 2N
Thus, average kinetic energy of each molecule  2 2 2
N
1  c2  c2  . . . .  c2 
 m  1 2 N
2  N 
 
1
m  c2rms

2
(v) The sharpness of maximum in curves decreases with increase in temperature which reveals that number of
molecules having speeds in the vicinities of cMP increase.

Kinetic Energy of Gas

The pressure exerted by the gas is :
1 m N 2 1 2 m N
P c rms or P crms where  = density of gas = 
3 V 3 V
Using the above relation and gas laws, a relation between the average translational kinetic energy  1 mc 2rms 
2 
of a molecule at the temperature, T of the gas can be derived.
Using PV = nRT
1 m N 2 N  1 m0 N 2 
 crms V  RT  Using P  3 V Crms 
3 V N  
Note :
 c2  c2  . . .  c2 2
1 1  c1  c2  . . .  c N  
K.E avg.  m c2rms  m c2avg  1 2 N   
2 2  N  N  
1 1
or m c2rms  RT
3 N
1 3 RT 3
 mc 2rms   k BT
2 2 N 2
 Average Translational K.E. of a molecule is directly proportional to the temperature of the gas.
3 R
K.Eavg = k BT [where k B  is known as Boltzmann constant]
2 N
3 3
PV  RT
Also, K.E./mole =
2 2
Illustration - 13 Find the temperature at which methane and ethane will have the same rms speed as car-
bon dioxide at 400C. Also calculate the mean velocity and most probable velocity of methane molecules at
400C.
SOLUTION :
3RT 673
crms  (b) TC 2 H6   30  458.86K
M 44
Let 1: CO2 and 2: Methane 8RT 8  8.31 673

Mean speed  
 CH4  M 3.14  16  103
For crms to be same for 1 and 2
T1 T = 943.68 m/s
  2
M1 M 2 2RT 2  8.31 673
Most probable speed  
673  CH4  M 16 103
(a) TCH 4   16  244.73K
44 = 836.11 m/s

Illustration - 14 A gas bulb of 1 L capacity contains 2.0  1021 molecules of nitrogen exerting a pressure of
7.57  103 Nm2. Calculate the root mean square (rms) speed and the temperature of the gas molecules. The
ratio of the most probable speed to the root mean square speed is 0.82, calculate the most probable speed for
these molecules at this temperature.
SOLUTION :
3RT 3  8.314  274.2
crms  T=? crms   494.22 m / s
M 28  103
Using, PV = nRT 1
Most probable speed (cMP) =  494.22
1.224
7.57 103  1 103
= 403.77 m/s
PV 2.0 1021
 T= =  8.314 = 274.2 K
nR 6.023  1023
Illustration - 15 Two gases A and B have the same magnitude of most probable speed at 298 K for A and
 MA 
150 K for B. Calculate the ratio of their molor masses  M  .
 B
(A) 2 : 1 (B) 1 : 0.75 (C) 1:2 (D) 3:1
SOLUTION :
1/ 2 M A TA 298
 2RT     2
Most Probable    M B TB 150
 M 
 M A : M B  2 :1
T T
According to the problem A  B
MA M B
Illustration - 16 What is the ratio of kinetic energy per mole of Argon at 27°C and Helium at 127°C ?
(A) 0.75 : 1 (B) 1:1 (C) 1 : 0.67 (D) 1 : 1.25
SOLUTION :
1/ 2
 3RT 
Crms   
 M 
3RT [3  8.314 107  T  2

 M

 2 

  2.15  10
5

 T = 371 K ; t = (T – 273)°C = 100°C

REAL GAS ANALYSIS Section - 4
Equation of state describes the variables of a gas (P, V, T) in a single equation completely. The gas equation
PV = nRT is an equation of state which is followed only by ideal gases. This equation is not always applicable
for a real gas (especially at high pressure and low temperature). There are many equation of states which can
be used to represent a real gas but the most commonly used equation is van der Waal’s Equation and is given
by :
 an 2 
 P  2   V  nb   nRT . . . . . . (i)
 V 

where P = Real Gas Pressure ; V = Volume occupied by the Gas ( Container Volume)
T = Gas temperature ; R = Universal Gas Constant ; n = Moles of Gas
a, b = Characteristic constants for a gas independent of the temperature but depends on the nature of the
gas.
L2 atm L
Note : (i) Units of a  ;b
mol2 mol
(ii) a  Relates to the forces interacting between the gas molecules and modifies the pressure term.
(‘a’ is high if the gas molecules have more attractive forces)
(iii) b  Relates to the volume occupied by the gas molecules and takes into account the fact that the space
actually occupied by the molecules themselves is unavailable for the molecules to move in and is given
by :
b = 4  volume of 1 mol of gas molecules.
(iv) For a given gas Van der Waal’s constant ‘a’ is always greater than ‘b’.
(v) The gas having higher values of ‘a’ can be liquefied easily. (to be discussed later)
Equation (i) is similar to the ideal gas equation with some correction factors taking into account the factors
responsible for a gas to deviate from the ideal gas behaviour.
Equation (i) is written in a more familiar form by dividing it by “n” :
 a 
  P  2   Vm  b   RT . . . . . .(ii)
 Vm 

V
where Vm  = Molar volume (volume occupied by 1 mole gas)
n

Pressure correction :
a
The term 2
is known as Pressure correction. The pressure exerted by a real gas is always less than
Vm
that by an ideal gas. So, this has to be added to the real gas pressure such that : Pideal  Preal  a
2
Vm
Note : Preal is the pressure exerted by the real gas and has been denoted by ‘P’ in the van der Waal’s equation.
Volume correction :
The term ‘nb’ is known as volume correction (also known as co-volume or excluded volume). The volume
of the gas molecules is not zero and hence the actual compressible volume is less thanVm and thus has to be
subtracted from Vm
We can also write a Universal Equation of state for any gas as :
PV = Z (nRT) . . . . . .(iii)
where Z = compressibility factor
Note : (i) For ideal gas, PV = nRT  Z = 1 at all conditions of P, V, T.

(ii) For real gas, PV = ZnRT
It should be clear that “Z” represents a quantitative deviation of real gas from ideal gas behaviour.
Explanation for deviation from Ideal Gas Behavior :

The deviation from ideal gas behavior is mainly due to two assumptions made while formulating the kinetic
molecular theory :
(i) Molecules were considered as point masses. However all real molecules have definite volume which
cannot be neglected when the volume occupied by the gas is small.
(ii) It was assumed that there are no intermolecular forces and molecules move independently. This cannot
be true as otherwise gases could not condense into liquid.
If we assume that gas molecules are hard spheres of radius say, 2  10–10 m, the volume of one mole of gas
molecules = (volume of each molecule)  No
4 3
=
3
 
 2  108  6  1023 cm3 = 2.01  10–2 L
and volume of the gas at P = 1atm and T = 0C is nearly 22.4 L

 % volume occupied by gas molecules  0.09%
It can be shown that at P = 10 atm and T = 0C, volume of the gas is nearly 2.24 L
% volume occupied by gas molecules  0.9%
Thus, as pressure increases, space available for gas molecules for free movement decreases.

With an increase in pressure, the average distance between the gas molecules decreases, then the molecular
interactions start operating. Thus, the number of molecular collisions with the walls of the container gets
affected resulting in smaller values of pressure than what actually would have been in the absence of intermo-
lecular interaction.
Let us plot the variation of Z as a function of P.

We can, theoretically, describe the above behaviour
by using van der Waal’s equation :
This equation is a cubic in Vm. Thus, verification for
the variation of Z versus P from this equation, directly,
is difficult. Instead, the whole variation can be divided
into three regions.
Region : I Low Pressure : This region is represented by that portion of the graph where Vm  b  Vm ,
i.e., Vm >> b or when the gas has a large molar volume or very small pressure.
 a 
Thus, we have :  P  2   Vm   RT
 Vm 

RT a a a
 P  [Here, both P and 2 are small numbers. So, P   P]
Vm Vm 2 Vm 2
Vm
PVm a
 Z 1 . . . . . . (iv)
RT RTVm
 In the region I, Vm is large  Z < 1 but Z  1
Thus, as P increases (Vm decreases), Z decreases [see equation (iv)]
Region : III High Pressure : This region is represented by that portion of the graph where
a
P
2
P  Vm  b  Vm 
Vm
 Van der Waal’s equation reduces to : P  Vm  b   RT

PVm Pb
 PVm = Pb + RT  Z 1 [Note : Z vs P is linear here]
RT RT
Thus, as P increases, Z increases and Z > 1.
Region : III Intermediate Pressure :

In this region, neither of the two approximations are valid, i.e.,
a
Vm  b  Vm and P  2
P
Vm
So, the direct analysis is difficult.

Observations from the graph :

(i) In the low pressure Region-I and in most of the Intermediate Pressure Region-II : Z < 1
 Gas is more compressible. Thus, attractive forces dominate between the gas molecules
(ii) In the high Pressure Region-III, Z > 1
 Gas is less compressible. Thus, repulsive forces dominate between the gas molecules.
The graph () shows the variation of Z vs P for different gases

and following can be observed :
(i) H2 and He gases have very low attractive forces between

the gas molecules and we can assume their van der waal’s
gas constant ‘a’  0.
 P  Vm  b   RT
[For H2 and He even at low Pressures we can assume
a
[P   P]
2
Vm
(ii) Z < 1 (as for CH4, CO2) can be attributed to the predominance of attractive forces among the mol
ecules of these gases at the temperature of experimentation whereas Z > 1 can be attributed to the
dominance of strong repulsive forces among the molecules.
(iii) All gases at sufficiently high pressure (i.e., when sizes of the molecules are comparable to the volume
of the gas) will have Z > 1.
Variation of Z vs Temperature (T) :
In the low pressure region : a (Z < 1)
Z 1
RTVm
 As T increases  Z increases and reaches close to 1.
In the high pressure region : Pb (Z > 1)

Z 1
RT
 As T increases  Z decreases and reaches close to 1.
It can be seen that Z approaches 1 as T increases and Z approaches 1 as P approaches 0.
Thus, a real gas behaves more closely to ideal gas at low pressure and high temperature.
Note : Large value of “a” denotes a larger dip in Z in the intermediate pressure region.
a NH3  a N2 as NH3 molecules exerts attractive forces due to Hydrogen Bonding but in N2 there are only
Van der Waal’s forces of attraction between the molecules which is actually small.
b NH3  b N 2 as N2 molecule is larger as compared to NH3 molecule.
All isotherms in the above graph will have a common point of intersection ‘A’.


 Find the temperature at which 3 mole of SO2 obeying van der Waal’s equation occupies a

volumes of 10 L at a pressure of 15 atm. a  6.71 L2atm / mol2 , b  0.0564 L / mol 
 n 2a 
Using van der Waal’s equation of state :  P  2   V  nb   nRT
 V 

 32  6.71 
we get,  15   (10 – 3  0.0564) = 3  0.0821  T  T = 349.8C
 102 
 The compressibility factor for 1 mole of a van der Waal’s gas at 0C and 100 atm pressure is
found to be 0.5. Assuming that the volume of gas molecular is negligible, calculate the van der
Waal’s constant ‘a’.
 a 

Using van der Waal’s equation of state :  P    Vm  b   RT
2 
 Vm
Now : Vm – b  Vm (given)
 a  PVm a
 The equation is reduced to :  P   V  RT or Z   1
 2  m RT RTVm
 Vm
100  Vm
Also, 0.5   Vm  0.112 L
0.0821  273
Substitute the values of Vm and T :  a = 1.25 L2 atm mol2

 Calculate the pressure exerted by 5 mole of CO2 in 1 L vessel at 47C using van der waal’s
equation. Also report the pressure of gas if it behaves ideally in nature.
(a = 3.592 atm L2/ mol2, b = 0.0427 L/mol)
Using van der Waal’s equation of state :
 n2 a 
 P    V  nb   nRT
 V 2 
 
Substituting the given values, we get :
 52  3.592 
P   (1 – 5  0.0427) = 5  0.0821  320
 12 
 
 P = 77.218 atm
If the gas behaves ideally, then using : PV = nRT
5  0.0821  320
 P atm = 131.36 atm.
1

 Van der Waal’s constant b of Ar is 3.22  10–5 m3 mol1. Calculate molecular diameter of Ar.
Use, b = 4  volume occupied by the molecules in 1 mol of a gas
4 
 b  4  N    r 3 
3 
4 22
3.22  105  4  6.023  10 23    r3
3 7
1/3
 3.22  105  3  7 
r   0.1472  109 m  0.1472 nm
23
 4  6.023  10  4  22 
d = 2r = 0.2944 nm.
Critical phenomenon and Liquefaction of gases :

The phenomenon of converting a gas into liquid is known as liquefaction. The liquefaction of gas is achieved
by controlling P and T as follows :
 Increasing pressure : An increase in pressure results in increase in attraction among molecules.
 Decreasing temperature : A decrease in temperature results in decrease in kinetic energy of molecules.
 The temperature of gas must be lower than its critical temperature TC.
Note :
(i) Condition for a real gas to get liquefied is :
Low Temperature : Molecules don’t have sufficient energy to overcome the attractive forces between the
gas molecules.
High Pressure : Molecules are close to each other so that they can exert sufficient attraction on each
other required for the liquefication of the gas.
(ii) An ideal gas can never be liquefied whatever be the temperature and pressure conditions due to the absence
of the attractive forces between its gas molecules.
Critical temperature (TC ) :

It is defined as the characteristic temperature for a given gas below which a continuous increase in pressure
will bring liquefaction of gas and above which no liquefaction is noticed although pressure may be increased
For example : TC for CO2 is 31.2C.
Critical pressure (PC ) :

It is defined as the minimum pressure applied on 1 mol of gas placed at critical temperature, to just liquefy the
gas.

Critical Volume (Vm,C) :

The volume occupied by 1 mol of gas placed at critical conditions.
(i.e. P = PC and T = TC ).
Note : (i) PC, Vm,C ,TC are characteristic values for each gas.
(ii) The numerical values of critical constants derived from Van der Waal’s equation are:
8a a
TC  ; PC  ; Vm, C  3b [a, b are the van der Waal’s gas constants]
27 Rb 27 b 2
(iii) The gas having its temperature much lower than its critical temperature, less pressure is sufficient to
liquefy it.
RTC 8
(iv) The numerical value of  (on substituting TC, PC, Vm, C ). Thus one can write that the
PC Vm, C 3
value of RT/PV at critical conditions is 8/3 of normal conditions.
RTC 8 8 RT  RT 
i.e.,     1
PC Vm, C 3 3 PV  PV 
PC Vm, C 3
 At critical conditions, Z  
RTC 8
Boyle’s Temperature (TB)

It is that temperature at which a real gas behaves ideally over a large pressure range as shown :
a
TB is given by : where a, b are van der Waals gas constant
Rb
Note : Boyle’s temperature of a gas is always higher than its critical temperature (TC ).

Collision Frequency and Mean Free Path

The collision rate (i.e., the number of collisions taking place in unit time per unit volume) is called collision
frequency (z) and is given by
n 2 2cavg
z
2
The average of distances traveled by a molecule between successive collisions is called mean free path
().
1

2n2
where n is the number of molecules per unit molar volume.
6.02  1023 3
n m
0.0224
cavg , average velocity, the collision diameter i.e., the minimum distance between the centres of two
molecules when at the point of collision.
T
Also based on kinetic theory of gases, mean free path   . Thus,
P
 Larger the size of the molecules, smaller the mean free path.
 Greater the number of molecules per unit volume, smaller the mean free path.
 Larger the temperature, larger the mean free path.
 Larger the pressure, smaller the mean free path.

MORE ILLUSTRATIONS
Illustration - 17 A mixture containing 1.12L of H and 1.12L of D (deuterium) at S.T.P., is taken inside a
2 2
bulb connected to another bulb by a stop-cock with a small opening. The second bulb is fully evacuated. The
stop-cock is opened for a certain time and then closed. The first bulb is found to contain 0.05 gm of H2.
Determine the percentage composition by weight of the gases in the second bulb.
SOLUTION :
In the first bulb : From Graham’s Law :

1.12 1 n 2
Initial moles of H2 =  
22.4 20 1/ 40 4
1.12 1 2
Initial moles of D2 =   n = moles of D2 in second bulb.
22.4 20 80
Now after opening of stop-cock, mass of H2 left in the In the second bulb:
first bulb = 0.05 1
The mass of H2 gas =  2  0.05 gm
40
0.05 1
 Moles of H2 =  2
2 40 The mass of D2 gas =  4  0.07 gm
80
 Moles of H2 effused into second bulb  Total mass = 0.05 + 0.07 = 0.12 gm.
1 1 1 0.05
=    100  41.67 %
20 40 40  % of H2 =
0.12
Let n be number of moles of D2 effused. 0.07
and % of D2 =  100  58.33%
0.12
Illustration - 18 A mixture of ethane and ethene occupies 40 L at 1.0 atm and 400K. The mixture reacts
completely with 130 gm of O2 to produce CO2 and H2O, Assuming ideal gas behaviour, calculate the mole
fractions of C2H4 and C2H6 in the mixture.
SOLUTION :
Let x = moles of C2H6 and y = moles of C2H4 7x 130

  3y   3.5x + 3y = 4.06
C2H6 + 7/2 O2  2CO2 + 3H2O 2 32
PV 1  40
C2H4 + 3O2  2CO2 + 2H2O Also, x + y =  = 1.218
RT 0.0821  400
 7x 
 moles of O2 used =   3 y  Solving for x and y, we get :
 2 
130  x = 0.812 and y = 0.406
and moles of O2 available =
32 0.812
 C 2 H 6   0.67 and C2H 4  0.33
1.218

Illustration - 19 1 mole of CCl vapours at 77C occupies a volume of 35.0 L. If van der Waal’s constants
4
are a = 20.39 L2 atm mol–2 and b = 0.1383 L mol–1, calculate compressibility factor Z under,
(a) low pressure region (b) high pressure region.
SOLUTION :
(a) Under low pressure region, Vm is high (b) Under high pressure region P is high,
(Vm – b)  Vm  a 
P  2   P
  Vm 
a  
  P  2  Vm  RT
 Vm   P(Vm – b) = RT or PVm – Pb = RT

a RT
PVm   RT  P
 Vm Vm  b
20.39 PVm Vm 1
Z 1  0.98 Z  
0.0821  350  35  RT Vm  b 1  b
 a  Vm
 Z  1  
 RTVm  1
 Z  1.004
0.138
1
35
Illustration - 20 At 20C, two balloons of equal volume and porosity are filled to a pressure of 2 atm, one
with 14 kg N2 and other with 1 kg of H2. The N2 balloon leaks to a pressure of 1/2 atm in 1 hr. How long will
it take for H2 balloon to reach a pressure of 1/2 atm ?
SOLUTION : 1
Thus, for N2 : P1 = 2 atm. P2  atm. at t = 1 hr
r1 M2 2
Note : r  w1 = 14 kg w2 = ?
2 M1
P1 w
n1 / t1 M2   1
 P2 w 2
 n2 / t 2 M1
2 14 14
 w1
M1  t1 M2    w2  kg N 2
 1 2 w2 4

w2 M2  t2 M1 14 42 21
Wt. of N2 diffused = 14    kg
w1 t1 M1 4 4 2
 
w2 t2 M2 1
Similarly, for H2 : P1 = 2 atm, P2  atm, at t = t hr
2
where w1, w2 are the weights of gas 1 and 2 effused in w1 = 1 kg w2 = ?
time t1 and t2 respectively.
P1 w1 2 1 1
At constant V and T for a gas P  w  P  w  
1 2 w2  w 2  kg
2 2 4

1 3 Alternative approach :
Wt. of H2 diffused  1   kg
4 4 r1 P M2
 1
rN 2  MH  r2 P2 M1
2
Now    for diffusion of N2 and H2
rH2  MN  P1 / t1 P M2
 2   1
P2 / t 2 P2 M1
w N2 t H2 M N2
  1
or w H2 t N2 M H2 Here : P1  P2  2  atm and
2
P1 = P2 = 2 atm
21 2 t H 2 28
   t2 M2
34 60 2 

60 t1 M1
 t H2  min
14 M H2 60
 t H2  t N2  min
M N2 14
Illustration - 21 A gaseous mixture of helium and oxygen is found to have a density of 0.518 g dm–3 at 25C
and 720 torr. What is the per cent by mass of helium in this mixture ?
SOLUTION :
We know, PMo = dRT Average molecular mass =   MHe + (1 – ) M O2
720  13.37 =   4 + (1 – ) 32
  M   0.518  0.0821  298
760   = 0.666
 Mo = 13.37 g/mol
0.666  4
Let mole fraction of He in mixture be . % by mass of He = 0.666  4  0.334  32  100
 χ He  , O 2  1    = 19.95%

THE LIQUID STATE Section - 5

The liquid state is intermediate between gaseous and solid states. In the gaseous state the molecular
interactions are very weak practically negligible and molecules are in random motion. Molecules continue to
move unless they are reflected back by the walls of the vessel. Otherwise molecules would continue to move
and the gas would expand to any volume. This is why gases do not have a definite volume.
In case of liquid, the molecular interactions are quite strong and a given quantity of liquid occupies a definite
volume. Molecules of the liquid have so much freedom that they can flow readily and take up the shape of the
container due to continuous breaking and making of weak van der Waal’s bonds between the neighbouring
molecules.
Molecules in solids completely lack in translation motion. The thermal motion of the molecules is so greatly
reduced that they can only oscillate with respect to their fixed positions in the crystals. Each molecule in a
solid has generally 6 to 12 nearest neighbours called coordination number. In the liquid state the coordination
number of a molecule is not fixed but is only slightly less than in solid. The distance between the nearest
neighbours in liquid is only slightly higher than that in solids. This is why there is very little expansion of solids
on melting.
Vapour Pressure
The kinetic theory is the idea that there is distribution
of kinetic energies and hence the molecular speeds,
depending on the absolute temperature. Therefore,
in any gas, liquid or solid at room temperature, a
small fraction of molecules have relatively high
kinetic energy. Some of these high energy molecules
at the liquid surface become free resulting into its
evaporation. With the departure of high energy
molecules the average kinetic energy decreases
leading to a fall in temperature of the liquid. This
explains why evaporation causes cooling.
In a closed vessel, some free space above the liquid, the evaporated molecules cannot escape to the
atmosphere. Initially the vapour pressure increases and then comes to a constant value. The volume of the
liquid decreases initially and then becomes constant over a period of time. Increase in pressure means more
number of collisions with the walls of the container.
Inside a closed vessel, the liquid and its vapours are in dynamic equilibrium. The pressure exerted by the
vapours is then known as equilibrium vapour pressure. Since the vapour pressure is a kinetic phenomena,
it is independent of the amount of a liquid .It only depends on the temperature. The temperature must,
therefore, be specified with the vapour pressure of a liquid.
A liquid is said to be at its boiling temperature if its vapour pressure is equal to external pressure. Therefore,
the boiling point of water in particular and of liquids in general decreases as altitude of a place increases
where the external pressure is less than one atmospheric pressure

Vapour pressure of solids

When a solid is directly converted to its vapour state, then the process is called sublimation. Substances like
ammonium chloride, iodine, camphor, solid carbon dioxide sublime at ordinary temperature and pressure.
The white cloud like trail that we see coming out of the high flying jet is water vapours issuing from the
exhausts of high flying jets, getting converted directly into microcrystalline ice which is slowly reconverted
into water vapour without passing through the liquid state. This property of sublimation is used in the process
called freeze drying.
Surface Tension
Surface tension is one of the characteristic properties of liquids. Each molecule in the liquid state is influenced
by the nearest neighbour molecules. A molecule in the bulk of liquid experiences equal attractive forces from
all sides. There is no resultant force on the molecule which tries to move it
in any direction, whereas for a molecule at the surface of the liquid, the net
attraction towards the liquid is greater than that towards the vapour state.
The energy required to increase the surface area of the liquid by one unit, is
defined as its surface tension. It is represented by the Greek letter 
(gamma). The liquid surface, in the absence of any other force tends to
attain a minimum area. Mathematically it can be shown that for a given
volume, the sphere has a minimum area. Hence the water drop acquires a
spherical shape. Liquid in a capillary tube rises due to its surface tension.
Surface tension is also defined as the force acting per unit length perpendicular
to the line drawn on the surface. The units of surface tension is Nm–1 .
Viscosity of liquids
The ease with which a fluid can flow is determined by its property called viscosity. Viscosity arises due to the
internal friction between layers of fluids as they pass over each other. When a liquid is steadily flowing over a
fixed horizontal surface the layer immediately in contact with the surface is stationary. The velocity of the layers
increases with the distance from the fixed surface. if we select a layer, the layer immediately below tries to
retard its flow(velocity),while the one above tries to accelerate the flow. Force required to maintain the flow in
the three layers described above is directly proportional to the area of contact and velocity gradient.
Example - 7

Force is proportional to area in contact and velocity gradient, i.e.,

FA (Area) . . . . . .(i)
dv
and F  (velocity gradient) . . . . . .(ii)
dx
dv
On combining (i) & (ii) , we get : F 
dx
dv
 F= A
dx
where  is a constant, called as the coefficient of viscosity and it has the unit of poise, g cm–1s–1.
THE SOLID STATE Section - 6
The substance is said to be in solid state if the molecular interaction energy predominates over the disruptive
thermal energy.
Covalent Solids
A covalent solid is a giant molecule having a three dimensional network of covalent bonds. Examples are
diamond, silicon carbide, silica. These are generally very hard.
Ionic Solids
Ionic solids are three dimensional arrangements of cations and anions bound by coulombic forces .The
crystal on the whole are electrically neutral. Such solids are characterized by high melting and boiling points.
The ionic solids do not conduct electricity as ions present therein are not free to move. Examples are sodium
chloride, barium oxide and calcium fluoride.
Metallic Solids
Metals are orderly collection of positive ions surrounded by and held together by free electrons, each metal
atom donating one or more electrons. The bonding is not directional. The metals are good conductors of heat
and electricity. They are highly malleable and ductile. These sets of properties can be attributed to this
structure of metals. Metals like sodium crystallize- in simple cubic lattice. The presence of a sea of mobile
electrons in a metal accounts for its high electrical and thermal conductivity.
Molecular Solids
Many combinations of elements result into covalent molecules. These are discrete units capable of independent
existence. Thus we have molecules like di-hydrogen, di-nitrogen, methane etc. which are called covalent
compounds. They have weak molecular interaction. Even mono-atomic molecules like the noble gases, form
molecular solids. These solids are characterized by low melting points.

THINGS TO REMEMBER
Recapitulating and Summarizing
2. Boyle’s Law : PV = constant (Keeping T and n constant)
V
3. Charle’s Law : = constant (Keeping P and n constant)
T
PV
4. Combined Gas Law : = constant(Keeping n constant)
T
P
5. Gay Lussac’s Law : = constant (Keeping V and n constant)
T
6. 1 mol Ideal Gas = 22.4 L at STP.
7. Ideal gas Equation : PV = nRT or PVm = RT (Vm = V/n)
8. Dalton’s law of Partial Pressure :

 n  n 2  . . .  RT
PTotal  1 Partial pressure of a gas = Gas  PTotal
V
n P V
9. Graham’s Law of Diffusion : Rate of diffusion/effusion = or or
t t t
P

M
3RT 8RT 2 RT
10. Maxwell’s speed distribution : Crms  ; Cavg  ; CMP 
M M M
[ T is in Kelvin : M is in kg/mol : R = 8.314 kJ/mol ]
3
11. Kinetic Energy of Gas : KE avg  k BT
2
 an 2 
12. Real Gas Equation :  P    V  nb   nRT and Z  PVm
 V 
2
RT

b = 4  volume of 1 mol of gas molecules.
8a a
13. Critical constants for a real gas TC  27Rb ; PC  , Vm, C  3b
27 b2
14.
 a  a
In low Pressure Region :  P  2  Vm  RT & Z  1  RT V
Example - 7  m  m
Pb
In High Pressure Region :  Vm  b   RT & Z  1 
RT
38 Things to Remember Self Study Course for IITJEE with Online Support
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes The Chemical Bond - I
The Chemical Bond - I

INTRODUCTION Section - 1
We have come across the terms molecules and compounds. Molecule can be defined as an uncharged
entity in which atoms of same kind or of different kinds are held together by some forces. Compound is the
collective name of a set of molecules of same kind.
For example : Sulphur dioxide is a compound which contains the molecules of SO2, which is made up of
atoms of S and O. Cane sugar consists the molecules of C12H22O11, which is made up of atoms of C, H and
O.
The forces that hold together the atoms in a molecule are known as Chemical forces or Valence forces. The
association between atoms in a molecule by valence forces is called as Chemical Bond.
An atom possesses its greatest stability when its valence electron shell (outer shell) is complete. The K shell
(n = 1) is complete when it contains two electrons, while the remaining shells are complete when they contain
eight electrons. This is referred to as Lewis Octet Rule.
Note : The arrangement of electrons in Noble Gases is the criteria of stability, i.e., fully filled sub-shells (ns2np6).
The atoms of these elements are in a state of great stability and hence do not form compounds and in general
are chemically inert.
So it is the valence electrons that determine the chemical behavior of an atom. In a compound, a definite
number of valence electrons are involved in the bonding process. The chemical association among atoms can
be achieved by many ways depending upon number of valence electrons contained in the atoms. Three
major types of chemical bonding are as follows:
Ionic Bonding : Stability through transfer of electrons.

Covalent Bonding : Stability through mutual sharing of electrons.
Coordinate Bonding : Stability through partial transfer and partial
sharing of electrons.
1. Kossel – Lewis’s Electronic Theory of Chemical Bonding :

Lewis pictured the atom in terms of :
(a) A positively charged ‘Kernel’ (the nucleus plus the inner electrons) and
(b) The outer shell that could accommodate a maximum of eight electrons. He, further assumed that these
eight electrons occupy the corners of a cube which surround the ‘Kernel’.

The Chemical Bond - I Vidyamandir Classes
When all the eight corners of the cube are occupied then an atom is said to have stable electronic configuration.
Clearly noble gases which have 8 outer most electrons already have stable configuration while all other
atomic achieve stable octet of electrons (set of 8) when they are linked by chemical bonds.
Note :
 Valence electrons : It refers to the outer shell electrons (of an atom) that take part in chemical combination
in the formation of a molecule.
 The inner shell electrons are well protected and are generally not involved in the combination process.
 Common or group valence of an element : It generally refers to no of valence electrons or 8 minus the
number of valence electrons.
 Atoms can combine either by transfer of valence electrons from one atom to another (gaining or losing) or
by sharing of valence electrons in order to have an octet in their valence shells. This is known as octet rule.
IONIC OR ELECTROVALENT BONDING Section - 2
The chemical bond formed due to electrostatic attraction between cations and anions (which are formed by
the complete transfer of electron(s) from one atom to the other atom) is called as Electrovalent or Ionic
Bond. The Ionic valency or Electrovalence is referred to as the number of electrons that an atom can give up
or gain. In other words it is equal to the number of unit charge(s) on the ion, eg. In NaCl, sodium is assigned
a positive electrovalence of one, while chlorine a negative electrovalence of one.
The formation of a positive ion involves ionization, i.e., removal electron(s) from the neutral atom and that of
the negative ion involves the addition of electron(s) to the neutral atom.
 M (g)  e  ;
M(g)  Ionization enthalpy
X(g)  e 
 X  (g) ; Electron gain enthalpy
M  (g)  X  (g) 
 MX(s) ; Lattice energy
Formation of Lattice :
The compounds which are formed by ionic bonds are mostly solids. These compounds crystallize in different
crystal structures determined by factors such as size of the ions, their packing arrangements etc. In the
crystalline state, these compounds consist of orderly three-dimensional arrangements of cations and anions
(which is called lattice) held together by coulombic interaction energies. The energy released when such an
arrangement is formed (due to electrostatic attraction) is known as Lattice Energy.
The lattice is a highly stable arrangement and hence all ionic compounds have high melting and boiling points.
The higher is the lattice energy, the more stable is the ionic bond.

Factors affecting lattice energy :

Magnitude of charge : More is the magnitude of charge on cation or anion, the more is the lattice energy.
For example, the lattice energy of MgCl2 is higher than that of NaCl.
Size of ions : For higher lattice energy, the cations should be smaller and anion should be larger. The smaller
is the cation, the more effective is the nucleus in pulling the neighbouring anions towards it. As a result, the
lattice formed is highly stable or we can say that the lattice energy is high. Eg : Lattice energy of NaCl is
greater than that of CsCl, as Na+ cation is smaller than Cs+ cation though the ionisation energy of Cs is much
lower than that of Na.
Elaboration :
 There is a formation of negative ion from a halogen atom and and a positive ion from an alkali metal
atom due to gain and loss of an electron by the respcetive atoms.
 The negative and positive ions thus formed attain stable noble gas electronic configurations. The noble
gases (with the exception of helium which has a duplet of electrons) have a particularly stable outer
shell configuration of eight (octet), electrons, ns2np6.
 The negative and positive ions are stabilized by electrostatic attraction.
For example, the formation of NaCl from sodium and chlorine, according to the above scheme, can be
explained as :
Na   Na+ + e–
[Ne] 3s1 [Ne]
Cl + e – 
 Cl–
[Ne] 3s2 3p5 
 [Ne] 3s2 3p6 or [Ar]
Na+ + Cl– NaCl or Na+ Cl–
Similarly the formation of CaF2 may be shown as :
Ca   Ca2+ + 2e–
[Ar] 4s2 [Ar]
F + e– 
 F–
[He] 2s2 2p5 [He] 2s2 2p6 or [Ne]
Ca2+ + 2F– 
 CaF2 or Ca2+ (F–)2
Other examples of molecules involving ionic bonds are MgO, AlCl3, KI, CaS, MgBr2 , etc.
Ionic Bonding formation depends on the following :
1. Ionisation Enthalpy (i H) or ease of formation of positive ions.
2. Electron Gain Enthapy (eg H) / Eectron Affinity (Ae) or ease of formation of negative ions.
3. Lattice Enthalpy
Ionisation Enthalpy (i H) : It is the energy required to remove an electron from an isolated gaseous atom
in its ground state.

Electron Gain Enthalpy (eg H) : It is the energy required to add an electron to a gas phase atom in its
ground state to form a negative gaseous ion.
Note : The electron gain process may be exothermic or endothermic. The ionization, on the other hand, is always
endothermic.
Electron affinity (Ae) : It is the energy released when an electron is added to a neutral gaseous atom in its
ground state to form a negative ion. Electron Affinity of an atom is defined only at absolute zero
temperature.
Lattice Energy : Energy released when gaseous positive and negative ions come together to form 1 mol of
solid (crystalline) ionic compound.
Lattice Enthalpy : The Lattice Enthalpy of an ionic solid is defined as the energy required to completely
separate one mole of a solid ionic compound into gaseous constituent ions. For example, the lattice enthalpy
of NaCl is 788 kJ/mole (and Lattice energy = –788 kJ/mol). This means that 788 kJ of energy is required
to separate one mole of solid NaCl into one mole of Na+(g) and one mole of Cl– to an infinite distance.
Note : Condition for formation of a stable ionic compound is :

Total Ionisation enthalpy + Total Electron Gain Enthalpy – Total Lattice Enthalpy < 0
Simple Binary Ionic Compounds

Metal Nonmetal General Formula Ions Present Example
IA VIIA MX  M , X  LiBr
HA VIIA MX2  M2 , 2X   MgCl2
HIA VIIA MX3  M3 , 3X   GaF3
IA VIA M2X  2M  , X 2  Li2O
IIA VIA MX  M 2 , X   CaO
IIIA VIA M2X3  2M3 ,3X 2  Al2O3
IA VA M3X 3M2 , X3  Li3N
IIA VA M3X2 3M2 , 2X3  Ca3P2
IIIA VA MX  M 3 , X 3  AlP

Properties of Ionic Compounds :

(i) The ionic substances are good conductors of heat and electricity in molten state or aqueous medium.
In both these states, the lattice is broken and ions are free to conduct electricity and heat.
(ii) Due to stability of lattice, ionic compounds have high melting and boiling points.
(iii) The bond in ionic compounds is non-directional. In these compounds, each ion (cation or anion) has a
uniformly distributed electric field, so one can not predict whether a particular ion is bonded to this or
that ion.
(iv) These are soluble in polar solvents like water, which acts as a dielectric (dielectric is a material
which weakens the electric field). When the electric field is weakened, the ions are relatively free to
go in water.
COVALENT BONDING Section - 3
Certain elements which have high ionisation energies are incapable of transferring electrons and other having
low electron affinities, fail to take up electrons. The atoms of such elements share their electrons with the
atoms of other elements (and sometimes among themselves) in such a manner that both the atoms form
complete outer shell. In this manner they achieve stability. Such an association through sharing of electron
pairs among atoms of different or of same kinds is known as Covalent Bond. This was proposed by G.N.
Lewis.
The covalent bonding can be achieved in two ways :
(i) Sharing electrons between atoms of same kinds, formation of F2, O2, Cl2, etc.
(ii) Sharing of electrons between atoms of different kinds, formation of HCl, CO2, H2O, CH4, etc.
Lewis Symbols : To represent valence electrons in an atom, Lewis introduced simple notations called as
Lewis symbols. For example, the Lewis symbols for the elements of second period are as under
The number of dots around the symbol represents the number of valence electrons. This number of valence
electrons helps to calculate the common or group valence of an element.
Formation of F2 and other like molecules : A Fluorine atom has seven electrons in its outermost shell
and thus it needs one more electron to complete an octet of electrons and attain a noble gas configuration. A
F2 molecule is thus formed by combination of two F atoms by sharing one electron each. It is represented by
Lewis dot structure as follows:

Note that now both of F atoms now have eight (8) electrons each in their outer shell. In a more simple way,
electron (Lewis) dot formula can be expressed by using ‘’ (a dash) instead of • x.
Note :
 Pair of electrons depicted as • • or x x is called as Lone pair (p) and that by x • is called as shared pair or
Bond pair (bp). Lone pair is the pair of electrons belonging to one atom only. Thus F2 has one bp(s) and six
p(s).
 When two atoms share one/two/three electron pair(s) they are said to be joined by a single/double/triple
covalent bond respectively. Eg in the above example of F2 molecule there is a single bond between the two
fluorine atoms.
The Lewis Representation of some molecules is as follows :
H2 H–H
O2
O3
NF3
CO32 
HNO3
CO 2 O C O O C O
H H
H H
C2H4 C C C C
H H
H H

N2 N N N N
C2H2 H C C H H C C H
Explanation for O2 and N2 :

O2 : Oxygen (O) has six electrons in valence shell, hence requires 2 more to achieve stability. It can accept
two electrons to form ionic bond. It can also share two electrons with another atom of O to form covalent
bond as shown in the above table. Here, 2 pairs of electrons are shared, thus double covalent bond is formed
between the two oxygen atoms. In simpler way it can be represented by sign ‘=’. So O2 molecule can be
shown as O = O.
N2 : Nitrogen (N) has five electrons in valence shell and requires 3 electrons to achieve stability. It does so by
sharing 3 electrons with another N atom to form covalent bond as shown above. Here, 3 pairs of electrons
are shared, so there is a triple covalent bond between two nitrogen atoms. In simpler way it can be represented
by sign ‘’. So N2 molecule can be written as N  N.
Rules for writing Lewis dot structures :

(i) Add valence electrons of combining atoms of the molecules to get total no. of electrons (T) to be
represented in the Lewis structure.
(ii) In case of ions, number of electrons equal to charge on the ion must also be added (for anions) or
subtracted (for cations) from T.
(iii) Least electronegative atom occupies the central position in the molecule/ion.
(iv) Draw skeletal structure of the compound/ion using chemical symbols of the combining atom.
(v) Now use pairs of electrons to represent single bonds between bonding atoms of the molecules/ion and
represent the rest of the electrons to as lone pairs of atoms or to show multiple bonds between them (in
case each of the bonding atom does not have an octet of electrons).
Note : Lewis dot structure, in general, do not represent the actual shapes of the molecules.

Illustration - 1 Write a Lewis structure for CCl2F2, one of the compounds implicated in the depletion of
stratospheric ozone.
SOLUTION :
Step : 1 Place the atoms relative to each other. In Step : 3 Draw single bonds to the central atom and
CCl2F2 carbon has the lowest group number subtract 2e– for each bond : single bonds use
and EN, so it is the central atom. The other 8e–,so 32e– – 8e– leaves 24e– remaining.
atoms surround it but their specific positions Step : 4 Distribute the remaining electrons in pairs,
are not important. beginning with the surround-atoms, so that
each atom has an octet.
Step : 2 Determine the total number of valence

electrons :
      
1  C 4e     2  F 7e  

  2  Cl  7e    32 valence e
–
 
Illustration - 2 Writing Lewis Structures for Molecules with More than One central atom. Write the Lewis
structure for methanol (molecular formula CH4O), an important industrial alcohol that is being used as a
gasoline alternative in car engines.
SOLUTION :
Step : 1 Place the atoms relative to each other. The Five bonds use 10e–, so 14e– – 10e– leaves
H atoms can have only 1 bond, so C and H 4e– remaining.
must be adjacent to each other. In nearly all Step : 4 Add remaining electrons in pairs.
their compounds, C has four bonds and has
two, so we arrange the H atoms to shown
this.
Step : 2 Find sum of valence electrons
      
1  C 4e   1  O 6e  

Carbon already has an octet, so the four
remaining valence e– form two lone pairs on
  4  H 1e    14e O and give the Lewis structure for methanol.
 
Step : 3 Add single bonds and subtract 2e– for each
bond.

Illustration - 3 Write the Lewis dot structure of CO molecule.

SOLUTION :
Step : 1 The skeletal structure of CO is written as :
CO
This does not complete the octet on carbon
Step : 2 Count the total number of outer valence shell and hence we have to resort to multiple
electrons of carbon (2s2 2p2) and oxygen bonding (in this case a triple bond) between
(2s2 2p4) atoms. C and O atoms. This satisfies the octet rule
Thus the total number of valence electrons condition for both atoms.
available are 4 + 6 = 10.
Step : 3 & 4 .
Draw a single bond (one shared electron pair)
between C and O and complete the octet on
O, the remaining two electrons will constitute
a lone pair on C.
Writing Lewis Structures for Molecules with Multiple Bonds
Illustration - 4 Write the Lewis structure of the nitrite ion NO 

2
SOLUTION :
Step : 1 The skeletal structure of NO 2 is written This, however, does not complete the octet
as : on nitrogen if the remaining two electrons
O N O constitute lone pair on it.
Step : 2 Count the total number of valence electrons
of the nitrogen atom, the oxygen atoms and Hence we have to resort to multiple bonding
the additional one negative charge (equal to between nitrogen and one of the oxygen
one electron). N(2s 2 2p3 ), O (2s 2 2p 4 ) atoms (in this case a double bond). This leads
to the following Lewis dot structures.
 5  (2  6)  1  18 electrons
Step : 3 & 4
Draw a single bond (one shared electron pair)
between the nitrogen and each of the oxygen
atoms completing the octets on oxygen
atoms.

Writing Lewis Structures for Molecules with Multiple Bonds
Illustration - 5 Write Lewis structures for the following :

(a) Ethylene (C2H4), the most important reactant in polymer manufacture
(b) Nitrogen (N2), the most abundant atmospheric gas
Plan : We begin the solution after Steps 1 to 4 : placing the atoms, counting the total valence electrons, making single
bonds, and distributing the remaining valence electrons in pairs to attain octets. Then are continue with step 5, if
needed.
SOLUTION :
(a) For C2H4. After Steps 1 to 4, we have (b) For N2. After steps 1 to 4 : we have
Step : 6 Neither N has an octet, so we change a lone
pair to bonding pair :
In this case, moving one lone pair to make a
Step : 5 Change a lone pair to a bonding pair. The C
double bond still does not give each N an
on the right has an octet, but the C on the left
octet, so we move another lone pair to make
has only 6e–, so we convert the lone pair to
a triple bond :
another bonding pair between the two C
atoms.
Formal Charge
Formal charge is an accounting procedure. If allows chemists to determine the location of charge in a molecule
as well as compare how good a Lewis structure might be. The formal charge of an atom in a polyatomic
molecule or ion may be defined as the difference between the number of valence electrons and the number of
electrons assigned to that atom in the Lewis structure. It is expressed as :
Formal charge = number of valence e– on neutral atom – (2  LP) – BP

The counting is based on the assumption that the atom in the molecule owns one electron of each shared pair
and both the electrons of a lone pair.

Let us consider the ozone molecule (O3). The Lewis structure of O3 may be drawn as :
The atoms have been numbered as 1, 2 and 3. The formal charge on :

1
 The centre O atom marked 1 62 (6)   1
2
1
 The end O atom marked 2  6  4  (4)  0
2
1
 The end O atom marked 3  6  6  (2)   1
2
Hence, we represent O3 along with the formal charges as follows :
If there are more than one possible Lewis structures for a molecule having same number of bonds, the better
structure is one which has the least formal charge on each individual atom. If takes energy to get a separation
of charge in the molecule (as indicated by the formal charge) so the structure with the least formal charge
should be lower in energy and thereby be the better Lewis structure. The non-zero formal charge on any
atoms in the molecule are written near the atom.
Formal charge and bond polarity

Formal charge calculations do not indicate how charge is actually distributed in molecules. Remember that
most bonds are polar, meaning that the electrons in an bond are skewed toward the more electronegative
atom. Formal charges, however, are found by assuming that all bonding electrons are shared equally. As a
result, formal charge calculations are extremely useful for assessing whether a valence electron distribution is
reasonable, but they do not reliably indicate actual bond polarity or the actual distribution of charge. Some of
the following examples illustrate this point.
In chlorine trifluoride, all formal charges are zero. Based on electronegativities, however, each F – Cl bond
is significantly polar. The electronegativity of F is 4.0. Indicating that a fluorine atom attracts electrons more
strongly than a chlorine atom. In a CIF3) molecule, each F atom has a small net negative charge (less than one
unit), and the Cl atom has a net positive charge of 3 times this amount (also less than one unit). These partial
charges are symbolized + or –.
The ammonium cation illustrates the difference between formal and actual charge even more dramatically.
The nitrogen atom of NH4+ has a formal charge of 5 – 4 = +1, but electronegativity values indicate that N
attracts electrons more strongly than H ( N = 3.0 = 2.1). Thus the actual electron distribution in an N – H
bond is skewed forward nitrogen, leaving each H atom with a partial positive charge and the N atom with a
partial negative charge.
The positively charged environment of the hydrogen atoms is reflected in its chemical behaviour. This ion
readily gives up a hydrogen cation to a hydroxide anion : NH 4   OH    NH3  H 2O

Remember that formal charge are not annual charges. Instead, formal charges are simply a device that helps
us determine the most stable distribution of a molecule’s valence electron.

CO-ORDINATE COVALENT BONDING Section - 4
The bonding in which one atom furnishes a pair of electrons to the other atom, in such a manner that both of
the atoms achieve stability (i.e. 8 electrons in outer shell), is called as Co-ordinate Covalent or Dative
Bonding.
Compounds such as NH3, having one lone pair readily forms coordinate bonds. It combines with H+ ion
(Hydrogen cation) to from Ammonium ion (NH4+) as follows :

 H 
 | 

H + + NH3 
 NH4 + H  N  H 
 | 
 H 
Similarly, H2O forms Hydronium ion (H3O+ ion) by combining with H+.

 
   
H + + H 2O 
 H3O+  H O  H 
 | 
 H 
Exception to Octet Rule

The octet rule, though useful, is not universal. It is quite useful for understanding the structures of most of the
organic compounds and it applies mainly to the second period elements of the periodic table. Up to now we
have studied the molecules which follow Lewis Octet Rule while forming bonds. It is observed that atoms in
some molecules could exist with some other number of electrons in their valence shells, rather than eight
electrons without affecting the stability.
There are three types of exceptions to the octet rule :

(i) The incomplete octet of the central atom
In some compounds, the number of electrons surrounding the central atom is less than eight. This is especially
the case with elements having less than four valence electrons. Examples are LiCl, BeH2, BCl3, AlCl3, BF3
etc. Li, Be and B have 1.2 and 3 valence electrons only.
BF3 : Boron atom has only six electrons in its outer-shell even after making three single F
FB
bonds with three F atoms (i.e., it completes only sixet).
F
BeCl2 : Beryllium has only four electrons in its outershell even after making two single
bonds with two Cl atoms.
(ii) Odd-electron molecules
In molecules with an odd number of electrons like nitric oxide, NO and nitrogen dioxide, NO2, the octet rule
is not satisfied for all the atoms (as shown below)
N=O O N O

(iii) The expanded octet

Elements in and beyond the third period of the periodic table have, apart from 3s and 3p orbitals, 3d orbitals
also available for bonding. In a number of compounds of these elements there are more than eight valence
electrons around the central atom. This is termed as the expanded octet. Obviously the octet rule does not
apply in such cases. Eg : PF5, SF6, H2SO4 and a number of coordination compounds.
Cl F O
Cl F F
Cl P S H O S O H
Cl F F
Cl F O
PCl5 SF6 H 2 SO4
10 electrons around 12 electrons around 12 electrons around
the P atom the S atom the S atom
PCl5 : Phosphorus after making five single bonds with five Cl atoms has ten electrons in its outershell.
SF6 : Sulphur makes six single bonds with six F atoms and thus has 12 electrons in its outershell.
H2SO4 : Sulphur makes 2 single bonds and 2 double bonds with 4 oxygen atoms and thereby has 12
electrons in its outermost shell
Other drawbacks of the octet theory
 It is clear that octet rule is based upon the chemical inertness of noble gases. However, some noble
gases (for example xenon and krypton) also combine with oxygen and fluorine to form a number of
compounds like XeF2, KrF2, XeOF2 etc.,
 This theory does not account for the shape of molecules.
 It does not explain the relative stability and energy of the molecules.
Some Terminologies related to a Chemical Bond :

(i) Bond Energetics
The basic rule followed when a chemical bond is formed is that the total energy of the system must be lower
in the bonded state than in the non-bonded state (or free atomic state). For both Ionic and Covalent bonding,
association can take place only when the combined state achieves the stability, i.e., a state of minimum
energy.
When two atoms combine to form ionic covalent bond, the total energy of the system must be lowered.
Therefore energy must be given off when bonding occurs. This energy is known as Bond Energy. It means,
whenever a bond is to be formed the energy will be released and to break it, energy must be supplied.
The covalent bonding is understood in terms of electrostatic interactions. The electrons in atoms are negatively
charged and protons are positively charged, so it is electrical columbic interactions between these particles
that give rise to covalent bonding.
We know that Ionic bonding is formed through electrostatic attractive force. So in both types of bonding the
formation of compounds is the result of electrical interactions by columbic forces in some sense or the other.
(You will study more about electrical forces in Physics).

(ii) Bond Length

rA rB
Bond length is defined as the equilibrium distance between the nuclei of
two bonded atoms in a molecule. In the case of a covalent bond, the
contribution from each atom is called the covalent radius of that atom.
R = rA + rB
(R is the bond length and rA and rB are the covalent radii of atoms A and
A B
B respectively The Bond length in a covalent molecule AB
(iii) Bond Angle

It is defined as the angle between the orbitals containing bonding electron pairs around the central atom in a
molecule/complex ion. Bond angle is expressed in degree which can be experimentally determined by
spectroscopic methods.
It gives some idea regarding the distribution of orbitals around the central atom in
a molecule/complex ion and hence it helps us in determining its shape. For example
H – O – H bond angle in water can be represented as under :
Ionic Character in covalent bonds (Polar Covalent Bond) :

Covalent bond when formed between two alike atoms, bonded pair of electrons is equally shared. However
when it is formed between two atoms of different kinds (unlike atoms), bonded pair is not equally shared. An
atom which has more tendency to attract the shared pair of electrons towards itself (high electronegativity)
will pull the bond pair towards itself.
For example: Let us consider a single covalent bond between A and B, i.e., A  B.
Let B be more electronegative than A, then the bond pair will be shifted towards B, i.e., the electron cloud of
bond will distort and moves slightly over to B. As a result B acquires a partial negative charge (denoted by 
). Since the molecule is neutral, A will acquire a partial positive charge (denoted by + ). Such a state where
+ve and ve charges are separated by a certain distance, is known as Polarised state and the process is
known as Polarisation, and the covalent bond is known as Polar Covalent Bond.
A molecule with positive and negative charge centres in equilibrium is called as dipole and is characterised
by possessing a quantity dipole moment (µ) defined as the product of the magnitude of charge (q) and the
distance (d) separating the centres of +ve and ve charges.  = q × d, Its unit in CGS system is debye (D).
1 D = 1 × 1018 esu.cm. The charge q is measured in esu. The distance d is measured in cm and is of order
of 1 Å, i.e., 108 cm. The direction of dipole moment is from +ve end to –ve end. Note : Charge on 1
electron = 1.6 × 1019 C = 4.8 × 1010 esu.
Here, A+  B- is characterised as dipole and is known as Bond Dipole. The overall dipole moment of a
molecule is the vector sum of the dipole moments of all bond dipoles in a molecule.
Now covalent molecules having bond dipoles are classified into two categories :
(a) Polar molecules (b) Non-polar molecules

A molecule is said to be polar if the net dipole moment of a molecule is not equal to zero. For example : HF,
H2O, NH3, CH3OH, etc, are polar as in all of these, the net dipole moment is not equal to zero (net  0).
For a molecule to be polar both of the following conditions must be satisf ied :
(i) There must be at least one polar bond present.
(ii) The polar bonds, (if there are more than one), and lone pairs must not be so symmetrically arranged
that their bond polarities cancel each other.
This means if there are no polar bonds or lone pairs on the central atom, the molecule cannot be polar. And
even if these are present, they may be arranged in such a manner that their polarities cancel each other,
resulting in a non-polar molecule. So a molecule is nonpolar if its net dipole moment is equal to zero. For
example : H2, Cl2, BF3, CO2, BeCl2, etc, are non-polar as net = 0. In such molecules, in spite of bond
dipoles, the molecules are non-polar.
HH Cl  Cl
(no bond dipole, net = 0) (no bond dipole, net = 0)
δ
δ
Cl — Be— Clδ 
(2 bond dipoles but net = 0) (3 bond dipoles but net = 0)

The conclusion is that, the dipole moment of a molecule, (zero or nonzero), depends upon the structure or
shape (or on geometry) of the molecule. For example H2O is polar whereas HgCl2 is nonpolar. The
difference lies in the shapes of two molecules. H2O is angular (  0) and HgCl2 is linear ( = 0). Both have
polar bonds, OH bond in water while HgCl bond in mercuric chloride, but due to structure of HgCl2 being
linear, the dipole moments of two bond dipoles cancel each other whereas in water, due to angular shape the
dipole moments of two bond dipoles do not cancel and give rise to a net dipole moment.
Applications of Dipole Moment

(i) To decide polarity of the molecule : Molecules having zero dipole moment are said to be non-
polar molecules and those having R  0 (resultant dipole moment) are polar in nature.
(ii) To determine percentage of ionic charcter : The value of dipole moment can be used for
determining the amount of ionic character in a bond.
 =q×d
Consider a diatomic molecules say HCl. Suppose this molecule is completely ionic. Under this condition H
and Cl ions would bear a unit charge equal to 4.8 × 1010 esu and the bond distance between H and Cl
atoms = 1.27 Å.
Thus, theoretical value of = 4.8 × 1010 × 1.27 × 108 = 6.09 D
Dipole moment of HCl is also determined experimentally. Let the experimental value be 1.03 D.

Percentage of ionic character in H — Cl bond in HCl molecule

Experimental value of μ 1.03
 100  100  16.9%
Theoretical valueof μ 6.09
Experimental value of dipole moment

Thus, Percentage of ionic character   100
Theoretical value of dipole moment
(iii) To determine geometry of molecules : The values of dipole moments provide value information
about the structure of molecules.
(a) CO2, CS2 molecules are linear as value of their dipole moments are zero.
(b) H2O is not a linear molecule as it has dipole moment. Actually it has V-shaped structure and
the bond angle is 105. Similarly, SO2 has a bent structure.
(c) In ammonia, three hydrogen atoms do not lie symmetrically with respect to nitrogen as it has
dipole moment. It has pyramidal structure.
Molecular Geometry and Dipole Moment

General Formula Molecular Geometry Dipole Moment Example
AX Linear May be non-zero HF, HCl
AX2 Linear Zero CO2, CS2

Bent or V-shape Non-zero H2O, NO2
AX3 Trigonal planar Zero BF3

Pyramidal Non-zero NH3, PCl3
T-shape Non-zero ClF3
AX4 Tetrahedral Zero CH4, CCl4

Square planar Zero XeF4
See saw Non-zero SF4, TeCl4
AX5 Trigonal bipyramidal Zero PCl5

Square pyramidal Non-zero BrCl5
AX6 Octahedral Zero SF6

Distorted octahedral Non-zero XeF6
AX7 Pentagonal bipyramidal zero IF7
(v) Bond moment : The contribution of individual bond in the dipole moment of a polyatomic molecule
is termed bond moment. The measured dipole moment of water molecule is 1.85 D. This dipole
moment is the vectorial sum of the individual bond moments of two OH bonds having bond angle
104.5.

Thus, μ obs  2μ O  H cos 52.25

1.85  2μ O H  0.6129
μ O  H  1.51 D
Illustration - 6 (a) A diatomic molecules has a diple moment of 1.2 D. If the bond distance is 1.0Å, what
fraction of an electron charge, e, exists on each atom ?
(b) The diple moment of LiH is 1.964 × 1029 Cm and the interatomic distance between Li and H in this
molecule is 1.596Å. What is the per cent ionic character in LiH ?
SOLUTION :
Dipole moment
(a) Partical charge  = (1 electronic charge) interatomic distance)
Bond distance
= (1.602 × 1019 C) (1.596 × 1010 m)
1.2×1018esu cm = 2.577 × 1029 Cm

1.0×108 cm Fractional ionic character
= 1.2 × 1010 esu Exp. vlaue of dipole moment


The fractional of an electronic charge Theoretical value of dipole moment
1.2×1010 1.964×1029
  0.25  25% of e.   0.768
4.8  1010 2.557×1029
(b) The diple moment of 100% ionic molecule (LiH) The bond in LiH is 76.8% ionic.
Illustration - 7 Predict whether each of the following molecules has a dipole moment :
(a) IBr (b) BF3 (c) CH2Cl2
SOLUTION :
(a) Since IBr molecules is diatomic, it has a linear (c) CH2Cl2 is similar to CH4 (tetrahedral), but it has
geometry. Bromine is more electronegative than three different bond angles : HCH, HCCl, and
iodine, hence, IBr is polar with bromine at the ClCCl, which are close to but not equal to 109.5°.
negative end. Thus, the molecules does have a dipole Since Cl is more electronative than C and which is
moment. more electronagetive than H, the bond moments
do not cancel and the molecule possesses a dipole
(b) Since fluorine is more electronegative moment. CH2Cl is thus a polar molecule.
than boron, each B – F bond in BF3
is polar and three bond moments are
equal. However, the symmetry of a
trigonal planar shape means that the
three bond moments exactly cancel
one another.
Resultant diple moment is indicated by

Covalent Character in Ionic bonds :

When a cation is placed near an anion, it distorts the spherical shape of the anionic electron cloud due to
its attractive force. Such a distorted anion is said to be polarized.
Since the electrons now have a better tendency to stay between the two nuclei rather than entirely on the
anion, the ionic compound is said to have acquired a certain covalent character. The tendency of cation to
polarize the anion is called its polarizing power.
The tendency of the anion to undergo polarisation is called its polarisability.
Greater the polarizing power of cation or polarisability of anion, greater is the covalent character of the
molecule.
The covalent character of an ionic compound is favoured by :

(a) A small cation : In a small cation the positive charge is concentrated over a small surface area and as
a result its effect in polarizing the anion would be large. e.g, the covalent character of the chorides of
the Be group decreases in the order, Be > Mg > Ca > Sr > Ba.
(b) A large anion : Large anions have a high polarisability since their outermost orbitals are shielded from
the positive nuclear field by a number of completely occupied orbitals and are thus readily polarized by
a suitable cation. E.g, the halides of Ca; the covalent character increases in order
CaF2 < CaCl2 < CaBr2 < CaI2. ; polarisability is F < Cl < Br < I
(c) There should be a high charge on either the cation or the anion or both. It is obvious that the electrostatic
forces which cause polarization will be considerably enhanced, if the ions are highly charged. e.g.,
polarizing power of cations increases in the order Na+ < Mg2+ < Al3+ (all the three are isoelectronic).
(d) The cation should possess an electronic configuration which is not that of an “inert” gas. It follows that
the noble gas electronic configuration must be the most effective in shielding the nuclear charge of a
cation from its surface. Cations without this configuration will have high positive field at their surface
and consequently will have high polarizing powers.
The combined influence, of ionic size and charge on the polarizing power of a cation is sometimes
cationic charge
expressed in terms of ionic potential.  
cation radius

Vidyamandir Classes The Chemical bond - I
Fazan rule is used to decide relative ionic and covalent character in molecules. According to this rule a
molecule is predominant covalent if :
 smaller the size of cation
 larger the size of anion
 greater the charge on cation and anion.
 ion does not have inert gas configuration.
We can also say that these factors favour polarisation.
Note : Greater the covalent nature
 lower the mp/bp
 smaller conducting nature
 lower solubility in polar solvent
 higher solubility in non polar solvent.
(a) LiCl, NaCl, KCl, RbCl, CsCl
Size of cation is the deciding factor (charge of each ion and size of Cl is same)
  
Li  Na  K  Rb  Cs  
  size of cation

 polarisation
LiCl  NaCl  KCl  RbCl  CsCl
 covalent
 mp/bp

 conductivity

 solubility in H2O (polar solvents)



 solubility in non polar solvent
(b) NaF, NaCl, NaBr, NaI
Deciding factor is the size of the anion. Larger size of the anion, greater the polarization hence greater
the covalent nature.
 
F  Cl  Br  I  
 size of cation
F  Cl  Br   I
 polarisation
NaF  NaCl  NaBr  NaI
 covalent nature

(c) NaCl, MgCl2, AlCl3, SiCl4, PCl5
Na   Mg 2   Al3  Si4   P5
 size of cation
 charge on cation


Note : Greater the charge, smaller the size then greater the polarisation
Na   Mg 2  Al3  Si4   P5

 polarisation
2NaCl  MgCl  AlCl  SiCl  PCl
3 4 5  covalent nature

(d) NaF, Na2O, Na3N
F  O 2   N 3
  size of anion
F  O2   N3
 charge on anion

F  O2   N3
  polarisation
NaF  Na O  Na N
2 3 covalent nature

(e) CuCl and NaCl
[Cu+] [Ar] 3d10
[Na+] [Ne]
Cations with 18– electron shells have greater polarising power than the 8-electron shell ions with the same
charge and size. This is due to the increased electronegativity of the 18-electron shell ions as the inner
electrons have poor shielding effect on the nucleus. Thus CuCl is covalent and NaCl is ionic.
SHAPES OF MOLECULES (VSEPR THEORY) Section - 5
The shapes or geometry of a molecule is quite accurately predicted by VSEPR (Valence Shell Electron Pair
Repulsion) theory. According to this theory all valence shell electron pairs surrounding the central atom
arrange themselves in such a manner as to be as far away from each other as possible. By separating
the electrons from each other, the electrostatic repulsion, (that is the cause of higher energy), is minimised. As
a result each molecule tends to acquire a state of lowest energy.
The basic ideas can be summarized as follows :
Valence shell pairs of electrons are arranged about the central atoms so that repulsion among them is minimised,
or so that there is maximum separation among the regions of high electron density (bond pairs) about the
atom. For instance, two regions of high electron density would be most stable on opposite side of the central
atom (Linear arrangement), while three regions would be most stable when they are arranged at the
corners of an equilateral triangle Trigonal planar arrangement). The resulting arrangement of these regions
is referred to as the electronic geometry of the the central atom.

Number of Bond Pairs Electronic Geometry Bond Angles

2 Linear 180o
3 Trigonal planar 120o
4 Tetrahedral 109o 28
5 Trigonal Bi-pyramidal 90o, 120o , 180o
6 Octahedral 90o, 180o
As mentioned earlier, there are two distinct types of electron pairs around the central atom : Bonding electron
pairs (bp) and Nonbonding electron pairs or lone pairs (–lp). The strength of repulsion between the electron
pairs varies as :
–lp-–lp > –lp-bp > bp-bp
This is very significant while deciding the final geometry of a molecule. We will divide our study of shapes in
two categories :
 The molecules containing only bondpairs of electrons and
 The molecules containing both bondpairs and lone (non-bonding) pairs.
Note : Before we go into the details of shapes, first let us discuss the Theory of Covalent Bonding.
THEORIES OF COVALENT BONDING Section - 6
Orbital theory of Covalent Bonding :

As discussed earlier that covalent bonding is the result of sharing of electrons between atoms. The main
requirement for sharing of electrons is: only a single electron must be present in an orbital of the outer
shell. Such an orbital (i.e. containing an odd electron) will combine with another orbital (containing an odd
electron but of opposite spin) of same kind or of another kind of atom to form covalent bond. This combination
of orbitals is known as overlapping of orbitals. So according to atomic orbital theory, the covalent bond is
formed by the overlapping of atomic orbitals having electrons with opposite spins, belonging to the
external shells of two atoms of same or of different kinds. After overlapping the electronpair now belongs
to both the orbitals of two atoms.
Depending upon the types of orbitals which take part in overlapping, we can classify overlapping as follows:
(a) ss overlapping (b) sp overlapping (c) pp overlapping
From above, we observe that overlapping can further be analysed as lateral and end to end. ss, sp and one
of pp type overlapping is of end-to-end type and one of the pp overlapping is of lateral type.

Sigma () bond : The bond formed as a result of end to end type of overlapping is called as  bond. Here
overlapping of orbitals takes place along the same axis. The bond formed by this type of overlapping is very
strong as the extent of overlapping is sufficiently high. The extent of overlapping determines the strength
of covalent bond. In sigma bond, the electron density accumulates between the centres of the atoms being
bonded and lies on the imaginary line joining the nuclei of bonded atoms.
Pi () bond : The bond formed between two atoms by the sideways overlapping (also called lateral
overlapping) of the two halffilled orbitals is called a pi () bond. The extent of overlapping in case of a pi
bond is much less than in sigma bond, so strength of pi bond is low. In this bond, the electron density lies
above and below the imaginary line joining the centres of nuclei of bonded atoms. Whenever there is multiple
bonding, i.e., double and triple bonds, pi bond is formed.
Hybridisation and Hybrid Orbital :

The electronic configuration of carbon (C), 1s2 2s22p2, is rather misleading if we talk about the tetravalency
of carbon (which is its most common valency in its compounds). Its configuration predicts the carbon to
divalent due to two unpaired p electrons. This is actually not the case. In bond formation, the atomic orbitals
of carbon atom are mixed in such a manner as to produce four equivalent orbitals, which are confined to
the corners of a regular tetrahedron, in order to maximise the separation among them (VSEPR theory). The
mixing of atomic orbitals in order to produce new orbitals is called as Hybridisation. This concept was given
by Linus Pauling in 1937. This concept not only predicts the correct shapes but also explains the actual
microscopic observations of the geometry of molecules. The different cases of hybridisation arise by mixing
of s, p and d orbitals are discussed below.
sp3 Hybridisation :
This type of hybridisation results from mixing of one s, three p orbitals of outer (valence) shell of an atom. To
understand the concept clearly, let us consider the formation of CH4 molecule. The outer-shell configuration
of C atom in ground state is 2s22px12py1. Note that 2pz orbital is empty. One of the electrons in the 2s2
orbital is excited (or promoted) to this vacant 2pz orbital. This results in the following picture.

Ground state Excited state

2s2 2px1 2py1 
 one electron excited   2s1 2px1 2py1 2pz1
to a 2pz orbital
(This step requires energy)
After the electron is promoted, all the four orbitals are mixed to give four equivalent hybrid orbitals (in sense
that all of them are of equal energy) called as sp3 hybrid orbitals.
2s1 2px1 2py1 2pz1   mixed or hybridised   four sp3 hybrid orbitals
These four hybrid orbitals are of same energy and equivalent in every other way. They are directed at the
corners of a regular tetrahedron. This is best geometry for four bonded pairs to be at the maximum distance
apart and thus minimise the repulsion and hence the energy of the system is minimised. Each of four sp3
orbitals in carbon can now combine with a 1s orbital of a hydrogen atom, forming four equivalent CH bonds
involving sp3s overlapping and forming four sigma bonds. The extent of overlapping by hybrid orbitals is
very high due to their strong orientation in space or one can now imagine a bond formed by hybrid orbital to
be highly stable. This additional stability accounts for the energy required in the promotion step before
mixing.
sp2 hybridisation :
To account for the shapes of molecules like BF3, BCl3 etc., let us consider the valence-shell configuration of
Boron: 2s2 2px1. Note that py and pz orbitals are vacant, so promotion of one 2s electron takes place to 2py
orbital to account for three B-F bonds in BF3.
2s2 2px1   2s1 2px1 2py1
 one electron excited 
to a 2py1 orbital
from a 2s orbital
The three orbitals in excited state are mixed to give three sp2 hybrid orbitals of equivalent energy. These are
all in a same plane with central atom (Boron) at the centre of an equilateral triangle with three sp2 orbitals at
its corners. This is the best possible geometry for three bondpairs to be at maximum distance (VSEPR
theory). Each of these orbitals now form three sigma bonds with three 2p orbitals of F atoms to form BF
bonds and hence forms a BF3 molecule.

sp hybridization :
A sp hybrid orbital is formed when in an atom one s and one p orbital mix with each other to form two
equivalent orbitals. Two such orbitals, i.e., sp hybrid orbitals are most stable when they adopt an angle of
180 between them so that they are at the maximum distance apart. It means that the molecule involving sp
hybrid orbitals will be linear in shape. The geometry of BeF2 is linear and is explained by sp hybridisation of
Be atom. The valence shell configuration of Be is 2s2 which means one electron from 2s orbital can be
promoted to vacant 2p orbital and form the excited state.
2s2   2s1 2px1
 promotion of one s electron 
to a px orbital
The 2s1 and 2px1 electron can now mix or hybridised to give two sp hybrid orbitals, which form two sigma
bonds with F atoms (as in BF3) to form BeF2 molecule.
sp3d hybridisation (PF5 molecule) :

Since phosphorus is the central element in PF5 molecules, it must have five halffilled orbitals to form bonds
with five Fluorine atoms. Hybridisation is again the answer. This time using one d orbital from the vacant set
of 3d orbitals in addition ot the 3s and 3p orbitals of the phosphorus atom.
3s2 3p3 3d0   3s13px1 3py13pz1 3d1
 promotion of one s electron 
to a vacant d orbital

The five sp3d hybrid orbitals are directed toward the corners of a trigonal
bipyramid. Each is overlapped by the (only) 2p orbital of a Fluorine atom
that contains a single electron. The resulting pairing of P and F electrons
forms a total of five covalent bonds.
sp3d2 hybridisation (SF6) :

The sulphur atoms can form six hybrid orbitals to accommodate six electron pairs, and in Valence Bond
theory terminology, we have :
2 4 0  3s13px1 3py13pz1 3d13d1
3s 3p 3d   promotion of one s electron 
and p electron to a vacant d orbitals
The six sp3d2 hybrid orbitals are directed toward the corners of a regular
octahedron. Each sp3d2 hybrid orbital is overlapped by a halffilled 2p
orbital from Fluorine to form a total of six covalent bonds.
We should note the sp3d hybridisation involves utilisation of an available d
orbital in the outermost shell of the central atom, P. The heavier Group 15
elements P, As, and Sb, can form five co-ordinate compounds utilising this
hybridisation. But it is not possible for Nitrogen (also in Group 15) to form
such fivecoordinate compounds. Why ?
(i) Nitrogen is too small to accommodate five (even very small) substituents without excessive crowding
which causes instability.
(ii) It has no low-energy d orbitals.
In fact, we can generalise; no element of the second period can be central element in five–coordinate molecules
(or higher–coordinate ones) because they have no low energy d orbitals available for hybridisation and
because they are too small.
It is important to realise that the set of s and p orbitals in a given energy level, and therefore any set of hybrids
composed only of them, can accommodate a maximum of eight electrons and participate in a maximum of
four covalent bonds.
In the following section, we will discuss the hybridisation of molecules in which the central atom has
lone pair(s). The actual geometry of the molecule containing one or more lone pairs of electrons is
different from the geometry (distorted Geometry) which is expected from the type of hybridisation
involved in the molecule.

sp2 hybridisation in SnCl2:

The outer electronic configuration of Sn is 5s2 5px1 5py1. To explain the
shape of SnCl2, the concept of hybridisation is applied. Here one 5s, two
5p orbitals hybridise to give three sp2 hybridised orbitals of equivalent
energy.
In this case one of the hybrid orbitals contains a lone pair, whereas other two contain an electron each. These
two orbitals containing one electron overlap with two 3p orbitals of two chlorine atoms to form two SnCl
bonds. The geometry of SnCl2 molecule should have been Trigonal planer, but due to presence of lone pair
over the central atom (Sn), there is some distortion in the shape of the molecule. The bond angle is slightly
less than 120 and the molecule is bent or Vshaped. The reason is the greater repulsion between a bp
and a –!p than normal bpbp repulsion.
sp3 hybridisation in NH3 and H2O molecule :

In Ammonia, NH3 : N is the central atom and its outershell configuration is
2s2 2px1 2py1 2pz1. One s orbital (containing a lone pair) hybridises with
three p orbitals (containing one electron each) to give four sp3 hybrid orbitals.
Of these four hybrid orbitals, the three orbitals containing one electron each
overlap with three 1s orbitals of three Hatoms to form NH bonds.
Due to lone pair over N, the geometry of the molecule gets distorted from regular tetrahedron (which is the
exact geometry for sp3 hybrid orbitals) and the bond angle changes from 109.5 to 107 The final shape is
pyramidal where N is at the centre with three Hatoms forming the base and the lone pair forming the apex
of the pyramid.
In Water, H2O : O is the central atom with 2s2 2px2 2py1 2pz1 as its
outershell configuration. Here, one s orbital (containing a p), one p
orbital (containing a p) and two p orbitals (containing one electron
each) hybridises to give four sp3 hybrid orbitals of equivalent energy.
Of these two orbitals (containing one electron each) overlap with two
1s orbitals of H atoms to form two OH bonds.
Due to two ps over O atom, the actual geometry of molecule is distorted. Apart from pbp repulsion,
pp repulsion also exists in this molecule, so the distortion is much greater than the ammonia molecule. The
bond angle changes form 109.5 to 104.5 in water and the final is bent or Vshaped.
Note : The actual geometry of the molecule containing one or more p of electrons is different form the geometry
which is expected from the type of hybridisation involved in the molecule.

Hybridisation and Multiple Bonding : (Shapes of C2H4 and C2H2)

Geometry of C2H4 molecule :
In ethylene (C2H4), two carbon atoms in the excited state
undergo hybridisation in a different manner than the carbon
atom in C2H4 molecule. After the promotion of one 2s
electron to the vacant 2p orbital, one s orbital and two p
orbitals of two carbon atoms hybridises to form three sp2
hybrid orbitals (leaving one p orbital in unhybridised state).
Now one of the sp2 hybrid orbitals of each carbon atom overlaps with each other to form one CC bond
(sigma bond) and other two hybrid orbital of two carbons overlaps with 1s orbitals of H atoms to form four
CH bond (sigma bonds) in total. It is important to note that two unhybridised p orbitals are perpendicular
to the plane of three sp2 orbitals. These two p orbitals form a pi () bond with each other (Recall the
formation of pi bond).
We, now observe that two covalent bonds that make up the double bond between the carbon atoms are not
equivalent, they are different. One of them is a sigma () bond and other is the pi () bond.
Geometry of C2H2 molecule :

In acetylene (C2H2), after achieving the excited states, both
the carbon atoms undergo sp hybridisation. One s orbital
and one p orbital hybridise to form two sp hybrid orbitals
(leaving two p orbitals in unhybridised state perpendicular
to the plane of sp hybrid orbitals). Now one sp hybrid
orbital belonging to each carbon atom form a CH sigma
bond and other sp hybrid orbital form sigma bond with 1s
orbital of H atom (in all two CH bonds).
Two unhybridised p orbitals of each carbon atom form two pi bonds with each other. This means that a
carbon-carbon triple bond comprises of one sigma bond and two pi bonds.

TYPES OF BONDING IN A COMPOUND & INTERMOLECULAR FORCES Section - 7
From the difference in electronegativities of the atoms forming a bond, it can be predicted what type of
bond is formed by the atoms. When the difference is zero or very small, the bond is essentially covalent,
and the electron density is more or less equally share d by two atoms. When the difference is large, one atom
more-or-less completely withdraws the electron pair to it (one having higher electronegativity) and the bond
is ionic. A bond AB (between two atoms A and B) is Ionic if difference in electronegativities of A and B is
greater than 1.7 and it is Covalent, if it is less than 1.7.
 Metals form Ionic bonds by losing electrons. However some metals form covalent bonds also and some
don’t form covalent bonds at all. The tendency of normal metals increases to form covalent bond as we
proceed from left to right across a period in the Periodic Table, e.g., Ce and Ba form only Ionic bonds, Pb
and Bi form both Ionic as well as Covalent bonds. Also metals rarely form bonds with other metals.
 Non-metals form Ionic bonds by gaining electrons. All non-metals can also form Covalent bonds as well.
The tendency to form Ionic bond increases in going from left to right across a period and in going down the
group, e.g., C forms only Covalent bond, F forms both Covalent as well as Ionic bonds. O forms O2– in few
compounds whereas S forms S2– in many compounds.
Note : Most compounds of metals with non-metals are ionic and most compounds of non-metals with nonmetals
are covalent.
 Some non-metals such as C, Si, Ge, N, P, O are very reluctant to form negative ions. C, Si, Ge form only.
Covalent bonds whereas N, P, O can form both Ionic and Covalent bonds.
Note : If these atoms form Ionic bonds, they also form Covalent bond with some other atom in the same compound.
For example: In KOH, O forms Ionic bond with K but forms Covalent bond with H.
Metallic Bond :
Metals have low ionisation energies and hence valence electrons in them
are weakly bounded to the positive charged nucleus or kernel (kernel
means nucleus and the electrons other than the valence electrons). In
metals the number of valence electrons is less than the number of orbitals
to hold them. This makes possible for an electron to pass from one another
through overlapping orbitals. Consider the case of Li, which has one s
valence electron. In the solid crystal, each Li atom is close to eight other
atoms, so that its orbitals will overlap with all of them at the same time and
this picture is continued throughout the crystal. The electrons are shared
by all the atoms, i.e., they are delocalised throughout the crystal.
So metal is network of ions (kernels) in a sea of electrons, with the electron sea acting as the binding force
which holds the metal ions (kernels) together.

The valence electrons are not associated with any particular atom and can therefore move here and there. If
the two ends of piece of a metal are connected to the poles of a battery, electrons will move towards the
positive pole of the battery where they will flow out of the metal into the battery, being replaced by fresh
electrons from the negative pole of the battery. In this manner an electric current can be conducted by the
metals.
Intermolecular Forces
Intermolecular forces are the sum of the forces of attraction and repulsion between interacting particles
(atoms and molecules). Attractive intermolecular forces are known as van der Waals forces, in honour of
Dutch scientist Johannes van der Waals (1837-1923), who explained the deviation of real gases from the
ideal behaviour through these forces (You will study about this in ‘States of Matter’). These forces are other
than due to covalent bonds, the hydrogen bonds, or the electrostatic interaction of ions with one another or
with neutral molecules or charged molecules. The term includes:
 force between two instantaneously induced dipoles (London disperison force)
 force between two permanent dipoles
 force between a permanent dipole and a corresponding induced dipole
Note that attractive forces between an ion and a dipole are known as ion-dipole forces and these are
not van der Waals forces.
Dispersion Forces or London Forces

Atoms and nonpolar molecules are electrically symmetrical and have no dipole moment because their electronic
charge cloud is symmetrically distributed. But a dipole may develop momentarily even in such atoms and
molecules. This can be understood as follows. Suppose we have two atoms ‘A’ and ‘B’ in the close vicinity
of each other [Figure (a)]. It may so happen that momentarily electronic charge distribution in one of the
atoms, say ‘A’, becomes unsymmetrical i.e., the charge cloud is more on one side than the other [Figure (b
and c)]. This results in the development of instantaneous dipole on the atom ‘A’ for a very short time. This
instantaneous or transient dipole distorts the electron density of the other atom ‘B’, which is close to it and as
a consequence a dipole is induced in the atom ‘B’.
The temporary dipoles of atom ‘A’ and ‘B’ attract each other. Similarly temporary dipoles are induced in
molecules also. This force of attraction was first proposed by the German physicist Fritz London, and for this
reason force of attraction between two temporary dipoles is known as London forces. Another name for this
forces is dispersion force.

These forces are always attractive and interaction energy is inversely proportional to the sixth power of the
distance between two interacting particles (i.e., 1/r6 where r is the distance between two particles). These
forces are important only at short distances (~500 pm) and their magnitude depends on the polarisability of
the particle.
Dipole - Dipole Forces

Dipole-dipole forces act between the molecules possessing permanent dipole. Ends of the dipoles possess
“particle charges” and these charges are shown by Greek letter delta (). Partial charges are always less
than the unit electronic charge (1.6 × 10–19 C). The polar molecules interact with neighbouring molecules.
Figure (a) shows electron cloud distribution in the dipole of hydrogen chloride and Figure (b) shows dipole-
dipole interaction between two HCl molecules. This interaction is stronger than the London forces but is
weaker than ion-ion interaction because only partial charges are involved.
The attractive force decreases with the increase of distance between the dipoles. As in the above case here
also, the interaction energy is inversely proportional to distance between polar molecules.
(a) Distribution of electron cloud in HCl a polar molecule, (b) Dipole-dipole interaction between two molecules
Dipole-dipole interaction energy between stationary polar molecules (as in solids) is proportional to 1/r3 and
that between rotating polar molecules is proportional to /r6, where r is the distance between polar molecules.
Besides dipoledipole interaction, polar molecules can interact by London forces also. This cumulative effect
is that the total of intermolecular forces in polar molecules increase.

Dipole-Induced Dipole Forces

This type of attractive forces operate between the polar molecules having permanent dipole and the molecules
lacking permanent dipole. Permanent dipole of the polar molecule induces dipole on the electrically neutral
molecule by deforming its electronic cloud. Thus an induced dipole is developed in the other molecule. In this
case also interaction energy is proportional to 1/r6 where r is the distance between two molecules. Induced
dipole moment depends upon the dipole moment present in the permanent dipole and the polarisability of the
electrically neutral molecule. We have already learnt in Unit 4 that molecules of large size can be easily
polarized. High polarisability increases the strength of attractive interactions.
In this case also cumulative effect of dispersion forces and dipole-induced dipole interactions exists.
Hydrogen Bonding :
Molecules that contain FH, OH, NH bonds (e.g., Water, Alcohols, Organic acids, Amines, Aromatic
alcohols, etc.) show a strong tendency to associate, i.e., to link up to form larger molecules. This feature
exists in solid form and as well as in solutions in certain solvents. In all of such compounds, OH, or NH or
FH, bond is highly polar due to large difference in electronegativity. The electrostatic attraction between
such molecules should be quite strong. The positive end of one molecule attracts and is strongly attracted by
the negative end of the neighbouring molecule. In this manner a large number of molecules are associated to
form a cluster of molecules. Since in each case the hydrogen atom is responsible for the formation of linkages,
this is known as Hydrogen bond or H-bond. It is impossible for hydrogen to form a second covalent bond
so the additional linkage is shown by a dotted line. Hydrogen bonds are always of type : AH....B,
where A and B may be atoms of O, F, N. Hydrogen bonds are comparatively weak, with bond energies of
10100 kJ/mol, but they are widespread and have important effect on many physical properties of many
Organic and Inorganic compounds.
δ δ δ δ δ δ
H  F ........... H  F R O ............ H  O
| |
H R

Hydrogen Bonding is of two types :

(i) Intermolecular H-bonding (ii) Intramolecular H-bonding
You will learn about Hydrogen Bonding in the Chapter Chemical Bonding-II
RESONANCE Section - 8
There are certain molecules whose properties can not be explained by a single structure.
For example : The molecules of CO32 ion, three Lewis dot structures are possible. Similarly Lewis structure
for ozone (O3) shows that one of O atom is bounded to a O atom by a double bond and by a coordinate
covalent bond to the other O atom and there are two possible structures for it.
2 2 2
 O   O   O 
 |   |   || 
 O  C  O    O  C  O 
  O  C  O 

The length of three bonds in CO32 ions and two bonds in O3 is expected to be different. However from
spectroscopic analysis, it is observed that the lengths of bonds are equal and lie somewhere between that of
a single and double bond. Hence a particular structure is not sufficient to account for the observed facts.
The actual structure of CO32 ion and O3 molecule has neither of these Lewis structures. The real structure is
an average (midway between) of these structures. This phenomenon of representing the actual structure in
such a manner is called as Resonance. The individual structures are known as Canonical forms or Resonance
structures. The actual structure is called as Resonance hybrid.
Thus resonance hybrid may be defined as the actual structure of all the canonical forms that are possible for
a given molecule without changing the relative positions of its atoms. The resonance hybrid is more stable
than any of the other canonical forms. The difference in the energy between the resonance hybrid and the
most stable canonical form is called as Resonance energy. The more the number of possible resonating
forms, the higher is the resonance energy and hence more is the stability of the compound.

The resonating structure of a few more molecules and ions are shown below :
Total number of bonds

Note : Bond order (B.O.) =
Number of resonating structure
Effects of Resonance :
 It imparts stability to the molecule and hence decreases its reactivity. The reactivity of the molecule is
decreased due to delocalisation of electrons over the entire surface of the molecule.
 Since the electrons are not localised between any particular atoms, and are uniformly distributed in the
resonance hybrid, all the bond are similar and are of equal bond lengths. The bond length of a single
covalent is decreased as a result of resonance.
Illustration - 8 The bond length of normal C = O double bond is 121 pm. However each carbon to
oxygen bond length in CO2 is found to be 115 pm. Explain the structure of CO2 molecule.
SOLUTION :
If we consider only structure I for CO2 molecules there should be two carbon to oxygen double bonds.
As per question the bond length of normal C = O double bond is 121 pm. However, each carbon to
oxygen bond length in CO2 is found to be 115 pm which is in between that of C = O DOUBLE BOND
(121 pm) and C = O triple bond (110 pm). Hence, CO2 is considered a resonance hybrid of the follow
ing three Lewis structures.
 
O = C = O  O  C  O   O  C  O
[I] [II] [III]

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Chemical Bonding - II Vidyamandir Classes
Chemical Bonding - II
Till now we have learnt about the various aspects of chemical bonding. In this part of the chapter we will try to
summarize the method to find shapes and hybridisation of molecules and will also learn about Molecular Orbital
Theory.
BACK BONDING Section - 1
Back () bond is a co-ordinate bond formed between electron rich atom (donor) and neighbouring electron
deficient atom or atom having vacant orbital (acceptor) of a molecular species. For example in BF3 back
bonding is due to by donation of an electron pair from filled orbital of fluorine atom to vacant p-orbital of
boron.
This back () bonding may results in change in hybridization state, molecular geometry, bond angle, bond
strength and Lewis basic strength. For example in N(SiH3)3 hybridization state of nitrogen atom is sp2 and it
is not a Lewis base.
Further this back () bonding can be PP and Pdtype depending upon type of filled orbital and
vacant orbital. For example:

Vidyamandir Classes Chemical Bonding - II
Illustration - 1 Account for the fact that Lewis acid character of BF , BCl and BBr increases as BF <
3 3 3 3
BCl3 < BBr3 .
SOLUTION:
The increasing order of Lewis acid strength (or the three BF bonds in BF3.
character) (BF3 < BCl3 < BBr3) can be
explained on the basis of the concept of (p Back bonding in BF3 molecule is supported
p) back bonding that takes place in given by the fact that the observed BF bond length
halides. in BF3 which is equal to 1.30 is significantly
shorter than the sum of the covalent radii of B
We know that in each of the given trihalide
molecules B-atom is sp2 hybridised and has and F atoms (B = 0.80 , F = 0.72 , Sum
one unused vacant 2p orbital. Each of the three = 0.80 +0.72 = 1.52 ).
halogen atoms in each BX3 molecule (X : F,
Cl, Br) has three pairs of electrons which are The formation of (pp) bond results in that
present in s and p-orbitals respectively ( F = the electron pair is transfered from Fatom to
2s2 2p2 2p2 2p1 ; Cl = 3s2 3p2 3p1 ; Br = 4s2 the electron deficient Batom and hence
4p2 4p2 4p1). porbital having unpaired electron density on Batom in BF3 molecule is
electron is used up in forming BX bond in increased or the tendency of Batom to accept
BX3 molecule by overlapping with singly-filled the electron pair is decreased, i.e. the Lewis
sp2 hybrid orbital of Batom. acid strength of BF3 molecule, according to
lewis concept, is also decreased.
In BF3 molecule, vacant 2p orbital on Batom
an fully-filled 2p orbital of Fatom overlap We have seen above that (pp) back
sidewise to form (FB) bond which is called bonding in BF3 molecule result from [2p2(F)
dative or (pp) bonding It is due to (p 2p0(B)] sidewise overlap, but the same in BCl3
p) back bonding that BF bond acquires and BBr3 molecules is obtained by [3p2(Cl)
2p 0(B)] and [4p 2(Br)2p 0(B)] sidewise
overlaps respectively.
Now since the energy and shape of two 2p
orbitals (one 2p orbital on Batom an one 2p
orbital on F-atom) involved in [2p2(F)2p0(B)]
overlap to from (pp) bonding in BF3
molecule is the same, this overlap is symmetrical
and hence is the most effective. Consequently
the transfer of electron pair from 2p orbital of
Fatom to the vacant 2p orbital of Batom
some double bond character. takes place to the maximum extent and hence
Formation of pp back bonding in one of maximum electron density developed on B

atom in BF3 molecule. Due to maximum and hence minimum electron density is
electron density developed on B-atom in BF3 developed on Batom in BBr3 molecule. Due
molecule, this molecule shows minimum to minimum electron density developed on B
tendency to accept electron pair donated by a atom, BBr3 molecule shows maximum tendency
Lewis base (electron pair donor species) and to accept electron pair donated by a Lewis base
hence is the weakest Lewis acid. On the other and hence is the strongest Lewis acid.
hand, since the energy and shape of 4p orbital
Above discussion shows that the tendency to
of Br atom and 2p orbital of B-atom involved
form (pp) back bonding decreases rapidly
in [4p2 (Br)2p0 (B)] overlap in BBr3 molecule
as we move from BF3 to BBr3 and hence the
is largely different, this overlap is unsymmetrical
tendency of BF3, BCl3 and BBr3 molecules to
and hence is the least effective.
accept electron pair from Lewis bases
Consequently the transfer of electron pair from increases in the same direction, i.e. Lewis acid
4p orbital of Bratom to the vacant 2p orbital strength (or character) increases as BF3 < BCl3
of B-atom takes place to the minimum extent < BBr3.
Illustration - 2 (pp) back bonding occurs in the halides of boron but not in those of aluminium. Explain.
SOLUTION :
The tendency of the central atom (A) in AX3 molecules (A = B or Al, X = halogen) to from (pp) back
bonding depends on the size of the central atom (A). Smaller is the size of the central atom, greater is its
tendency to form (pp) back bonding. Since Batom is smaller in size than Alatom, BX3 molecules
have (pp) back bonding while AlX3 molecules do not have this type of back bonding.
Illustration - 3 Explain why AlCl exists as a dimer, (AlCl ) or Al Cl while BCl exits as a monomer.
3 3 2 2 6 3
OR Explain the formation of dimeric structure of AlCl3 in benzene (inert solvent) and in the vapour state.
OR Explain why all Al-Cl bonds in Al2Cl6 are not equivalent.
SOLUTION :
In AlCl3 molecule, Al-atom is surrounded by six electrons which are less by two electrons from an octet. In
dimeric structure (Al2Cl6), Alatom of both AlCl3 molecules completes its octet by accepting an electron
pair from Cl-atom of the other AlCl3 molecule as shown. Thus we see that in Al2Cl6 dimer each Al-atom is
holding four large-sized Cl-atoms around it.
Since B-atom is very small in size, this atom is not capable of holding four large-sized Cl-atoms around it in
B2Cl6 molecule and hence BCl3 molecule cannot dimerise to form dimeric molecule, (BCl3)2 or B2Cl6.

The formation of dimeric molecule, Al2Cl6 can be explained on the basic of hybridisation concept as follows.
We know that in AlCl3 molecule Al-atom (Al = 3s1 3p1 3p1 3p0) is sp2 hybridised and one 3p orbital remains
vacant and unhybridised. In AlCl3 molecule Al has coordination number equal to 3. In the formation of
Al2Cl6, the vacant and unhybridised 3p orbital on Al-atom of one AlCl3 molecule receives a lone pair of
electrons from 3p orbital of Cl-atom (Cl = 3s2 3p2 3p2 3p1) of the other AlCl3 molecule and thus forms a
[3p2 (Cl) 3p0 (Al)] coordinate bond. In this way each Al-atom completes its octet and coordination
number of Al-atom is increased from 3 (in AlCl3) to 4 (Al2Cl6). Thus we see that two bridges are formed by
two Cl-atoms between two Al-atoms.
The structure of Al2Cl6 has six Al-Cl covalent bonds and two Cl Al coordinate bonds, these bonds
donot have equal length, i.e. all Al-Cl bonds in Al2Cl6 are not equivalent.
APPLICATION OF DIPOLE MOMENT Section - 2
(i) To decide polarity of the molecule : Molecules having zero dipole moment  are said to be non-polar
molecules and those having R 0 (resultant dipole moment) are polar in nature.
(ii) To determine percentage of ionic charcter : The value of dipole moment can be used for determining
the amount of ionic character in a bond.
 = q  d
Consier a diatomic molecules say HCl. Suppose this molecule is completely ionic. Under this condition H+
and Cl– ions would bear a unit charge equal to 4.8 × 10–10 esu and the bond distance between H and Cl
atoms = 1.27 Å.
Thus, theoretical value of  = 4.8 × 10–10 × 1.27 × 10–8 = 6.09 D
Dipole moment of HCl is also determined experimentally. Let the experimental value be 1.03 D. Percentage
Experimental value of  1.03
of ionic character in H — Cl bond in HCl molecule = 100  100  16.9%
Theoretical valueof  6.09
Experimental value of dipole moment

Thus, percentage of ionic character =  100
Theoretical value of dipole moment
(iii) To determine geometry of molecules : The values of dipole moments provide value information
about the structure of molecules.
(a) CO2, CS2 molecules are linear as value of their dipole moments are zero.
(b) H2O is not a linear molecule as it has dipole moment. Actually, it has V-shaped structure and the
bond angle is 105°. Similary, SO2 has a bent structure.
(c) In ammonia, three hydrogen atoms do not lie symmetrically with respect to nitrogen as it has dipole
moment. It has pyramidal structure.

(iv) To determine orientation in benzene ring : Dipole moment is useful to ascertain the orientation of
substituents. In general, dipole moment follows the order :
Ortho-isomer > meta-isomer > p-isomer
Observe that :
o   m   p
In ortho isomers, experimental value of dipole moment is found different from theoretical value of dipole
moment. This difference is due to dipole-dipole interaction of two groups.
(v) Bond moment : The contribution of individual bond in the dipole moment of a polyatomic molecule is
termed bond moment. The measured dipole moment of water molecule is 1.85 D. This dipole moment is
the vectorial sum of the individual bond moments of two O — H bond having bond angle 104.5°.
Thus, obs = 2O — H cos 52.25
1.85 = 2O — H × 0.6129
O — H = 1.51 D

PREDICTION OF GEOMETRY (SHAPE) OF COVALENT MOLECULES Section - 3
Geometry of a molecule can be predicted if the state of hybridization at central atom is known. State of
hybridization at central atom in a molecule can be known by counting the number of orbitals involved in co-
axial overlapping and the number of orbitals with lone pair of electons, i.e., by counting the number of -
bonds and the number of lone pair of electrons at central atom. Adding the two if total is 4, the hybridization
is sp3, if this total is 3, the hybridization is sp2 and if this total is 2, the hybridization is sp. A few examples are
being given below :
(a) Beryllium chloride (BeCl2)

Outer Electronic Configuration of Be = 2s2
Since there are two chlorine atoms, hence Beryllium must be forming a single bond with each of them (as
chlorine has a valency equal to 1).
 This implies that before bonding there should be two orbitals around Beryllium having exactly one
electron in each of them so that they are available for overlapping with the respective orbitals of the
chlorine atoms.
 Thus we excite one of the electrons present in 2s orbital to 2p orbital to generate two singly occupied
orbitals.
 Outer Electronic Configuration of Be (after excitation of electrons) = 2s1 2p1.

 Now before bonding 2s and 2p orbital hybridize to produce two sp orbitals of same energy and
same shape which overlap with p orbital of incoming chlorine atom to form two sigma bonds.
 Number of -bonds (bond pairs) at Be atom = 2 and
Number of lone pair of electrons at Be atom = 0 , Total number of electron pairs = 2 + 0 = 2
Hybridization is sp, i.e., BeCl2 is linear and bond angle is 180
(b) Boron trichloride (BCl3)
Boron is forming three bonds with three chlorine atoms.

Outer Electronic Configuration of B = 2s2 2p1
 Outer Electronic Configuration of B (after excitation of electrons)
= 2s1 2px1 2py1
 Number of -bonds (bond pairs) at B atom = 3
Number of lone pair of electrons at B atom = 0, Total number of electron pairs = 3
Hybridization is sp2, i.e., BCl3 is trigonal planar and bond angles are 120 each.
(c) Carbon tetrachloride (CCl4)

Carbon is forming four bonds with four Chlorine atoms.
Outer Electronic Configuration of C = 2s2 2p2
 Outer Electronic Configuration of C (after excitation of electrons)
= 2s1 2px1 2py1 2pz1
 Number of -bonds (bond pairs) at C atom = 4
Number of lone pair of electrons at C atom = 0, Total number of electron pairs = 4
Hybridization is sp3, i.e., CCl4 is tetrahedral and bond angles are 10928 each.
(d) Ammonia (NH3)

Nitrogen is forming three bonds with three hydrogen atoms.
Outer Electronic Configuration of N = 2s2 2p3
 Outer Electronic Configuration of N (before bonding)
= 2s2 2px1 2py1 2pz1
 Number -bonds (bond pairs) at N atom = 3
Number of lone pair of electrons at N atom = 1, Total number of electron pairs = 3 + 1 = 4

Hybridization is sp3 and geometry of NH3 molecule is tetrahedral, however the shape is trigonal pyramidal
and bond angles are not 10928 but 10645.
(e) Water (H2O)

Oxygen is forming two bonds with two hydrogen atoms.
Outer Electronic Configuration of O = 2s2 2p4
 Outer Electronic Configuration of C (before bonding)
= 2s2 2px2 2py1 2pz1
 Number of -bonds (bond pairs) at O atom = 2
Number of lone pair of electrons at O atom = 2 Total number of electron pairs = 2 + 2 = 4
Hybridization is sp3 and geometry of water molecule is tetrahedral, however the shape is bent and bond
angles are not 10928 but 104.5.
Molcecular Shapes
Note : (a) For Column 2 (Type) : Type AB3L2 means in this molecule central atom (denoted by A) has three
bond pairs (denoted by B3) and two lone pairs (denoted by L2) .
(b) For Column 3 : E = B + L
E : stands for total number of electron pairs present in the outer most shell of the central atom.
B : stands for the number of bond pairs present around the central atom.
L : stands for the number of lone pairs present around the central atom.
Hybridisation and Geometry Type E(B + L) Actual shape Bond Examples

of molecules of molecules Angle
CO 2 , HgCl2 ,
AB2 2(2  0) o
180 BeF2 , ZnCl2 ,
MgCl2 , C2 H 2 ,
HCN, BeCl2
ABL 2(1  1) N 2 , CN 

BF3 , AlCl3 ,
AB3 (3(3  0) 120o SO3 , C2 H 4 ,
NO3 , CO 2  ,
HCHO, C6 H 6
NO 2 , SO 2 ,
AB2 L 3(2  1)  120o
SnCl2
CH 4 ,SiH 4 ,
AB4 4(4  0) 109o 28 ' SO 24  , SnCl4
ClO 4 , BF4 ,
NH 4
 109.5o NH3 , PCl3 ,

AB3L 4(3  1)
PH3 , AsH3 ,
ClO3 , NF3
 109.5o H 2 O, H 2S,
AB2 L 2 4(2  2) ~ (90o PbCl2 , OF2 ,
104o ) NH 2 , ClO 2

120o
(equatorial)
AB5 5(5  0) PCl5 , SbCl5
and 90o
(Axial)
 120o
TeCl4 ,SF4 ,
AB4 L 5(4  1) and
XeO 2 F2 , IF4
 90o
AB3L 2 5(3  2)  90o CIF3 , IF3
AB2 L3 5(2  3) 180o I3 , XeF2
AB6 6(6  0) 90o SF6 , PF6 ,

SnCl6

90o
AB5L 6(5  1) (equatorial) ICl5 , BrF5
and  90o IF5 , XeOF4
(axial)
AB4 L 2 6(4  2) 90o XeF4 , ICl4
72o
AB7 7(7  0) (equatorial) IF7
and 90o
(axial)
90o
AB6 L 7(6  1) (equatorial) XeF6
and 90o
(axial)
A summary of possible shapes is given on the next page.


VSEPR and More than six Electron Pairs
It is considerably less easy to draw a distinction between apparently reasonable seven coordinate
geometries.There are several possibilities, including the pentagonal bipyramid and the capped octahedron.
Iodine heptafluoride, IF7, is a good example of a pentagonal bipyramidal geometry. The molecule XeF6 is
an interesting case. As with IF7, application of VSEPR rules suggests seven electron pairs, XeF6 is made up
from six bonding pairs and one lone pair. In fact, the structure of XeF6 is based upon a distorted octahedron,
probably towards a monocapped octahedron.
Illustration - 4 Determine the hybridisation, geometry, number of lone pair, bond pairs in the following
compounds.
SO2, SO3, NH4+, IF4+, ClF3, I3-, PF6, XeOF4
SOLUTION :
(a) Sulphur dioxide (SO2)  Each Oxygen will form another bond
with the Sulphur atom by sideways
In SO2 molecule sulphur forms bonds with (overlap or  bond).
two oxygen atoms
 Each Oxygen atom forms 1 sigma and
Outer Eletronic Configuration of O = 2s2 2p4 1 pie bond with Sulphur atom.
= 2s2 2px2 2py1 2pz1
 Sulphur atom will make 2 sigma and 2
Now between any two atoms there can only pie bonds with the oxygen atoms.
one sigma (diect) overlap. Outer Eletronic Configuration of S
 Each oxygen atom will form one sigma = 3s2 3p4 = 3s2 3px2 3py1 3pz1
bond with the sulphur atom.
 However, to complete its octet of

electrons each oxygen atom needs 2
more electrons and hence it needs to
form two bonds (or two overlaps).

Vidyamandir Classes
Since Sulphur will form 2 pie bonds, hence Each Oxygen atom forms 1 sigma and 1 pie
remove two of its outer electrons as they will bond with Sulphur atom.
take part in sideways overlap (to form the pie  Sulphur atom will make 3 sigma and 3
bond). pie bonds with oxygen atoms.
 Outer Electronic Configuration of S Outer Electronic Configuration of S
(with electrons removed) = 3s2 3px2 = 3s2 3p4 = 3s2 3px2 3py1 3pz1
 Outer Electronic Configuration of S Since Sulphur will form 3 pie bonds, hence
(before bonding) = 3s2 3px1 3py1 remove three of its outer electrons as they will
 Now before bonding 3s, 3px and 3py take part in sideways overlap (to form the pie
orbitals hybridize to produce three sp2 bond).
orbitals of same energy and same shape,  Outer Electronic Configuration of S
out of which one orbitals has two (with electrons removed) = 3s2 3px1
electrons and two orbitals are singly
occupied (one electron each) which  Outer Electronic Configuration of S
overlap with p orbitals of incoming (before bonding) = 3s1 3px1 3py1
Oxygen atoms to form two sigma  Now before bonding 3s, 3px and 3py
bonds. orbitals hybridize to produce three sp2
 Number of -bonds (bond pairs) at S orbitals of same energy and same shape,
atom = 2 which are singly occupied (one electron
each) which overlap with p orbitals of
incoming Oxygen atoms to form three
Number of lone pair of electrons at S sigma bonds.
atom = 1
 Number of s-bonds (bond pairs) at S
atom = 3
Total number of electron pairs
=2+1=3 Number of lone pair of electrons at S
atom = 0
Hybridization of sulphur in SO2 is sp2 and
geometry of the molecule is trigonal planar, Total number of eletron pairs = 3+ 0 = 3
however sinxe one of the electron pair, hence Hybridization of sulphur is sp2 and geometry
its actual shape is bent and the O-S-O bond as well as shape of SO3 is trigonal planar.
angle is less than 120o (as lp-bp) repulsion is
more than bp-bp repulsion). of incoming hydrogen atoms to form four sigma
bonds.
(b) Sulphur trioxide (SO3)
In SO3 molecule, sulphur is bonding with three
oxygen atoms.
Outer Electronic Configuration of O
= 2s2 2p4
= 2s2 2px2 2py1 2pz1

(c) Ammonium ion (NH4+) Outer Electronic Configuration of I = 5s2 5p5

In NH4+ ion, nitrogen forms four bonds with Since there is a positive charge on the ion,
four hydrogen atoms. hence remove one electron from I.
Outer Electronic Configuration of N  Outer Electronic Configuration of I (with
electron removed) = 5s2 5p4
= 2s2 2p3
 Electronic Configuration of I (after
Since there is a positive charge on the ion,
excitation of electrons)
hence remove one electron from N.
= 5s2 5px1 5py1 5pz1 5d1
 Outer Electronic Configuration of N
(with electron removed) = 2s2 2p2  Now before bonding 5s, 5px, 5py, 5pz
and 5d orbitals hybridize of produce five
 Outer Electronic Configuration of N
sp3d orbitals of same energy and same
(after excitation of electron)
shape, out of which one orbital has two
= 2s1 2px1 2py1 2pz1
electrons and the other four orbitals are
 Now before bonding 2s, 2px, 2py and singly occupied (one electron each)
2pz orbitals hybridize to produce four which overlap with the p orbitals of
sp3 orbitals of same energy and same incoming fluorine atoms to form four
shape, which are singly occupied (one sigma bonds.
electron each) which overlap with s
 Number of -bonds (bond pairs) at I
orbitals
atom = 4
 Number of -bonds (bond pairs) at N
Number of lone pair of electrons at I
atom = 4
atom = 1
Those number of electron pairs = 5
Number of lone pair of electrons at N
atom = 0. Thus hybridisation of iodine is sp3d and
geometry of IF4+ is trigonal bipyramidal,
Total number of electron pairs = 4
however since one of the electron pairs is a
Hybridization in nitrogen is sp3 and geometry lone pair, hence its actual shape is seesaw.
as well as shape of NH4+ is tetrahedral
(d) IF4+
In IF4+ ion, iodine forms four bonds with four
flourine atoms.

(e) ClF3 (f) I3-
In ClF3 molecule, chlorine forms three bonds In I3- ion, iodine forms two bonds with two
with three flourine atoms. other Iodine atoms.
Outer Electronic configuration of I = 5s2 5p5
Outer Electronic Configuration of Cl
= 3s2 3p5 Since there is a negative charge on the ion,
hence add one electron in I.
 Outer Electronic Configuration of Cl
(before bonding  Outer Electronic Configuration of I (with
= 3s2 3px2 3py1 3pz1 3d1 an electron added) = 5s2 5p6
 Electronic Configuration of I (after
 Now before bonding 5s, 5px, 5py, 5pz
excitation of electrons)
and 5d orbitals hybridize to produce five
sp3d orbitals of same energy and same = 5s2 5px2 5py2 5pz1 5d1
shape, out of which two orbitals has two
 Now before bonding 5s 5px 5py 5pz 5d
electrons and the other three orbitals are
orbitals hybridize to produce five sp3d
singly occupied (one electron each)
orbitals of same energy and same shape,
which oerlap with the p orbitals of
out of which three orbitals have two
incoming fluorine atoms to form three
electrons each and two orbitals are
sigma bonds.
singly occupied which overlap with p
 Number s-bonds (bond pairs) at Cl orbitals of incoming iodine atoms to form
atom = 3 two sigma bonds.
 Number of -bonds (bond pairs) at I
Number of lone pair of electrons at Cl
atom = 2
atom = 2
Number of lone pair of electrons at I
Total number of electron pairs atom = 3
=3+2=5
Total number of electron pairs = 5
Hybridization of chlorine is sp3d and geometry
Thus hybridization of iodine is sp3d and
of ClF3 molecule trigonal bipyramidal,
geometry of I3- ion is trigonal bipyramidal,
however it actually is a T-shaped molecule
however its actual shape is a linear because of
becuase of the presence of two lone pairs of
the presence of three lone pair of electrons.
electrons.

(g) PF6- The Oxygen atom forms 1 sigma and 1 pie

bond with Xenon atom and the four fluorine
In this ion phosphorous forms six bonds with
atoms form 1 sigma bond each with the xenon
six flourine atoms.
atom.
Outer Electronic Configuration of P = 3s2 3p3
 Xenon atom forms 5 sigma bonds and
Since there is a negative charge on the ion,
1 pie bond.
hence add one electron in P.
Since Xenon will form 1 pie bond, hence
 Outer Electronic Configuration of P
remove one of its outer electrons as they will
(with an electron added) = 3s2 3p4
take part in sideways overlap (to form the pie
 Outer Electronic Configuration of P bond).
(after excitation of electrons)
 Outer Electronic Configuration of Xe
1
= 3s 3px1 3py1 3pz 3dxy1
1
3dyz1 (with an electron removed)
 Now before bonding 3s, 3px, 3py, 3pz, = 5s2 5px2 5py2 5pz1
3dxy and 3dyz orbitals hybridize to
 Outer Electronic Configuration of Xe
produce six sp3d2 orbitals of same
(before bonding)
energy and same shape, having one
= 5s2 5px1 5py1 5pz1 5dxy1 5dyz1
 Number of -bonds (bond pairs) at P
atom = 6  Now before bonding 5s, 5px, 5py, 5pz,
5dxy and 5dyz orbitals hybridize to
Number of lone pair of electrons at P
produce six sp3d2 orbitals of same
atom = 0
energy and same shape, out of which
Total number of electron pairs = 6 one orbital has two electrons and 5
orbitals are singly occupied which
Thus hybridisation of PF6- is sp3d2 and
overlap with p orbitals of incoming
geometry as well as shape is a Octahedral.
oxygen and fluorine atoms to form five
sigma bonds.
 Number of -bonds (bond pairs) at Xe
atom = 5
Number of lone pair of electrons at Xe
atom = 1
Total number of electron pairs
(h) XeOF4 =5+1=6
In this molecule xenon forms bonds with one Thus hybridisation of Xenon in XeOF4 is sp3d2
oxygen and four fluorine atoms. and geometry is octaheral, however its actual
shape is square pyramidal as one of the
Outer Electronic Configuration of Xe electron pairs is a lone pair.
= 5s2 5p6
= 5s2 5px2 5py2 5pz2

Illustration - 5 Match the column.

Column 1 Column 2
(A) ClO2F3 (P) Central atom is sp3d hybridised.
(B) ClOF3 (Q) All fluorine atoms lie in the same plane
(C) XeO2F2 (R) All fluorine atoms does not lie in same plane
(D) XeO3F2 (S) All oxygen atoms lie in equatorial plane.
(T) All lone pair of central atom lie in equatorial plane.
SOLUTION:
(A) : PQS (B) : PRST (C) : PRST (D) : PQS
Structures of Mulitcentre Polyatomic Species :

Remember : For oxy-anions, negative charge is carried by oxygen.
1. S2 O32  ; 2. S2 O52  ;
3. S2 O 62  ; 4. S2 O 72  ;

5. S4 O 62  ; 6. S2 O82  ;
7. P2O5 ; 8. N 2 O5 ;
9. N 2 O3 ; 10. N 2O ;
11. P4O6 ; 12. P4O10 ;
13. N 2O 4 ; 14. NO 2 ;
15. S2 O 42  ; 14. H 2O 2 ;

14. Berylium Chloride

(a) In vapour state (at very high temperature T > 1200 K) Cl-Be-Cl
(b) In vapour state (at lower temperature T < 1200 K)
(c) In solid state
18. Diborane
Note : Diborane is a dimer of borane BH3 and it shows 3c-2e bond (banana bond) a multicentre
bond.
19. Inorganic Benzene: = =
20. P4S3 : 21. Sulphur (S8) :

22. Carbon suboxide (C3O2) : O=C=C=C=O 23. Hydrazoic acid(HN3) : H  N  N  N
24. Phosphorus (P4) :

Illustration - 6 IF5 in liquid state can conduct electricity because it dissociate to form cation and anion
according to the following reaction, 2IF5  IF4  IF6 . Draw the structure and determine hybridisation of
all the species.
SOLUTION :
Species N/ 2 Value No. of l  p Shape Structure
12
IF5 6 1 Sq. pyramidal
2
10
IF4+ 5 1 See-saw shaped
2
14
IF6- 7 1 Capped octahedron
2
Illustration - 7
I2Cl6 is a yellow solid. In liquid state, it dissociated to form ions, the cation has sp 3
hybridisation and anion has sp3d2 hybridization and anion has sp3d2 hybridization. Find the exact structure of
cation and anion, if 1 molecule of I2Cl6 dissociate to form 1 cation and 1 anion having unit charge each.
SOLUTION :
I 2Cl6  ICln+ + ICl6 n
N 7  n 1 6  n
ICl+n : 4 
2 2 2
8 = 6+ n, n = 2
 Cation is ICl2+ and anion is ICl4-.

Illustration - 8 PCl5 is covalent in gaseous state but ionic in liquid and solid state. Find the actual structure
of covalent PCl5, cationic form and anionic part in liquid or solid state.
SOLUTION :
PCl5  PCl4  PCl6
Species N/2 Value No. of l  p Shape Structure
10
PCl5 5 0 Trigonal bipyramidal
2
8
PCl4+ 4 0 Tetrahedral
2
12
PCl6- 6 0 Octahedral
2
Illustration - 9
PBr5 exist in solid state as PBr4+ and Br . Find the hybridisation of PBr4+. PI5 exist in the
same manner as that of PBr5 as PI4+ and I. Draw the structure of PI4+.
SOLUTION :
N 5  4 1 8 N 5  4 1 8
PBr4+ :   4 PI +4 :   4
2 2 2 2 2 2
sp3 hybridization, tetrahedral shape. sp3 hybridisation, tetrahedral shape.

Illustration - 10 Discuss the hybridization of carbon atoms in allene (C3H4) and show the p-orbital overlaps.
SOLUTION :
I II III
Allene is CH 2  C  C H 2 carbon atoms I and III are in sp2 hybridized state while carbon II is in sp
hybridized state. Two unhybridized orbitals of carbon II overlap sidewise to form -bonds besides it also
forms a sigma bond with each of the carbon atoms using hybridized orbitals. Two hybridized orbitals of each
of carbon I and III form sigma bonds with hydrogen atoms.
Effect of Electronegativity
NF3 and NH3 both have structures based on tetrahedron with one corner occupied by a lone pair. The high
electronegativity of F pulls the bonding electronics further away from N than in NH3. Thus, repulsion
between bond pairs is less in NF3 than NH3. Hence, the lone pair in NF3 causes a greater distortion from
tetrahedral and gives F  N  F bond angles of 102 30 compared with 10748 in NH3. The same effect
is found in H2O (bond angle 104 27) and F2O (bond angle 102) and also in H2O (bond angle 104 27’)
and H2S (bond angle 90).
Isoelectronic Principle
Isoelectronic species usually have the same structure. This may be extended to species with the same number
of valence electrons (on the central atom).
Species Structures
CH 4 , NH 4 , BF4 Tetrahedral
CO32  , NO3 , SO3 Planar Triangle
CO 2 , N 3 , NO 2 Linear

Illustration - 11 One member of each of the following sets of compounds is not iso-electronic with the
others. Which one in each set is the odd one out?
(a) NO 2 , CO 2 NO 2 and N 3 (b) CN - , N 2 , CO, NO + and O 22 
(c) SiF62  , PF6 , AlF63 and BrF6

SOLUTION :
(a) NO +2 , CO and N 3 are isoelectronic and have same structure that is linear while NO 2 is angular
(b) CN  , N 2 , CO and NO  are isoelectronic, all have 14 electrons.
(c) SiF62  , PF6 , AlF63 are iso-electronic and have octahedral geometry. BrF6 has pentagonal bipyramidal
geometry.
Illustration - 12
According to valence bond theory which one of the following isoelectronic species shows
resonance.
N 2 , CO, [CN] , [NO]
SOLUTION :
CO, [CN]- and [NO]+ shows resonance and N2 does not show resonance.
; ;
MOLECULAR ORBITAL THEORY Section - 4
Molecular Orbital Theory for the Formation of Covalent Bond

1. This theory suggest that when two atoms come close towards each other, then the atomic orbitals of
each atom overlaps with each other to form new bigger orbitals known as Molecular Orbitals (MO).
2. When atomic orbitals overlap then two MOs are produced.
(a) Bonding Molecular Orbital (BMO)
(b) Anti-bonding Molecular Orbital (ABMO)

3. Bonding molecular orbital has less energy than separate atomic orbital.
4. Anti-bonding molecular orbital has higher energy than separate atomic orbital.
5. These new MOs are spread over the atomic nuclei of both the atoms, consequently, the electrons
present in the MOs are attracted by both the nuclei.
Linear Combination of Atomic Orbitals (LCAO)

According to the principle of Linear Combination of Atomic Orbitals (LCAO), bonding MO is formed by
addition of wave functions (constructive interference) of the electron waves of atomic orbitals while anti-
bonding MO is formed by substraction of the wave functions of the atomic orbitals (destructive interference).
Illustration - 3
Note :  MO is an in-phase (bonding) interaction whereas *MO is an out of phase (anti-bonding) interaction.
Further out of phase interaction results in a nodal plane in the MOs.
1. Only AO’s of comparable energies and proper orientations combine to form MO’s. For example, 1s
can combine with 1s and not with 2s. Similarly, if z is the molecular axis pz can combine with pz but
not with px or py to form -molecular orbitals.
2. The bonding MO’s are represented as  and  while the corresponding anti-bonding MO’s are
represented as *, and *. Of the 2p orbitals, if z is the molecular axis, two pz orbitals form 
bond, i.e.  (2pz) while 2px and 2py orbitals form - bonds, i.e.,  (2px),  (2py), * (2px) and
* (2py).
3. The shapes of MO’s formed depend upon the type of the combining AO’s.

Atomic Orbital Interaction diagrams :
4. The filling of the MO’s occurs according to the same principle as applicable to filling of AO’s i.e.,
Aufbau principle (MO’s are filled in order of their increasing energies), Pauli’s exclusion principle (a
MO can have a maximum of two electrons and these must have opposite spins) and Hund’s rule of
maximum multiplicity (pairing of electrons in degenerate MO’s does not take place until each one of
the them has one electron with the same spin).

5. Molecular Orbital Diagram :
For atoms with atomic number greater than 7 e.g., For atoms with atomic number less than or equal to
O2 , F2 or For species with total number of 7 e.g., H2 , C2 , N2 or For species with total number
electrons greater than 14 e.g., NO of electrons less than 14 e.g., B2 C 2 ,CN
Atomic Molecular Atomic Atomic Molecular Atomic

orbitals orbitals orbitals orbitals orbitals orbitals
Note : The ordering of the MOs in B2, C2 and N2 is different from that in F2 and O2 because of orbital mixing.
6. Magnetic Character :
If all the electrons in a molecule are paired, the compound is diamagnetic; while when the molecule
has one or more electrons unpaired, it will be paramagnetic.
7. The stability of the molecule formed or the strength of bonds between the bonding atoms is determined
by bond order.
N - Na
Bond order = b
2

Nb : Number of electrons in bonding molecular orbitals.

Na : Number of electrons in anti-bonding molecular orbitas.
 Greater the bond order, greater is the stability of the molecule.

 A bond order of +1 indicates that the specie is stable and that the two atoms in a molecule are held
together by a single bond. A bond order of +2 indicates that the specie is stable and that the two
atoms are united together with a double bond. A bond order of +3 indicates that the specie is stable
and that the two atoms are held together by a triple bond.
 Bond order may be fractional and even zero.
 A zero bond order indicates the equal number of bonding and anti-bonding electrons.
 When bond order is less than zero, the species does not exist.
 A bond order of + 1/2 indicates that the species exists but is unstable, e.g. H2+ and He2+.
 The bond order of a molecule is directly proportional to its bond dissociation energy and inversely
proportional to its bond length. For example,
Molecule Bond order Bond length Bond diss. Energy (kJ mol–1)
Li2 (Li  Li) 1 267 pm 110
B2 (B  B) 1 159 pm 297
F2 (F  F) 1 142 pm 158
C2 (C  C) 2 127 pm 607
O2 (O = O) 2 121 pm 498
N2 (N  N) 3 110 pm 945
 
CO ( C  O ) 3 113 pm 1076
Note : We cannot exactly correlate particular values of the bond dissociation enthalpy and distance with a given
bond order. Factors such as inter-nuclear and inter-electron repulsion play an important part in determining
the observed values of these parameters.

Structures of some Homonuclear Diatomic Molecules

(i) Hydrogen molecule (H2) :
Total number of electrons in 2H atoms = 1 + 1 = 2
Electronic configuration of H 2 molecule =  1s2
1 1
Bond order =  N b  Na    2  0   1
2 2
(ii) Hydrogen molecule ion, H2+ :
Number of electrons in H 2   2  1  1
Electronic configuration =  1s1
1 1
 Bond order 1  0  
2 2
1
Since the bond order is , H 2 ion can exist but it is unstable. Further as it has 1 unpaired electron,it
2
is paramagnetic.
(iii) B2 : B2 is found only in the gas phase ; solid boron is found in several very hard forms with complex
bonding, primarily involving B12 icosahedra [Structure of B12 icosahedron is described in chapter p-
Block Elements - I.
B2 is paramagnetic. The Lewis dot model cannot account for the paramagnetic behaviour of this
molecule. The electronic configuration of boron atom shows that it has 5 electrons, hence the molecular
orbitals of B2 molecule have 10 electrons which are distributed in the following manner.
KK*, (2s)2 (*2s)2 (2px)1 (2py)1
Note : K indicates first bonding MO and K* antibonding MO, thus KK* is same as 1s2 *1s2 .
Thus molecular orbital of B2 has 6 electrons in bonding and 4 electrons in anti-bonding molecular
orbitals. Thus the bond order of B2 molecule is calculated as below:
1
Bond order  [Number of bonding electrons] - [ Number of anti-bonding electrons]
2
1 1
 [6  4]   2  1
2 2

The highest energy occupied molecular orbital (HOMOs) of B2 is 2 P x and 2 Py .
Note : B2 is a good example of the energy level shift cause by the mixing of s and p orbitals. In the absence of
mixing the 2 Pz orbital is expected to be lower in energy than the 2Px and 2Py orbitals and the resulting
molecule would be diamagnetic. However, mixing of orbitals lowers the energy of the 2s orbital and
increases the energy of the 2 Pz orbitals to a higher level than the 2 Px and 2 Py orbitals, giving the order
of energies shown in molecular orbital diagram. The lowest energy unoccupied molecular orbital (LUMOs)
of B2 molecule is 2 Pz .
(iv) C2 : C2 is found only in the gas phase. It is not a commonly encountered chemical species (carbon is
more stable as diamond, graphite and the fullerenes described in chapter p-block-I).
The electronic configuration of carbon atom shows that it has 6 electrons, hence the molecular orbitals,
hence the molecular orbitals of C2 molecule have 12 electrons which are distributed in the following
manner.
KK*, (2s)2, (*2s)2, (2Px)2 (2Py)2
Thus molecular orbitals of C2 has 8 electrons in bonding and 4 electrons in anti-bonding molecular
orbitals. The bond order of C2 molecule is calculated as below:
1
Bond order = [Number of bonding electrons]-[Number of anti-bonding electrons]
2
1 1
= [8 - 4] =  4  2
2 2
The simple MO picture of C2 predicts a double bonded molecule with all electrons paired, but with
both highest occupied molecular orbitals (HOMOs) having p symmetry. It is unusual because it has
two  bonds and no -bond.
Note : The acetylide ion, C 22  , is well known, particularly in compounds with alkali metals (Na2C2), alkaline earth
metal (CaC2), and lanthanides. According to the molecular orbitals model C 22  should have a bond order of
3. This is supported by the similar C-C distances in acetylene (C2H2) and calcium carbide (CaC2).
C-C bond distance (pm)
HC  CH 120.5
Ca 2  C  C 119.1

(v) Nitrogen (N2) :

The electronic configuration of nitrogen atom shows that it has 7 electrons, hence the molecular
orbitals of nitrogen molecule have 14 electrons which are distributed in the following manner :
K K * , ( 2s)2 (*2s)2 (2px)2 (2py)2 (2pz)2
Thus the molecular orbital of nitrogen has 10 bonding and 4 electrons in anti-bonding orbitals. Thus
the bond order or the number of bonds in nitrogen molecule may be calculated as below :
1
Bond order = [Number of bonding electron – Number of anti-bonding electrons]
2
1 1
 [10  4 ]   6  3
2 2
(vi) Oxygen (O2) :
Oxygen (Z = 8) has the electronic configuration 1s2 2s2 2p4, so 12 electrons are to be filled in the
molecular orbitals of oxygen (leaving aside the electrons of the K shell). These 12 electrons are filled
in the following manner :
KK*, (2s)2 (*2s)2 (2pz)2 (2px)2 (2py)2 (2px)1 (2py)1
Note that the 11th and 12th electrons in the molecular orbital of oxygen go to 2px and 2py
orbital (Hund’s rule) ; it is because of the fact that these two anti-bonding orbitals are of equal
energy. Since now there are two unpaired electrons, the oxygen molecule is paramagnetic.
1
Bond order = [Number of bonding electron – Number of anti-bonding electrons]
2
1
 [10  6 ]  2
2
Hence, the two oxygen atoms in oxygen molecule are linked by a double bond.
(v) Molecular orbital configuration of O2+ :

Number of electrons in O2+ = 16 – 1 = 15
MO configuration : KK*, (2s)2 (*2s)2 (2pz)2 (2px)2 (2py)2 (*2px)1 (*2py)0
1 1
Bond order = [10  5]  2
2 2
1
Bond order of 2 indicates that O 2 is more stable than O2. As O 2 has 1 unpaired electrons, it is
2
paramagnetic.

Note : The addition of one or more electrons corresponds to reduction and the removal of one or more
electrons is oxidation. The addition of electrons will follow the aufbau principle ; the removal of electrons
follows the same rules but in reverse.
MO Electronic Configuration of Diatomic Species having upto 14 electrons :
Paramagnetic(P)
Electronic Configuration
Diamagnetic (D)
Molecule Total No.
or ion of
Electron 1s *1s 2s *2s  2px  2py 2p z N B NA Bond
order
H2 2 2 2 0 1.0 D
H2+ 1 1 1 0 0.5 P
He2 4 2 2 2 2 0.0 D
He2+ 3 2 1 2 1 0.5 P
Li2 6 2 2 2 4 2 1.0 D
Be2 8 2 2 2 2 4 4 0.0 D
B2 10 2 2 2 2 1 1 6 4 1.0 P
C2 12 2 2 2 2 2 2 8 4 2.0 D
N2 14 2 2 2 2 2 2 2 10 4 3.0 D
O22+ 14 same as N2 10 4 3.0 D
N 2+ 13 2 2 2 2 2 2 1 9 4 2.5 P
CN- 14 same as N2 10 4 3.0 D

MO Electrionic Configuration of Diatomic Species having more than 14 electrons :
Paramagnetic(P)
Electronic Configuration
Diamagnetic (D)
Molecule of ion
Total No. of
Electrons 1s *1s 2s *2s  2pz 2px 2py  2px 2py 2pz NB NA Bond
order
O2 16 2 2 2 2 2 2 2 1 1 10 6 2.0 P
O 2+ 15 2 2 2 2 2 2 2 1 10 5 2.5 P
NO 15 2 2 2 2 2 2 2 1 10 5 2.5 P
O2- 17 2 2 2 2 2 2 2 2 1 10 7 1.5 P
O22- 18 2 2 2 2 2 2 2 2 2 10 8 1.0 D
F2 18 2 2 2 2 2 2 2 2 2 10 8 1.0 D
Ne2 20 2 2 2 2 2 2 2 2 2 2 10 10 0.0 D
Note : O2 superoxide ion , O 22  : peroxide ion [Rmember as a fact : Bond order of CO+ is 3.5]
Illustration - 13 Which of the two peroxide ion or superoxide ion has larger bond length ?
SOLUTION :
The bond length in a molecule is dependent on Superoxide ion, O 2
bond order. The higher is the bond order,
smaller will be the bond length.
O 2 : KK*( 2s)2 ( 2s)2 ( 2pz)2 ( 2px)2
Peroxide ion, O 22  (2py)2 (2px)2 (2py)1
10  7
O 22  : KK*(2s)2 ( 2s)2 ( 2pz)2 Bond order =  1.5
2
(2px)2 (2py)2 ( 2px)2 ( 2py)2
Bond order of superoxide ion is higher than
10  8 peroxide ion, hence bond length of peroxide
Bond order = 1
2 ion is larger.

Illustration - 14 (a) How bond energy varies form N 2 to N 2 and why ?

(b) On the basis of molecular orbital theory what is similarity between
(i) F2 and O22– (ii) CO, N2, NO+ ?
SOLUTION :
(a) Bond energy of N2+ = Bond energy of N2– (b) (i) Both F2 and O 22  have same bond order same
because bond order is same in both the species.
bond length and are diamagnetic.
[However, N2+ is slightly more stable than N2–
as antibonding electrons number is higher in (ii) These are isoelectronic species, possess same
N2– than in N2+.] bond order and same bond length.
Illustration - 15 Arrange the following compounds in the increasing order of bond length of O – O bond O ,
2
O2 [AsF6], KO2 and peroxide ion. Explain on the basis of ground state electronic configuration of dioxygen in
these molecules.
SOLUTION :
O2[AsF6] has O 2 ion while KO2 has O 2 ion (superoxide ion) and peroxide is O2–.
E.C. of O2 = KK * (2s) 2  *(2s) 2 (2p z ) 2 (2p x ) 2 (2p y ) 2  *(2p x )1  *(2p y )1
E.C. of O 2 = KK * (2s) 2  *(2s) 2 (2p z ) 2 (2p x ) 2 (2p y ) 2  *(2p x )1
E.C. of O 2  KK * (2s) 2  *(2s) 2 (2p z ) 2 (2p x ) 2 (2p y ) 2  *(2p x ) 2  *(2p y )1
E.C. of O 22   KK * (2s)2  *(2s) 2 (2p z ) 2 (2p x ) 2 (2p y ) 2  *(2p x ) 2  *(2p y ) 2

B.O. of O2 = 1/2 (10 – 6) = 2
B.O. of O 2 = 1/2 (10 – 5) = 2.5
B.O. of O 2 = 1/2 (10 – 7) = 1.5
B.O. of O 22  = 1/2 (10 – 8) = 1

Higher is the B.O., smaller is the bond length. Hence, order of O – O bond length is
O 2 > O2 > O 2 > O 22  i.e.,
1
O2[AsF6] > O2 > KO2 > O 22  Note : bond strength 
bond length

CONCEPT OF HYDROGEN BONDING Section - 5
Molecules that contain FH, OH, NH bonds (e.g., Water, Alcohols, Organic acids, Amines, Aromatic
alcohols, etc.) show a strong tendency to associate, i.e., to link up to form larger molecules. This feature
exists in solid form and as well as in solutions in certain solvents. In all of such compounds, OH, or NH
or FH, bond is highly polar due to large difference in electronegativity. The electrostatic attraction be-
tween such molecules should be quite strong. The positive end of one molecule attracts and is strongly
attracted by the negative end of the neighbouring molecule. In this manner a large number of molecules are
associated to form a cluster of molecules. Since in each case the hydrogen atom is responsible for the
formation of linkages, this is known as Hydrogen bond or Hbond. It is impossible for hydrogen to form a
second covalent bond so the additional linkage is shown by a dotted line. Hydrogen bonds are always of
type : AH....B, where A and B may be atoms of O, F, N. Hydrogen bonds are comparatively weak,
with bond energies of 1030 KJ/mol, but they are widespread and have important effect on many physical
properties of many Organic and Inorganic compounds.
     
H  F .......... H  F R O .......... H  O
| |
H R
Types of H-Bonding :
Intermolecular H-Bonding :
This type of H-bonding takes place between H and electronegative element present in the different mol-
ecules of the same substance (as in between H2O and H2O) or different substances (as in between H2O and
NH3).
       
(a) In water molecules : H  O --- -H
|
 O --- -H
|
|
O --- -H  O
|
Due to polar nature of H2O, there is association of
H  H  H  H 
water molecules giving a liquid state of abnormally
high b.p.
If we actually observe, one water molecule is joined
to four water molecules, two with H-atoms and
other twowith O-atom. Thus coordination number
of water molecules in water is four as shown in
figure :

Note : Although many compounds can form intermolecular hydrogen bonds, the difference between H2O and
other polar molecules, such as NH3 and HF, is that each oxygen atom can form two hydrogen bonds, the
same as the number of lone electron pairs on the oxygen atom. Thus, water molecules are joined together
in an extensive three-dimensional network in which each oxygen atom is approximately tetrahedrally
boded to four hydrogen atoms, two by covalent bonds and two by hydrogen bonds. This equality in the
number of hydrogen atoms and lone pairs is not characteristic of NH3 or HF or, for that matter, of any
other molecule capable of forming hydrogen bonds. Consequently, these other molecules can form rings
or chains, but not three-dimensional structure.
When ice is formed from liquid water, some air gap is formed (in tetrahedral packing of water molecules).
Due to this volume of ice is greater than liquid water and thus ice is lighter than water. We can say that
density decreases when ice is formed. Reversely when ice melts, density increases but only upto 4C,
after this intermolecular H-bonding between water molecules breaks hence volume increases and hence
density increases. Thus water has maximum density at 4C.
(b) In hydrofluoric acid (HF), there is again association by H-bonding.
However in the gaseous state, several polymeric forms of the HF molecules exist in which the
monomers are held together through H-bonding to form a pentagonal arrangement.
(c) There is also similar H-bonding in alcohol (R  OH) ammonia (NH3) and phenol (C6H5OH)
molecules.
(d) Carboxylic acid dimerizes is gaseous state due to H-bonding.
(e) Alcohol is said to be highly soluble in water due to crossed intermolecular H-bonding (between H2O
and R – OH molecules).

However isomeric ether is less soluble in water due to ether’s non-polar (or weakly polar) nature.
  
CH3  CH 2  O  H CH3  O  CH3
 
polar less polar
(f) Though the hydrogen atoms in a methyl groups are not polarized, if an electronegative group like
chloro, carbonyl, nitro or cyano is attached to it, the C  H bond gets polarised due to the inductive
effect and the hydrogen atom becomes slightly acidic resulting in the formation of weak hydrogen
bonds.
Consequences of the Intermolecular Hydrogen bonding :

(a) Due to H-bonding boiling points of water, ammonia, hydrofluoric acid are abnormally high shown in
figure.
(b) Solubility of the organic compounds in water is due to H-bond formation.
(c) Due to hydrogen-bonding, viscosity () of the liquid increases as given below in centipoises (CP).

Intramolecular H-bonding :
This type of H-bonding occurs when polar H and electronegative atom are present in the same molecule.
The necessary conditions for the formation of intramolecular hydrogen bonding are :
(a) The ring formed as a result of hydrogen bonding should be planar.
(b) A five or six membered ring should be formed.
(c) Interacting atoms should be placed in such a way that there is minimum strain during the ring closure.
In case of anti-form of pyridine-2-carboxaldoxime there is intramolecular hydrogen bonding but it is not shown in
syn-form.
In this type of Hbonding, the bonding occurs within two atoms of same molecule. Such type of bonding generally
occurs in aromatic organic compounds. It is also known as Chelation.
Consequences of the Intramolecular Hydrogen bonding :

Presence of Intramolecular H-bonding decreases the boiling points as well as there solubility in water :
(a) Hydrogen bonding between two atoms of the same molecule (intramolecular H-bonding) leads to unavailability
of these atoms to bond with atoms of other molecule. In other words intra-molecular H-bonding between
atoms of same molecule, makes them unavailable for inter-molecular H-bonding and hence compounds
showing such type of bonding tends to show lower boiling points. For example, o-chlorophenol, o-nitrophenol
and other o-derivatives (isomers) of hydroxy, carbonyl and acids show low boiling as well as melting points
as compared to their m-or p- derivatives (which exhibit intermolecular H-bonding).
(b) The solubility of all such compounds also decreases for the same reason i.e., bonding between atoms of
same molecules or chelation, does not allow these molecules to form inter-molecular bonds. For example in

o-Nitrophenol, O-H group is busy making intramolecular H-bond with O atom of the NO2- group and
becomes unavailable for intermolecular H-bonding and hence it is very less soluble in water.
Illustration - 16 Why H2O is liquid while H2S is a gas at ordinary temperature ?

SOLUTION :
Oxygen has high electronegativity than sulphur. As a result, H2O forms hydrogen bonding. Consequently,
molecules of water come nearer to each other through hydrogen bonding. This result is higher boiling point
of water and hence it is a liquid.
Illustration - 17 The density of ice is less than that of water or ice floats over water. Explain.
SOLUTION :
In ice, water molecule is associated with four other molecules through hydrogen bonding in a tetrahedral
manner, i.e., it has open-cage like structure in which lesser molecules are paked per unit volume. When ice
melts, the molecules come closer to one another. Consequently the density of water in liquid state is more
than solid state. Thus, ice floats over water.
Illustration - 18 The boiling point of H2O is more than the boiling point of HF although fluorine is more
electronegative than oxygen and form stronger H-bond.
SOLUTION :
The strength of a hydrogen bond is determined by the coulombic interaction between the lone-pair
electrons of the electronegative atom and the hydrogen nucleus. Fluorine is more electronegative
than oxygen, and so we would expect a stronger hydrogen bond to exist in liquid HF than in H2O. But
boiling point of HF is lower than that of water because each H2O takes part in four intermolecular
hydrogen bonds. Therefore, the forces holding the molecules together are stronger in H2O than in HF.
NOW ATTEMPT IN-CHAPTER EXERCISE B

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Chemical Equilibrium
Chemical Equilibrium
ANALYSIS OF REVERSIBLE CHEMICAL REACTION Section - 1
Chemical reactions in one sense can be divided into two categories : molecular chemical reactions
(involving molecules as reactants and products) and ionic reactions (involving ions along with
molecules as reactants and products).
In another sense, reactions can also be divided into two categories : Irreversible chemical reactions
(the reactions which proceed to completion and the products fail to recombine to give back reactants)
and reversible reactions (the reactions which never go to completion and that can occur in either
direction, i.e., the products recombine to give back reactants).
Analysis of reversible chemical processes is of great importance and interest. We divide their study in two
parts :
(i) molecular (reversible) reactions and (ii) ionic (reversible) reactions.
In chemical equilibrium, we will consider molecular reversible reactions, such as :
3Fe(s) + 4H2O(g)   Fe3O4(s) + 4H2 (g)
 2NH3(g)
N2(g) + 3H2 (g) 
 2 NO (g)
N2(g) + O2 (g) 
 2 SO2 (g) + O2 (g)
2SO3(g) 
Each reversible reaction consists of one pair of reaction : One is forward reaction and other is backward or
reverse reaction and these two are referred to as two opposing chemical changes.
At one stage during reversible reactions, two reactions, i.e., forward and backward reactions proceed at
the same time with the same speed, the reaction is then said to be in equilibrium. A chemical equilibrium
is the state that exists when two opposing reactions, i.e., forward and backward reactions are proceeding at
the same rate in a reversible reaction.
For a simple case :  C + D

A + B 
Initially, when A and B are mixed, they react. When they react, the rate of forward reaction decreases since
the concentration of A and B decreases with time. As C and D are formed, they react to give back A and B.
The rate of reaction between C and D increases with time as more C and D molecules are formed, more they
collide and react. Eventually, the two reactions occur at the same rate and the system is at equilibrium.
To understand the concept more clearly, let us consider the manufacturing of NH3 (ammonia) from N2 and
H2. The reaction between N2 (g) and H2 (g) to form NH3 (g) is a reversible reaction. Instead of “ 
 ”,
 ” i.e. N2 (g) + 3H2 (g) 
we use double arrow for a reversible reaction “   2NH3 (g)
Forward Reaction : N2 (g) + 3H2 (g)  
  2NH3 (g) . . . . (i)
Backward Reaction :2NH3 (g)  
  N2 (g) + 3H2 (g) . . . . (ii)

Chemical Equilibrium Vidyamandir Classes
Note :
 Regardless of whether we start with NH3 or with pure hydrogen and nitrogen, the reaction does not go to
completion.
 If we start with only H2 and N2, the reaction (ii) cannot at first occur because there is no NH3. As the
forward reaction proceeds, NH3 forms and reaction (ii) starts.
 Initially, the rate of forward reaction is fast. But as the time goes on, rate of forward reaction decreases and
the rate of reaction (ii) i.e., reverse reaction increases.
 Eventually, the rate at which NH3 is being formed (Forward Reaction) becomes equal to the rate at which
NH3 is being decomposed (Reverse Reaction). This state is called as Chemical equilibrium.
 Once the equilibrium is reached, relative concentrations of H2, N2 and NH3 do not change as long as
temperature remains constant.
 At equilibrium, both reactions, i.e., forward and backward continue to perform (but their rate is same) and
such a state of equilibrium where both opposing forces balance each other and molecular activity still continues,
is known as dynamic equilibrium.
 In dynamic chemical equilibrium, molecular activity never ceases, at each instant some molecules are
being formed and some are being broken ; only the rate of two forces is same.
At Equilibrium Stage (at a given temperature) :

(i) Rate of forward reaction = Rate of backward reaction
(ii) At no instant, any reaction (forward or backward) stops.
(iii) Relative concentrations of reactants and products do not change.
(iv) Any change i.e., external stress (pressure, temperature or concentration) causes disturbance in
equilibrium state. The state of equilibrium being stable, is again reached by some adjustment.
Reaction Coefficients and Equilibrium Constant (Q and K)

In 1863, Guldberg and Waage (two Norwegian chemists) stated that, at constant temperature, the rate of
chemical reaction is directly proportional to the product of active masses (raised to power their stoichiomet-
ric coefficients) of reactants present at any given time.
kf
For a reversible reaction : 
mA + nB  pC + qD
k b
Forward reaction. : kf
mA + nB    pC + qD
Rate of forward reaction (rf )  aAm aBn a : denotes activity (active masses)
 m n
rf = kf aA kf = rate constant for forward reaction
aB
kb
Backward reaction : pC + qD  mA + nB
Rate of backward reaction (rb )  aCP aDq

 rb = kb aCP aDq kb = rate constant for backward reaction
aCp aD
q
For a reversible reaction, reaction coefficient (Q) is defined as Q 
m n
aA aB

At equilibrium :
p q
k f  aC aD 
rf = rb and Q is called equilibrium constant (Keq ) at this stage K eq   
m n 
k b  aA
 a B  at equilibrium
Note :(i) Activity is denoted by a.

Activity of aqueous solution is expressed in concentration (Mol/L)
Activity of gases is expressed in partial pressure (atm).
Activity of pure solids and liquids is unity i.e. asolid = 1 [for example aFe = 1, awater = 1]
(ii) When activities are expressed in concentration (Mol/L), then equilibrium constant Keq is denoted as KC .
KC 
 C  p  D q
where [ ] denotes concentration.
 A m  B n
When activities are expressed in terms of partial pressure, then equilibrium constant Keq is denoted as KP .
p q
KP 
 PC   PD 
P : partial pressure (= mole fraction  total pressure)
 PA m  PB n
When activities are expressed in terms of mole fraction, then equilibrium constant Keq is denoted as K .
p q
K 
 C   D 
where  denotes mol fraction.
  A m   B n
(iii) Keq changes only when the temperature changes. There is no effect of change in pressure or concentrations
on the value of Keq.
(iv) Analysis of a reversible system on the basis of activities of reacting species is done in terms of reaction
coefficient (Q). First an expression for Q (or Keq at equilibrium) is written properly and activity values are
then substituted.
Comparing the value of Q with the standard value of Keq (at a given T), one can comment on the status of
reversible system by following the table given below.
Q < Keq it means equilibrium has not yet reached. The system is essentially moving to right (forward
direction) increasing product concentration and simultaneously decreasing reactant concen-
trations. One can say that forward reaction is dominant at this instant over backward
reaction.
Q = Keq it means equilibrium has been established and concentrations of reactants and products will
remain constant.
Q > Keq it means equilibrium has not yet established. The reaction must proceed to left (Reverse or
backward direction), increasing reactant concentrations and simultaneously decreasing product
concentrations.


Consider the reaction SO2Cl2 (g)  SO2(g) + Cl2(g) ; at 375C, the value of equilibrium constant
for the reaction is 0.0032. It was observed that concentration of the three species is 0.050 mol/L each
at a certain instant. Discuss what will happen in the reaction vessel ?
SOLUTION :
In this question, concentration of three species, i.e., SO2Cl2(g), SO2(g) and Cl2(g) each is given, but it is not
mentioned that whether the system is at equilibrium or not. So first check it.
Find reaction coefficient for given equation.
Q
SO2  Cl2    0.05  0.05  0.05
SO2Cl2   0.05
 Q  Keq , so system is not at equilibrium state.
As Q > Keq, the concentrations must adjust till Q = Keq for equilibrium. This can happen only if reaction shifts
backwards, and products recombine to give back reactants. Hence in the reaction vessel, the system will
move backward so that it can achieve equilibrium state.
Writing Keq for reversible reactions :

Homogenous Reactions : (Reactions in which all the reactants and products are in the same phase)
Here, we will discuss some important reversible reactions and explain how to approach while analysing the
equilibrium state for those reactions.
H2 (g) + I2 (g) 

 2 HI(g)
Let ‘a’ moles of H2 and ‘b’ moles of I2 are taken initially and let at equilibrium ‘x’ moles each of H2 and I2
are reacted at a total pressure of P atm.
We will write the expression for Kp for this reaction.
KP 
 p HI 2
pi = Partial pressure
 p H 2   pI 2 
[for each mole of H2 and I2 ,2 moles of HI are

produced]
Total moles at equilibrium = (a  x) + (b  x) + 2x = (a + b) [Note : Consider only the gaseous moles]

pHI 
2x
P ; pH2 
a  x  P ; p   b  x P
 pHI = mole fraction  P  I2
ab a b a b
2
 2x 
2  P
 pHI   ab  4x2
Kp   

 pH 2   pI2   a  x   b  x  a  x b  x
 P  P
ab  ab 
Note : Try to write expression for KC and observe.

2NH3 (g) 
 N2 (g) + 3H2 (g)
Let ‘a’ moles of NH3 are given initially and let x moles of NH3 are decomposed at equilibrium and V Lt be
the capacity of vessel in which reaction is being studied. We will write an expression for Kc for this reaction.
Kc 
 N2   H 2 3
 NH3 2
Concentrations (mol/L) at equilibrium
3
 x   3x 
 a  x , 3   
x 3x
 K c   2   2 
N H 2V   2V  27 x 4
 NH3    N2   , H2    
V 2V 2V 2 2
16V 2  a  x 
2
NH 3  ax
 
Note : Try to write expression for KP .  V 

 PCl3 (g) + Cl2 (g)
PCl5 (g) 
If a moles of PCl5 be put in a container of volume V Lt and at equilibrium ‘x’ moles of it were decomposed,
find its Kp and Kc at equilibrium pressure of P atm.
pPCl3  pCl2
Kp  Find partial pressures of each component at equilibrium
pPCl5

Total moles (nT )  (a  x)  x  x  a  x
pPCl 5 
 a  x  P, pPCl3  pCl2 
x
P

 a  x ax
 x  x 
 P  P
pPCl3  pCl2 ax  ax  x2 P
 Kp   Kp    Kp 
pPCl5 ax 

ax 
P  a 2  x2 
Kc 
PCl3  Cl2 
For
PCl5  , find molar concentrations of each component
2
at equilibrium.
x
ax x V x2
 PCl5   ;  PCl3    Cl2    KC    
V V  a  x  a  x V
 
 V 
 CH3COOH(aq) + C2H5OH(aq)

CH3COOC2H5 (aq) + H2O () 
Kc 
CH3COOHC2H5OH
CH3COOC2H5 
Note : [H2O] = 1, as it is pure solvent. For reactions in aqueous medium, KP has no meaning.
Heterogeneous Reactions : (Reactions involving reactants and products in more than one phase)

  Fe3O4(s) + 4H2 (g)
3Fe(s) + 4H2O (g) 
4
Kp 
 pH2 
4
 pH2 O 
Note : Activities of Fe(s) and Fe3O4(s) are equal to unity as both are pure solids.
  CaO(s) + CO2(g)
CaCO3 (s) 
Kp  pCO2
Note : Activities of CaCO3 (s) and CaO(s) are equal to unity as both are pure solids.
  NH3 (g) + H2S (g)
NH4HS (s) 
Kp  pNH3 .pH2S
Note : For heterogeneous reactions, genrally Kp is written and the anaysis is done in terms of partial ressure of
components.

 C + D, then
 If K1 be the equilibrium constant for A + B 
 A + B is 1/K
Equilibrium constant for reverse reaction C + D  1
 nC + nD is (K )n , n can be fraction also (+ve only)

Equilibrium constant for nA + nB  1
 Q and K be equilibrium constant for R 

 If K1 be equilibrium constant for P   S
2
 Q + S is K . K
then equilibrium constant for P + R  1 2
 B and K be the equilibrium constant for C 

 If K1 be the equilibrium constant for A   D
2
K1
 B  D i.e. A + D 
then equilibrium constant for the reaction : A  C   B + C is
K2
Relation between Kp , Kc and K

 pC + qD
For the equilibrium mA + nB 
p q p q p q
KP 
pC pD
and KC 
 C   D
and K 
 C    D 
pm n
A pB  A m  Bn   A m   B n
n
Use ideal gas equation : pV = nRT  p RT  CRT (where C [ ] is the concentration)
V
Thus, pA = [A] RT ; pB = [B] RT ; pC = [C] RT ; pD = [D] RT
Substituting the values of partial pressure in terms of concentration to get : KP  KC  RT ng
ng = number of moles of gaseous products  number of moles of gaseous reactants = (p + q)  (m + n)

[Note : Only gaseous moles have been considered since PV = nRT is applicable only for ideal gas]
p q
ppC pqD  C PT   D PT  n g
Also, K P   KP    PT  K  (where P = Total Pressure)
pm n
A pB  A PT m  B PT n T
Note : For ng = 0, KP = KC  K
For example ; (i)  2HI(g)

H2(g) + I2(g)  (ii)  CO(g) + H2O(g)
CO2(g) + H2(g) 
Illustration - 1
 Z (g), at 473 K, the value of
For a homogenous gaseous reaction X (g) + 2Y (g) 
Kc = 0.35 concentration units. When 2 moles of Y are mixed with 1 mole of X, at what pressure 60% of X is
converted to Z ?

SOLUTION :
Since pressure is to be calculated, so first find Kp  Total moles (nT) = 3  2x
using the relation between Kc and Kp.
Let P = equilibrium pressure
Kc = 0.35, R = 0.0821, T = 473, ng
= 1  3 = 2 1 x
 PX  P,
 ng 2
3  2x
K p  K c  RT   0.35   0.0821  473 
2  2x x
4 pY  P, p Z  P
 2.32  10 3  2x 3  2x
[Note : V of flask is also not given. So, convert x 2
P x  3  2x 
Kc to Kp] Kp  3  2x 
2 2
 1  x  2  2x  P2 1  x  2  2 x 
PZ P P
 3  2 x  3  2 x 
  
The expression for Kp is : K p  p 2
X  pY   x = 0.6 (given)
2
0.6  3  1.2 
Kp   2.32  104
2 2
P 1  0.6   2  1.2 
 P2 = (1.8  102)2  P = 180 atm
[Z]
Alternative approach : Solve for volume of flask using KC  and use PV = nRT to solve for P]
[X][Y]2
Illustration - 2
Solid NH4HS (s) (Ammonium hydrogen sulphate) dissociates to give NH3(g) and H2S (g)
and is allowed to attain equilibrium at 100C. If the value of KP for its dissociation is found to be 0.34, find
the total pressure at equilibrium and partial pressure of each component.
SOLUTION :
 NH3(g) + H2S(g) ; since
NH4HS(s)  Total moles at equilibrium = moles of NH3 +
H2S = 2x (Only gaseous moles)
NH4HS is a solid, hence a NH 4HS = 1 and its un- P = ? Kp = 0.34
dissociated amount will not effect the total pres- x P x P
sure (due to gaseous NH3 and H2S only). Let pH2S  P  and pNH3  P 
2x 2 2x 2
‘x’ be its moles decomposed at equilibrium and (for equimolar proportions, partial pressures
P be the equilibrium pressure. are equal)
KP  pH2S .pNH3 ( a NH4HS = 1)
P P
 0.34  
2 2
P2
  0.34  P  4  0.34  1.17 atm
4

P 1.17 P 1.17
 p NH3    0.585 atm and pH2S    0.585 atm
2 2 2 2
Note :In heterogeneous reactions, or even in homogenous gaseous reactions, sometimes it is better to analyse the
species directly in terms of partial pressures, rather first taking moles and then calculating their partial pressures.
Illustration - 3  2AB(g) at 100C is 49. If 1.0 L

The value of Kc . for the reaction : A2(g) + B2(g) 
flask containing one mole of A2 is connected with a 2.0 L flask containing two moles of B2 , how many moles
of AB will be formed at 100C ?
SOLUTION :
 2AB(g) Concentration of species at equilibrium are :
A2(g) + B2(g) 
[A2] = (1  x)/3, [B2] = (1  x)/3, [AB]
As the two vessels are connected, the final vol-
ume is now 3.0 L. Let x mole each of A2 and = 2x/3
B2 react to form 2x moles of AB2 (from sto- 2
ichiometry of reaction)  2x 
  4 x2
KC   3    49
 1  x   1  x  (1  x)2
  
 3  3 
Taking square root on both sides :
2x
2   7  x  0.78
KC 
 AB  49 1 x
 A 2   B2   Moles of AB(g) formed at equilibrium
= 2x = 1.56
Illustration - 4
 2HI (g) is 64 at 773 K. If one mole
The value of Kc for the reaction : H2 (g) + I2 (g) 
of H2 , one mole of I2 and three moles of HI are taken in a 1L flask, find the concentrations of I2 and HI at
equilibrium at 773 K.
SOLUTION : For the reaction Let x mole of H2 and I2 combine to produce 2x

mole of HI.
2
 HI  32
Q   9[V  1L]
 H 2 I2  1  2
Note : When ng = 0, not only KP = KC , but
volume terms always cancels in the expression
of K.
 Q < Keq (= 64). Hence the reaction pro- [HI]2 = 64

KC 
ceeds to forward direction to achieve equilib- [H 2 ][I2 ]
rium.

Concentration of species at equilibrium are :  x = 0.05

H2] = (1  x)/1, [I2] = (1  x)/1, [AB] = (3 +
2x)/1 1 x
[I 2 ]   1  0.5  0.5 M
1
2
 3  2x 
KC  

1 


 3  2 x 2  64 [HI] 
3  2x
 3  1.0  4.0 M
1
1 x 1 x 
   1  x 2
 1  1 
Illustration - 5 At 1000 K, the pressure of iodine gas is found to be 0.1 atm due to partial dissociation of
I2(g) into I(g). Had there been no dissociation, the pressure would have been 0.07 atm. Calculate the value of
 2I (g).
KP for the reaction : I2 (g) 
SOLUTION : Analysing in terms of pressure directly :  p = 0.03 atm.
(p I ) 2 (2p) 2 (2  0.03) 2
KP   
pI2 (0.07  p) 0.07  0.03
Substituting value of p
 Total pressure at equilibrium  KP = 0.09 atm units.
= (0.07  p) + 2p = 0.1 (given)
Illustration - 6 Calculate the % age dissociation of H2 S(g) if 0.1 mole of H2S is kept in a 0.5 L vessel at
 2H2(g) + S2(g) is 1.0  107.
1000 K. The value of KC for the reaction 2H2S(g) 
SOLUTION :
 2H (g) + S (g) ;
2H2S (g)  Assuming 0.1 – 0.1x  0.1, we get :
2 2
Volume of vessel = V = 0.5 L

x3
Let x be the degree of dissociation   106  x  0.01
2V
Check : 0.1–0.1x  0.1
Degree of dissociation
Amount dissociated 0.1x

  x
2 Initial amount 0.1
 0.1 x   0.1 x 
2
 H  S2    V   2V   107
KC  2  1 % dissociation of H2S.
 H2S2  0.1  0.1 x 
2
 
 V 

LE-CHAPTELIER’S PRINCIPLE Section - 2
How an equilibrium state relieves the external stress ?

How a state in equilibrium (a stable state) adjusts to the external stress (change in Temperature, pres-
sure or concentration of reactants/products) is generalised in Le Chatelier’s principle.
Le Chatelier’s Principal states that :

If a stress is applied to a system in equilibrium, the equilibrium condition is upset; A net reaction
occurs in that direction which tends to relieve the external stress and finally a new equilibrium is
attained.
To understand its application to a system, let us consider following example.

 2NH3(g)
N2(g) + 3H2(g) 
H =  92 kJ for Forward Reaction
H = + 92 kJ for Backward Reaction
Note : H : Enthalpy Change is a measure of heat evolved or heat absorbed in a chemical reaction. It is negative
when heat is evolved and positive when heat is absorbed during a chemical change. You will learn details of
it later in the Chapter on Chemical Energetics.
Note that in the above reaction :

(a) Forward reaction is exothermic (favours formation of NH3) and backward reaction is endothermic
(favours decomposition of NH3)
(b) Formation of NH3 results in decrease in number of moles (from 4 total moles of N2 and H2 to 2 total
moles of NH3) is a decrease in volume to right (in forward reaction)
(c) Both reactants and products are gases and they will be influenced by changes in P, T and changing
concentrations.
Effect of Temperature
Temperature can be increased by adding heat and can be decreased by taking out heat from the system.
 Increase the temperature by supplying heat: According to Le Chatelier’s principle the disturbed equi
librium state will move in that direction where heat is being absorbed (where stress is relieved) i.e. in
endothermic direction. In case of given situation, reverse direction will be favoured (that being endot
hermic) till whole of extra heat in consumed.So NH3 will decompose on increasing temperature.
 Decrease the temperature by extracting heat: According to Le Chatelier’s principle the system will go
in the direction where heat is evolved i.e. in exothermic direction. In given situation, forward reaction
will be favoured (i.e. formation of NH3) till the new equilibrium is again established.
Note : The new equilibrium state has a new value of equilibrium constant K on changing the temperature.

Effect of Pressure
 Increase in pressure would result in decrease in volume thereby increasing the concentration (mol/L).
The system will shift in a direction where number of moles decreases (decreasing concentration). In
given situation, there is decrease in number of moles in forward direction, so increasing pressure
favours forward reaction (i.e, formation of NH3).
 Decreasing the pressure would mean lower number of moles/L. The system will shift in a direction
which will produce more moles. In given situation, there is increase is number of moles in reverse
direction, so decreasing pressure favours backward reaction (i.e., decomposition of NH3)
Effect of Concentration :
The Concentration can be changed in two ways :
(a) By removing some of a component or (b) By adding some more of a component.
According to Le Chatelier’s principle :
 The addition of any component to a side (reactants and products) of a reaction in equilibrium shifts the
equilibrium in the direction away from that side or one can say that equilibrium shifts in that direction
which consumes the increased concentration.
 In given situation ;
increasing amount of pure N2 and H2 would favour formation of NH3.
increasing amount of NH3 would favour decomposition of NH3
 The removal of any component from a side (reactants and products) of a reaction in equilibrium shifts
the equilibrium in the direction towards that side, or one can say the equilibrium shifts in that direction
which produces the decreased concentration.
 In given situation :
Decreasing the amount of NH3 from right side drives the equilibrium to forward direction i.e. favours
formation of NH3 ; Decreasing amount of N2 or H2 from left drives the equilibrium to reverse direc-
tion i.e. favours decomposition of NH3
Effect of Catalyst :
 Catalyst increases the rate of both forward and backward reactions simultaneously and to the same
extent in a reversible reaction. By increasing both rates, catalyst reduces the time to reach
equilibrium state.
 Catalyst does not change the relative amounts of either reactants or products, hence it has no effect on
equilibrium constant
Evaluation of Keq at different temperatures :
If K1 be the equilibrium constant at T1 (in Kelwin) and K2 be the equilibrium constant at T2 (in Kelwin)
(T2 > T1), the two constants are related by Van’t Hoff equation as follows :
K2 H  T2  T1 
log10    Where R is gas constant and H is the standard heat of reaction.
K1 2.303R  T1T2 
Note : The value of H is negative for exothermic reaction and is positive for endothermic reaction

Le Chatelier’s principle and Physical equilibrium :

Consider the physical equilibrium of change of state :
 liquid
solid 
Effect of pressure on melting :

When a solid melts, there is a decrease in volume for some solids (ice, diamond, carborundum, magnesium
nitride, quartz etc.) and there is an increase in volume for some solids (sulphur, iron, copper, silver, gold
etc.).
When ice melts, there is a decrease in volume. On this kind of system where there is a decrease in volume
due to melting, increasing pressure will reduce the melting point of the system. Thus, increasing the pressure
will favor the melting of ice.
Similarly, when sulphur melts, there is an increase in volume. On this kind of system where there is an
increase in volume due to melting, decreasing pressure will reduce the melting point of the system. Thus,
decreasing the pressure will favor the melting of sulphur.
Vapour pressure of liquids :
 vapour equilibrium :

Consider liquid 
This is an endothermic reaction in forward direction. Hence rise in temperature will favour evaporation. This
means, increase in temperature results in increase in vapour pressure of the system.
Effect of pressure on boiling point :
As we increase pressure on the system : Liquid   vapour; vapours condense lowering the vapour
pressure of system. This means boiling point rises on increasing pressure as to reach the pressure required
for the liquid to start boiling, needs to be increased.
Effect of temperature on solubility :

In most cases, formation of solution (solute in solvent) is an endothermic process. In such cases, increasing
temperature, increases the solubility of solutes. In cases, where dissolution of solute is followed by evolution
of heat ; increasing temperature lowers the solubility of solutes.
Solubility of gases in liquid : As the temperature increases, the solubility of a gas decreases. This means that
more gas is present in a solution with a lower temperature as compared to a solution with higher tempera-
ture.
Effect of pressure on solubility :
When a gas dissolves in liquid, there is a decrease in volume of the gas  X(g)  X(aq)  . Thus, increase

 
of pressure will favour the dissolution of gas in liquid.

Illustration - 7  CO(g) + H2O (g), K is 0.63 at 727C and 1.26

For the reaction : CO2 (g) + H2 (g) 
at 927C.
(a) What is the average H for the temperature range considered ? [Use log10 2 = 0.3]
(b) What is the value of K at 1227C ?
SOLUTION :
(a) T1 = 1000 K, T2 =1200 K, (b) Let K2 be the equilibrium constant at T2 = 1500K
K1 = 0.63, K2 = 1.26 T1 = 1000 K and then K1 = 0.63

Using the Vant’ Hoff equation :  K  8.32  103  1500  1000 
 log10  2    
K2 H  T2  T1   0.63  2.303  2   1500 1000 
log10   
K1 2.303R  T1T2 
K2
 1.26  H  1200 1000   log10  0.6  log10 4
 log10     0.63
 0.63  2.303  2  1200  1000 
 K2 = 0.63 4 = 2.52
 H = 8.32 kcal/mol
Note : The units of R and H must be same.
Illustration- 8 What would be the effect of increasing the volume of each of the following systems at
equilibrium ?
(i)  2CO2 (g)
2CO (g) + O2(g)  (ii)  Ni(CO)4(g)
Ni(s) + 4CO(g) 
(iii)  2NO2(g)
N2O4 (g) 
SOLUTION :
Increasing volume (at constant temperature) will result in a decrease in the concentration of all the gases. As
per Le-Chatelier’s Principle, the reaction should move in a direction of increase in total number of gaseous
moles (thereby increasing concentration). Thus, shift is in a direction of n g  0
(i)  2 CO 2 (g)

2 CO(g)  O 2 (g)   Backward direction  0]
[Backward direction  ng
(ii)  Ni (CO) 4 (g)

Ni(s)  4CO(g)  [Backward direction   ng Backward direction  0]
(iii)  2 NO 2 (g)
N 2 O 4 (g)  [Forward direction  (ng )forwarddirection  0]
Illustration- 9 What happens when an inert gas is added to

(i)  PCl3 (g) + Cl2(g)
PCl5 (g)  (ii)  2SO3 (g) at equilibrium at :
2SO2 (g) + O2 (g) 
(a) constant volume and temperature, (b) constant pressure and temperature.
SOLUTION :
Lets discuss what happens when an inert gas is  p C  g   q D  g 
m A  g   n B  g  
added to the following reaction at equilibrium stage

If the reaction is at equilibrium, we have :

 2 SO 3 (g)
Similarly, 2 SO 2 (g )  O 2 (g ) 
K eq  Q . . . .(i)
 n g  1  0  Q  K eq
Any factor (e.g. change in conc. of Reactants/Prod-
ucts or both) can have impact (in terms of change in (Reaction will move in the backward direction)
the conc. of reactants/products) On that reaction at
equilibrium only if that factor changes the equations (b) Inert gas addition at constant volume :
(i) so that K eq  Q p q
pC p D
K eq  Q  (at equilibrium)
Two cases occur : pm n
A pB
(a) Inert gas addition at constant pressure : and partial pressure (p)  PTotal
p pC p qD
K eq  Q  (at equilibrium)  n 
pm n
A pB
 where   n  Mole fraction 
and partial pressure (p)  PTotal  Total 
 n  Now, when inert gas is added at constant volume,

 where   n  Mole fraction 
 Total  PTotal  and   but partial pressure of each gas
Thus, when an inert gas is added, of each of the remains same, since :
gas decreases and since PTotal is constant, partial n
pressure decreases leading to a new equation : Partial pressure (p)  . PTotal and using
nTotal
Q > Keq or Q < Keq Dalton’s Law and ideal gas equation :
which will depend on whether PTotal . V  n Total RT
 n g   (n g ) R   (n g ) R  0 or  0
 PTotal RT 
 Check : n   const.
respectively  Total V 
 PCl 5 (g)  PCl 3 (g)  Cl 2 (g)
 Thus, Keq = Q even on adding inert gas at constant
n g  1  0  Q  K eq volume Thus, adding inert gas at constant volume
(Reaction will move in forward direction) has no effect on a reaction at equilibrium.
Degree of Dissociation and Density :

When a gas decomposes (dissociates), its volume increase in accordance with increase in the total number
of moles (at constant pressure). As the total mass remains same, its density decreases in the same proportion.
 Initial mass of gas mixture = mass of gas mixture at any time  i Vi  f Vf [mass = density 
volume]
= niMmix,i = nfMmix, f [mass = moles  Mole. mass]
where i  Initial density of the mixture ; f  Final density of the mixture ; Vi and Vf = Initial and final
volume of the system
Mmix,i  Initial molecular weight of the mixture and Mmix, f  Final molecular weight of the mixture.

nf M mix,i d
 =  i
ni M mix, f df
where di  Initial vapour density of the mixture and df  Final vapour density of the mixture.
Consider the dissociation of PCl5 to clearly understand the concept.
 PCl3  g  + Cl2  g 

PCl5  g  
where   degree of dissciation of  x / a
Total moles = a  a
a d d
 = mix  mix d mix = density of mixture PCl5, PCl3, Cl2
a + a d0 d PCl5
M mix, i M PCl5 1

Using the correlation for vapour density and moles, we have :  
M mix, f M mix, f 1
Mmix, f can be found out by experiments. Thus,  can be calculated.
Illustration - 10 When PCl5 is heated, it dissociates inot PCl3 and Cl2. The vapor density of the gas mixture
at 200oC and at 250oC is 70 and 58 respectively. Find the degree of dissociation at two temperatures.
SOLUTION :
d0 v.d.PCl5 M /2 a a
 PCl3  g  + Cl2  g 
PCl5  g      0 
d mix v.d .mix 70 a
208.5 / 2
 1     0.49
70
At T 250 C
Total moles  a  a  Using the resutl d0 v.d.PCl5 M0 / 2 a  a 
= = 
d mix v.d.mix 58 a
 d a + a
 0 = 
 d mix a 
208.5 / 2
d 0 = density of PCl5   1     0.80
58
At T = 200 C (v.d.  vapour density)

Illustration - 11  PCl3(g) + Cl2(g) at 250C is 0.82. Calculate the

KP for the reaction PCl5 (g) 
degree of dissociation at given temperature under a total pressure of 5 atm. What will be the degree of
dissociation if the equilibrium pressure is 10 atm. at same temperature.
SOLUTION :
Let 1 mole of PCl5 be taken initially. If ‘x‘ moles x2
 Kp  P = 0.82
of PCl5 dissociate at equilibrium, its degree of 1  x2
dissociation = x
x 2 (5) 0.82
or  0.82  x 2 
2 5.82
1 x
x = 0.375 (or 37.5%)
Now the new pressure P = 10 atm.
Let y be the new degree of dissociation. As the
temperature is same (250 C), the value of KP
Total moles  1  x  x  x  1  x will remain same
P = 5 atm and Kp = 0.82 Proceeding in the same manner,
1 x  x (y)P y2
pPCl 5    P ; pPCl 3  P Kp  0.82   10
 1 x  1 x 
1  y2 1  y2
x
and pCl 2  P
1 x 0.82
 y or y = 0.275 (or
(PPCl5 )(pCl2 ) 10.82
Now, Kp  27.5%)
(pPCl5 )
Note :
 By increasing pressure, degree of dissociation has decreased, i.e., the system shifts to reverse direction.
Compare the result by applying Le Chatelier’s principle.
 Read the following example very carefully, In the following example, the volume is suddenly doubled, so first
the initial concentration of all species at equilibrium will be halved and a new equilibrium will be re-established.
Illustration - 12 At a given temperature and a total pressure of 1.0 atm for the homogenous gaseous
 2NO2 (g), the partial pressure of NO2 is 0.5 atm.
reaction N2O4 (g) 
(a) Find the value of KP .
(b) If the volume of the vessel is decreased to half of its original volume, at constant temperature, what
are the partial pressures of the components of the equilibrium mixture ?

SOLUTION :
For equilibrium system, N2O4 (g)  2NO2 direction, as there is a decrease in mole (ng = 2
(g), the total pressure is 1.0 atm.  1 = 1) i.e, the NO2 will be converted to N2O4.
 The total pressure = PN2O4  PNO2  1.0 Let the decrease in pressure of NO2 be x atm.
 PN2O4 = 0.5atm and PNO2 = 0.5 atm
(PNO 2 ) 2 0.52
(i) KP    0.5 atm
PN 2 O 4 0.5
(ii) As volume is decreased to half its original (1  x)2

 KP   0.5
volume, equilibrium is disturbed and the new (1  x / 2)
initial conditions for the re-establishment of
new equilibrium are :  4x2  9x + 2 = 0
 x=2 or 0.25
PN2O4 = 1.0 atm and PNO2 = 1.0 atm
(x  2, as initial pressure = 1.0)
[ P is doubled as V is halved at cons tan t T]
 x = 0.25
According to Le Chatelier principle, when volume
is decreased, the system moves in that direction x
PN2O4  1   1.125 atm
where there is decrease in number of moles. 2
Hence, the system (here) will move in reverse
and PNO2  1  x  0.75 atm
Illustration - 13 1 mole of N2 and 3 moles of PCl5 are placed in a 82.1L container heated to 127 C. The
equilibrium pressure is 2 atm. Assuming ideal behaviour, Calculate the degree of dissociation of PCl 5 and
value of Kp for its dissociation.
SOLUTION :
Dissociation of PCl5 is written as :  nT = moles of (PCl5 + PCl3 + Cl2 ) +
 PCl3 + Cl2(g)
moles of N2
PCl5 (g) 
 nT = 3  x + x + x + 1 = 4 + x
Let x be the no. of moles of PCl5 decomposed
at equilibrium. The mixture behaves ideally, hence PV = nT
RT
Let us calculate no. of moles by using gas
equation
PV 2  82.1
 nT    nT = 5
RT 0.082  400
Now total gaseous moles in the container = nT Now, equating the two values of nT, we have :
4+x=5  x = 1.

 Degree of dissociation = 1/3 = 0.333 2

  2.05  0.8 atm
PPCl3  PCl2 5
KP  x 1
PPCl5 PCl2  PPCl3  P   2.05  0.4 atm
3 x
4 x 5
Now PPCl5  P P = equilibrium pressure
4 x 0.4  0.4
 Kp   0.20 atm
0.8
Note :
 The inert gases like N2 or noble gases (He, Ne etc) though do not take part in the reaction, but still they affect
the degree of dissociation and equilibrium concentrations for the reactions in which ng  0. They add to the
total pressure of the equilibrium mixture (p  n).
Illustration - 14 At temperature T, a compound AB2(g) dissociates according to the reaction :

 2AB(g) + B2(g)
2AB2(g) 
with a degree of dissociation x which is small compared to the unity. Deduce the expression for in terms of
the equilibrium constant Kp and the total pressure P.
SOLUTION :
a / 2
 2AB(g) + B2(g)
2AB2(g)  ; p B2  .P
a  a / 2
a
As a << 1 a a
2
a  a  a

 pAB  P ; pAB2  pB2  P
a 2
 Total moles = nT = a 
2  
 P 2 . P
3
(pAB )2 (pB2 )  Kp  2   P
2
Kp 
2 P 2
(pAB2 )
a a  a 2K p
pAB  .P ; pB2  P;  3
a  a / 2 a  a / 2 P
Illustration - 15
 2 SO3  g  is 900
The equilibrium constant Kp of the reaction: 2SO2  g   O2  g  
at 800 K. A mixture containing SO3 and O2 having initial partial pressures of 1 and 2 atm. respectively
heated at constant volume is allowed to equilibrate. Calculate the pratial pressures of each gas at 800 K.

SOLUTION :
x2  4  x  1
 2 SO3  g  K p  900
Now : 2SO2  g   O2   2

2 1  x  900
 2SO2  g 
 2SO3  g   Assume that x is very small (as Kp <<1and
O2 is already present at the time of
 O2  g  K p  1 / 900 dissociation).
and initial pressure of SO3 = 1 and O2 = 2 atm.
  4  x   4 and 1 x   1
Let x be the decrease in pratial pressure of
SO3 at equilibrium. x2  4  1 1
   x  0.023
2 900 30 2
2 1
 PSO2  x  0.023 atm
and PSO3  1  x  0.977 atm

2
 Kp 
 PSO2   PO2 x
and PO 2  2   2.0115 atm
2
 PSO3 
Note: Check t he correctness of yo ur
 x
x2   2   a p p r o x i ma i o n .  4  x    4  0.023  4
 2 1
 KP  
1  x 2 900 and 1  x   1  0.023  1

Example - 1 H2 and I2 are mixed at 400C in a 1.0 L container and when equilibrium is established, the
following concentrations are present : [HI] = 0.8 M, [H2] = 0.08 M and [I2] = 0.08 M. If now an additional 0.4
mol of HI are added, what are the new equilibrium concentrations, when the new equilibrium
 2HI (g) is re
H2 (g) + I2 (g)  eestablished ?
SOLUTION :
First determine the equilibrium constant Let 2x = concentration of HI consumed (while

going left) then concentration of each of H2 and
 2HI (g)
Kc for H2 (g) + I2 (g)  I2 formed = x
 [HI] = 1.2  2x, [H2]= 0.08 + x,
[HI]2 (0.8)2
Kc    100 [I2] = 0.08 + x and Kc = 100
[H 2 ][I2 ] 0.08  0.08
2
When 0.4 mol of HI are added, equilibrium is
Kc 
1.2  2 x 
 100
disturbed. 
 0.08  x   0.08  x 
At that instant, [HI] = 0.8 + 0.4 = 1.2 M
 Take square root on both side to get :
(1.2)2 x = 0.033
 Q > Kc since Q   225
0.08  0.08 Finally, the equilibrium concentrations are :4
[HI] = 1.2  2x = 1.2  0.033  2 = 1.13 M
 Backward reaction dominates and the
equilibrium shifts to the left. [H2] = 0.08 + x = 0.08 + 0.033 = 0.11 M
[I2] = 0.08 + x = 0.08 + 0.033 = 0.11
Example - 2 0.25 mol of CO taken in a 1.5 L flask is maintained at 500 K along with a catalyst so that the
following reaction can take place ; CO(g) + H2g   CH OH(g). Hydrogen is introduced until the total
3
pressure of the system is 8.2 atm. at equilibrium and 0.1 mol of methanol is formed. Calculate :
(i) Kp and Kc
(ii) The final pressure if the amount of CO and H2 as before are used but no catalyst so that the
reaction does not take place.
SOLUTION :
First balance the equation as : Let y moles of H2 were present initially
CO(g) + 2H2(g)  CH3OH(g)


KC 
CH 3OH 
CO  H 2 2
Self Study Course for IITJEE with Online Support Solved Examples 21
x  0.10 (given) 0.10

 moles of CO = 0.25 – 0.10 = 0.15, Kc 
CH3OH   1.5  600
2 2
moles of H2 = y – 0.2 and CO  H 2  0.15  0.05 
 
1.5  1.5 
moles of CH3OH = 0.10
Now find Kp using the relation :
 Total moles = nT = 0.15 + (y – 0.2) +
0.10 = 0.05 + y n g
K p  K c  RT 
Equilibrium pressure (P) = 8.2 atm
Volume of vessel (V) = 1.5 L, T = 500 K ng 1  3   2
Using the Gas equation, PV = nRT, we have : 2

 K p  600  0.0821  500   0.356
PV 8.2 1.5
nT    0.3 (ii) When no reaction takes place, then the total
RT 0.0821  500
pressure is simply due to H 2 and CO
 0.30 = 0.05 + y y = 0.25 moles present initially.
 moles of H2 at equilibrium = y – 0.2 nT  nCO   nH 2  0.25  0.25  0.5

= 0.25 – 0.2 = 0.05
nRT 0.5  0.0821 500
Now find Kc as follows :  P   13.68 atm
V 1.5
Example - 3 Ammonia under a pressure of 15 atm. at 27oC is heated to 327oC is a closed vessel in the
presence of catalyst. Under these conditions, NH3 partially decomposes to H2 and N2. The vessel is such that
the volume remains effectively constant, whereas the pressure increases to 50 atm. Calculate the % age of
NH3 actually decomposed.
SOLUTION :
P1 P2
Ammonia decomposes to N2 and H2 as follows :  
T1 T2
 3H 2  g   N 2  g 
2 NH 3  g   PT 15  600
 P2  1 1   30 atm
NH 3 
 NH 3 T1 300
at 27oC at 327oC
(15 atm.) (P = ?) V remains constant
First, let us find initial pressure of NH3 at 327oC.
 P  T (V is constant) Now final equilibrium pressure = 50 atm
22 Solved Examples Self Study Course for IITJEE with Online Support
3 x
 50  30  x  x   x  20 atm  Total mole  a  a 
2 2
initial moles initial presseur
20 
% NH3 decomposed = 100  66.7 % final moles final pressure
30
Alternative method : a 30 20
  
a  a 50 30
 3H 2 ( g )  N 2 ( g )
2 NH 3  g  
20
 % dissociation   100  66.7%
30
Let  be the degree of dissociation

 Total mole  a  a 
Example - 4 Solid Ammonium carbamate dissociates as : NH2COONH4(s)   2NH (g) + CO (g). In a
3 2
closed vessel solid ammonium carbamate is in equilibrium with its dissociation products. At equilibrium
ammonia is added such that the partial pressure of NH3 at new equilibrium now equals the original total
pressure. Calculate the ratio of total pressure at new equilibrium to that of original total pressure. Also find
the partial pressure of ammonia gas added.
SOLUTION : 31
P
PNew 31
NH2COONH4(s)   2NH (g) + CO (g)  Ratio =  27 
3 2 Poriginal P 27
Let P = original equilibrium pressure,
From the mole ratio of NH3 and CO2 at Let x be the partial pressure of NH3 added at
equilibrium, we have ; original equilibrium.
2 P NH2COOHNH4(s)   2NH3(g) + CO2(g)
PNH 3  P and PCO2 
3 3 2 1
At eq : P P
2 3 3
 
K P  PNH 3  . PCO2
2 1
When NH3 is added : P x P
2 3 3
2  P 4
  P     P3
 3   3  27
2 1
Now NH3 is added such that , PNH 3  P At new eq : P  x  2y P y
3 3
Find the pressure of CO2.
2
4 3 4  p  x  2 y  PNH 3
 P  P 2 PCO  PCO2  P 3
27 2 27
1 4
Total new pressure = Pnew  PNH 3  PCO2  P and P  y  PCO2  P
3 27
4 31 19
 PNew  P  P P  Solve to get : x  P
27 27 27
Example - 5 Two solids X and Y dissociates into gaseous products at a certain temperature as follows :
 B(g) + C(g). At a given temperature, pressure over excess solid X is

 A(g) + C(g), and Y(s) 
X(s) 
40 mm and total pressure over solid Y is 80 mm. Calculate.
(a) the value of KP for two reactions.
(b) the ratio of moles of A and B in the vapour state over a mixture of X and Y.
(c) the total pressure of gases over a mixture of X and Y.
SOLUTION :
 A(g) + C(g)

(a) X(s)  Not that the pressure of C due to dissociation
of X will also be a mm and similarly the ressure
At equilibrium, A and C are in equal proportions,
of C due to dissociation of Y will also be b mm.
so their pressures will be same.
 pB   a  b  mm
pA = pC
Also pA  pC  40  pA = pC  20 mm K p  for X   p A .pC  a  a  b   400 …(i)
 K P = p A .pC  202  400 mm 2 K p  for Y   p B .pC  b  a  b  1600 …(ii)
Form (i) and (ii), we get :

 B(g) + C(g),
Similarly for Y(s) 
a 1

PB = PC = 40 mm  PB + PB = 80  b 4
as volume and temperature are constant, the mole
 K P = PB .PC = 402 =1600 mm 2 ratio will be same as the pressure ratio.
(b) Now for a mixture of X and Y, we will have (c) The total pressure = PT = p A + p B + pC
consider bo th t he equilibrium
simultaneously.  a  b   a  b  2  a  b 
 A  g   C  g 
X  s   Adding (i) and (ii),
a + b = K PX + K PY = 2000 = 20 5 mm
 B  g   C  g 
and Y  s  
 Total pressure = 2 (a + b) = 89.44 mm
Let p A  a mm, pB  b mm
Example - 6  R  g  . When the reaction between P and

Consider the equilibrium : P  g   2Q  g  
Q is carried out at a certain temperature, the equilibrium concentrations of P and Q are 3 M and 4 M
respectively. When the volume of the vessel is doubled and equilibrium is allowed to re-established, the
concentration of Q is found to be 3 M. Find the :
(a) Value of KC
(b) Concentration of R at two equilibrium stages.
SOLUTION :
 R  g 
P  g  + 2 Q  g   Given : [Q] = 3 M at new equilibrium
at equilibrium, [P] = 3 M, [Q] = 4 M and let  2 + 2y = 3  y = 0.5 M

[R] = x M,  At new equilibrium, [P] = 1.5 + 0.5 = 2 M;
R  = x  x [Q] = 3 M (given) ; [R] = x/2 – 0.5 M
KC = …(i)
 P  Q2 3 × 42 48  R  =  x / 2 -0.5 
 Q=
Now the volume is doubled, hence the  P Q2  2 32
concentrations are halved and a new equilibrium
will re-established with same value of KC. Equating this value of KC with (i)
Calculate Q and determine the direction of
equilibrium.  x / 2  0.5   x  x4M

[ R] x/2 x  2  32 48
Q 2
 2

[ P][Q ]  3 / 2  4 / 2  12
Hence [R] = 4 M and
 Q > K C Hence the system will at new equilibrium [R] = x/2 – 0.5 = 1.5 M
predominately move in backward direction
x 1
so as to achieve new equilibrium state. Let and K C = =
y M be the decrease in concentration of R. 48 12
Example - 7 The degree of dissociation of HI at a particular temperature is 0.8. Find the volume of 1.6 M
sodium thiosulphate solution required to react completely with the iodine present at equilibrium in acidic
condition, when 0.1 mol each of H2 and I2 are heated at 440 K in a closed vessel of capacity 2.0 L.
SOLUTION :
2
First find the value of KC for dissociation of HI K =
 HI
=
 2 x / V 2 =
1
 C
from its degree of dissociation.  H 2  I2   0.1  x    0.1  x  4
V V
 H 2  g  + I 2  g 
2 HI  g  
 x  0.02
(degree of dissociation is 0.8)
Now find the moles of I2 left un-reacted at
equilibrium.
n  I2   0.1  0.02  0.08
I2 reacts with sodium thiosulphate (Na2S2O3)

as follows :
KC 
 H 2  I2    a / 2  a / 2    2  Na 2S4O6 + 2 NaI
2 Na 2S2O3 + I2 
 HI2  a  a  2 4 1   
2
Applying the mole concept, we have,
0.82 2 moles of Na 2S2O3  1 mole of I2

Here   0.8  K C  4
2
4 1  0.8   0.08 mole of I2  2  0.08
Now we have to start with 0.1 mol each of H2 = 0.16 moles of Na 2S2O3
and I2 and the following equilibrium will be
established.  Moles = MVL
(M = molarity, VL = volume in litres)
 0.16 = 1.6 VL
 VL = 0.1 L = 100 mL
 2 HI with K C  1 / 4
H 2  I2 
Example - 8  2 NO2  g 

At 25oC and 1 atm, N 2O4 dissociates by the reactio n N 2O4  g   If it
is 35% dissociated at given condition, find the volume of above mixture will diffuse if 20 ml of pure O2 diffuses
in 10 minutes at same temperature and pressure.
SOLUTION :
a + aa M mix,i M N 2O 4
For equilibrium system, Using = 
a M mix, f M mix, f
 2 NO 2  g  ,
N 2O4  g  
92
 1  0.35 
M mix, f
92
 M mix, f = = 68.15
1.35
 Total moles at equilibrium = a + a 
Let V(ml) volume of mixture diffused in.
a a 2a 
p N 2 O4  P and p NO2  P From Graham’s law of diffusion.
a a  a a 
Here P = 1.0 atm and rO2 M mix, f

=
rmix, f MO2
p2NO 4a 2 p
2
Kp = =   0.35
p N 2 O4 1 2 20 / 10 68.15
  V 13.70 ml
V/10 32
2
4×  0.35 
 Kp = 2
×1= 0.56 atm
1-  0.35 
Example - 9
 1 N 2  g   3 H 2  g  ;
For the reaction NH 3  g  
2 2
1/ 2
 3 3 P 
Show that the degree of dissociation of NH3 is given as   1   where P is the equilibrium
 4 K p 
pressure and  is the degree of dissociation. If Kp of the above reaction is 82.1 atm at 727oC, determine the
value of Kc.
Let  be the degree of dissociation of  3 3 P   2 

NH3(g).   
2
 4  1   
 1 N 2  g  + 3 H 2  g 
NH3  g  
2 2 1 2 3 3 P
 
Initial moles 1 0 0 2 4 Kp

At equilibrium 1  /2 3 / 2
Total number of moles at equilibrium 1   1  3 3 P 
Now,   1  
2  4 KP 
1  /2
p NH3  P, p N 2 
1  1  1/ 2
 3 3 P 
or   1  
3 / 2 4 Kp 
and pH 2  P 
1 
1/2 3/2  n g , change in number of the moles of the
Kp =
 p N2   pH2  given reaction = +1
p NH3
ng ng
K P = K C  RT   K C = K P  RT 
1/2
    3 
 P  P 1
 2 1      2 1      K C = 82.1× 0.0821×1000  =1.0 mol/ L

1 
P
1 
THINGS TO REMEMBER
1. To predict the net direction of a system, calculate Q and compare it with its Keq.
Use : Q < Keq (Forward reaction) ; Q > Keq (Backward reaction)
Q = Keq (No net reaction i.e. system is at equilibrium)
2. 2. Le Chatelier’s Principle : ( : increases ;  decreases)
(i) TReaction is shifted in a direction where energy is getting absorbed
T  Reaction is shifted in a direction where energy is getting absorbed
(ii) P: Reaction is shifted in a direction where ng < 0

P: Reaction is shifted in a direction where ng > 0
(iii) Inert gas addition :
Constant V : No effect
Constant P : Reaction is shifted in a direction where ng > 0
(iv) V: Reaction is shifted in a direction where ng > 0
V: Reaction is shifted in a direction where ng < 0
(v)  S (l)

Melting (with increase in volume e.g. S (s) 
P  More melting ; T  More melting

P  Less melting ; T  Less melting
 water
Melting (with decrease in volume) e.g. Ice 
P  Less melting ; T  More melting
P  More melting ; T  Less melting
(Note that Melting is endothermic process)
3. Degree of dissociation and Density :

n i M mix, f d
= = f
n f M mix,i di
 1 
  Y  g   Z  g  
for a sample reaction : X  g  
 1  
4. Whenever an approximation is applied, always check for approximations assumed before finalizing
the answer.
Self Study Course for IITJEE with Online Support Things to Remember 29
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Ionic Equilibrium
Ionic Equilibrium
CONCEPT OF ACIDS AND BASES Section - 1
Concept of Acids and Bases

Three main concepts in defining the acids and bases are :
1. The Arrhenius concept
2. Bronsted-Lowry concept
3. Lewis concept
1. The Arrhenius concept :
According to this concept, an acid and a base can defined as follows :
Acid : It is a substance that produces hydrogen ions (H  ) in water..
Base : It is a substance that produces hydroxyl ions (OH  ) in water..

HCl, H 2SO4 , HNO3 etc. are the examples ofArrhenius acids while NaOH, KOH, Mg(OH)2 etc.
are the examples Arrhenius bases.
Let us represent an acid as HX and a base as BOH.
The ionization of acid as (HX) can be represented by the following equation :
HX(aq)  H 2O()  H3O (aq)  X  (aq)

(hydronium ion)
or simply, HX(aq)  H  (aq)  X  (aq)
Hydronium ion (H3O  ) is used to represent a hydrated H  ion i.e., H  , ion surrounded by
water molecules.
Note : The Arrhenius concept of acids and bases is only limited to aqueous solutions.
Limitations of Arrhenius Concept

(i) It is applicable only to aqueous solutions. For the acidic or basic properties, the presence of water is
absolutely necessary. Dry HCl shall not act as an acid.
(ii) The concept does not explain acidic or basic properties of acids and bases in non-aqueous solvents
respectively.
(iii) It fails to explain the acidic nature of the non-protic compounds such as SO 2 , NO2 , CO 2 , P2O5
etc. which do not have OH in the molecules to furnishing H  ions.

Ionic Equilibrium Vidyamandir Classes
(iv) It fails to explain the basic nature of compounds like NH3 , Na 2CO3 etc. which do not have OH
in the molecules to furnish OH  ions.
(v) It fails to explain the acidic nature of certain salts such as AlCl3 in aqueous solution.
2. Bronsted-Lowry Acids and Bases

According to this concept, an acid and a base can defined as follows :
Acid : It is a substance that can donate a proton.
Base : It is a substance that can accept a proton.
Example :
When HCl is dissolved in water, it donates a proton to H 2O which behaves as a base.
HCl(aq)  H 2 O( )  Cl  (aq)  H 3O  (aq)
Other examples of Bronsted Lowry acids (underlined) are :
(a) NH 4 (aq)  H 2O()  NH3 (aq)  H3O (aq)
(b) HSO4 (aq)  H 2O()  SO 42  (aq)  H3O (aq)
(c) HCl(aq)  NH3 (aq)  Cl (aq)  NH 4 (aq)
(d) HCO3 (aq)  NH3 (aq)  CO32 (aq)  NH 4 (aq)

Some examples of Bronsted Lowry bases (underlined) are :
(a) O 2  (aq)  H 2 O( )  OH  (aq)  OH  (aq)
(b) NH 3 (aq )  H 2O()  NH 4 (aq )  OH  (aq)
(c) CO32  (aq)  H 2O()  HCO3 (aq)  OH  (aq)
Note :  This theory requires that an acid must contain transferable hydrogen and it offers great freedom in
defining what constitutes base.
 When an acid has donated its proton, the remaining portion of the molecule or ion is a base.
 When a base accepts a proton, it forms an acid.
 The base must have an unshared pair of electrons so as to accept a proton.
The base formed from an acid is known as the conjugate base of the acid. Correspondingly, the acid
formed from a base is called the conjugate acid of the base.
HCl  NH 3  Cl   NH 4
Acid1 Base Base1 Acid
2 2

In the above reaction, Cl is the conjugate base of HCl and NH 4 is the conjugate acid NH3 .

Note : (i) The conjugate acid always has one more proton than its conjugate base.
(ii) To obtain a conjugate acid of a compound, add a proton (H  ) from it and to obtain the conjugate
base of the same, remove a proton to the compound, e.g., Conjugate acid of NH3 is NH 4 while
the conjugate base of NH3 is NH 2 .

(iii) This concept has the advantage that it can be applied to a solvent other than water, having the tendency
to accept or lose a proton.
(iv) The terms acid and base are comparative. A substance can behave as an aid in one solvent and as a
base in another.
For example : Acetic acid (CH3COOH) behaves as an acid in water but as a base in HF..
CH 3COOH(aq)  H 2O(aq)  CH3COO  (aq)  H 3O + (aq)

Acid Base
CH3COOH(aq) HF(aq)  CH3COOH 2+  F (aq)

Base Acid
Strength of Bronsted-Lowry Acid and Bases :

The strength of an acid or base is measured by its tendency to lose or gain proton. A strong acid is a
substance which loses a proton easily to a base. Consequently, the conjugate base of a strong is a weak
base.
The ability of an acid to lose a proton is experimentally measured by its equilibrium constant know as Ka.
The larger the value of K a , the more complete reaction or higher the concentration of H3O+ and the
stronger is the acid Similarly: For bases, we have the equilibrium constant, K b which determines the extent
of the completion of the reaction.

Acid-Base Chart Containing Some Common Conjugate Acid-Base Pairs
Note : In general, solvents can be of four types :

(a) Protophillic : Solvents having a tendency to accept protons. For example water, alcohol, liq. Ammonia
etc.
(b) Protogenic : Solvents having a tendency to donate protons. For example water, liq. HF, liq. HCl
etc.
(c) Amphiprotic : Solvents having a tendency to accept or donate. For example water, liq. ammonia
etc.
(d) Aprotic : Solvents which neither accept nor donate protons. For example benzene, carbon tetrachloride
etc.
Amphoteric Compounds :
The compounds which can act either as acids or as bases, H 2O, NH3 and CH3COOH are some of the
examples.
(a) Water : H 2O  NH3  OH   NH 4 H 2O  H 2O  H3O+  OH 

Acid Base Acid Base

(b) Blcarbonate : HCO3  NH3  CO32   NH 4 HCl HCO3  Cl  H 2CO3

Acid Base Acid Base
Note : The reaction H 2O  H 2O  H3O+  OH  is known as auto-ionization of water..
Limitations of Bronsted Concept :

(i) A substance is termed as an acid or base if it reacts with some other substance, i.e., if it donates
proton to other substance, it is an acid and if it accepts proton from substance, it is a base.
(ii) There are number of acid-base reaction in which no proton transfer takes place, e.g.,
SO 2  SO 2  SO 2+  SO32 
Acid1 Base 2 Acid 2 Base1
Thus, the protonic definition cannot be used to explain the reaction occurring in nonprotonic solvents
such as COCl2 ,SO 2 , N 2O4 etc.
3. Lewis Acid and BasesAcid :
Acid : It is a substance that can form a covalent bond by accepting a shared pair of electrons.
Base : It is a substance that possess at least one unshared pair of electrons.
Monoprotic Acids : Acids that give up one proton per molecule.

Polyprotic Acids : Acids that can give up more than one proton per molecule.
Substance that are bases in the Bronsted sysem are also bases according to the Lewis concept. However
the Lewis definition of an acid considerably expands that number of substances that are classified as acid.
A Lewis acid must have an empty orbital capable of receiving the electron pair of the base.
Lewis acids include molecules or atoms that have incomplete octets. For example molecules like
BF3 , AlCl3 etc., act as Lewis Acid.
Many simple cations can act as Lewis acids :

Cu 2+  4 NH3  Cu(NH3 )2+
4 Fe3+  6 : C  N : Fe(C  N)36
Some metal atoms can function as acids in the formation of compounds such as:
Ni  4 C    Ni(CO)4
Compounds that have central atoms capable of expanding their valence shells are Lewis acids in reactions
in which this expansion occurs.

SnCl4  2 Cl  SnCl62  SiF4  2 F  SiF62  PF5  F  PF6

Some compounds have an acidic site because of one or more multiple bonds in the molecule.
BASICS OF IONIC EQULIBRIUM Section - 2
The type of equilibrium studied in Chemical Equilibrium is known as molecular equilibrium (the
involvement of molecules only). Now, we will study reversible reactions involving formation of ions in water
under Ionic Equilibrium.
Ionic Equilibrium is the study of equilibrium in the reactions where formation of ions takes place in aqueous
solution.
Ions in solution arises mainly from two ways :
 When solute is ionic compound i.e., strong electrolyte (a compound whose aqueous solution conducts
electricity) e.g. NaCl, MgCl2, KBr, NaNO3, NaOH etc. In such compounds, ions maintain their
identity even in solid state. As such solutes are dissolved in water, ions get separated. In solution,
whole of electrolyte is ionised i.e., ionisation is almost 100% complete.
 When solute is polar covalent compound and reacts with water to form ions. These may be strong or
weak electrolytes depending upon their respective degree of ionizations () e.g., HCl, NH3, H2SO4,
HNO3, CH3COOH, HCN, NH4OH etc.
Dissociation (or ionisation) of strong electrolytes and some weak electrolytes such as HNO3, HCl, H2SO4
etc. is nearly complete in dilute solution i.e. almost 100% of electrolyte is converted to ions or one can say
that degree of ionisation () is nearly 1.
Let BA be an electrolyte and dissolved in water. It ionises as follows : BA + aq.  B  aq. + A  aq.
Case - I : (  1)
The extent of forward reaction is very high (i.e. such reactions are nearly complete). So, it is of no use to
study equilibrium in such reactions.
Case - II : (  1)
In aqueous solution of these compounds, only slight amount of reactant (i.e. electrolyte) undergoes dissociation
and there exists an equilibrium between ionised molecules and unionized molecules (ions). Such electrolytes
are weak electrolytes.
BA  aq.  B+ (aq .)  A  (aq .)
 ionised molecules (ions)
unionised molecules 

Weak Electrolytes are categorized into three types for easy understanding :
1. Weak Acids : CH3COOH , HCN (and all organic acids)
2. Weak Bases : NH4OH and all organic bases
3. Sparingly soluble salts : AgCl, PbCl2, Ag2C2O4, MnS, H2S, PbS etc.
Weak Acids (HA) and Weak Bases (BOH)

Weak Acids :
Let HA be a monoprotic (monobasic) acid whose equilibrium is to be studied. The aqueous solution of HA
can be studied in either of two ways :
HA + H2O  H O+ (aq) + A(aq)

 (H3O+ = hydronium ion)
3
or simply as : HA(aq)  H+(aq) + A(aq)


The equilibrium constant for the above reaction is known as ionisation constant for an acid (Ka).
[ ] = concentration in mol/L
[CH 3COO  ][H  ]

e.g., CH 3COOH(aq)  CH 3COO  (aq)  H + (aq) Ka 
CH3COOH 
Note : The ion A– formed due to the ionization of HA is known as its Conjugate base. Thus, to find a conjugate
base of any acid, simply remove a Proton (H+) ion from that acid.
 Conjugate base of CH3COOH is CH3COO ; of H 2PO 4 is and so on.

Lets study the equilibrium of a weak acid HA in an aqueous solution as follows :
If ‘c’ be the molar concentration of weak acid HA and ‘’ be its degree of dissociation (i.e. the fraction of
total concentration which exist in ionic state), then : HA  aq   H   aq   A   aq 
[H  ][A  ] (cα ) (cα ) cα 2

 Ka   
 HA  (c - cα ) 1- α
[H ][A ] [H ] 2

Also, Ka   ( [H ]  [A ]  c )
 HA c  H 
 
For weak acids having  << 1, we can take 1   1

Ka
 Ka = c 2  α=
c
Note : (i) In general, if Ka < 105 and ‘c’ is fairly high (generally 0.1 M or 0.01 M) then 1   can be taken as
unity.
If c is very low (i.e. for very dilute solutions),  is higher. In that case, we can’t take 1   as 1. In
such cases we have to solve a quadratic equation in . i.e. (1  ) Ka = c 2.
(ii) Basically, if decision on whether to go for approximation or not, is not easy, then just use approximation
and solve but remember that you should always validate your approximation before reaching to a final
answer. We will see more on this in illustrations and examples.
Weak Bases :
Let BOH be the weak base, its aqueous solution is represented as follows :
 B+(aq) + OH(aq)

BOH(aq) 
The equilibrium constant for the above equilibrium is known as ionisation constant of a base (Kb).
[B ][OH  ]
Kb  [ ] = concentration in mol/L
 BOH 
[NH 4 ] [OH  ]
 NH4
For : NH4OH(aq)  +(aq) + OH(aq) Kb 
 BOH 
Note : Similar to the concept of Conjugate base, there is a concept of Conjugate acid. e.g. NH 4 is a conjugate acid
of base NH3. Thus, to find a conjugate acid of any base, simply add a Proton (H+) ion to that.
 H2PO4– : Its conjugate base is H2PO42– and its conjugate acid H3PO4
 H2O : Its Conjugate base is OH– and its conjugate acid is H3O+
A substance is known as amphiprotic if it can both donate or accept a proton e.g. , H2O
Now, if ‘c’ be the molar concentration of BOH and ‘’ be its degree of dissociation, then :
 B+(aq) + OH(aq)
BOH(aq) 
[B ][OH  ] (cα) (cα) cα 2

 Kb   
 BOH  (c - cα) 1- α

[B ][OH  ] [OH  ] 2

Also, K b   ( [B ]  [OH  ]  c)
 BOH  c  OH  
 
For weak bases having  << 1, 1   1
Kb
 Kb = c 2 or α=
c
Note : At a given temperature, Ka and Kb are directly proportional to  i.e. comparing Ka of different acids
(Kb for bases), one can compare their strengths or comparing ‘’ of different acids (or bases) at a given
temperature and given concentrations, acids strengths (base strengths) can be compared.
For example in case of bases :
α1 K b1
= (two bases having same concentrations)
α2 K b2
or Kb = c112= c222 (two samples of same base have same value of Kb)
α1 c
 = 2
α2 c1
In the above relations, it has been assumed that the degree of dissociation is small as compared to unity.
Self Ionisation of Water
Water ionises as follows : H2O ( ) 
 H+ (aq) + OH(aq)
The equilibrium constant here is denfined in a different way, and is called as ionic product (Kw) of water
and is given by :
 Kw0 = [H+] [OH] where K w = K a [H 2O]

K a : ionisation constant of H O and[H O]is
2 2
constant at a given temperature
At 25C (298 K) ; Kw = 1.0  1014
Since pure water is neutral, [H+] = [OH] = K w = 107 M at 25C.
 If a strong acid is added to it, [H+] increases and hence [OH] < 107 M (at 25C) and solution is said
to be acidic.
 If a strong base is added to it, [OH] increases and hence [H+] must decrease in order to keep Kw
constant. Now [OH] > 107 M and solution is basic (or alkaline)
Note : The dissociation of water is an endothermic reaction. Thus, increasing the temperature will increase Kw of
water and thereby increasing the [OH] and [H+].

pH Scale :
Sorensen, a French chemist developed a scale to measure the acidity in terms of concentrations of H+ in a
solution. As defined by him :
pH of a solution is the negative logarithm to the base 10 of the concentration of H+ ions which it contains.
(Basically “p” acts as a mathematical operator : p(A) = log10 [A])
 pH =  log10 [H+] and pOH = log10 [OH–]
At 25C, using this definition, a scale called pH Scale is developed as follows:

For pure H2O ; [H+] = [OH] = 107 M
pH =  log10 (107) = 7 = pOH  For pure water at 25C ; pH = pOH = 7
(i) If [H+] > 107 M in a solution i.e., solution is acidic then pH < 7
(ii) If [H+] < 107 M (or [OH] > 107 M) i.e. solution is basic then pH > 7
In general, we talk about pH of a solution, whether it is basic or acidic.

For an aqueous solution : pH + pOH = pKW [Use Kw = [H+] [OH] and take “log10 on both sides]
At 25C, pH + pOH = pKw = 14 [Kw = 1  1014 at 25C]
Now one can very easily re-define pH of a basic solution as : pH = 14 + log10 [OH]
Note : “p” operator is generally applied on any variable whose value is < 1. In most of the cases, we will use pKw,
pKa, pKb etc.
Also, we can see that as temperature increases, both pH and pOH of pure water will decrease since there
will be an increase in [H+] and [OH–] due to increased dissociation.
Dissociation constant (K a and K b ) of conjugate ion of weak acid and weak base :

HA is a weak acid and A is its conjugate base.
Dissociation equilibrium of HA :
+  [H + ][A  ]
HA(aq)  H (aq) + A (aq) : K a = …(i)
[HA]

Dissociation equilibrium of conjugate base A  :
[HA][OH  ]
A  (aq) + H 2O()  HA(aq) + OH  (aq): K b = ...(ii)
[A  ]
H 2O()  H  (aq)  OH  (aq) : K W
1
H  (aq)  A  (aq)  HA(aq) :
Ka
A  (aq)  H 2O()  HA(aq)  OH  (aq): K b
K a acid  K bconjugatebase  K W  pK a(HA)  pK  pK w

b(A  )
Similarly for dissociation constant of weak base (K b ) and dissociation constant of conjugate acid (K a ) we
can write
Kbweak base  Kaconjugatebase  KW  pKb(BOH)  pK  pKw
a(B+ )
pH of a Weak Acid and Weak Base :

Weak acid (HA)
 H+(aq) + A(aq)
HA(aq) 
For c molar HA, we have : [H+] = c  pH = log10 c
Ka
Also : α = [If the approximation 1 –   1 is valid]
c
1
 pH =  log10 K a c  (pK a  log10 c)
2
Weak base (BOH) :

 B+(aq) + OH(aq)
BOH(aq) 
For c molar BOH, we have : [OH] = c  pH = 14 + log10 [OH] = 14 + log10 c
Kb
Also : α = [If the approximation 1 –   1 is valid]
c
1
 pH  14  log10 K bc  14  (pK b  log10 c)
2

Illustration - 1 Determine the hydrogen ion concentration in 1.0 M solution of HCN, if its dissociation
constant is 4.0  1010
SOLUTION :
HCN (aq)  H+ (aq) + CN (aq) i.e. c  [H+]  c = 1.0 M (given)
C 0 0
C – C C C  [H  ]  K a c  2 105 M
[H+] = c and [H+] = [CN] Now, check the approximation : c  [H+]  c
[H  ]2  c  [H+] = 1" 2  105  1.0 M = c

Use Ka  ; c = 1.0 M
c  [H  ]
Thus, the answer obtained as above is correct.
Neglecting [H+] against c, as the given acid is
very weak (Ka = 4.0  1010) and c is quite
high .
Illustration - 2 What is the pH of a 0.2 M solution of acetic acid ? To what volume must one litre of this
solution be diluted so that the pH of the resulting solution will be twice the original value ?
Given : Ka = 2.0  105
SOLUTION :
(Doubling the pH value is simply equivalent to
CH 3COOH(aq)  CH 3COO  (aq)  H  (aq)
squaring the [H+])
C 0 0
C – C C C [H  ]2
Using : Ka =
c  [H  ]
[H  ]2 [H  ]2
 Ka  
c  [H  ] c
 [H  ]2
 c  [H ]  4.8  106 M
(as Ka is too Low) Ka
Thus, [H+] = K a c = 2  103 M ; Check yourself that new degree of dissociation
[H  ] [H  ]new
Also,   0.01  c  [ H  ]  c of acetic acid = new   0.83
c cnew
 pH = 2.7 (pH = log10[H+]) which clearly suggests that using approximations
would have generated poor/wrong results.
Now solution is diluted to make pH = 5.4 (twice
the original) Originally the solution was 0.2 M and 1 L, using
molarity equation we have :
Note :On dilution,  increases, so 1  can’t be
taken as unity. So solve the quadratic in . 4.8  106  V = 0.2  1
For pH = 5.4, [H+] = 4  106 M (C1V1 = C2V2)

 V = 4.17  10 4 L3

Illustration - 3 Calculate [H+] and % dissociation of 0.1 M solution of ammonium hydroxide solution. The
ionisation constant for NH4OH is Kb = 2.0  105.
SOLUTION :
 NH +
NH4OH  + OH Kb
4
 α  2 104
C 0 0 c
2
C  C C C = 1.41  10 =1.41 %
[Check that 1   1 holds]
[NH 4 ][OH  ] cα 2 [OH] = C = 0.1  1.41  102
Kb    cα 2 and
[NH 4OH] 1 α
= 1.41  103 M
(Neglecting , in denominator i.e. 1    1)
Kw
 [H + ]   7.09 1012 M

[OH ]
Illustration - 4 Calculate the pH of 108 M HCl solution.

SOLUTION :
 H+ + OH
H2O 
[HCl] = 108 M
x x
 [H+] = 108 M
 K w = [H + ][OH  ] = 10 14
 pH = 8 which is absolutely wrong since the
solution must be acidic as it is an acidic solution [H+]total = [H+]acid + [H+]water = 108 + x
i.e., pH < 7  Kw = (x + 108) x = 1014
The catch here is that since HCl has been added in  x2 + 108 x  1014 = 0
water (which also dissociates) so we need to Solve the above quadratic equation to get :
consider [H+] from dissociation of H2O as well. In x = 9.52  108 M
the earlier illustrations, we didn’t consider this
because [H+] from acid comes out to be much higher Now, [H+]total = 108 + 9.52  108
than that furnished by water but in this case we can = 1.05  107 M
not neglect the water contribution.
 pH =  log10 [1.05  107] = 6.978

COMMON ION EFFECT Section - 3
The addition of an ionic salt having a common ion (anion or cation) to weak acids or weak bases, suppresses
their degree of dissociation (following LeChatelier’s principle).
Weak Acids :
Let HA be a weak acid (like CH3COOH, HCN etc) and B+ A be the ionic salt (100% dissociation in
solution) containing common anion (A) that is added to the acid.
 H+ (aq) + A (aq)
HA (aq) 
BA (aq)  B+ (aq) + A (aq)

Now, the solution has excess of A ions. This means increasing concentration of products, in an equilibrium
 H+ + A ) must go in backward direction,
state, (following LeChatelier’s principle) the reaction (HA 
in order to nullify the effect of added A ions. As a consequence, amount of H+ in new equilibrium state will
be less than before, or one can see that the degree of dissociation of acid (HA) is decreased.
Quantitative Aspect :
Consider a weak acid HA which dissociates as :  H+ (aq) + A (aq)
HA(aq) 
Ka
Its degree of dissociation =  = [Assuming Ka to be small]
c
Let M molar BA be added to it and  be its new degree of dissociation
BA 
 B+ (aq) + A (aq) (Assuming BA to be 100% ionised)
M M
HA 
 H+ (aq) + A (aq)
c  c c c
Now in solution : [HA] = c  c ; [H+] = c

[A]total = [A]From HA + [A]From BA = c + M
[H  ][A  ]  cα  cα  M  α  cα  M 

Ka   
 HA   c  cα 1  α
 Ka = c α2  Mα (Assuming 1    1)
 K a = Mα (Neglecting c '2 in comparison to M as  << 1  α2  1 ]

Ka
 α =
M
By looking at the expressions of  and , we can clearly figure out that ’ >> 
Note : On similar lines, you can find  for a weak base, BOH and adding B+ ions to it.

[H  ][A  ]ext.
Also, expression for Ka becomes : K a  where [A  ]ext . is the externally added salt
 
HA
Buffer Solutions
A solution whose pH does not change very much when H+ (H3O+) or OH are added to it is referred to as
a buffer solution.
A buffer solution is prepared by mixing a weak acid and its salt having common anion (i.e. HA + BA forms
an acidic Buffer) or a weak base and its salt having common cation (i.e. BOH + BA forms a Basic Buffer).
It can be prepared to have a desired value of pH by controlling the amounts of acids and their salts in case
of acidic buffer and of bases and their salts in basic buffer.
Acidic buffer : CH3COOH + CH3COONa, HCN + NaCN
Basic buffer : NH4OH + NH4Cl
Note : See yourself that buffer solutions are actually conjugate acid-base pairs.
Consider an acidic buffer containing an acid HA and say common ions A. Now, any H+ (or H3O+) added
externally to this solution with in certain limits are neutralized by A ions as :
H  A 
 HA
external from salt undissociated acid
While, addition of OH ions externally (with in certain limits) are neutralised by acid HA as :
 H O + A
HA + OH  2
Hence in both the cases, effect of addition of H+ or OH is almost compensated for (i.e. pH almost remains
constant).
Such a system (may be acidic or basic) finds enormous use not only in industrial processes but also (most
importantly) in biological reactions. Like the pH of normal blood is 7.4 and for good health and even for the
survival, it should not change below 7.1 or greater than 7.7, the body maintains it through a buffer system
made of carbonate and bicarbonate ions and H2PO4 and HPO42 . Similarly, the pH of gastric juice is
kept constant in order to operate good digestive functions.
pH of an Acidic Buffer
If [acid] = concentration of a weak acid and [salt] = concentration of the salt that is mixed with acid to make
the buffer
K a  HA  K a  acid 
We have : [H+] =  [See the derivation in the Common Ion effect section]
 A  salt 
  ext.
 pH = pKa + log10
salt  (pKa =  log10 Ka)
acid 
pH of a Basic Buffer
We have : pH = 14  pOH
If [base] = concentration of weak base and [salt] = concentration of salt that is mixed to make the buffer
K b  BOH  K b  base 
 [OH ] = 
 B  salt 
  ext.
salt 
 pOH = pKb + log10 base (pKb = log10 Kb)
 
salt 
 pH = 14  pKb  log10 base
 
Note : The above equations representing the pH of a buffer are known as Henderson’s Equations.
pH of a Buffer (When an acid or a base is added)

We have just discussed that addition of H+ ions or OH ions to an acidic buffer (HA/A) does not appreciably
changes the pH of buffer. Similarly, we can analyse the same for a basic buffer (BOH/B+).
In actual, pH of a buffer solution changes by a small quantity. Let us calculate this change in pH quantitatively.
Consider an acidic buffer HA/A where [salt] = [A] and [acid] = [HA]
An acidic buffer is rich in A ions. Let us add x mole per litre of HCl to it. This added HCl (H+) reacts with
A (salt) to give undissociated acid as : H   A    HA

 salt   acid 
After adding x M H+ ions : [salt  x] [acid + x]
salt 
Now using Henderson’s Equation : pH ( original buffer) = pKa + log10 and pH (new)
 acid 
= pKa + log10
salt  x 
 acid  x 
 pH of buffer decreases.
Change or difference in pH = pH (new)  pH (original)

Let us add x M NaOH to the buffer. This added NaOH (OH ions) react with acid (HA) to produce salt
and H2O.
OH   HA 
 A   H 2O
 acid   salt 
After adding x M OH ions : [acid  x] [salt + x]
salt  x 
 pH (new) = pKa + log10 acid  x  pH of buffer increases.
 
Change in pH = pH (new)  pH (original)
Note : (i) In exactly similar manner, we can calculate the change in pH of a basic buffer (BOH/B+). Try to get a
relation like this for basic buffer. Remember, it is not to be used as standard result.
(ii) A buffer solution is assumed to be destroyed if on addition of strong acid or base, its pH changes
by  1 unit i.e.,
pH (new) = pKa  1 [if the initial pH of the buffer solution was pKa].
salt  salt 
This means the ratio acid OR base = 10 or 1/10.
   
Illustration - 5
To 1.0 L of a decimolar solution of acetic acid, how much dry sodium acetate be added
(in moles) so as to decrease the concentration of H+ ion to 1/10th of its previous value ? Ka = 2.0  105.
SOLUTION :
 CH COO (aq)+ H+ (aq)
CH3COOH (aq)  3
 [H+] = c  = K a c  2.0  10 5  0.1  1.41  103 M [Ceck yourself that approximations are valid]
Note that when salt, CH3COONa is added, the solution will behave just like an acidic Buffer solution.
[salt] [acid] [acid]

Using, Henderson equation : pH = pK a + log10  [H + ] = K a or [salt] = K a
[acid] [salt] [H + ]
1
Now, [H + ]new =  1.41 103 M = 1.41  10–4 M
10
(2.0 × 105 )(0.1)

 [salt] = = 0.0142 M
1.41  104
 moles of salt, sodium acetate = 0.0142 ( 14.2 mmoles) per 1.0 L is required. (V = 1.0 L)

Illustration - 6 (a) A buffer solution of pH value = 4 is to be prepared, using CH3COOH and

H3COONa. How much amount of sodium acetate is to be added to 1.0 L of M/10 acetic acid ?
Ka = 2.0  105.
(b) What will be the pH if 0.01 mol of HCl is dissolved in the above Buffer solution ? Find the change in pH
value.
(c) How will the pH be affected if 1.5 L of H2O is added to above buffer ?
SOLUTION :
(a) For an acidic buffer containing acetic acid, CH3COO + H+   CH3COOH
CH3COOH and sodium acetate, CH3COONa, 0.02 0.005 0.1
we have : 0.015 0.105
K a  acid  [acid] = 0.11 M and [salt] = 0.01 M [V
+
[H ] =
salt  = 1.0 L]
[salt] 0.015
Use this rather than : pH = pK a + log10  pHnew = pKa + log10
[acid] 0.105
[CH3COOH] = 0.1 M ; = 4.7 + (  0.84) = 3.86 [Use log107 = 1.0.84]

 Change in pH = 3.86  4.0 = -0.14
[H+] = 10–4 M and let [CH3COONa] = x M
(c) Now, if 1.5 L of H2O is added, it just increases the
5 volume, thereby decreasing concentrations of both
2 10  0.1
 [H+] = 104 
x [salt]
 x = 0.02 moles i.e. 0.02 moles of acid and salt. The ratio log10 remains constant.
[acid]
CH3COONa is required. Hence pH remains same.
(b) Now 0.01 mol of HCl ([H+] = 0.01 M) is added
to 1 L of buffer, this will react with acetate ion
(CH3COO ) as :
Illustration - 7 How many of the following combination can act as buffer.

(i) HCl + NaOH (ii) HCl  CH 3COO  Na  (iii) H 2 SO4  NaHSO4
(iv) H 2CO3  NaOH (v) NaOH  PhCOOH (vi) HBr  NH 4OH
(vii) CH 3COOH  NH 4OH (viii) NaOH  NH 4OH (ix) HCl  CH 3COOH
(x) Borax ( Na2 B4O7 )  Boric acid ( H 3 BO3 ) (xi) NaH 2 PO4  Na2 HPO4
(xii) Na2CO3  NaHCO3
SOLUTION :
As we know that buffer is a mixture having weak acid and its salt with strong base or weak base and its salt
with strong acid. Further a mixture of acid and base may also acid and base may also acts as buffer depend
-ing on the nature of acid and base (strong or weak) and their moles taken for preparation of mixture,

because acid and base reacts to form salt. The combination (i) and (iii) can’t acts as buffer because it does
not contain weak electrolyte (weak acid or base) but combination (ii) can act as buffer if axcess of
CH 3COONa is mixed with limited amount of HCl.
Resulting mixture contains weak acid (CH3COOH) and its salt with strong base (CH3COONa). Similarly
combinations (H2CO3 + NaOH),(PhCOOH + NaOH),(NH4OH + HBr)can also act as buffer..
The combinations(viii) and (ix) can’t acts as buffer because salt component is missing.
Mixture of two salts of weak polyprotic acid can also acts as buffer because because in such cases we will
visualize a mixture of acid and its conjugate base as salt.
NaHCO3 [having weak acid HCO3 ] and Na 2CO3 [having conjugate base CO32  ] acts as buffer.fer.
Hence the combination (ii), (iv), (v), (vi), (vii), (x), (xi) and (xii) can acts as buffer.

Illustration - 8 The pH of blood stream is maintained by a proper balance of H 2CO3 and NaHCO3 con-
centrations. What volume of 5M NaHCO3 solution, should be mixed with 10 mL sample of blood which is
2M in H 2CO3 in order to maintain a pH of 7.4 Ka for H 2CO3 in blood is 4.0  10–7 ?
SOLUTION :
(5  V)
[H2CO3] in blood = 2M [NaHCO3] in mixture = (V  10)
Volume of blood = 10 mL
[salt]
[NaHCO3] = 5M pH = pKa + log
[acid]
Let volume of NaHCO3 used = V mL
2  10 (5  V) / (V  10)
[H2CO3] in mixture = 7.4 = log 7.8  107 + log (2  10) / (V  10)
(V  10)
V = 40 mL
Illustration - 9 Consider a buffer solution containing 0.1 mole each of acetic acid and sodium acetate in
1.0 L of solution. 0.01 mole of NaOH is gradually added to this buffer solution. Calculate the new [H+] is the
resulting solution. [Ka = 2  10–5]
SOLUTION :
pH of the solution is given by : [salt] = 0.11 M and [acid] = 0.09 M
[salt]  Final pH of solution :

pH = pK a + log10
[acid] 0.11
pH = pK a + log10  4.787
Initial pH of solution : 0.09
[acid]
0.1  [H + ] = K a
pH = pK a + log10  4.7 [salt]
0.1
5 0.09
When 0.01 M NaOH is added,   2  10   1.64 10 5 M
0.11
Illustration - 10 500 ml of 0.2 m aqueous solution of acetic acid is mixed with 500 ml of 0.2 M HCl at
25C .
(i) Calculate the degree of dissociation of acetic acid in the resulting solution and pH of the solution.
(ii) If 6g of NaOH is added to the above solution, determine the final pH. [ K a acetic acid  2 105 ]
SOLUTION :
0.2
(i) [CH 3COOH ]Just after mising   0.1 M
2
0.2
[ HCl ] just after mising   0.1M  [ H  ]From HCl
2

Note : Equal volumes added.
CH 3COOH  CH 3COO   H 
i0 c 0 0
(conc.)
t  ieq c  c c c
[CH 3COO  ][ H  ] c .(c  0.1)

Ka  
[CH 3COOH ] c  c
 [ H  ]   
 Total  [ H ]From CH 3COOH  [ H ]From HCl 
 c  0.1  0.1 ; c  c  c
[   will be small due to common ion effect]
 K a    0.1
Ka
   2  104 [Check : 1    1  2  104  1] and
0.1
[H ]Total  c  0.1  0.1 2104  0.1 0.1M
 pH  1
6
(ii) 6gm NaOH   0.15 gmeq  150 mmoles NaOH
40 / 1
Mmoles HCl = 500  0.2  100 mmoles.
NaOH will first react with HCl and if there is a leftover then it will react with CH 3COOH
 Mmoles NaOH left  150  100  50
These will react with CH 3COOH as :
NaOH + CH3COOH  CH3COONa + H 2O

50 100 
 50 50
 Formation of an acidic buffer
[Salt]
 pH = pK a  log10
[Acid]
50 / VTotal
= 4.7 + log10 = 4.7
50 / VTotal

HYDROLYSIS OF SALTS Section - 4
It involves the study of the reactions between a salt and water to yield an acid and a base. The salts are
generally ionised in water. Here we will deal with salts which are almost fully soluble (not sparingly soluble
salts).
Water in the presence of ionic impurites is visualized as follows :
 H+ (aq) + OH (aq) with [H+] = [OH] (i.e neutral)
H 2O (aq) 
Now, when a salt is put in the water, there is an interaction between ions of salt and ions of water. The
phenomenon of interaction of cations and anions of the salts with H+ and OH ions furnished by water so
that there is some net change in the pH of the resulting solution is known as Hydrolysis of a salt.
Four cases have been discussed here to understand the behavior of various type of salts.
1. Salts of strong acids and strong bases [SA-SB]

When such salts are dissolved in water, they do not undergo hydrolysis. They simply ionises and fail to
change the H+ ion concentration of solution and hence the pH of the solution remains same. e.g. NaCl,
CaCl2, BaCl2, KCl, NaNO3, Na2SO4, Ca(NO3)2
 Na+ (aq) + Cl(aq)
NaCl (aq) 
 H+ (aq) + OH (aq)
H2O (aq) 
The final pH of the solution remains 7 at 25C.
(If NaOH and HCl are formed, they neutralises each other to keep the pH same)
2. Salts of weak acids and strong bases [WA-SB]

Such salts give alkaline solutions in water. Some of such salts are : CH3COONa, Na2CO3, K2CO3, KCN
etc . For our discussion, we consider CH3COONa (sodium acetate) in water. When CH3COONa is put in
water, it completely ionises to give CH3COO (acetate) ions and Na+ ions.
Now acetate ions (CH3COO) absorb some H+ ions from weakly dissociated H2O molecules to form
undissociated CH3COOH. Na+ remains in ionic state in water.
Now for Kw (ionic product) of water to remain constant, H2O further ionises to produce more H+ and OH
ions. H+ ions are taken up by CH3COO ions leaving OH ions in excess and hence an alkaline solution.
Let BA represents such a salt. As it is put in water ;
 BOH (aq) + HA (aq)
BA (aq) + H2O (aq) 
BA dissociates into ions and BOH being strong base also ionises.
 B+ (aq) + OH (aq) + HA (aq)
B+ + A + H2O 
So, the net reaction is :  OH (aq) + HA (aq)

A (aq) + H2O  [Anionic Hydrolysis]

The above equation is known as equation of hydrolysis and equilibrium constant for such reactions is
called as Hydrolysis Constant (Kh).
[OH  ][HA]
Kh 
[A  ]
Degree of Hydrolysis :
It is defined as the fraction of total salt that has undergone hydrolysis on attainment of equilibrium. It is
denoted by h.
Let c be the concentration of salt and h be its degree of hydrolysis.
A + H2O 
 OH + HA (Equation of hydrolysis)
c
c  ch ch ch
[OH  ][HA]  ch  ch  ch 2
Kh   
[A  ] c - ch 1- h
Kh
 Kh = ch2 [assuming h <<1]  h=
c
Now considering, dissociations of weak acid HA and H2O
[H  ][A  ]
 H+ + A
HA  ; Ka = . . . . (i)
[HA]
 H+ + OH
H2O  ; Kw = [ H+] [OH] . . . . (ii)
Kw
 Kh = (Subtracting (i) from (ii), we get equation of hydrolysis)
Ka
Note :  Weaker is the acid, greater is the hydrolysis constant.

 Degree of hydrolysis increases when ‘c’ decreases i.e. with dilution.
Now substituting the value of Kh in expression of h,

Kw
 h
Ka c
pH of solution :
pH of a basic solution is given as :
pH = 14 + log [OH] and [OH] = ch = K h c

Substituting for Kh , we get :
Kwc Kwc
[OH] = Ka  pH = 14 + log10
Ka
1 1
 pH = (pKw + pKa + log10 c) or pH (at 25 C ) = 7 + (pKa + log10 c)
2 2
3. Salts of strong acids and weak bases [SA-SB]

Such salts give acidic solutions in water. Some of such salts are : NH4Cl, ZnCl2, FeCl3 etc. For the purpose
of discussion, we will consider hydrolysis of NH4Cl.
When NH4Cl is put in water, it completely ionises in water to give NH4+ and Cl ions. NH4+ ions combine
with OH ions furnished by weakly dissociated water to form NH4OH (weak base). Now for keeping Kw
constant, water further ionises to give H+ and OH ions, where OH ions are consumed by NH4+ ions
leaving behind H+ ions in solution to give an acidic solution.
Let BA be one of such salts. When it is put into water, the reaction is as follows.
B+ + A + H2O   BOH + H+ (aq) + A (aq) [HA is strong acid]
The net reaction of hydrolysis is :
 BOH (aq) + H+(aq)
B+ + H2O  [Cationic Hydrolysis]
c  ch ch ch
[BOH][H ] (ch)(ch) ch2 Kh

 Kh =   ch2 (h << 1)  h =
 c  ch 1 h 2
[B ] c
Considering ionisation of weak base BOH and H2O.
[B ][[OH  ]
 B+ + OH
BOH  ; Kb 
[BOH]
 H+ + OH
H2O  ; Kw = [H+] [OH–]
From expressions for Kh, Kb and Kw , we have : (As done in previous case)
Kw Kw
Kh   h
Kb K bc
pH of solution :
Now, pH = log [ H+]
Kh Kw c
and [H+] = ch = c = K h c  [H+] =
c Kb

Kwc
 pH =  log10 Kb
1 1
 pH   pK w  pK b  log10 c  or pH (at 25C) = 7   pK b + log10 c 
2 2
Try Your Self :

1. Calculate pH of M/100 solution of CH3COONa at 25C where Ka of CH3COOH is 2.0  105.
[Ans : 8.37]
2. Calculate pH of M/100 solution of NH4Cl at 25C where Kb for NH4Cl is 2.0  105.
[Ans : 5.63]
3. In above two cases, find the degree of hydrolysis taking Kw = 1014.
Note : The results of above two cases of hydrolysis of salts can be used directly.
4. Salts of weak acids and weak bases [WA-WB]

Let us consider ammonium acetate (CH3COONH4) for our discussion. Both NH4+ ions and CH3COO
ions react respectively with OH and H+ ions furnished by water to form NH4OH (weak base) and
CH3COOH (acetic acid).
Let BA represents such a salt.
B  A   H 2O 
 BOH  HA
 weak base   weak acid 
Initially c c 0
At equilibrium c  ch c  ch ch ch
[BOH] [HA] c h  c h 
 Kh = =
[B ][A  ]  c  ch 2
h2
 Kh  ; Taking square root on both sides to get :
1  h 2
Kh
h (Here, 1  h  ; Think why ?)
1 Kh
Hence the degree of hydrolysis of such salts is independent of concentration of salt solution.
Now considering the dissociation of both weak base and acid.
[H  ][A  ]
HA 
 H+ + A ; Ka =
[HA]
[ B  ][OH  ]
BOH 
 B+ + OH ; Kb 
[ BOH ]

 H+ + OH
H2O  ; Kw = [H+] [OH–]
Combining Kh , Kb , Ka and Kw , we have

Kw Kh
Kh = and h= [Cation - Anionic Hydrolysis]
Ka K b 1  Kh
(Observe that 1  h  1 )
pH of Solution :
[H  ][A  ] [HA]
Consider, Ka =  [H+] = K a
[HA] [A  ]
Since, base and acids are weaker, hence,
[BOH ] = [HA]  [B+] = [A]
[BOH][HA] [HA]2 K w Ka
 Kh    [H+] = K a K h =
   2 Kb
[B ][A ] [A ]
K w Ka
pH =  log [H+] =  log Kb
1 1
 pH   pK w  pK a  pK b  or at 25C, pH = 7 +  pK a  pK b 
2 2
Illutrating the concept :
What is the pH of a 0.50 M aqueous NaCN solution ? pKb of CN– is 4.70.
SOLUTION :
NaCN is a salt of weak acid and strong base. The pH of its aqueous solution is given by :
1
pH (at 25C) = 7 + (pKa + log10 c)
2
Remember that for any acid and its conjugate base or vice-versa : pKa + pKb = pKw
e.g. For acid (say HA), pKa corresponds to HA and pKb corresponds to its conjugate base : A
Thus, pKa of HCN = 14  4.7 = 9.3
1 1
So, pH (at 25C) = 7 + (pKa + log10 c) = 7 + (9.3 + log10 0.5) = 11.5
2 2

Illustration - 11 Calculate the degree of hydrolysis of a mixture of aniline and acetic acid each of them
being 0.01 M. Ka of acetic acid = 1.8  105 and Kb (aniline) = 4.5  1010. Also calculate pH of the mixture.
SOLUTION :
C6 H 5 NH 2 + CH 3COOH  C6 H 5 NHCOCH3 + H 2O
(Acetanilide)
Now when we mix equal concentrations of aniline and acetic acid, they will neutralise each other to form
acetanilide (salt). The salt is of weak base and weak acid, so hydrolysis takes place. The degree of hydrolysis
of the salt of weak acid and weak base is given by :
Kh
h
1 Kh
Kw 1014
Here, K h  
K a .K b 1.8  105  4.5  1010
= 1.23
 h = 0.52
However the pH of solution can be calculated by using the standard result :

1
pH  7   pK a  pK b 
2
1
 pH= 7 
2

 log 101.8  105   log10 4.5  1010 

1 4.5  1010
 pH  7  log10  4.7
2 1.8  105
Note :  Solution in this case is acidic. In such salts, pH depends upon which of two i.e. weak acid or weak
base is stronger than the other, i.e. by comparing Ka and Kb; one can theoretically get an idea about
the pH of solution.
1
 The formula pH  7   pK a  pK b  is applicable even when ‘h’ is large as no approximation of
2
‘h’ comparison with unity, has been taken in the derivation (see derivation yourself).

Illustration - 12

2.5 mL of 0.4 M weak mono-acidic base K b  1 10
12
at 25 C is titrated with 2/15 M


HCl in water at 25C. Find the concentration of H+ ions at equivalence point. K w  1 10
14
at 25 C 
SOLUTION :
First find the volume of HCl required to reach the equivalence point.
meq. of Base = meq of HCl
 2 
 2.5  (0.4  1)   1 VHCl
 15 
 VHCl  7.5 mL
The net volume of the solution at the equivalent point = Vbase + VHCl = 2.5 + 7.5 = 10 mL
0.4  2.5
 salt   c  10
 0.1M
pH of an aqueous solution of such a salt is given by :

1 1
pH  7   pK b  log10 c   7  12  log10 0.1  1.5
2 2
  H    101.5  1  3.2  102 M

  10 10
Please note that the above solution is Incorrect. (Why?)
1
Actually, pH  7   pK b  log10 c  is valid only when 1  h  1
2
To check, calculate h using :
Kh Kw 1014
h    0.1  1  0.1  1
c Kb c 1012  0.1
So we have solve from basics as follows :
 BOH  H 
B  H 2O 
c – ch ch ch
[BOH][H  ] (ch) (ch) Kw [H  ]2
 Kh 

[B ]

c  ch
 Kh 
Kb
 102 
c  [H  ]
 ch  [H ]
 102  104  4 103
 [H ]    2.7  102 M
2

SOLUBILITY PRODUCT (Ksp) AND PRECIPITATION OF SALTS Section - 5
Here, we will study those salts which are generally considered as insoluble in water. (e.g. AgCl, BaSO4,
Ag2S, PbS etc) Actually no insoluble salt is actually completely insoluble, they have a very small solubility.
Consider a vessel containing water with a sufficient amount of AgCl being put into it. A very small amount of
it dissolves in water (because generally salts are composed of ions or contain polarised atoms). The
small amount which is soluble is almost 100% ionised.
The situation achieved at this stage is Dynamic in nature; with same of ions (soluble) being solidifying and
some solid always dissolving. Thus a state of equilibrium exists (like in earlier cases). This means at a given
temperature, the concentration of Ag+ ions and Cl ions in aqueous solution remains constant. The following
equilibrium exists. In this equilibrium, the equilibrium state is known as Saturated state.
 Ag+ + Cl

AgCl (s)  [insoluble  soluble (ions)]
The equilibrium constant for this reaction is known as solubility product (Ksp) and is written as :
Ksp = [Ag+] [ Cl]
Ksp is expressed in concentration units. The reaction coefficient, Q in such system is known as ionic product
(I.P)
Note :  The solubility of a salt in water depends upon other substances (ions) present is water (at that time)
and the solubility product is a constant value (at a given temperature) and is independent of presence
of any other ion present. Like other equilibrium constants such as : Kp, Kc, Ka and Kb , it is also
constant at a certain temperature and can change only when temperature changes.
 The salts like AgCl are regarded as sparingly soluble salts. Some of them are : Ag2SO4, Ag2CO3,
PbCl2, PbCrO4, PbS, ZnS, Al(OH)3, Ca3(PO4)2, BaSO4, CaSO4, MnS etc.
Ksp for Ag2SO4 :  2Ag+ + SO 2(aq)

Ag2SO4 (s) + aq.  4
Ksp = [Ag+]2 [SO42]
Ksp for Ca3(PO4)2 :  3Ca2+ + 2PO 3(aq)

Ca3(PO4)2(s) + aq.  4
Ksp = [Ca2+]3 [PO43]2
Note : In the solubilities of sparingly soluble salts, we will deal with mainly two types of problems : one to find out
the solubility in water if Ksp of a salt is given and vice-versa. Second, to find out solubility of a salt in
presence of other (common) ions in water.

Illustration - 13 If K of calcium iodate Ca(IO ) = 6.3  107 at 18C, find the solubility of salt in (i) gm/
sp 3 3
L (ii) mol/L in water at 18C.
SOLUTION :
In questions, solubility is sometime asked Now, Ksp = [Ca2+] [IO3]2
(or given) to be expressed in gm/L.  6.3  107 = (x) (2x)2
Now the following equilibrium is established :  4x3 = 6.3  107
 Ca2+ (aq) + 2IO3(aq)

Ca(IO3)2   x = 5.4  103 M.
Now answer is to expressed in gm/L
Let x mole/L be solubility of Ca(IO3)2 in water
 solubility = x  M0
 [Ca2+] = x M and [IO3]= 2x M = (5.4  103)  390 = 2.106 g/L
Illustration - 14 The K of AgCl at 25°C is 1.5  1010. Find the solubility of AgCl (in gm/L) in an aqueous
sp
solution containing 0.01 M AgNO3.
SOLUTION :
Now this is quite similar to finding the degree of dissociation of a weak acid or weak base in presence of its
common ion (Le Chatelier’s principle).
Here 0.01 M AgNO3 will give 0.01 M Ag+ ions in solution before the addition of AgCl.
(AgNO3 is 100% soluble in water).
Let the solubility be c mol/L in AgNO3.
 Ag+ + Cl
AgCl 
c c
 Ag+ + NO3
AgNO3 
0.01M
In solution :
[Ag+] = c + 0.01 and [Cl] = c
Now Ksp is a constant and is independent of presence of any ion in water.
 Ksp = [Ag+][Cl] = (0.01 + c) (c) = 1.50  1010
(Now assuming 0.01 + c  0.01 as c << 1 for sparingly soluble salt)
K sp
 c  1.5  108 M
0.01
[Check that c + 0.01  0.01 M]
or solubility = (1.5  108)  143.5 = 2.15  106g/L
Note : The solubility of AgCl in water containing Ag+ (a common ion) is much less than in pure water.

Illustration - 15 The solubility of BaSO4 in water is 2.33  104 gm/100 mL. Calculate the % age loss in
weight when 0.2 gm of BaSO4 is washed with
(a) 1 L of water (b) 1 L of 0.01 N H2SO4.  M 0 BaSO4  233 gm / mol 
SOLUTION :
(a) Solubility is in general expressed in gm/L, Now let x be solubility in mol/L in H 2SO 4
so solubility of BaSO4 = 2.33  10 3
g/L  [Ba2+ ] in solution = x mol/L
Loss in weight of BaSO4 = amount of BaSO4 and [ SO42] in solution = (x + 0.005) mol/L
soluble. Ionic product = [ Ba2+ ] [SO42]
2.33 103 = (x) (x + 0.005)
 % loss =  100 = 1.16 %
0.2
Ksp = Ionic Product at equilibrium (saturation)
(b) 0.01 N H2SO4  0.01 N SO42 ions  1.0  1010 = (x) (x + 0.005)
 0.005 M SO42 ions Assuming x to be a small number
x + 0.005 ~ 0.005
Now presence of SO42 prior to washing
BaSO4 will suppress the solubility of BaSO4 1010
 x= = 2  108 mol /L
(due to common ion effect). The suppression 0.005
will be governed by Ksp value of BaSO4. So
= 2  108  233 g/L
first calculate Ksp of BaSO4.
= 4.66  106 g /L
Solubility of BaSO4 in fresh water
 4.66  106 gm of BaSO4 are washed
= 2.33  103 g/L
away.
2.33 103
 mol/L =105 M 4.66 106 100
233  % loss =
0.2
Ksp = [ Ba2+] [ SO42] = (105)2 = 1010
= 2.33  103 %
Note : Third type of problem are related to the precipitation of salts (sparingly soluble). To understand and
solve such problems, let us read following article carefully.
Precipitation of salts
Now we will study (application of Ksp) how to determine whether or not a precipitate will form when we
mix known concentrations of ions which combine to give a sparingly soluble salt. To understand and solve
such problems let us analyse the expression of solubility product.
For a salt (sparingly soluble) when dissolved in water :  B+ (aq) + A (aq)
BA 
At equilibrium (saturation) : Ksp = [B+] [A]

When we mix ions or if there be two or more ions in water, we define reaction coefficient (Q) called as
ionic-product (I.P.), giving the products of ions in water (ions of soluble salts and other common ions).
I.P. is product of ionic concentration due to ions already present in water or from a salt. It may be and
may not be equal to Ksp. To illustrate it more clearly, consider a case when 500 ml of 0.005 M solution
of AgNO3 is added to 500 ml of 0.001 M solution of KCl. Now in solution (mixture), there are Ag+,
NO3, K+ and Cl ions. The concentration of [Ag+] = [NO3] = 0.005/2 = 0.0025 M (equal volumes
0.001
are mixed) and [K+] = [Cl]   0.0005 M as equal volumes of two solutions are mixed.
2
Now, we know that Ag+ will react with Cl ions to form AgCl since :
 Ag+ + Cl is a reversible reaction with a high tendency towards left (solidifying or precipitating).
AgCl 
Now, question is, whether AgCl will be formed or not (precipitation of Ag+ and Cl as AgCl) and if it
formed, how much of it will be formed ? For this we define some rules.
1. If Ionic Product (IP) > Ksp ; precipitation takes place till I.P. equals Ksp.
2. If Ionic Product < Ksp ; a precipitate will not be formed and the solution will be unsaturated.
3. If Ionic Product = Ksp ; a precipitate will not be formed and the solution is saturated in that salt.
(or we can say that solution is at a critical stage, when precipitation just begins, but actually
has not occurred)
In present case, I.P. = [Ag+] [Cl] = (0.0025) (0.0005) = 1.25  107

(Only for the salt which is sparingly soluble not for KNO3)
Ionic product > Ksp in this case (Ksp AgCl = 1.56  1010) which mean precipitation takes place.
Illustration - 16 When 15mL of 0.05 M AgNO is mixed with 45.0 mL of 0.03 M K CrO , predict whether
3 2 4
precipitation of Ag2CrO4 occurs or not ? Ksp of Ag2CrO4 = 1.9  1012.
SOLUTION :
First find the concentrations of Ag+ and CrO42 The ionic product for Ag2CrO4 is given as
ions in the resulting mixture. follows.
 2Ag+ + CrO 2
Ag2CrO4  4
15× 0.05
[Ag + ] = = 1.25×102 M Ionic product (I.P.) = [Ag+]2[CrO42]
15 + 45
= (1.25 102)2 (2.25  102)
45  0.03 = 3.51  106 > Ksp
[CrO 24  ]   2.25  10 2 M
15  45 Hence precipitation occurs.

Illustration - 17 The concentration of Ni2+ ions in a given NiS solution is 2.0  106 moles/L. Find the
minimum S2 ions necessary to cause precipitation of NiS. The solubility product, Ksp of NiS = 1.4  1014.
SOLUTION :
Note :Solubility product, Ksp gives an idea of maximum K sp

 For [S2] = , NiS will just start to
possible concentration of an ion which can be [Ni2  ]
retained in solution.
precipitate and
Ksp = ionic product (I.P.) for saturated solution
K sp
 If [S2] > , NiS will precipitate.
For  Ni2+ + S2
NiS  [Ni2  ]
Now, Ksp = [Ni2+][S2] K sp
This means is minimum concentration
K sp [Ni2  ]
 [S2] =
[Ni2  ] of S2 ion above which precipitation occurs.
It is the maximum permissible concentration 1.4  1014
 [S2]min=  7  109 M
of S2 ion in solution. 2  10 6
Illustration - 18 A solution contains 0.01 M each of CaCl and SrCl . A 0.005 M solution of SO 2 is slowly
2 2 4
added to the given solution.
(a) Which substance begins to precipitate first ?
(b) If H2SO4 is continuously added, determine when will other salt be precipitated ?
(c) When second salt starts to precipitate, find the concentration of cation of first salt.
Assume that CaCl2 and SrCl2 are 100% ionised and volume of the solution remains constant.
Ksp of CaSO4 = 1.3 × 104 and Ksp of SrSO4 = 3.2 × 107.
SOLUTION :
K sp [SrSO4 ]
The solution contains 0.01 M Ca2+ ion and 0.01 SO 24   
  Min. for SrSO4 [Sr
2
]
M Sr2+ ions (100% ionization). Now SO42 ions
are added gradually and slowly……………..
(a) First calculate the minimum [SO 42 ions 3.2 107
  3.2 105 M
required to start precipitation of CaSO4 and 0.01
SrSO4 Since [SO42] for SrSO4 is much lower that
K sp [CaSO4 ] required for CaSO4, so SrSO4 will precipitate
SO 24    FIRST.
  Min. for CaSO4 [Ca
2
]
(b) Now, if i.e., SO42 ions are continuously added,
at some instant, its concentration will become
1.3 104
  1.3 102 M equal to that minimum required for precipitating
0.01 out Ca2+ ions.

Hence CaSO4 will start precipitating if [SO42]

2
 2.46  105 M
= 1.3 × 10 M.
(c) Now, find the concentration of Sr 2+ ions  2.46 105 M  0.01M 
 
when[SO42] = 1.3 × 102 M in the solution.
Can you observe that when CaSO4 starts to
K 7 precipitate, SrSO4 is almost precipitated out as
Sr 2    sp SrSO 4  3.2  10 the value of Sr2+ is very very low ?
  [SO 2  ]
4 1.3  102
Note : The above illustration represents a case of selective precipitation (or separation of metals cations) by adding
a common anion. Observe that there is a vast difference in the Ksp values of two sulphates, and hence in the
minimum values of sulphate ion for precipitating out the two metals ions.
Illustration - 19 How much the concentration of Ag+ ions in a saturated solution of AgCl diminish if such
an amount of HCl is added to it that the concentration of Cl ions in the solution becomes equal to 0.03 M ?
Also fine the amount of AgCl precipitated at the given concentration. Ksp of AgCl = 1.8 × 1010.
SOLUTION :
HCl is added to a solution containing Ag+ ions in
I.P.  [Ag+ ] [Cl ]  Ksp
saturated solution. First find the concentration of
Ag+ ion in this solution. K sp 1.8  1010
 [Ag + ]    6.0  109 M


AgCl (s)  +
 Ag + Cl
 [Cl ] (0.03)
Now this is the amount of Ag+ ions left un-precipitated.
 Ksp = [Ag+][Cl] = x2 where x is solubility
of AgCl in mol/L  [Ag+] diminishes in the solution by
6.0  109  1 
 +
[Ag ]  Ksp  1.8  10 10   times
5  2233 
1.34  10
= 1.34  10–5 M The concentration ofAgCl precipitated out of the solution
When HCl is added, the ionic product of AgCl = [Ag+]initial – [Ag+]left
approaches the Ksp value of AgCl, the precipitation = 1.34  10–5 – 6.0  10–8 M
of Ag+ ions will occur. As ionic product increases
It means almost whole of AgCl is precipitated out of the
(i.e. becomes greater than Ksp value), an appreciable
solution at [Cl] = 0.03 M.
amount of AgCl precipitates out, and precipitation
continues till ionic product (I.P.) equals solubility
product (Ksp).

Precipitation through H2S

The most typical technique used in precipitating the metals ions or selectively precipitating (separation) the
two metal ions, is passing H2S gas in a solution of metal ion (s) whose acidity is externally controlled (or
preset by adding HCl). First consider the ionisation (equilibrium) of H2S gas in an aqueous solution and then
in an acidic solution.
 Passing H2S(g) in an aqueous solution :

H2S is a dibasic acid. We have to visualize two stage ionisation for it as follows:
H 2S(aq) 
 H  (aq)  HS (aq) ; K1 . . . (i)
HS (aq) 

 H  (aq)  S2  (aq) ; K2 . . . (ii)
K1 and K2 are Ist and IInd ionisation constants respectively for H2S (aq). Since K2 << K1 (due to common
ion effect), we usually neglect the concentration of H+ ions from second equilibrium.
 [H  ]in Solution  [H  ]from H 2S  [H  ]  [H  ]from H 2S
from HS
   2
[H ][HS ] [H ][S ]
Now, K1  and K2 
[H 2S] [HS ]
From (i), [H + ] = [HS ] and neglecting [H+] from (ii), we have from second ionisation constant :
[H  ][S2  ]
K2   [S2  ] or [S2  ]  K 2

[HS ]
So if we pass H2S in an aqueous solution, sulphide ion concentration is simply equal to the value of second
ionisation constant. We can determine whether precipitation of metal sulphide will occur or not by comparing
ionic product (I.P.) with solubility constant (Ksp).
 Passing H2S(g) in an acidic solution :

Now if we pass H2S in an acidic solution of a metal ion till saturation, we simply neglect the concentration of
H+ ion from H2S (both from first and second ionisations) totally as the concentration of H+ from acid (strong
acid added externally) is very high. In that case we can simply add two equilibriums (i) and (ii) to get :
 2H  (aq)  S2  (aq) ; K a (H 2S)

H 2S(aq) 
[H  ]2 [S2  ]
K a  K1  K 2 
[H 2S]
Note that in a saturated solution of H2S at 25C, [H 2 S] is constant at 0.1 M.
 Ka  (0.1 M) = [H+]2 [S2–]

([H+] [S2–] = Ksp of H2S)

K a  (0.1 M) K  K 2  (0.1 M)
 [S2 ]   1
[H  ]2 [H  ]2
In this way, we now know the concentration of sulphide ion in an acidic solution, so accordingly we can plan
precipitation of metal ions. The important aspect of this method is that we can always increase or decrease
the concentration of sulphide ion by controlling the amount of acid.
Illustration - 20 Calculate the maximum possible concentration of Mn2+ in water that is saturated with
H2S (which is 0.1 M at 300K) and maintained at pH = 3 with HCl. The equilibrium constant(s) for dissociation
of H2S are :
 H+ + HS ;
H2S  K1 = 9  108
 H+ + S2- ;
HS  K2 = 1  1012 and Ksp of MnS = 3  10–22.
SOLUTION :
Note that solution contains S2 ions (from H2S).
So Mn2+ will react with S2 ions to give a precipitate of MnS (being sparingly soluble salt). Hence the
concentration of S2– at saturation will determine the maximum possible concentration of Mn2+ ions in solution
that will not be precipitating. So first calculate [S2] at saturation.
Calculate Ka for dissociation of H2S.
Ka of H2S = K1  K2 = 9  1020
 2H+ + S2
H2S 
[H  ]2 [S2  ] K a  H 2S
 Ka =  [S2] =
[H 2S] [H  ]2
Note that pH of solution is maintained at 3 (externally).

 [H+] = 103 M
9 1020  0.1
 [S2] = 2
= 9  1015
10 
3
In a saturated solution, ionic product = Ksp

Now ionic product = [Mn2+] [S2] = [Mn2+] (9  1015)
 [Mn2+] (9  1015) = 3  1022
 [Mn2+] = 3.33  108 M
NOW ATTEMPT IN-CHAPTER EXERCISE-D BEFORE PROCEEDING AHEAD IN THIS EBOOK

ACID BASE TITRATIONS Section - 6

pH of Mixtures of Acids and Bases
Let us take x millimoles of acid (HA) and y millimoles of base (BOH). Note that acid is monobasic and base
is monoacidic.
(a) Strong acid and strong base
 If x = y, then complete neutralization takes place and we get x (= y). Millimoles of salt (BA) of strong
acid and strong base which means no hydrolysis takes place and pH of solution = 7.
 If x > y, then there is an excess of strong acid and resulting solution is acidic with millimoles of acid
left in excess = x  y. Now if V (in cc) be the volume of mixture, then :
x y
 M= . Now calculate pH using the equation pH = log10 [H+]
V
 If x < y, then there is an excess of strong base and resulting solution is basic with millimoles of base left
in excess = y  x. Now if V (in cc) be the volume of mixture, then :
yx
 M . Now calculate pH using the equation pH = 14 log10 [OH  ]
V
(b) Strong base and weak acid
 If x = y, first of all neutralization takes place to give x (= y) millimoles of salt (BA). The salt will now
undergo hydrolysis to give an alkaline solution. Calculate pH by using the standard result :
1
pH  7   pK a  log10 c  ; c is concentration expressed in M (mol/L)
2
 If x > y, there is excess of weak acid whose millimoles = x  y and y millimoles of salt is formed. This
will give an acidic buffer solution. Calculate pH of buffer solution using Henderson’s Equation.
salt  y
pH = pKa + log10 acid = pKa + log10
  x-y
 If x < y, the solution in this case contains excess of strong base whose millimoles are y  x.
y -x
M= Calculate pH using the equation pH = 14 log10 [OH–]
V
(c) Strong acid and weak base

 If x = y, first of all complete neutralisation takes place to produce x (= y) millimoles of salt (BA). The
salt (BA) is of strong acid and weak base, hence hydrolysis takes place to give an acidic solution.
Calculate its pH by using standard result.
1
pH  7   pK b  log10 c  ; c : mol/L
2
 If x > y, then solution contain excess of strong acid whose millimoles = x  y.

x y
M Now calculate pH using the equation pH = log10 [H+]
V
 If x < y, then there is an excess of weak base whose millimoles are y  x and millimoles of salt (BA)
are x. This will give a basic buffer solution. Calculate the pH by using Henderson’s Equation.
pH  14  pK b  log10
salt  x
= 14  pKb  log10
 base  yx
(d) Weak acid and weak base
 If x = y, neutralisation takes place completely with the formation of x (= y) millimoles of salt (BA) of
weak acid and weak base. So hydrolysis takes place. Calculate the pH by using :
1
pH  7   pK a  pK b 
2
Indicators
Definition : An “indicator” is a dye (or substance) which change color over a short pH range.
Example: Methyl orange changes color in the pH range of 3.1 to 4.5
pH Range and color change of some common Acid-base indicators

End Point : It is the point at which the reaction between an acid and a base is “observed” to be
complete i.e. the pH at which an indicator changes it color.
Equivalence Point: It is the point at which the reaction between an acid and a base is “theoretically”
complete (as per the balanced equation for the reaction).
Note :  At “equivalence point”, meq. of acid = meq. of base but the “end point” can only be detected by
measuring the pH at different points of time during the titration. It is usually more convenient to add an
indicator to the solution and detect the “observed end” of the reaction through a color change in the
solution.
 An indicator is usually a weak acid or a weak base for acid-base titration. The color change occurs
when protons are transferred to form a conjugate base or a conjugate acid of a different color.

Let us represent an indicator as HIn (Weak Acid)


HIn  H 2O  H3O  In 
Acid Conjugate Base
(color 1) (color 2)
or simply, HIn  H+ + In
(color 1) (color 2)
Necessary property of Indicator : Color of ionised form must be remarkably different from that of
unionized form.
[H  ][In  ]
Now, KIn = Equilibrium Constant for the dissociation of the indicator =
[HIn]
[In  ]
 pH = pKIn + log10
[HIn]
Note :  An indicator changes color over a pH range (the so called “transition range”). It is the range over
which color change in the solution is detectable by the “observer”.
 The smaller the transition range, the better the indicator in detecting “equivalence point”. (Equivalence
Point  End Point)
With indicator in which both the forms, ionized and unionized form are colored, generally one colored is
visible if the ratio of the concentration of the two forms is 10 : 1.
 HIn   10
Thus, when only the color of un-ionized (HIn) form is seen :
[In  ] 1
 pH1 = pKa + log10 1 = pKa  1

10
[In  ] 10

and when only the color of ionized (In ) form is seen: 
 HIn  1
10
 pH2 = pKa + log10 = pKa + 1
1
Thus, pH change required in going from one color to other is pH = pH2  pH1 = 2
In the midway between the two colors (i.e. in the transition range), one can assume that [HIn] = [In]
 pH = pKa + log10 1 = pKa  pH = pKa
 The pKa of the indicator should be close to the pH of the equivalence point
For weak-base indicators, same transition range is observed and pOH = pKb at the midway.

(i) Phenophthalein : It is a weak acid represented by PhH.

PhH  Ph + H+
 . . . . (i)
Colorless Pink in base
 Phenolphthalein is colorless in acid solution and pink in basic solution.
 When a strong base like NaOH is added, it displaces the equilibrium (I) towards left direction and
there is a color change.
(ii) Methyl Orange : It is a weak base represented as MeOH.

MeOH   Me+ + OH . . . . (ii)
Yellow in base Red in acid
 When a strong acid is added, equilibrium (II) is shifted towards right and color change to red is
detected..
(a) What is the equivalence point of 0.1 M NH4Br solution ?
[ (pK b ) NH 4OH = 4.74]
When a strong acid reacts with a strong base, equivalence point is the neutralisation point (i.e pH of
the solution = 7 if both of acid and base have same meq.) but when a strong acid reacts with a weak
base or vice-versa, pH at the equivalence point  7 as the salt formed will get hydrolysed and pH
of the solution > 7 or < 7 at the equivalence point. NH4Br is a salt of Strong acid and Weak base.
1 1
 pH = 7   pK b + log10 c  = 7   4.74 + log10 0.1  5.13
2 2
(b) What will be the color of the mehtyl red indicator in the solution of NH4Br in part (a) ? At pH <
3.1, the indicator methyl red is colored pink, at pH > 6.3, it is yellow and at the intermediate
values of the pH it is orange.
Since the pH of NH4Br solution is 5.13 and it lies in the intermediate range of methyl orange, its color
will be orange. (3.1 < pH < 6.3)
(c) An acid indicator has pKIn = 5.3. In a certain solution, this indicator is found to be 80% ionised.
What is the pH of the solution ?
 H+ + In
HIn 
1 0 0
1x x x
Indicator is 80% ionized in acid form :  x = 0.8
[In 1 ] 0.8
 pH = pK a + log10  pH = 5.3  log10  5.9
[HIn] 0.2

Acid Base titration curves :

Titration Curve : It is a curve in which pH of the solution is titrated against volume of the titrate
added.
(i) Strong Acid and Strong Base :
(HCl) (NaOH)
In this case, both the titrants are completely ionized.
 NaCl + H O
HCl + NaOH  2
As OH is added to an acid solution, [H+] decreases and [OH] increases  pH goes on increasing.
As the equivalence point is reached, [H+] is rapidly reduced. Above this point, [OH] increases
rapidly from 107 M and after that pH of the solution remains fairly constant. Thus, there is an inflexion
point at the equivalence point.
The difference in the volume of NaOH solution between the end point and the equivalence point is
not significant for most of the commonly used indicators as there is a large change in the pH value
around the equivalence point and most of them change their color across this pH change.
(ii) Weak Acid and Strong Base :

(CH3COOH) (NaOH)
Initially, when a few drops of OH are added to the weak acid, it forms an acidic buffer CH3COOH/
CH3COONa and thus, pH of the solution changes slowly. At the equivalence point, solution will be
alkaline. If OH addition is continued after the equivalence point, [OH] will increase rapidly.

1 1
(pH) at equivalence point = 7 +  4.76 + log10 c   7 +  4.76 + log10 0.05   8.72
2 2
[Here c = concentration of the salt formed at equivalence point]
Thus, methyl red, methyl orange are inappropriate for use in the detection of the end point between a
weak acid and a strong base.
Also note that the buffer capacity of the buffer solution will be maximum at 50% equivalence point i.e.
when the volume of NaOH is 10 ml.
(iii) Strong Acid and Weak Base :

(HCl) (NH4OH)
Initially, when a few drops of H+ are added to the weak acid, it forms a basic buffer NH4OH/
NH4Cl and thus, pH of the solution changes slowly. At the equivalence point, solution will be
alkaline. If H+ addition is continued after the
equivalence point, [H+] will increase rapidly.

Thus, phenolphthalein, thymolphthalein are quite inappropriate to be used as an indicator to detect the end
point between a strong acid and weak base neutralization.
Also note that the buffer capacity of the buffer solution will be maximum at 50% equivalence point i.e. when
the volume of HCl is 10 ml.
Note : The selection of an indicator therefore is determined by the pH of the solution at the equivalence point.
Illustration - 21 0.1 M NaOH is titrated with 0.1 M, 20 ml HA till the end point. K ( HA) = 6 × 10-6 and
a
degree of dissociation of HA is negligible (small) as compared to unity. Calculate the pH of the resulting
solution at the end point [Use log10 6  0.8]
SOLUTION :
2
NaOH + HA   NaA + H2O Here c = [NaA] =  0.05 M
20  20
At end point 2 2 -
(mmoles) ( 0.1  20) and pKa = –log10 (6  10–6) = 5.2
- - 2 - 1
Note : 20ml of NaOH is required for the complete
pHat end point  7   pK a  log10 c 
2
neutralisation of HA.
1
NaA is a salt of strong base and weak acid. 7  5.2  log10 0.05   8.95
2
Thus, will undergo hydrolysis and solution will
become basic.

Illustration - 22 The equivalence point in a titration of 40.0 mL of a solution of a weak monoprotic acid
occurs when 35.0 mL of a 0.10 M NaOH solution has been added. The pH of the solution is 5.5 after the
addition of 2.0 mL of NaOH solution. What is the dissociation constant of the acid ?
SOLUTION :
Let x milimoles of HA are taken initially. Find x :
 millimoles of HA left x  y  1.5
Consider the equation of neutralization : and millimoles of NaA formed = 2
Now such a solution will behave as an acidic buffer,
HA  NaOH 
 NaA  H 2O
whose pH is given as :
x y 
K a [acid] 1.5
x y  y [H + ] =  1055 = K a =
[salt] 2
At equivalent point, millimoles of acid = milimoles of
aicd = NaOH [i.e. x = y]  K a  4.22  106 [105.5  10  106 ]
 millimoles HA = x = 3.5 [35 ml of 0.1 M NaOH]
At pH = 5.5, millimoles of NaOH added = 2 = y
[20 ml of 0.1 M NaOH]
NOW ATTEMPT IN-CHAPTER EXERCISE-E BEFORE PROCEEDING AHEAD IN THIS EBOOK
SIMULTANEOUS EQUILIBRIUM Section - 7
When two slats having a common ion (either cation or anion) are together in water, then their respective
solubilities are not independent of each other.
Consider a solution containing two salt : CaF2 (K sp = 3.4 × 1011 ) and SrF2 (K sp = 2.9 × 109 ). Compare
their Ksp values. Let us assume that most of F ion concentration in the saturated solution is from SrF2 ,
as its Ksp is much higher than that of CaF2 . It means that first SrF2 will establish its equilibrium (as if there
is no CaF2 ), then CaF2 will dissolve in presence of ions furnished only by SrF2 .
Let the solubility of SrF2 bw x mol/L.
SrF2 ( s )  Sr 2  (aq)  2 F  (aq )

 [Sr 2  ]  x and [ F  ]  2 x
K sp  [ Sr 2  ][ F  ]2  ( x) (2 x) 2  4 x3
1/3
 K sp 
 x   9 104
 4 

Now the solubility of CaF2 is determined in presence of 9  104 M F ions. It means neglect the
contribution of F  ions from CaF2 .

K sp 3.4  1011
K sp  [Ca 2  ][ F  ]2  [Ca 2  ]    1.0  105 M
 2 4 2
[F ] (2  9  10 )
Hence the solubility of CaF2 is 1.0  10 5 mol/ L.
Note : Let us check our assumption. F  ions from CaF2 is twice the amount of Ca 2  ions i.e., 2.0  105 M ,
whereas, F  ions from SrF2 is 2  9.0  104 i.e. 1.8  103 M, which is much higher than 2.0  105 M.
Illustration - 23 Calculate the simultaneous solubilities of AgSCN and AgBr.
K sp ( AgSCN )  1.0  1012 ; K sp ( AgBr )  5.0  1013

SOLUTION :
In this case, please note that the Ksp values of two
and [ Ag  ][ SCN  ]  K sp AgSCN
salts are very similar. So the concentration of Ag +
Note that : [ Ag  ]  [ Br  ]  [ SCN  ]
ions (the common ion) can not be calculated from a
[This is an Electrical charge neutrality equation]
single salt alone and we have to consider the
equilibrium of the two salts simultaneously. K sp AgBr K sp AgSCN
[ Ag  ]  
Let the simultaneous solubilities ofAgSCN and AgBr [ Ag  ] [ Ag  ]
be x and y respectively in mol/L.
 [ Ag  ]  K sp AgBr  K sp AgSCN
 
AgSCN (s )  Ag (aq )  SCN (aq )
x x  x  y  1.22  106 . . . (i)
AgBr ( s)  Ag  (aq )  Br  (aq ) [ Br  ] y K sp AgBr

Also,    0.5 . . . (ii)
y y [SCN  ] x K sp AgSCN
At equilibrium : Using (i) and (ii), we get :
[ Ag  ]  x  y ; [ SCN  ]  x ; [ Br  ]  y x  8.0  107 ; y  4.0  10 7
[ Ag  ][ Br  ]  K sp AgBr

Illustration - 24 Two weak monobasic organic acids HA and HB have dissociation constants as 3.0  105
and 1.5 105 respectively at 25C . If 500 ml of 1 M solutions of each of these two acids are mixed to
produce 1 litre of mixed acid solution, what is the pH of the resulting solution ?
SOLUTION :
Note that K a of two acids is nearly same. In such ( x  y) x
cases, we have to consider H  from both HA and  K a( HA)  and
c
HB simultaneously. The concentration of HA and
( x  y) y
HB in the mixture = 5.0 M K a ( HB ) 
c
[equal volume are mixed] = cM Divide the two expressions to get :
HA  H   A 1 x
  x  2y
c x x 2 y
HB  H   B 
1 x 2  xy
Substitute for y  x in K a ( HA) 
2 c
c
c y y y x 2  0.5 x 2
 3.0  105 
0.5
Now, [ H  ]final  [ H  ] from HA  [ H  ] from HB
 x  10  103 M
( x  y) x ( x  y) y
 K aHA  and K aHB  10
cx cy and y   103 M
2
As K a of both acid  105 and H  from one acid
3 10
acts as common ion for other’s dissociation, x and y [H  ]  x  y   103 M
are very less as compared to c.
2
 c  x  c and c  y  c  3 10 
pH   log10   103   pH  2.32
 2 
 
Illustration - 25 Determine the solubility of AgCN in a buffer solution maintained at pH = 3.

K sp ( AgCN )  2.0 1016 ; K a ( HCN )  6.0  1010
SOLUTION :
AgCN is a sparingly soluble salt in aqueous The CN  ions will react with H  in the solution to
medium. form HCN. (a weakly dissociated acid) and we have
AgCN (s )  Ag  (aq )  CN  (aq) to assume that in solution [CN  ]  y M finally which
Let the solubility of AgCN be x M. Thus, will be decided by the dissociation of HCN as
[ Ag ]  xM and [CN  ]  x M from salt but it

explained below : AgCN (s )  Ag  (aq )  CN  (aq)
will not be equal to x finally.

K sp ( AgCN )  [ Ag  ][CN  ]  xy  2  1016

H  CN  
 HCN
and
103 x
103  x [ H  ][CN  ] 103 y
x K a ( HCN )    6  1010
HCN x y
Solve the equation to get :

HCN  H  CN
K sp
x 103 x  [ Ag  ] 
Ka
[ H  ]  K a   1.82  105 M
x y 103  y y
Note that in the solution :
 103
[ Ag  ]  [CN  ]  [ HCN ]
We have two equations now : (Electrical charge neutrality equation)
Note : In this example, since the dissociation constant
of acid is very low and pH of the solution is
fairly high, we could have assumed that [ H  ]
and K a in the expression for x.
Illustration - 26 How much AgBr could dissolver in 1.0 L of 0.4 M NH ? Assume that Ag ( NH ) is the
3 3 2
 
only complex formed Given: The dissociation constant for Ag ( NH 3 )2  Ag  2 NH 3 ; K d  6.0  108
and K sp ( AgBr )  5.0 1013.

SOLUTION :

Let solubility of AgBr be xM. Thus, [ Br ]  x M Ag    Ag ( NH 3 )2
2 NH 3 
 x 0.4
but [ Ag ]  x M since it will react with NH 3 to
form a complex and thus, its concentration will be 0.4  2 x x
decided by the dissociation of the complex. So, let
[ Ag  ]  y M.
Ag ( NH 3 )2  Ag   2 NH 3 ; K d  5.0  1013
AgBr ( s )  Ag  (aq )  Br  (aq ) x 0.4  2 x
 K sp  [ Ag  ][ Br  ]  y x  5.0  1013 x y y 0.4  2 x  2 y ( 0.4)
Since the formation constant ( K f ) of the complex [ Ag  ][ NH 3 ]2y (0.4  2 x  2 y ) 2

Kd    6  108
is very high, assume that whole of Ag  formed is 
[ Ag ( NH 3 ) 2 ] x y
consumed.

Assuming x  y  x since K d is low and << 0.4, Solving for x : x  1.15  103 M
we get : (Verify the approximation yourself)
y (0.4)2
Kd 
x
Illustration - 27 HN (hydroazoic acid) is a weak acid dissociating as : NH  H   N  . Find the con-

3 3 3
centration of Ag  ions, if excess of solid AgN3 is added to a solution maintained at pH = 4. The ionization
constant K a of NH 3 is 2.0 105. The solubility of AgN3 in pure water is found to be 5.4 103 M at
25C.
SOLUTION :
AgN3 is a sparingly soluble salt, dissociating in Now HN3 dissociates as follows :
water as : AgN3  Ag   N 3 HN3  H  N3
K sp  [ Ag  ][ N3 ] x 104 
Since solubility of AgN3 in water is 5.4  103 , x y 104  y  104 y
K sp  (5.4  103 )2  2.92 105 [As pH is maintained at 4 hence [ H  ]  104 M ]

Now we have a simultaneous equilibrium in aqueous
Now we have to find the solubility of AgN3 in
solution involving dissociation of AgN3 and HN 3.
solution having pH = 4.
Let solubility of AgN3 be x M at pH = 4. K sp of AgN3  [ Ag  ][ N3 ]  xy … (i)

 [ Ag  ]  xM , but [ N3 ]  x M [ H  ][ N3 ] [ H  ] y
K a of HN3   … (ii)
( [ N 3 ] will be decided by dissociation of HN3 ). [ HN 3 ] ( x  y)
Solving (i) and (ii) simultaneously, we have :
Let [ N3 ]  yM
K sp
First, assume that whole of N3 (xM) formed from x  [ Ag  ] 
Ka
[ H  ]  K a 
AgN3 reacts with H  ions to form HN 3.
Substitute the values of K sp , K a and [ H  ] to
 [ HN 3 ]  xM
get x = 0.0132 mol/L
Note : In this example, since the dissociation constant of acid is quite high and pH of the solution is quite low, we
can not assumed that x  y  x. You can check the same by comparing [ H  ] and K a in the expression
for x.

Example - 1 A solution contains a mixture of Ag+(0.1M) and Hg22+ (0.10 M) which are separated by
selective precipitation. Calculate maximum concentration of Iodide ion at which one of them gets precipitated
almost completely. What % age of that metal ion is precipitated ?
 Ksp AgI  8.51017 M; Ksp HgI 2

 2.51026 
SOLUTION :
First determine, which ion starts precipitating. first But when [I] reaches 5  1013 M then precipitation
of Hg2I2 also starts.
Ksp of AgI So [Ag+] left at that stage is given as :
[I ]Min.for AgI 

[Ag ] K sp of AgI
[Ag+] =
8.5 1017 [I ]Hg 2 I 2
=  8.5 1016 M
0.1
8.5  1017
K sp of Hg 2 I 2 =  1.7  104 M
 13
[I ]Min.for Hg 2 I2  5.0  10
2 +
[Hg 2 ] % of Ag left un-precipitated
1.7 104
2.5 1026 =  100 = 0.17%
= = 5  1013 M 0.1
0.1
 % age of Ag+ = 99.83 %
This means that AgI will be precipitated first as [I ] This means when Hg2I2 starts precipitating, Ag+ is
required for AgI is less. almost precipitated.
Example - 2 Carbonic acid, H CO , is a diprotic acid for which K  107 and K  1011. Which solution
2 3 1 2
will produce a pH closest to 9 ?
(A) 0.1M H 2CO3 (B) 0.1M Na2CO3
(C) 0.1 M NaHCO3 (D) 0.1 M NaHCO3 and 0.1 M Na2CO3
SOLUTION :
Amphiprotic salt is a salt that can donate proton well as can accept a proton. For example : NaHS, NaHCO3
etc.
 Na   HS 
NaHS 
HS   H   H 2 S
HS   S 2   H 
pH of amphiprotic salt of weak acid is calculated by using following expression.

1
pH   pK a  pK a 
2 1 2
1 1
pH   pK a1  pK a2   [7  11]  9
2 2
Example - 3 For the reaction Ag(CN)     Ag+ + 2CN, in an aqueous medium, the equilibrium
2
constant KC at 25°C is 4  1019. Calculate the Ag+ ion concentration in the solution which was originally 0.1
M in KCN and 0.03 M AgNO3.
SOLUTION :
[Ag  ][CN  ]2
0.1 M KCN and 0.03 M AgNO3 are mixed.  4 1019
KC = 
 Ag(CN)  is very-
Since Keq for Ag+ + 2CN  [Ag  CN 2 ]
2

 1 19  KC [Ag  CN2 ]
very high  K   10  , first assume that whole +
 [Ag ] =
 4  [CN ]2
of Ag is converted to Ag(CN)2.
+
4  1019  0.03  x 
=
Ag   2CN  
 Ag(CN)2  0.04  2 x 2
0.03 M 0.1 M 0
Solve the above equation by assuming ‘x’ to be very
0 0.1  2  0.03 M 0.03 M
small.
Now, Let 0.03 M Ag(CN)2 (Keq = 4  1019) to
dissociate as follows : 4  1019  0.03
 Ag+ + 2 CN
+
 [Ag ] = 2 = 7.51018 M
Ag (CN)2   0.04 
0.03 M - 0.04 M [Verify the approximation yourself]
0.03  x x (0.04 + 2x)
Example - 4 Calculate [NH4+] (derived from NH4Cl) needed to prevent Mg(OH)2 from precipitating in a
litre of solution which contains 0.2 mole of ammonia and 0.001 mole of Mg2+ ions. The ionisation constant of
ammonia is 2.0  105 and Ksp of Mg(OH)2 is 1.0  1011.
SOLUTION :
 Kb 
Note that aq. ammonia is NH4OH.     102  1   ~ 1
 c 
First check whether we need to add NH4Cl.
 I.PMg(OH)2  103  (2  103 ) 2
 3
[OH ]From NH3  K b c  2  10 M
 4  109  K sp
Thus, precipitation will take place if NH4Cl is not added If [OH]  1.0  104M, Mg2+ ions will not be
and hence, NH4Cl is required to be added so as to precipitated. So, maximum concentration of OH in
suppress the dissociation of NH4OH. As a result, the solution should be 1.0  104 M. As [OH] is
[OH–] will decreases. derived from dissociation of ammonia.
Now, calculate the concentration of OH ions in  NH + + OH
NH4OH  4
equilibrium with Mg2+ ions from Ksp of Mg(OH)2.
K b [NH 4OH]
Ksp of Mg(OH)2 = [Mg2+] [OH]2  [NH 4 ] 
[OH  ]
 K sp 1.0  10 11 (2.0  105 ) (0.2)

 [OH ]    1.0  104  [NH 4 ]min 
[Mg 2  ] 0.001 [1.0  104 ]
 4.0  10 2 M
For this much concentration of NH4+ ions, Mg2+ will
not be precipitated.
Example - 5 When a 40 mL of a 0.1 M weak base, BOH is titrated with 0.10 M HCl, the pH of the solution
at the end point is 5.5. What will be the pH if 10 mL of 0.10 M NaOH is added to the resulting solution ?
SOLUTION :
At the end point, pH = 5.5 (i.e. an acidic solution). K wc (10 14 )  (0.05)
 Kb    5.0  10 5
It means salt formed at the end of neutralisation  2  5.5 2
[H ] (10 )
undergoes hydrolysis.
When 10 mL of 0.12 M NaOH is added :
For 4 millimoles (40  0.1) of weak base, 4 millimoles
BCl + NaOH   BOH + NaCl
of acid is required at the end point.
Initially 4 m.moles 10  0.10
 BCl + H O
BOH + HCl  Finally 4  10  0.10
2
4 4 4  1 = 3.0 – 1.0
– – 4
It means a basic buffer containing 3.0 m.moles of BCl
 millimoles of salt (BCl) formed = 4 and 1.0 m.moles of BOH is fomed. Find the pH by using
 [BCl] = 4/V where V = VHCl + Vbase Henderson’s equation for basic buffer.
At the end point : 4 = 0.10  VHCl [BCI]
 VHCl = 40 mL pOH  pK b  log
[BOH]
 V = 40 + 40 = 80 mL
[3.0 / V ]
 [BCl] = 4 / 80 = 0.05 M  pOH   log(5  105 )  log
[1.0 / V ]
Note that BCl is a salt of strong acid and weak base.
 pOH = 4.77 (pKb = 4.3)
 K wc
 [H ]   pH = 14  pOH = 9.22
Kb
Example - 6
It is given that 0.001 mol each of Cd2+ and Fe2+ ions are contained in 1.0 L of 0.02M HCl
solution. This solution is now saturated with H2S gas at 25°C.
(a) Determine whether or not each of these ions will be precipitated as sulphide ?
(b) How much Cd2+ ions remain in the solution at equilibrium ?
K1 ( H 2 S ) = 1.0 × 107 ; K 2 ( H 2 S ) = 1.0 × 1014 ; K sp (CdS ) = 8 × 1027 ; K sp ( FeS ) = 3.7 × 1019
SOLUTION :
Note that two salts are of same type (i.e., AB type) 1021  0.1
 [S2  ]   2.5  1019 M
and Ksp of CdS is lower than that of FeS. This means 0.02 2
CdS will precipitate first if at all any precipitation takes
place. 8 1027
 [Cd 2  ]Left   3.2 108 M
Calculate the minimum concentration of Sulphide ion 2.5 10 19
required to initiate the precipitation of each of the metal
Thus, only CdS will get precipitated.
sulphide.
[S2–]Min for CdS To calculate the remaining concentration of Cd2+ ion
(more accurately) ion in the solution, first assume that
K sp CdS 8  1027 whole of the Cd2+ has been precipitated as :
=   8 1024 M
[Cd 2  ] 0.001
Cd2+ + H2S 
 CdS + 2 H+
[S2–]Min for FeS Thus, [ H +]new = 0.02 + 0.001  2 = 0.022 M
K sp FeS 3.7  1019 1021  0.1
=   3.7  1016 M 2–
[Fe 2
] 0.001  [S ]At new equilibrium =
0.0222
Now calculate the sulphide ion concentration in the = 2.07  10–19 M
saturated solution, using :
8 1027
[H ] [S ]  2 2  [Cd2 ]Left   3.86 108 M
19
K a  K1  K 2   1021 2.07 10
[H 2S]
Note : FeS will not be precipitated at all.
Example - 7
The solubility product, K sp of Ca(OH )2 at 25C is 4.0  106. A 500 mL of saturated of
Ca(OH )2 is mixed with equal volume of 0.4 M NaOH solution. How much Ca(OH )2 in milligrams is
precipitated ?
SOLUTION :
First find the concentration of Ca 2  ions at saturation using K sp of Ca(OH )2 .
Ca(OH ) 2  Ca 2   2OH 
 K sp  [Ca 2  ][OH  ]2
Let [Ca 2  ]  x mol / L  [OH  ]  2 x
K sp
 K sp  4 x3 or x  3  0.01 M
4
 [Ca 2  ]  0.01 M and [OH  ]  0.02 M

As equal volumes of saturated solution and 0.4 M NaOH are mixed :
0.01
[Ca 2  ]   5  103 M
2
 0.02 0.4
and [OH ]Total    0.21 M
2 2
[ [OH  ]Total  [OH  ]NaOH  [OH  ]From Ca (OH )2 ]
Now, calculate I. PCa (OH )2  [Ca 2  ][OH  ]2  (5  103 ) (0.21) 2  2.2 104  K sp
Since concentration of OH  is quite high, Ca 2  will be precipitated till a new saturation state is reached.
Let at new saturated state. [OH  ]  0.21 M (Assuming no change in [OH  ] )
2 K sp (4  106 )
[Ca ]left    9.07  105 M
 2 2
[OH ] (0.21)
 [Ca 2  ]precipitated  5  103  9.07  10 5 M  4.91 103 M
 amount of Ca 2   4.91 103  74  103 mg / L  363.3 mg / L
Check the approximation : [OH  ]left  0.21 M . How ??
Find out the [OH  ]used  2[Ca 2  ]used (see Reation’s Stoichichiometry)
 2  4.91 103 M  9.8  103 M

 [OH  ]left  0.21  9.8 103 M  0.2M  0.21M
Alternate Approach :
Ca (OH )2  Ca 2 (aq)  2OH  (aq )

t  teq : concentration : 0.01 0.02 I .P.  K sp
t  0(new) concentration : 5 103 0.21 I .P.  K sp

( After mixing equal volumes with NaOH )
t  teq (new) 5  103  x 0.21  2 x I .P.  K sp
Now, I.P. = K sp at equilibrium
(5  103  x ) (0.21  2 x ) 2  4  10 6  This equation in ‘x’ is clearly a cubic.

To solve the above equation approximately, assume 0.21  2 x  0.21 which is what has been done in the
previous approach.
Example - 8 The solubility product of Ag C O at 25C is

2 2 4 1.20  1011. A solution of K 2C2O4 containing
0.15 moles in 500 ml water is mixed with excess of Ag 2CO3 till the following equilibrium established :
Ag 2CO3  K 2C2O4  Ag 2C2O4  K 2CO3.
At equilibrium, the solution contains 0.03 mole of K 2CO3. Assuming that the degree of dissociation of
K 2C2O4 and K 2CO3 to be equal, calculate the solubility product of Ag 2CO3. [Take 100% ionisation of
K 2C2O4 and K 2CO3 ]
SOLUTION :
0.15 Now find [ Ag  ] at equilibrium as :
[ K 2C2O4 ]   0.30 M  P
initial 0.5
K sp of Ag 2C2O4
0.03 [ Ag  ] 
and [ K 2CO3 ]  0.5  0.06 M  x [C2O42  ]
final
Ag 2CO3  K 2C2O4  K 2CO3  Ag 2C2O4 1.20  1011 1.20  1011

 
P  Px 0.3  0.06
Px x  7.07  10 6 M
1 mol K 2CO3  1 mole K 2C2O 4 and since both [CO32  ] final  x  0.06 M
are completely ionized :
Now, K sp of Ag 2CO3  [ Ag  ]2 [CO32 ]
 K sp of Ag 2CO3  (7.07 106 ) 2  0.06
 3  1012
Example - 9 Malonic acid is an organic dibasic acid like H 2 S having first ionization constant,
K1  1.42 103 and second ionization constant, K 2  2.0  106. Compute the divalent malonate ion
concentration in :
(a) 0.001 M Malonic acid (b) in a solution that is 0.0001 M in malonic acid and 0.0004 M HCl.
(c) in a solution that is 0.0001 M in malonic acid and 0.1 M HCl.
SOLUTION :
(a) Consider malonic acid to be H 2 A, where malonate ion is A2  . For dibasis acids, we consider ionization
in two stages as follows :
[ H  ][ HA ] x2
 K1    1.42  103
[ H 2 A] cx
Solving the quadratic, x 2  1.42  103 x  1.42  106  0  x  6.75  104 M

Note that K1  K 2 . so concentration of H  in solution is considered only from dissociation i.e.,
[ H  ]  x M (neglect H  concentration from second ionization).

Consider second ionisation :
[ H  ][ A2 ] ( x  y) y
 K2  
 x y
[ HA ]
Note : [ H  ] [ H  ]  x  y  x [ HA ]  x  y  x ( y  x )
 K 2  y  [ A2  ]  2.0 106 M
Note : Usually, [ A2  ] for H 2 A (dibasic acid) can be approximately taken to be K 2 .
(b) Here  104 M , [ H  ]  4  104 M (From HCl)
[ H  ][ HA] (4 104  x ) ( x)
 K1    1.42  103
[ H 2 A]  4
10  x
Important : Note that, we can not go for approximation in this case, since the concentration of HCl
is so low that H  is considered both from HCl and molonic acid.
Solving the quadratic, x 2  1.82  103 x  1.42  107  0  x  7.5  105 M
Now consider, second ionisation and substitute for value of x.
[ H  ][ A2  ] (4  104  x )
K2    2.0  106
[ HA] x
(4  104  7.5  105 ) y

  2.0  106
5
7.5  10
 y  [ A2  ]  3.2 107 M
(c) Here c  104 M , [ H  ]  0.1M
[ H  ]2 [ A2  ] (0.1)2 [ A2  ]
 K a  K1K 2    2.84  109
[ H 2 A]  4
10
 [ A2  ]  2.84 1011 M
Important : Note that, we will do the approximation in this case, since the concentration of HCl is so high
that H  is considered from malonic acid is negligible. Recall the ionization of H 2 S (g) in an
acidic solution.
Example - 10
Calculate the [ F  ] in a solution saturated with respect to MgF2 and SrF2 .
K sp ( MgF2 )  6.0  109 ; K sp ( SrF2 )  3.0 109

SOLUTION :
In this case, please note that the K sp values of two salts are very similar. So the concentration of F  ions
(the common ion) can not be calculated from a single salt alone.
Let the simultaneous solubilities of MgF2 and SrF2 be x and y respectively in mol/L.
MgF2 ( s )  Mg 2   2F 
x 2x
SrF2 ( s )  Sr 2 2 F 
y 2y
At eq : [ F  ]  2 x  2 y ; [ Mg 2  ]  x ; [ Sr 2  ]  y
 [Mg 2  ][ F  ]2  K sp MgF2
and [Sr 2  ][ F  ]2  K sp Sr F2
Note that : 
[ F  ]  2 [Mg 2 ]  [ Sr 2  ]  [This is an Electrical charge neutrality equation]
 K sp MgF2 K sp SrF2 
[F  ]  2   
 [ F  ]2 [ F  ]2
 
 
[ F  ]  3 2 K sp MgF2  K sp SrF2   2.62  10 3 M
THINGS TO REMEMBER
1. Weak Electrolyte
[H  ]2 c 2 [H  ]2
(a) Weak Acid : K a   ; c  [H  ] 
c  [H  ] 1  Ka
If 1 –  ~ 1, then Ka = c2 and [H  ]  K a c
[OH  ]2 c 2 [OH  ]2
(b) Weak Base : Kb   ; c  [OH  ] 
c  [OH  ] 1  Kb
If 1 –  ~ 1, then Kb = c2 and [OH  ]  K b c
 For any acid – conjugate base pair, Ka.Kb = Kw

 “” of weak electrolytes increase on dilution.
 
H 2O  
 H  OH

Kw = [H+] [OH–] or pH + pOH = pKw

Kw increases as T increases and decreases as T decreases.
2. Buffer solution :
salt 
(a) Acidic : HA + A–  pH = pKa + log10
 acid 
salt 
(b) Basic : BOH + B+  pOH = pKb + log10 base
 
 Buffer capacity of the buffer solution is maximum at pH = pKa or pOH = pKb.
 pH of a buffer solution does not change on dilution.
3. Hydrolysis :
 Salts of SA – SB do not get hydrolysed.
 Salts of SA – WB on hydrolysis give acidic solution.
ch 2 K 1
Kh   w ; pH   pK w   pK b  log10 c 
1 h Kb 2
 Salts of WA – SB on hydrolysis give basic solution.
ch 2 K 1
Kh   w ; pH   pK w   pK a  log10 c 
1 h Ka 2 
 Salts of WA – SB on hydrolysis may give acidic, basic or neutral solution.
h2 Kw 1
Kh   ; pH   pK w   pK a  pK b  
1  h 2 Ka . Kb 2
Kh : hydrolysis constant ; h : degree of hydrolysis
4. Sparingly soluble salts and Precipitation :

 Solubility of a sparingly soluble salt is expressed in mol / L or gm/L
1/  x  y 
 (Ksp ) 
 Solubility (in Mol/L) of any salt AxBy in pure water is given by : So lub ility  
x y
 x  y 
 Solubility of a salt decreases in the presence of a common ion.
In general, we can neglect the contribution of common ion from the sparingly soluble salt.
Ksp AgCl K sp AgCl
e.g. solubility of AgCl in pM NaCl = 
[Cl ] p
 Selective precipitation : When difference in the minimum concentrations of common cation/anion
required to start the precipitation is very high.
To check, always calculate the conc. of the cation/anion left in the solution when the second cation/
anion starts to precipitate, and so on……….
 Simultaneous Solubility : Solubility of two or more salts having a common cation / anion when
their Ksp values are comparable. Solve the governing equations simultaneously.
5. Use of Indicators :
 Transition range of an indicator : pKIn– 1 to pKIn + 1
 For SA - SB titration, almost every indicator is effective.
 For SA - WB and WA - SB, indicator selection is important and depends on the pH at equivalence
point.
6. Miscellaneous :
 For dissociation of H2A, [A2–]  K2 ; For H3A, [A3– ]  K3 and so on.
 For any polyprotic acid, K a1 >> K a 2 >> K a 3 and so on.
 Solubility of a salt can be increased by adding a substance that makes a stable complex / compound
with any of the cation / anion in the salt.
e.g. AgCl dissolves more in aq. NH3 solution due to the formation of Ag(NH3)2+ and AgCN dissolves
more in an acidic solution due to the formation of HCN (weak electrolyte)
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Chemical Thermodynamics
Chemical Thermodynamics - I
BASICS Section - 1
Internal Energy :
When we talk about our chemical system losing or gaining energy, we need to introduce a quantity
which represents the total energy of the system. It may be chemical, electrical, mechanical or any other
type of energy you may think of, the sum of all these is the energy of the system. In thermodynamics,
we call it the internal energy, U of the system, which may change, when
heat passes into or out of the system,
work is done on or by the system,
matter enters or leaves the system.
Let us consider the general case in which a change of state is brought about both by doing work and by
transfer of heat. We write change in internal energy for this case as : U = q + w . . . .(i)
For a given change in state, q and w can vary depending on how the change is carried out. However,
q + w = U will depend only on initial and final state. It will be independent of the way the change is
carried out. If there is no transfer of energy as heat or as work (isolated system) i.e., if w = 0 and
q = 0 , then U = 0.
The equation, U = q + w is mathematical statement of the first law of thermodynamics, which states
that the energy of an isolated system is constant.
Many chemical reactions involve the generation of gases capable of doing mechanical work or the
generation of heat. It is important for us to quantify these changes and relate them to the changes in the
internal energy. Let us see how!
Pressure-Volume work :
For understanding pressure-volume work, let
us consider a cylinder which contains one
mole of an ideal gas fitted with a frictionless
piston. Total volume of the gas is Vi and
pressure of the gas inside is p. If external
pressure is pex which is greater than p, piston
is moved inward till the pressure inside
becomes equal to pex. Let this change be
achieved in a single step and the final volume
be Vf.
During this compression, suppose piston
moves a distance, and is cross-sectional area
of the piston is A (figure shown).

Chemical Thermodynamics Vidyamandir Classes
force
We also know, pressure = Therefore, force on the piston = p ex . A
area
If w is the work done on the system by movement of the piston then
w = force  distance = pex . A . l = pex . (–V) = –pex V = –pex (Vf – Vi) . . . .(ii)
The negative sign of this expression is required to obtain conventional sign for w, which will be positive.
It indicates that in case of compression work is done on the system. Here (V f – Vi) will be negative
and negative multiplied by negative will be positive.
If the pressure is not constant at every stage of compression, but changes in number of finite steps,
work done on the gas will be summed over all the steps and will be equal to – pV.
If the pressure is not constant but changes during the process such that it is always infinitesimally
greater than the pressure of the gas, then, at each stage of compression, the volume decreases by an
infinitesimal amount, dV. In such a case we can calculate the work done on the gas by the relation
Vf
w  pex dV . . . .(iii)
Vi
Here, pex at each stage is equal to (pin + dp) in case of compression. In an expansion process under
similar conditions, the external pressure is always less than the pressure of the system i.e., pex = (pin –
dp). In general case we can write, p ex = (pin  dp). Such processes are called reversible processes.
A process or change is said to be reversible, if a change is brought out in such a way that the process
could, at any moment, be reversed by an infinitesimal change. A reversible process proceeds infinitely
slowly by a series of equilibrium state such that system and the surroundings are always in near equilibrium
with each other. Processes other than reversible are known as irreversible processes.

In chemistry, we face problems that can be solved if we relate the work term to the internal pressure of
the system. We can relate work to internal pressure of the system under reversible conditions by
writing equation (iii) as follows:
Vf
w rev    pex dV
Vi
Since dpxdV is very small we can write
Vf
w rev    pin dV
Vi
Now, the pressure of the gas (p in which we can write as p now) can be expressed in terms of its
volume through ideal gas equation. For n mol of an ideal gas i.e., pV = nRT
nRT
 p
V
Therefore, at constant temperature (isothermal process),
Vf
dV Vf
w rev    nRT  2.303nRT log
Vi
V Vi
Free Expansion: Expansion of a gas in vacuum (pex = 0) is called free expansion. No work is done
during free expansion of an ideal gas whether the process is reversible or irreversible (equation (ii) and
(iii)).
Now, we can write equation (i) in number of ways depending on the type of processes.
Let us substitute w = – pex V from equation (ii) in equation (i), and we get :
U = q – pex V
If a process is carried out at constant volume (V = 0), then
U = qv
the subscript v in qv denotes that heat is supplied at constant volume.

Isothermal and free expansion of an ideal gas :

For isothermal (T = constant) expansion of an ideal gas into vacuum : w = 0 since pex = 0. Also, Joule
determined experimentally that q = 0 ; therefore, U = 0.
Equation U = q + w can be expressed for isothermal irreversible and reversible changes as follows:
1. For isothermal irreversible change q = – w = pex (Vf – Vi)
V V
2. For isothermal reversible change q   w  nRT ln f  2.303 nRT log f
Vi Vi
3. For adiabatic change, q  0, U  w ad

4. For isochoric process : –w = 0
5. For isobaric process : –w = P gas V
Note :  In many cases, an irreversible process can be easily recognized by using the fact that the process
involving constant external pressure is an irreversible process.
 In a reversible process, an equilibrium exists (known as quasi-equilibrium) at every stage of the

process.
 Work done by system in a reversible expansion process will always be greater than that in irreversible
expansion process.
Heat Capacity :
Heat Capacity (C) : Heat required to raise the temperature of a system by 1°C or 1 K.
Units : J/K; kJ/K
Specific Heat Capacity (c) : Heat required to raise the temperature of a 1gm of a system by 1°C
or 1 K.
Units : J/g/K; kJ/Kg/K
Molar Heat Capacity (Cm) : Heat required to raise the temperature of a 1 mole of a system by 1°C
or 1 K.
Units : J/mole/K; kJ/mole/K
Mathematically, the above quantities are defined as :
q  C  T; q  n  C m  T; q  m  c  T
where q = amount of heat absorbed by the system; T = Rise in the temperature;
m = mass of the system;
n = moles of the system

Note : Molar heat capacity has 2 forms : CP (at constant pressure) and Cv (at constant volume) defined as :
 q   H   q   U 
CP      ; CV      [H  q P ; U  q V ]
 T  P  T  P  T  V  T  V
The subscript after the brackets in the above equation denotes the parameter kept constant during the
process.
 H 
i.e.  T  denotes change in Enthalpy per unit change in Temperature keeping Pressure constant.
 P
In terms of differentials :
 dq   dH   dq   dU 
CP      ; CV      [dH  dq P ; dU  dq V ]
 dT  P  dT  P  dT V  dT  V
C
Also, C P  C V  R ; P  
Cv
Determination of w, q, H and U for a process and a reaction :

Clearly, we need to create 4 equations to solve 4 variables (w, q, H and U) as follows :
Whether it is a process or a reaction, the first equation will always be applicable :
q  U  (  w) . . . . (i) [From First law of Thermodynamics]
Calculating H and U will be different in case of a process and a reaction and explained as follows :
(i) For a process :
H  nC P T . . . . (ii) [From definition of CP]
T2
or H   nCP dT [When CP is also a function of Temperature]
T1
U  nC V T . . . . (iii) [From definition of CV]
T2
or U   nC VdT [When CV is also a function of Temperature]
T1
Also, H  U   (PV) or dH  dU  dPV  VdP [ H  U  PV]
Many a times, we also write : (PV)  P2 V2  P1V1   ( nRT  nRT )
(ii) For a reaction :

For a reaction, H is the most important parameter and can be calculated as :
H   H Pr oducts  H Re ac tan ts . . . . (ii)
Also,  r H   r U  P V [As Chemical reactions occur at constant pressure and constant tem
-perature]

or  r H   r U   n g RT . . . . (iii)
Thus, to get the interconversion between  r H and r U , we must need to write down the balanced
chemical reaction with states of all the reactants and products and then calculate the change in the
number of gaseous moles.
The fourth variable can be calculated based on the process / situation as explained in the illustrations
below :
Illustration - 1 Calculate w, q, H and U for an ideal gas expanding in vaccum (i) isothermally (ii)
adiabatically
SOLUTION :
(i) w=0 [As PExt. = 0]
H = U = 0 [As T = constant for isothermal process]
q=0 [Using First law of Thermodynamics]
(ii) q=0 [Adiabatic Process]
w=0 [As PExt. = 0]
U = 0 [Using First law of Thermodynamics]  T is constant
H = 0 [As T = constant]
Note : For an ideal gas, U = U(T) and H = H (T) but for real gas, U = U(T,V) and H = H (T,P)
Illustration - 2 Five mole of an ideal gas at 293 K are expanded isothermally from an initial pressure 0.4
kPa to a final pressure of 0.1 kPa against a constant external pressure of 0.1 kPa.
(a) Calculate q, w, U and H.
(b) Calculate the corresponding value of q, w, U and H if the above process is carried out reversibly.
SOLUTION :
(a) For an isothermal expansion against a constant pressure, we have:
 w = PExt (V2 – V1)
 nRT nRT  1 1 
= PExt  P  P   PExt nRT  P  P   w = 9135 J
 2 1   1 2
Since temperature is constant: U = 0, H = 0
q = w = 9135 J [Using First law of Thermodynamics ]
(b) For isothermal reversible expansion :
P 0.4
  w  2.303nRT log10 1  2.303  5  8.314  293log10  w = 16888 J
P2 0.1

Since temperature is constant : U = 0H = 0,

q = w = 16888 J [Using First Law of Thermodynamics]
Illustration - 3 The magnitude of enthalpy changes for reversible adiabatic expansion of a gas from vol-
ume V1 to V2 (in L) is H1 and for reversible adiabatic expansion for the same expansion is H2. Then :
(A) H1 > H2 (B) H1 < H2 (C) H1 = H2 (D) H1 = U1 and H2 = U2
where U1 and U2 are the changes in magnitudes for internal energy of gas in the two expansions.
SOLUTION : (A)
We know that work done in a reversible expansion process is always greater than in an irreversible expan-
sion process.
Using First Law of Therodynamics : q = 0 = U + (–w)
Thus, decrease in U will be larger in reversible adiabatic than irreversible adiabatic expansion and since
U = nCvT, we can conclude that T in reversible adiabatic expansion will be greater than in irreversible
adiabatic expansion.
Now, H1 = nCpT1 , and H2 = nCPT2  H1 > H2
SPONTANEITY Section - 2
The first law of thermodynamics tells us about the relationship between the heat absorbed and the work
performed on or by a system. It puts no restrictions on the direction of heat flow. However, the flow of heat is
unidirectional from higher temperature to lower temperature. In fact, all naturally occurring processes whether
chemical or physical will tend to proceed spontaneously in one direction only. For example, a gas expanding
to fill the available volume, burning carbon in dioxygen giving carbon dioxide.
Second Law of Themodynamics :
It is impossible to construct a machine that is able to convey heat by a process from a colder to a hotter
body unless work is done on the machine by some outside agency.
Second law of Thermodynamics also helps in predicting the spontaneity of a reaction/process.
A process which proceeds of its own accord without any outside help is termed as a spontaneous process. To
understand the concept of spontaneity, we first need to understand the most important factor involved which
is Entropy (S) and is explained below :
1. Entropy (S) :
Entropy is a thermodynamic state quantity which is a measure of randomness or disorder of the system. More
is the randomness in the system, more is the entropy of the system.
(i) Entropy is a state function and depends only on initial and final states of the system.

(ii) Whenever heat is added to the system, it increases molecular motions causing increased randomness
in the system. The distribution of heat also depends on the temperature at which heat is added to the
system.
Entropy change of the system for a reversible process is mathematically defined as :
dq Rev dq Rev  q Rev 

dS = or ΔS =  =  [when the heat is absorbed reversibly at constant T]
T T  T 
If heat is absorbed, then S is positive (increase in entropy). If heat is released, then S is negative
(decrease in entropy). Also, for the same amount of heat absorbed, increase in entropy will be more
at lower temperature than at higher temperature.
(iii) If the temperature of a system increases, entropy increases. If the temperature of a system decreases,
entropy decreases.
(iv) For a fixed volume system, entropy increases if the number of molecules is increased in the system
and vice – versa.
(v) For a system with fixed number of molecules, entropy increases as volume increases and vice – versa.
(vi) Entropy of a system increases with change in the state of a system as : S(s) 
 S( ) 
 S(g)
(vii) Entropy of more complex molecules is larger than those of simpler molecules as in more complex
molecules there are more ways of arranging atoms in 3D (i.e. more ramdomness).
e.g. S propane > Sethane.
(viii) Entropy of compounds with similar molecular masses increases (with increase) in their sizes.
e.g. SAr  SCO2  SC3H8
(ix) Entropies of ionic solids becomes larger as the attraction amongst the ions become weaker.
e.g. SNaF > SMgO as in MgO, +2 and –2 charges result in greater attraction.
(x) Harder substances have smaller entropies than softer substances.
e.g. SC(diamond) < SC(graphite) < SFe < SAl < SNa
(xi) All spontaneous processes are irreversible processes or vice - versa.
(xii) When a system is in equilibrium, the entropy is maximum, and the change to entropy, S  0.
For both reversible and irreversible expansion for an ideal gas, under isothermal conditions, U  0,
but  STotal is not zero for irreversible process. Thus,  U does not discriminate between reversible
and irreversible process, whereas  S does.

2. Criteria for Spontaneity :

First law of thermodynamics is basically the law of conservation of energy. It has no restriction on the way
energy can flow. Thus, energy can flow from higher to lower temperature or lower to higher temperature, as
per first law of thermodynamics. But, natural processes tend to flow only in one direction (known as direction
of spontaneity).
It has been observed that in most of the spontaneous processes/reactions, there is a decrease in energy which
seems to be the crieria for spontaneity but it is not the only criteria, Evaporation of water is an endothermic
reaction yet it spontaneous.
There are two criterias which decide the direction of spontaneity :
(a) Decrease in energy (b) Increase in entropy
In other words, a chemical reaction or process tends to follow the direction of minimum energy and maximum
randomness, i.e. reaction will be more probable to occur if it is exothermic or there is an increase in entropy.
A reaction will occur if the value of H is negative and the value of S is positive. But the endothermic
reactions in which H is positive, also take place. There are also reactions in which there is decrease in
entropy, i.e., S is negative but still they occur. It is, thus, clear that for the spontaneity of a reaction both H
and S should be considered simultaneously.
Thus, for processes which do not involve a heat change, increase in entropy is the only criteria. It should be
noted that the criterias for the prediction of direction of spontaneity have been derived through mere observations.
No process/reaction has been found to violate these.
Consider the adiabatic expansion of an ideal gas in vaccum. This system is an isolated system (as no exchange
of energy and mass between system and surroundings). So, direction of spontaneity is expansion process
because expansion will cause an increase in the entropy of the system.
3. Finding the direction of spontaneity :
For spontaneity, Second Law of Thermodyamics defines the following statements:
(i) In an isolated system, direction of increase in entropy of the system is the direction of spontaneity.
(ii) In a non-isolated system, direction of increase in total entropy i.e. STotal = SSystem + SSurroundings, is
the direction of spontaneity.
 For a reaction/process to be spontaneous: STotal = SSystem + SSurroundings > 0
To focus on the system for thermodynamic analysis, SSurroundings is defined and eliminated as :
(a) For a reaction :
q Surroundings q System
SSurroundings  
T T
HSystem
SSurroundings  [Chemical reactions occur at constant T and P]
T
H System
 STotal  SSystem   – TSTotal = HSystem – TSSystem
T

(b) For a process:

T T
STotal  SSystem  SSurroundings [In a short while, we will learn to calculate SSystem ]
Also, a new thermodynamic function, Gibbs energy ‘G’ is introduced to check the spontaneity of the reaction
directly and is defined as :
G = H – TS
 G = H – (TS) or dG = dH – TdS – SdT
Thus, for a reaction taking place at a certain temperature, we can also define spontaineity of a reaction in
terms of change in Gibbs energy as : G System   T STotal =HSystem – TSSystem
(i) If STotal  0  G System  0 [Spontaneous]
(ii) If STotal  0  G System  0 [Non- spontaneous]
(iii) If STotal  0  G System  0 [At Equilibrium]
The free energy of a reaction is the chemical analogue of ‘potential energy’ of mechanical systems. A body
moves in the direction in which there is decrease in potential energy. Similarly, in chemical system, the substance
moves in a direction in which there is decrease in free enrgy, i.e., G is negative.
For any system in which a reaction/process taking place, G = 0 denotes the attainment of equilibrium. In
other words, a reaction/process proceeds till its entropy has become maximum i.e. no furthur change in
entropy is possible. A very famous example is the mixing of two ideal gases which happens till the new system
has become homogenous (because in that state only it will have maximum entropy).
Calculation of Gibbs energy is very important in finding out the direction of spontaineity and is widely, mostly
and mainly used in chemical reactions. We will discuss more on this in the upcoming portions of this chapter.
SSystem  0 
Case (i) :   STotal > 0
SSurroundings  0 
SSystem  0 
Case (ii) :   STotal > 0 or < 0
SSurroundigs  0 
SSystem  0 
Case (iii) :   STotal > 0 or < 0
SSurroundigs  0 
SSystem  0 
Case (iv) :   STotal < 0
SSurroundigs  0 

Clearly, Case (i) is always spontaneous since change in total entopy is always positive i.e. total entropy is
increasing. Case (ii) and (iii) may or may not be spontaneous. Case (iv) is always non-spontaneous since
change in total entopy is always negative i.e. total entropy is decreasing.
4. Calculating entropy change in phase change :

When a substance changes phase (e.g., solid to liquid), there is a change in entropy associated with it (even
though temperature is constant at phase change).
H melting
(a) Melting : Smelting  = Entropy change due to melting (takes place at constant
Tmelting
temperature)
e.g. Entropy change for 1 kg ice at its melting point :
 1000 
 18   6  1000
 Smelting     1220.8 J / K
273
[ Enthalpy of fusion of water = 6 kJ/mole ]
H vaporisation
(b) Vaporisation : Svaporisation 
Tboiling
e.g. Entropy change for 1 kg water at its boiling point :
 1000 
 18   44  1000
Svaporisation     6552.8 J / K
373
[ Enthalpy of vaporisation of water = 44 kJ/mole ]
H Transition
(c) Allotropic Transition : STransition  T
Transition
e.g. Transition of 1 mole of Sulphur from Rhombic to Monoclinic :
402
Stransition   1.09 JK 1 mol1
368.5
[ Enthalpy of transition from rhombic to monoclinic Sulphur = 402 J mole–1 and Ttransition = 368.5 K ]

Entropy of a substance :
First of all, we need to know an important law helpful the entropy of a substance i.e. Third Law of
Thermodynamics. As per Third Law of Thermodynamic (also knows as Nernst heat theorem) :
(a) All substance have same heat capacities at 0 K.
(b) Heat capacity of every substance is zero at 0 K.
(c) Entropy of a perfectly crystalline substance is zero at 0 K.
This law provides an absolute reference point for the determination of entropy. The entropy determined
relative to this point is the absolute entropy.
Entropy change of a reaction :

To calculate Ssystem for a reaction at say T (K), simply balance the reaction and use the following formula:
q  qSys. HSys.
ΔSSystem =  rS   S Products  SReactants and ΔSSurroundings  Surr.  
TSurr. TSurr. TSurr.
as chemical reactions occur at constant T and P.
At standard conditions :  rSΘ   SΘ Θ

P   SR
Note : Every reactant/product will have a non-zero Entropy for T above 0 K.
Variation of Spontaneity of a reaction with temperature :

We can have an idea of the spontaneity of reaction with temperature using :
In general, |H| >> |TS|. Clearly, Entropy factor increases as T increase and decreases as T decreases.
For an exothermic reaction proceeding with a decrease in entropy, G is in general, negative i.e. spontaneous
reaction.
For an endothermic reaction proceeding with an increases in entropy, G is in general, positive i.e. non-
spontaneous reaction.
Thus, in general, exothermic reaction are spontaneous at room temperature and may tend to become non-
spontanceous (if Ssystem < 0) at higher temperatures. In general, endothermic reactions are non-spontaneous
at room temperature and may tend to become spontaneous (if S > 0) at higher temperatures.
Thus, we need to calculate :STotal = SSystem + SSurroundings for the reaction/process and if it comes out
to be > 0 then that direction will be spontaneous.

Note :  The decrease in Gibbs energy is a measure of the maximum useful work that can be obtained from
a system. The Gibbs energy is the maximum amount of non-expansion work that can be extracted
from a system and this maximum can be attained only in a completely reversible process.
 We can have a rough idea of temperature about which there is a spontaneity change for a reaction and
is given by :
Θ
HSystem
TSwitch  Here, we have assumed that H ΘSystem and SSystem
Θ
doesn’t vary with
Θ
SSystem
temperature just to get an idea of TSwitch
Illustration - 4 Assuming  r H Θ and  r S Θ to be independent of temperaturee, at what temperature will the

reaction given below becomes spontaneous?
N2(g) + O2(g) 
 2NO(g) ;  r H Θ = 180.8 kJ mol1.
S Θ / JK 1mol 1 191.4 204.9 210.5

SOLUTION :
First calculate  rSΘ for the given reaction as follows :
 rSΘ   SΘ Θ Θ Θ Θ –1
P   SR  2S NO  S N 2  S O 2 = 2  210.5 – 191.4 – 204.9 = 24.7 J K mol
–1
Using:  r G Θ   r H Θ  T  rSΘ = 180.8 – 298  24.7  10–3 = 173.4 kJ mol–1

Clearly, the given endothermic reaction is non–spontaneous at room temperature. So, we need to increase the
temperature to make the reaction spontaneous.
 r G Θ = 180.8 – (T  24.7  10 ) kJ mol
–3 –1

For spontaneity, put  r G Θ = 0 to get :

Θ
 r HSysstem 180.8  103
TSwitch   Tswitch   7320 K
Θ 24.7
 r SSystem
The reaction becomes spontaneous above a temperature of 7320K.
Illustration - 5 Sulphur exists in more than one solid form. The stable form at room temperature is rhombic
sulphur. But above room temperature the following reaction occurs :
S (rhombic)   S (monoclinic)
If  r H = 276.144 J at 298 K and 1 atm and  r G = 75.312 J
(a) Calculate  r S at 298 K
(b) Assume that r H and  r S do not vary significantly with temperature, calculate Teq, the temperaturee
at which rhombic and monoclinic sulphur exist in equilibrium with each other.
SOLUTION :
(a) Since  r G =  r H  T rS
 H   r G 276.144  75.312
 rS  r  = 0.674 J K– 1
T 298
(b) Under equilibrium condition  r G = 0
 r H 276.144
  r H  Teq  r S = 0  Teq  
 rS 0.674 = 409.7 K
Free energy change of a reaction :

rG for a reaction can be calculated using following two methods :
(i) Using : rG = rH – TrS
(ii) Using : rG =  G Poducts   G Reactants
Take note of the followings while calculating Gibbs energy change for a reaction :
(a) Chemical reaction in which a compound in its standard state is formed from its elements in their
standard states, the Gibbs energy change is the Standard Gibbs energy of formation,  f G Θ .
(b)  f G Θ = 0 for an element in its standard state.
(c) f GΘ =  G Θproducts   G Θreactants =  r H Θ  T rSΘ

(d) rG is an extensive property.
(e) rG changes sign when a process is reversed. [ It can be treated in a similar manner as with rH]

Illustration - 6 Compute the Gibbs energy change of the reaction at 27C for the combustion of methane.
CH4(g) + 2O2(g) 
 CO (g) + 2H O()
2 2
 f H Θ (in kJ mol–1) –74.8  –393.5 –285.8

Θ (in J K–1 mol–1) 186 205 214 70
Sm
SOLUTION :
Θ Θ Θ
 r H Θ =  f H (CO 2 )  2 f H (H 2O)   f H (CH 4 ) = –393.5 + 2  (–285.8) – (–74.8) = –890 kJ mol
–1
Θ Θ Θ Θ
 rSΘ = S(CO )  2S(H O)  S(CH )  2S(O )  214  2  70  186  2  205  242 J/ K/ mol
2 2 4 2
  r G =  r H Θ  T  rSΘ = –890 – 300  (–242  10–3) = –890 + 72.6 = –817.4 kJ mol–1
Illustration - 7 Show that the reaction CO(g) + (1/2)O2(g)   CO2(g) at 300 K, is spontaneous and
1 1
exothermic, when the standard entropy change is 0.094 kJ mol K . The standard Gibbs free energies of
formation for CO2 and CO are 394.4 and 137.2 kJ mol1, respectively.
SOLUTION :
1
For the given reaction, we have : CO(g) + O (g) 
 CO2(g)  r SΘ  0.094 kJ K 1 mol 1
2 2
The free-energy change of the reaction is :
1
 rG Θ  f G Θ
CO 2
 f GΘ Θ
CO   f G O 2
2
Θ
= (–394.4 + 137.2) kJ mol1 = – 257.2 kJ mol–1 [  f G O  0 ]
2
Since  r G Θ is negative, the reaction is spontaneous. The enthalpy change of the reaction is:
 8.314 J mol1 K 1 = [– 257.2 + (300) (– 0.094)] kJ mol = –285.4 kJ mol

–1 –1
Since  r H Θ is negative, the reaction is exothermic.
Gibbs energy and Equilibrium Constant:

We can relate rG for a reaction under any set of conditions to its value for standard conditions, that is, to
 r G Θ by:
rG =  r G Θ + 2.303 RT log10 Q where Q is reaction quotient.
If a system is at equilibrium,  r G Θ = 0. Thus from the above equation :

 r G Θ = 2.303 RT log10 Keq where Keq is thermodynamic equilibrium constant.

Magnitude of  r G Θ determines the value of Keq. Consider three cases:
(i) Keq >> 1 : Reaction proceeds mainly in forward direction and is almost complete
(XProducts  1; XReactants  0)
(ii) Keq << 1 : Reaction does not “wish” to proceed in forward direction (XProduts  0; XReactants  1)
(iii) Keq  1 : Both products and reactants exists in appreciable amounts, at equilibrium.
We have seen how a knowledge of the sign and magnitude of the free energy change of a chemical reaction
allows :
1. Prediction of the spontaneity of the chemical reaction.
2. Prediction of the useful work that could be extracted from it.
So far we have considered free energy changes in irreversible reactions. Let us now examine the free energy
changes in reversible reactions.
‘Reversible’ under strict thermodynamic sense is a special way of carrying out a process such that system is all
times in perfect equilibrium with its surroundings. When applied to a chemical reaction the term ‘reversible’
indicates that a given reaction can proceed in either direction simultaneously, so that a synamic equilibrium is
set up. This means that the reactions in both the directions should proceed with a decrease in free energy,
which seems impossible. It is possible only if at equilibrium the free energy of the system is minimum. If it is
not, the system would spontaneously change to configuration of lower free energy.
So, the criterion for equilibrium
A  B  C D is
r G  0
Variation of Gibbs Energy and Equilibrium Constant :
Note :  Equilibrium is the point of minimum in the above diagrams.

 If we move away from the point of minimum, there will be an increase in Gibbs energy which is non-
spontaneous.

Equilibrium constant vs. Temperature :

For a reaction : r G  r H T r S
At standard conditions :  r G Θ   r H Θ  T  rSΘ
When the reaction reaches equilibrium at temperature T, we have :  r G Θ   RT ln K eq
Thus, we have at temperature T1 :  RT1 ln (K eq )1   r H Θ  T1  rSΘ
and at temperature T2 :  RT2 ln (K eq ) 2   r H Θ  T2  rSΘ
(K eq .) 2  r HΘ 1 1 
Solve to get : ln    
(K eq .)1 R  T1 T2 
Illustration - 8 A certain gas in expanded from (1L, 10 atm) to ( 4 L, 5 atm) against a constant external
pressure of 1 atm. If the initial temperature of gas is 300 K and heat capacity for the process is 50J / C, the
enthalpy change during the process : ( Use : 1 L atm  100 J )
(A) 15 kJ (B) 15.7 kJ (C) 14.3 kJ (D) 14.7 kJ
SOLUTION : (B)
Use : H  U   (PV)  U  (P2 V2  P1V1 )
Calculate U as follows :
P1V1 P2V2 10  1 5  4
(i) Use :     T2  600 K
T1 T2 300 T2
(ii) q  CT  50  (600  300)  15 kJ
(iii)  w  PExt V  (4  1)  3 L atm  0.3 kJ

(iv) q  U  (  w)  15  U  0.3  U  14.7kJ
 H  14.7  (5  4  10 1)  100  103  15.7 kJ

Illustration - 9 For the reaction : N2O4(g)   2NO (g)

2
Calculate rG of the system in a mixture of 5 mol of N2O4 (g) and 5 mol of NO2(g) at 298 K at a total pressure
of 20 atm. Use the following data in kJ mol :  f G Θ (NO2,g) = 50 ;  f G Θ (N2O4,g) = 100
–1
SOLUTION :
We need to calculate rG.. Use : rG =   r G Θ + RT n Q
So, first calculate rG° using :  r G Θ =  G ΘPoducts   GΘReactants

=    f G Θ Pr oducts    f GΘ Reactants
[ At standard conditions : G Θ Θ
compound   f G compound ]
= 2 ×  f G Θ (NO2, g) –  f G Θ (N2O4, g) = 2 × 50 – 100 = 0
 102  –1
and  r G   r G Θ + RT nQ= 0 + 8.314 × 298 n   = 5.70 kJ mol
 10 
 
 2
 5 
 p 2NO   20  
10
 Q  2
  
 p N 2O 4  5  
   20  
  10  
Note :  f G Θ of an element in its standard state is zero.
Illustration - 10 Calculate  G at 298 K for the following reaction if the reaction mixture consists of 1 atm
r
of N2, 3 atm of H2 and 1 atm of NH3.  2 NH 3 ( g );  r G Θ   33.32 kJ

N 2 ( g )  3H 2 ( g ) 
SOLUTION :
–1
 2NH 3 ( g )  r G Θ = – 33.2 kJ mol
N 2 ( g )  3H 2 ( g ) 
Using : rG =  r G Θ + RT nQ
p2
NH 3 l2 l
 
where Q p p3 1  33 27 ; T = 298 K ; R = 8.314 J mol 1 K 1
N2 H2
–3 l –1
 rG = – 33.2 + (8.314 × 10 ) × 298 × 2.303 log10 = – 33.2 – 8.16 = – 41.36 kJmol
27

Illustration - 11 The temperature dependence of equilibrium constant of a reaction is given by :

2059
ln K eq  4.8  Find  r G Θ ,  r H Θ ,  r S Θ .
T
SOLUTION :
2059  rSΘ  r H Θ
Compare ln K eq  4.8  with ln K eq  
T R RT
 rSΘ
We have :  4.8   rSΘ = 4.8 × 8.314 J/K = 39.9 J/K
R
 r HΘ
 2059   r H Θ = 2059 × 8.314 J/K = 17.12 kJ /K
R
 r G Θ   r H Θ  T  rSΘ = 17.12 – 298 × 39.9 × 10 = 5.31 kJ/K
–3
and
Illustration - 12 –5 –5
Ka for acetic acid at 27°C is 2.0 × 10 and at 77° C, Ka is 2.5 × 10 . What are
H Θ and S Θ for the ionization of acetic acid ?
SOLUTION :
 K eq 2  r HΘ  1 1 
Using : n    
 K eq 1 R  T1 T2 
 2.5  10 5   r H Θ  1 1 
n   
  2.0 10  8.314  300 350 
 5
 
–1
  r H Θ = 3.89 kJ mol
Also,  r G Θ = – RT n Keq
–5 –1
   r G Θ = – 8.314 × 298 ×n (2.0 × 10 ) = 26.81 kJ mole
 Taking (K eq ) 25C  (K eq ) 27C 
 
Using :   r G Θ   r H Θ  T  rSΘ
–3 –1 –1
 26.81 = 3.89 – (298 × 10 ) ×  rSΘ    rSΘ = 76.9 J mole K

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Chemical Thermodynamics - II
BASICS Section - 1
1. Heat Capacity :
Heat Capacity (C) : Heat required to raise the temperature of a system by 1°C or 1 K.
Units : J/K; kJ/K
Specific Heat Capacity (c) : Heat required to raise the temperature of a 1gm of a system by 1°C
or 1 K.
Units : J/g/K; kJ/Kg/K
Molar Heat Capacity (Cm) : Heat required to raise the temperature of a 1 mole of a system by 1°C
or 1 K.
Units : J/mole/K; kJ/mole/K
Mathematically, the above quantities are defined as :
q  C  T; q  n  C m  T; q  m  c  T
where q = amount of heat absorbed by the system; T = Rise in the temperature; m = mass of
the system;
n = moles of the system
Note : Molar heat capacity has 2 forms : CP (at constant pressure) and Cv (at constant volume) defined as :
 q   H   q   U 
CP      ; CV      [H  q P ; U  q V ]
 T  P  T  P  T  V  T  V
The subscript after the brackets in the above equation denotes the parameter kept constant during the
process.
 H 
i.e.  T  denotes change in Enthalpy per unit change in Temperature keeping Pressure constant.
 P
In terms of differentials :
 dq   dH   dq   dU 
CP      ; CV      [dH  dq P ; dU  dq V ]
 dT  P  dT  P  dT V  dT  V
C
Also, C P  C V  R ; P  
Cv

Illustration - 1 The molar heat capacity of water in equilibrium with ice at constant pressure is :
(A) zero (B) infinity () (C) 40.45 kJ K 1mol 1 (D) 75.48 kJ K 1mol 1
SOLUTION :
We know that heat capacity at pressure is given by Since the phase transformation i.e., ice  water,,
 H  taken plane at a fixed temperature so T  0.
Cp   
 T P H
 Cp    (B)
0
2. Reversible and Irreversible process :

Reversible process : Process which is carried out in such a manner that it could be reversed by an infinitesimal
change. A reversible process takes infinitesimally small, infinite steps to complete and
time taken to complete the process is infinite. So, it is a theoretical process and it sets
a ceiling on the processes carried out practically.
Irreversible process : Process which doesn’t satisfy the reversible criteria.
Examples of irreversible process :
1. Fee expansion of gas
2. Melting of ice in warmer liquid
3. Anything that is real.
We can also define the reversible and irreversible process in a more of mathematical sense as follows :
Reversible process : Process in which there is an infinitesimally small difference between the driving
force and opposing force.
Irreversible process : Process in which there is a finite difference between the driving force and opposing
force.
For example :
(i) Consider the following two diagrams showing reversible and irreversible expansions :
Here, Opposing force is PExt. and Driving force is PGas .

(ii) Consider the following two diagrams showing reversible and irreversible compressions :
Here, Driving force is PExt. and Opposing force is PGas.

Note :  In many cases, an irreversible process can be easily recognized by using the fact that the process
involving constant external pressure is an irreversible process.
 In a reversible process, an equilibrium exists (known as quasi-equilibrium) at every stage of the
process.
3. Calculating Work (w) for Reversible and Irreversible process :

To calculate work, use the formula :  w   PExt.dV
(i) For an irreversible process, PExt. is constant, thus  w  PExt.V . . . . (iv)
(ii) For a reversible process, PExt.  PGas  dP   w   PGas dV   dPdV   PGas dV
Thus, work (w) depends on the process equation i.e. how PGas and V varies in the process :
I. For Isothermal process :
V  P 
w  2.303nRT log10  2   2.303nRT log10  1  [ P1V1  P2 V2 ]
 V1   P2 
(P V  P2 V2 )
II. For Adiabatic process  w  1 1   U  nC v (T2  T1)
(  1)
Cp
where   (ratio of molar heat capacities at constant P and constant V)
Cv
5 3
(a) Monoatomic gas: C p  R, C v  R,   1.66
2 2
7 5
(b) Diatomic gas : C p  R, C v  R,   1.40
2 2
(c) Polyatomic gas : Cp = 4R, CV = 3R,  = 1.33
III. For Isochoric process : –w = 0
IV. For Isobaric process :  w  PGas V
Note : Work done by system in a reversible expansion process will always be greater than that in irreversible
expansion process.

4. Graphical interpretation of Work :

(i) For a reversible process :
Work can also be graphically calculated for a reversible
process.
It is the area under Pressure vs. Volume diagram as shown :
(ii) For an irreversible process :

For an irreversible process, Pressure vs. Volume graph cannot
be plotted.However, we can represent the irreversible work
(PExt. V) on a Pressure vs. Volume diagram as shown :
5. Types of Irreversible expansion :

(i) Free expansion : Expansion of a gas against vaccum (i.e. PExt. = 0)
(ii) Intermediate expansion : Expansion of a gas when PExt.  0
6. Calculate w, q, H and U for a process and a reaction :

Clearly, we need to create 4 equations to solve 4 variables (w, q, H and U) as follows :
Whether it is a process or a reaction, the first equation will always be applicable :
q  U  (  w) . . . . (i) [From First law of Thermodynamics]
Calculating H and U will be different in case of a process and a reaction and explained as follows :
(i) For a process :
H  nC P T . . . . (ii) [From definition of CP]
T2
or H   nCP dT [When CP is also a function of Temperature]
T1
U  nC V T . . . . (iii) [From definition of CV]
T2
or U   nC VdT [When CV is also a function of Temperature]
T1

Also, H  U   (PV) or dH  dU  dPV  VdP [ H  U  PV]

Many a times, we also write : (PV)  P2 V2  P1V1   ( nRT )  nRT
(ii) For a reaction :

For a reaction, H is the most important parameter and can be calculated as :
rH   HPr oducts  H Re ac tan ts . . . . (ii)
Also,  r H   U  P  V [As Chemical reactions occur at constant pressure and constant tem-
perature]
or r H  U  n g RT . . . . (iii)
Thus, to get the interconversion between  r H and  r U, we must need to write down the balanced
chemical reaction with states of all the reactants and products and then calculate the change in the
number of gaseous moles.
The fourth variable can be calculated based on the process / situation as explained in the illustrations
below :
7. Calculating final temperature T2 in a reversible and irreversible adiabatic expansion pro-
cess :
(i) For a reversible adiabatic expansion process, use :
T1V1 1  T2V2 1 or P11 T1  P21 T2

(ii) For an irreversible adiabatic expansion process, we cannot use the equation :
TV r 1  const . or P1 T   const .
We have to find another way out (use first law of thermodynamics).
Proceed as follows : q  0  U  ( w)
[  Adiabatic process and using First Law of Thermodynamics]
 0 = nC v (T2 - T1 ) + PExt .  V [  w = PExt .  V]
 0  nC v (T2  T1) + PExt . (V2  V1 )
  PExt  
 Cv    R
 nRT2 nRT1   T2    P1  T
 0  nCv (T2  T1 )  PExt.    1
 P  
 P2 P1   Cv   Ext  R
  P2  
Where PExt . is the constant pressure against which system is doing work.
 C   PExt .   R 
If P2 = PExt . (i.e. system expands to external pressure)  T2   v  T1
 Cv  R 

Illustration - 2 1 mole of an ideal gas at 400 K and 10 atm is allowed to expand, adiabatically, against 2.0
 5 
atm external pressure. Find the final temperature of the gas. Use : CV  R 
 2 
SOLUTION :
Finally P2  PExt. and  U  Pext V (as q  0)
 nRT2 nRT1 
n C v (T2  T1)  2   
 2 10 
5 2 
 2 R  10 R   2.7 R 
 T2     400 K     400 K = 308.6 K
5  3.5 R 
 RR 
 2 
8. Comparison between reversible isothermal and reversible adiabatic process :

We can compare reversible isothermal (I) and reversible adiabatic (II) process for two cases through P–V
diagram as follows :
Clearly, work done in reversible isothermal process is greater than in reversible adiabatic process.
Also, we can see that in case (i), final volume is greater in reversible isothermal process and in case (ii) final
pressure is greater in reversible isothermal process.
Note : Sometimes P–V diagrams come as a handy tool to calculate the final conditions rather than doing
rigorous calculations.
 Adiabatic curves are steeper than isothermal curves [madiabatic =  misothermal where ‘m’ denotes slope].

Illustration - 3  3 
1m3 of neon gas  Cv  2 R  at 273.2 K and 10 atm undergoes three different expansions
 
to a final pressure of 1 atm. Calculated the final volume and the work done in three different expansions.
(i) Isothermal reversible expansion (ii) Adiabatic reversible expansion
(iii) Irreversible adiabatic expansion
SOLUTION :
PV (1) (10) The final temperature is obtained from
(i) Final volume, v2  1 1   10 m3
P2 (1) P2V2  nRT2
The work done by the gas in expanding equals
the heat absorbed by the gas from its surrounding.
T2  

P2V2 (1) 3.981  10
3

 108.8 K
V nR (446.1) 0.0821
  w  q  nRT ln 2
V1 For an adiabatic process, q = 0 &  E = w
10  103  3 
w  nCv (T2  T1 )   n R  T2  T1 
n  446.1mol
0.0821  273.2  2 
 w  (446.1) (8.314) (273.2) (2.303) log10 10 3 

 (446.1)  R  (108.8  273.2)  914.1 kJ
 232.85 kJ 2 
(ii) For adiabatic reversible expansion, (iii) For irreversible adiabatic expansion,
1 T T 
Cv (T2  T1)  nRP2  2  1 
 P1  
V2     V1  P2 P1 
 P2 
3 T 273.2 
 T2  273.2   nR(1)  2  
3 2  1 10 
Cp RR 5
  2   T2  174.8 K
Cv 3 3
R
2 3
 E  w  nR(174.8  273.2)  547.4 kJ
2
 V2  (10)3/5 (1)  3.981 m3 Note that there is considerable less cooling
of the gas and less work is done by the gas
in the irreversible adiabatic expansion than
in the reversible adiabatic expansion.

Illustration - 4 A sample of argon gas at 1 atm pressure and 27C expands reversibly and adiabatically
from 1.25 dm3 to 2.50 dm 3 . Calculate the enthalpy change in process ?
SOLUTION :
PV 1.25  1 On solving, T2 = 188.55 K

n=   0.05
RT 0.0821  300  H  nCp  T  0.05  20.794  111.45
TV 1 = constant for adiabatic process  115.87 J
 T1V1 -1 = T2 V2 -1
Illustration - 5 An ideal gas having initial pressure P, volume V and temperature T is allowed to expand
adiabatically until volume becomes 5.66 V while its temperature falls to T/2.
(i) What is the atomicity of gas molecules.
(ii) Obtain an expression for the work done by the gas during the expansion as a function of the initial
pressure P and volume V.
SOLUTION :
For a adiabatic process,
TV 1  constant
T
 T1V1 1  T2V2 1  1 (5.66 V1 ) 1
2
Hence, 2  (5.66) 1 or log 2  (  1) log 5.66    1.4
The gas is, therefore a diatomic gas.
P V P V
The work done by a gas during an adiabatic process is W  2 2 1 1
 -1
Since P1V1 = P2 V2 = P2 (5.66 V1 )
P1  P1(5.66 V1 )  1
P2 =  W  P1V1   1.25 P1V1 or W  1.25 PV

(5.66)  (5.66)  0.4

9. Second Law of Thermodynamics :

It is impossible to consstruct a machine that is able to convey heat by a cyclic process from a colder to
a hotter body unless work is done the machine by some outside agency.
Second law of Thermodynamics also helps in predicting the spontancity of a reaction/process.
A process which proceeds of its own accord without any outside help is termed as a spontaneous process. To
understand the concept of spontaneity, we first need to understand the most important factor involved which
is Entropy (S) and is explained below :
1. Entropy (S) :
Entropy is a thermodynamic state quantity which is a measure of randomness or disorder of the system. More
is the randomness in the system, more is the entropy of the system.
(i) Entropy is a state function and depends only on initial and final states of the system.
(ii) Entropy change of the system for a reversible process is mathematically defined as :
dq Rev dq Rev  q Rev 
dS = or ΔS =  =  [when the heat is absorbed reversibly at constant T]
T T  T 
If heat is absorbed, then S is positive (increase in entropy). If heat is released, then S is negative
(decrease in entropy). Also, for the same amount of heat absorbed, increase in entropy will be more
at lower temperature than at higher temperature.
(iii) If the temperature of a system increases, entropy increases. If the temperature of a system decreases,
entropy decreases.
2. Criteria for Spontaneity :
First law of thermodynamics is basically the law of conservation of energy. It has no restriction on the way
energy can flow. Thus, energy can flow from higher to lower temperature or lower to higher temperature, as
per first law of thermodynamics. But, natural processes tend to flow only in one direction (known as direction
of spontaneity).
A chemical reaction or process tends to follow the direction of minimum energy and maximum randomness,
i.e. reaction will be more probable to occur if it is exothermic or there is an increase in entropy. A reaction
will occur if the value of  H is negative and the value of S is positive. But the endothermic reactions in
which  H is positive, also take place. There are also reactions in which there is decrease in entropy, i.e.,
S is negative but still they occur. It is, thus, clear that for the spontaneity of a reaction both H and S
should be considered simultaneously.
Thus, for processes which do not involve a heat change, increase in entropy is the only criteria. It should be
noted that the criterias for the prediction of direction of spontaneity have been derived through mere observations.
No process/reaction has been found to violate these.
Consider the adiabatic expansion of an ideal gas in vaccum. This system is an isolated system (as no exchange
of energy and mass between system and surroundings). So, direction of spontaneity is expansion process
because expansion will cause an increase in the entropy of the system.

3. Finding the direction of spontaneity :

For spontaneity, Second Law of Thermodyamics defines the following statements:
(i) In an isolated system, direction of increase in entropy of the system is the direction of spontaneity.
(ii) In a non-isolated system, direction of increase in total entropy i.e. STotal = SSystem + SSurroundings, is
the direction of spontaneity.
 For a reaction/process to be spontaneous: STotal = SSystem + SSurroundings > 0
To focus on the system for thermodynamic analysis, SSurroundings is defined and eliminated as :
(a) For a reaction :
T T
HSystem
SSurroundings  [Chemical reactions occur at constant T and P]
T
H System
 STotal  SSystem   – TSTotal = HSystem – TSSystem
T
(b) For a process:
T T
STotal  SSystem  SSurroundings
[In a short while, we will learn to calculate SSystem ]
Also, a new thermodynamic function, Gibbs energy ‘G’ is introduced to check the spontaneity of the reaction
directly and is defined as :
G = H – TS
 G = H – (TS) or dG = dH – TdS – SdT
Thus, for a reaction taking place at a certain temperature, we can also define spontaineity of a reaction in
terms of change in Gibbs energy as : G System   T STotal =HSystem – TSSystem
(i) If STotal  0  G System  0 [Spontaneous]
(ii) If STotal  0  G System  0 [Non- spontaneous]

(iii) If STotal  0  G System  0 [At Equilibrium]
The free energy of a reaction is the chemical analogue of ‘potential energy’ of mechanical systems. A body
moves in the direction in which there is decrease in potential energy. Similarly, in chemical system, the substance
moves in a direction in which there is decrease in free enrgy, i.e., G is negative.
For any system in which a reaction/process taking place, G = 0 denotes the attainment of equilibrium. In
other words, a reaction/process proceeds till its entropy has become maximum i.e. no furthur change in
entropy is possible. A very famous example is the mixing of two ideal gases which happens till the new system
has become homogenous (because in that state only it will have maximum entropy).

4. Calculating entropy change in phase change :

When a substance changes phase (e.g., solid to liquid), there is a change in entropy associated with it
(even though temperature is constant at phase change).
H melting
(a) Melting : Smelting  = Entropy change due to melting (takes place at constant
Tmelting
temperature)
e.g. Entropy change for 1 kg ice at its melting point :
 1000 
 18   6  1000
 Smelting     1220.8 J / K [ Enthalpy of fusion of water = 6 kJ/mole ]
273
H vaporisation
(b) Vaporisation : Svaporisation 
Tboiling
e.g. Entropy change for 1 kg water at its boiling point :
 1000 
 18   44  1000
Svaporisation     6552.8 J / K
373
[ Enthalpy of vaporisation of water = 44 kJ/mole ]
H Transition
(c) Allotropic Transition : STransition  T
Transition
e.g. Transition of 1 mole of Sulphur from Rhombic to Monoclinic :
402
Stransition   1.09 JK 1 mol1
368.5
[ Enthalpy of transition from rhombic to monoclinic Sulphur = 402 J mole–1 and Ttransition = 368.5 K ]

Illustration - 6 A mole of steam is condensed at 100C , the water is cooled to 0C and frozen to ice.
What is the difference in entropies of the steam and ice? The heats of vaporization and fusion are 540 cal gm1
and 80 cal gm1 respectively. Use the average heat capacity of liquid water as
SOLUTION :
Entropy change during condensation of steam
18  540
S1  cal /   26.06 cal / 
373
Entropy change during cooling of water from 100C to 0C
273
S2  18  1ln cal /   5.62 cal / 
373
Entropy change during freezing of water at 0C
18  80
S3   cal /   5.27 cal / 
273
So total entropy change  26.06  5.62  5.27  36.95 cal / 
Hence difference in entropy between steam and ice  36.95 cal / 
5. Calculating S for a process :

To calculate Ssystem for a reversible process, proceed as follows :
dq rev
As per the definition : dS =
T
 TdS = q rev = dU + ( dw) [From First Law of Thermodynamics]
or TdS = n C v dT + P dV [dU = nC v dT and dw = PdV]
nRT nC vdT nR
or TdS = n C v dT + dV  dS = + dV
V T V
Integrating the above equation with appropriate limits, we get :
T  V  q qSys.
Ssystem  nC v In  2   n R In  2  and SSurroundings  Surr. 
 T1   V1  TSurr. TSurr.
Note: Although the above relation has been derived asuming the process to be reversible but this relation can also be
used for an irreversible process as well since Entropy change is a state function.

Illustration - 7 Calculate the total entropy change for the following reversible processes :
(a) Isothermal (b) Adiabatic.
SOLUTION :
T V qsystem
Entropy change for a process is given by : Ssystem  n C V n 2  nR n 2 ; Ssurrounding =
T1 V1 Tsurr.
(a) For isothermal process : T2 = T1
V2
V2 qsystem  n R T  n
 Ssystem  n R n Ssurroundings  V1
  n R n 2
V
V1 and Tsurr  T V1
V2
[ qsystem = nRTn V for isothermal process]
1
 S Total  S system  Ssurroundings  0

T2 V2
(b) For adiabatic process : Ssystem  n CV n T  n R n V
1 1
nR T V
  n 2  n R n 2
   1 T1 V1
 1
T V 
Also, TV –1
= const.  T1V1 1  T2 V2  1  2  1
T1  V2 
nR  V    1  V
 Ssystem  n   1    n R n 2  0
   1  V2   V1
qsystem
and Ssurroundings  0 [ q = 0 in adiabatic process]
Tsurr.
 STotal  Ssystem  Ssurroundings  0
T2 V2
Note : Ssystem  n C V n T  n R n V for both reversible and irreversible process since S is a state
1 1
function.
 Ssystem for irreversible adiabatic process is > 0. This is because (T2)Reversible adiabatic (T2)Irreversible adiabatic
 STotal = 0 for any reversible process and STotal > 0 for any irreversible (i.e. spontaneous) process.

The table below shows the Ssystem and Ssurroundings for some of the famous type of processes in
thermodynamics :
6. Entropy change due to isothermal mixing of two gases (at constant P):
Consider the following diagram which shows two gases before and after mixing :
To find the change in entropy of the system due to mixing, proceed as follows :
V 1  V2  1 
SGas1 due to mixing = n1R  n  n1R  ln   [For ideal gases : n  V at const T and P]
V1  1 
V 1  V2  1 
SGas2 due to mixing = n1R  n  n1R  ln   [For ideal gases : n  V at const T and P]
V2  2 
Total change in entropy of the system : Ssystem (mixing) = S Gas1due to mixing + S Gas2 due to mixing
= –n1R n 1 – n2R n2= –R [n1 n 1 + n2 n 2]
Thus, in general, Ssystem (mixing) = R  n i n i
The above expression can also be expressed as :
 n1 n2 
Ssystem (mixing) 
= –R (n1 + n2) (n  n  n 1   n  2
 1 2) (n1  n 2 ) 

=  R   n i   1  n 1   2  n  2 
Ssystem (mixing) = –R   n i     i n  i 
Illustration - 8 Two vessels divided by a partition contain one mole of N2 and two moles of O2 gas. If
partition is removed and gases mixed isothermally, find the change in entropy due to mixing assuming initial
and final pressure are same.
SOLUTION :
Using Ssystem (mixing) = R  n i n i
 1 2 
= R 1   n    2   n   
 3 3 
  3 
= R   n 3  2  n    = 8.314(1.0 + 2 × 0.4) = 15.9 JK–1
  2 
6. Calculating entropy for a substance :

First of all, we need to know an important law helpful in finding the entropy of a substance i.e. Third Law of
Thermodynamics.
As per Third Law of Thermodynamics (also knows as Nernst heat theorem) :
(a) All substance have same heat capacities at 0 K.
(b) Heat capacity of every substance is zero at 0 K.
(c) Entropy of a perfectly crystalline substance is zero at 0 K.
This law provides an absolute reference point for the determination of entropy. The entropy determined
relative to this point is the absolute entropy.
dq dU + (  w) dU + PdV dU
(d) dS = = = =
T T T T
nC v dT dT
= = n(b + 2 cT) 
T T
T2 T2
nbdT T
 S   T
  2ncdT  nbn T12  2nc(T2  T1)
T1 T1
600
 S  1  16  n  2  1  6  103  (600  300)  14.8 J mol 1K 1
300
T2 V2
Note : Here, we can apply S system  nCv n T  nRn V as Cv  Cv (T )
1 1

Illustration - 9 A sample of an ideal gas is expanded to twice its original volume of 1m3 in a reversible
process for which P  V 2 where   5atm / m 6 . If CV,m = 20 J mol–1 k–1, determine molar change in entropy
(Sm ) for the process.
SOLUTION :
T V
S  nC V  n 2  nR  n 2 (n  1)
Using : T1 V1
P1V1 P2 V2 T2 P2 V2 V23
and     
3 (P =  V2) = 8 ( V2 = 2V1)
T1 T2 T1 P1 V1 V1
–1 –1
 S = 1 × 20 × n 8 + 8.134n 2 = 45.8 J mol K
10. Calculating rG for a process :
By definition : G = H – TS  dG  dH  TdS  SdT . . . .(i)

Also, H  U  PV  dH  dU  PdV  VdP . . . . (ii)
and dq  dU  ( dw) . . . . (iii)
and TdS  dq . . . . (iv)
Using (i), (ii) (iii) and (iv), we have : dG = VdP – SdT
(a) For a process at constant pressure : dP = 0  dG 

 dG   SdT     S
 dT  P
Since ‘S’ is always positive, above equation tells us that as temperature increase keeping pressure
constant, Gibbs energy decrease with rise in temperature.
 dG 
(b) For a process at constant temperature : dT = 0  dG = VdP    V
 dP T
Thus, at constant temperature, Gibbs energy increases with a rise in pressure since ‘V’ is always
positive.
Illustration - 10 1.0 mol of an ideal gas, initially present in a 2.0 L insulated cylinder at 300 K is allowed to
expand against vacuum to 8.0 L, Determine, w, U , H , STotal and G.
SOLUTION :
w   Pext V  0; q = 0 (Insulated Cylinder)  U  0  H
 T f  300 K

V
S sys  nR ln 2  2 R ln 2  11.52 JK 1
V1
and S surr  0  qsys  qsurr  0
 STotal  11.52 JK 1  G  T STotal  300  11.52  3456 J .
Illustration - 11 Which of the following processes thermodynamic relation(s) is (are) correct ?

(A) In a cyclic process,  dS  0 (B) G  H  T S
 G 
(C)    S (D)  r G   r G   RT ln Q, Q = Reaction quotient
 T  P
SOLUTION :
As we know for a cyclic process For constant pressure
 dS  0  G 
 T    S
Also dG = Vdp – SdT  T
dG VdP G  H  T S true for a reaction only..
  S
dT dT G  G  RT n Q true for a reaction only..
Illustration - 12 Calculate the entropy change per mole of substance in each of the following cases.
(i)  Liquid )  4540 J mol 1.

The freezing of isobutene at 160C. H ( Solid 
(ii) Vapour )  407 mod 1 .

The vaporization of water at its boiling point, 100C. H ( Liquid 
(iii) Expansion reversible and isothermally of an ideal gas from a volume of 2 dm3 to 10 dm3 at 27C .
Also calculate entropy change of surroundings due to the process.
(iv) Expansion irreversibly and isothermally of an ideal gas from dm3 to 10 dm3 against a constant pressuree
of 1 atm, at 27C . Also calculate entropy change of surrounding due to the process.
SOLUTION :
(i) Freezing temperature of isobutene  160C  (160  273) K  113K
q
S  rev
T
4540
Here qrev  4540 J mol 1  S   40.2 JK 1mol 1
113

Note that is freezing, the substance becomes more ordered. Hence, entropy is lost by the substance
(S is  ve).
(ii) For the reversible vaporization of water at 100C ,
q L H vap 407000
S  rev     1091.2 JK 1mol 1
T T T 373
P
(iii) For an isothermal process, S  R ln 1
P2
1 1  P2V2
At constant temperature, PV
P1 V2 V 10
   S  R ln 2  8.314  2.303 log  13.4 JK 1 mol
P2 V1 V1 2
If we treat system and surroundings as an isolated system, entropy change of surrounding
 S  13.4 JK 1mol 1.
 For a reversible process entropy of universe remains constant. Total entropy change for isolated
system = 0
(iv) Total entropy change of the system, has to be calculated assuming a reversible path,
dqrev V
S system    R ln 2  13.4 JK 1mol 1 [Same as in (iii)]
T V1
If we consider system and surrounding as an isolated system, entropy change of surrounding,
Heat exchanged by surrounding q
S surrounding  
T T
For the system,
E '  0  q  w   w  P (V2  V1 ). For surrounding, q   P(V2  V1 ).
1(10  2) L atm 8 8.314
 S surrounding     2.7 J / mol 1K .
300 K 300 0.0821
Entropy change of isolated system S system  S surrounding  13.4  2.7  10.7 J / mol 1K . For an
irreversible process, entropy of universe increase.

IN - CHAPTER EXERCISE
1. One mole of an ideal gas is put through a series of reversible changes

as shown in the graph A, B, C. At each stage the variables are shown
in the graph. Calculate the pressure at three stages of the system and
net work done in the cylic process.
2. A gas contained in a cylinder fitted with a frictionless piston expands against a constant pressure 1
atmosphere from a volume of 4 litre to a volume of 14 litre. In doing so, it absorbs 800 J thermal energy
from surroundings. Determine U for the process.
SOLUTIONS TO IN-CHAPTER EXERCISE
n RT 1  0.08 2  300
1. Using PV = nRT  PA  A A   1.02 atm
VA 24
1  0.082  600 1  0.082  300
and PB   2.04 atm ; PC   2.04 atm
24 12
 w A  B  0 ;  w B  C  PBV  2.04(12  24) Latm  w B  C  24.48 Latm  2.48 kJ
(Isochoric) (Isobaric)
V 24
 w C  A  nRT n 2  1  8.314  300 n  w C  A   1.73 kJ
V1 12
(Isothermal)
 wnet = 0 + 2.45 – 1.73 = 0.72 KJ
2. 800  U  1  (14  4)  101.3  U  800  1013  213 J
ANSWERS TO IN - CHAPTER EXERCISE
1. PA  1.02 atm ; PB  2.04 atm ; PC  2.04 ; 0.72 kJ 2. 213 J
Self Study Course for IITJEE with Online Support Solutions & Answers 19
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Thermochemistry
Thermochemistry
BASICS Section - 1
In this chapter, we will study the heat changes that take place when a chemical process occurs. Heat
(a form of energy) is either evolved or absorbed in the course of chemical reaction. The study of energetics
considers the relationship between thermodynamical functions : heat (q), work (W) and internal energy
(U or E).
1. Definitions :
System :
A small portion of the universe with-in which we confine our study of energy changes is called as a system.
Surroundings :
The remainder of the universe (i.e., apart from the system), which can interact with the system is called as
surroundings.
Open System :
This type of system can exchange matter as well as energy
with surroundings. The boundary is not sealed and not
insulated. Sodium reacting with water in an open bea-
ker is an example of open system.
Closed System :
This type of system can exchange energy in the form of
heat, work or radiations but not matter with its sur-
roundings. The boundary between system and surround-
ings is sealed but not insulated. For example, liquid in con-
tact with vapour in a sealed forms a closed system. Heat
can be transferred through the walls of the tube to the sur-
roundings but total amount of matter remains the same as
vapours cannot escape.

Thermochemistry Vidyamandir Classes
Isolated System :
This type of system has no interaction with its sur-

roundings. Neither matter nor energy can be exchanged
with surroundings. A substance contained in an ideal ther-
mos-flask is an example of an isolated system.
2. Thermodynamics Properties :
(i) Intensive Properties :
The properties which do not depend upon the quantity of matter present in the system are called
Intensive properties. Pressure, temperature, specific heat, surface tension, refractive index, viscos-
ity, melting point, boiling point, volume per mole (molar volume), concentration, colour potential
electrical field electrical resistivity, specific energy, etc. are examples of intensive properties of the
system.
(ii) Extensive Properties :
The properties whose magnitude depends upon the quantity of matter present in the system are
called Extensive Properties. Internal energy, total moles, volume, enthalpy, entropy, Gibbs en-
ergy, length, mass, electrical resistance etc. are examples of extensive properties.
3. Internal Energy (U) :
All the possible forms of energy that are associated with a system are referred to as Internal Energy. It
includes kinetic energy due to all kind of motion of the particles of the system, and their potential energy due
to intermolecular forces (interaction). It is impossible to measure the exact value of the internal energy of a
system. It can be measured when the system changes its state i.e. as change in internal energy (U).
The internal energy change of a system depends upon the state of the system and not on how the system
achieved the particular state. Such a thermodynamic function is called as state function. Other examples
are: temperature, pressure volume, enthalpy, entropy, Gibbs energy etc.
If U1 is the internal energy of a system in state 1, and U2 in the state 2, then the change in the internal energy
of the system (U) is given by : U = U2 – U1
As stated above, U is independent of the process which takes the system from state 1 to state 2.

4. First law of Thermodynamics :

Energy can neither be created nor destroyed, although it can be transformed from one form
to another.
If we supply an amount of heat (= q) to the system in state 1, the system does a work w and goes to achieve
the state 2. The heat supplied to the system gets converted into two parts :
(a) Work done by the system
(b) Change in internal energy of the system.
From law of conservation of Energy, we have :
q = U + (– w) . . . . (i)
This equation is known as First Law of Thermodynamics.
5. Sign Convention :
 w is positive, when the work is done on the system.
 w is negative, when the work is done by the system.
 q is positive, when the heat is supplied to the system.
 q is negative, when the heat is lost by the system.
6. Enthalpy :
It is a thermodynamic function (H) defined to study heat changes in chemical reactions. It is also known as
heat content of the stem defined as :
H = U + PV where P : Pressure V : Volume
If the change of state takes place at constant pressure, q is denoted as qp (heat transfer at constant pres-
sure). It is also known as change in enthalpy of the system, represented as
H = qp (H : Enthalpy of the system).
In such a process, volume of the system will change and work done is given as :
w = – P V V : change in volume
 qp = U + P V [Using first law of thermodynamics]
or qp = U2 – U1 + P (V2 – V1)
or qp = (U2 + PV2) – (U1 + PV1)
or qp = H2 – H1 = H where H1 = U1 + PV1 = enthalpy of the system in state 1
and H2 = U2 + PV2 = enthalpy of the system in state 2
Enthalpy change like internal energy change in a state function.

Heat change in all chemical reactions is studied as enthalpy change of the reaction (rH). System in state 1
is taken as system of reactants and in state 2 taken as system of products. Enthalpy change (Heat change)
accompanying the reaction is given as :
rH = Enthalpy of products – Enthalpy of reactants =  (Hproduct) –  (Hreactants)
If the change of state takes place at constant volume, q is denoted as qv (heat transfer at constant volume).
U = qv
7. Exothermic and Endothermic reactions :

(a) Exothermic reactions :
Chemical reactions in which heat is evolved are known as exothermic reactions.
For example : 2Mg(s) + O2(g) 
 2MgO(g)
N2(g) + 3H2(g) 
 2NH3(g)
Both of the above reactions are exothermic reactions because heat is evolved in them.
In general, an exothermic reaction is represented as : Reactants 
 Products + heat
Here enthalpy (or heat content) of reactions is partially transferred to the enthalpy of the products
and partially evolved as heat.
If HR : enthalpy of reactants and HP : enthalpy of products
Clearly, HP < HR  rH < 0 [rH = HP – HR]
i.e. for exothermic reaction, rH (reaction enthalpy) will bear a – ve sign (evolution of heat)
Note : In exothermic reaction, for some time (i.e. during the change) temperature of the products will rise above
room temperature. But, very soon the heat is lost to surroundings and the same temperature is maintained.
(b) Endothermic Reactions :

Chemical reactions in which the heat is absorbed from the surroundings are known as
endothermic reactions.
For example : N2 (g) + O2 (g) 
 2 NO (g)
H2 (g) + I2 (g) 
 2 HI (g)
Both of the above reactions are endothermic reactions because in them heat is absorbed from the
surroundings.
In general, an endothermic reaction can be expressed as :
Reactants + heat 
 Products

Here, enthalpy of products is derived from enthalpy of reactants plus the absorbed heat.
Clearly HP > HR
 rH > 0 [rH = HP – HR]
i.e. for endothermic reactions, rH (reaction enthalpy) will bear a +ve sign (absorption of heat)
Note : In endothermic reactions, (unlike exothermic reactions), temperature of the reacting mixture falls during the
change. But very soon, heat is absorbed from the surrounding and same temperature is restored.
8. Enthalpy Change at Standard Conditions :

rH depends upon the conditions under which a reaction is performed. So to compare enthalpy changes of
various reactions, they are performed at standard conditions.
Standard conditions for temperature and pressure are 298 K (or 25°C) and 1.0 atm pressure. Any enthalpy
change measured under these conditions is known as Standard Enthalpy change or Standard Heat of
reaction and it is denoted as  r H  .
It is also important to specify the states of all reactants and products in a reaction. [‘s’ for solids, ‘l’ for
liquids, ‘g’ for gases (or free atoms), ‘aq’ for solution in water].
A chemical reaction which clearly informs about the heat change accompanying it (i.e. exothermic or endot-
hermic) and the physical state of all reactants and products is known as Thermochemical Equation.
1
For example :  CO( g ) ;
C(s)  O2 ( g )  rH1 = – 385.2 kJ (Exothermic)
2
1 1
N2 ( g )  O2 ( g ) 
 NO( g ) ; rH = + 90.25 kJ (Endothermic)
2 2
Note : rH is the reaction enthalpy for a reaction in any form (i.e. stoichiometric coefficients) e.g. refer to the
reaction below :
2C(s) + O2 (g) 
 2 CO(g) ; rH2 = – 770.4 kJ (Exothermic)
Here, rH2 =2 rH1
9. Enthalpy of a Compound :
To define the enthalpy of a compound, it is taken that the enthalpy of an element in its most stable state at
standard conditions is zero.

Standard states of some elements :

C : Graphite ; S : Rhombic ; Br as Br2 () ; I as I2 (s); H as H2 (g) ;
Cl as Cl2 (g); N as N2 (g) ; O as O2 (g);
P : White (Exception : Red Phosphorus is more stable than White Phosphorus)
e.g. H
Cl 2 (g)
 0 ; H
H 2 (g)
0; H
O 2 (g)
 0; H
Br2 ( )
 0 ; H
I2 (s)
0;
Consider the following thermochemical equations at 25°C and 1 atm.
1 1
H2 (g) + Cl2 (g) 
 HCl (g)
2 2
It represents formation of HCl at standard conditions i.e.  f H   H of given reaction
From definition : rH =  (Hproducts) –  (Hreactants) =  ai (H)m, products –  bi (H)m, reactants
[Hm is the molar enthalpy of the compound and ai & bi the stoichiometric coefficients of products and
reactants respectively]
1  1  
  r H   f H   H 
HCl   H H 2  H Cl2  [see definition of  f H  in Section – 2]
2 2 
  f H   H HCl  0 [Enthalpy of elements in standard state = 0]
 H 
(HCl)   f H(HCl)
Hence the enthalpy of a compound is the standard heat of formation of the compound OR enthalpy
of a compound is often taken as standard enthalpy of formation of that compound.
Enthalpy of a compound A at standard conditions =  f H  of A
 
Note : By convention,  f H  H   aq   0
Illustration - 1 How much heat is evolved by the preparation of 100 gm of iron by the following
reaction ?
 2 Fe(s) + Al2O3 (s) ; rH = – 202.6 kcal/mol
2 Al (s) + Fe2O3 (s) 
SOLUTION :
From thermochemical reaction, it is clear that 202.6 kcal of heat is involved when two moles of Fe (iron) is
formed.
 2 moles of Fe  202.6 kcal
 1 mole of Fe  101.3 kcal
 100/56 mole of Fe  101.3 × 100/56 = 180.9 kcal

Heat of Reaction Section - 2
The heat of a reaction can be assigned special names in the following manner :
(a) Standard Heat of Formation (  f H  ) :

The heat evolved or absorbed when one mol of any compound is formed from its elements in their
standard states. It is usually denoted by  f H    f H  can be given –ve or +ve sign, depending
upon whether formation is exothermic or endothermic.
C(s, graphite) + 2 H2 (g) 

 CH4 (g) ;  f H  = – 74.3 kJ/mol
1 1
H2 (g) + I2 (s) 
 HI (g) ;  f H  = 25.92 kJ/mol
2 2
Note : To write chemical equations for formation, balance the reaction for one mole of compound whose formation
is to be studied.
(b) Standard Heat of Combustion (  c H  ) :

The heat evolved (or enthalpy change) when one mole of any substance is completely burnt in excess
of oxygen.
 c H  will always bear –ve sign for it being enthalpy change of an exothermic reaction.
CH4(g) + 2 O2(g) 
 CO2(g) + 2 H2O() ;  c H  = –212 kcal/mol
C(s, graphite) + O2(g) 

 CO2 (g) ;  c H  = –94 kcal/mol
Note : To write chemical equations for combustion, balance the reaction for one mole of compound whose com
bustion is to be studied.
Illustration - 2 15
Calculate  r H  for the reaction : C6H6 () + O (g) 
 6 CO2 (g) + 3 H2O ()
2 2
Given the standard heat of formations (  f H  ) of H2O (), CO2 (g) and C6H6 () are – 57.80 kcal/mol,
– 94.05 kcal/mol and 19.8 kcal/mol respectively.
SOLUTION :
Whenever, standard heat of formation (  f H  ) of a compound is given it means that enthalpy of
that particular compound at standard state is given. Also, note that in the question, molar enthalpy
changes are given.

Using the definition of enthalpy change as : rH = H(products) – H (reactants)
For the given reaction :  r H   (H  

products )   (H reactants )
or  r H   (f H  
products )  (  f H reactants )
15
C6H6 () + O (g) 
 6 CO2 (g) + 3 H2O ()
2 2
f H 19.8 0 (–94.05) (–57.8)
  r H  = [6 × (–94.05) + 3 × (–57.8)] – [19.8] = – 757.50 kcal/mol.
(c) Heat of Dissociation (  bond H  ) :

It is the amount of energy required to break one mole of bonds in a molecule (in gas phase) into
gaseous atoms.
 2H (g) ;  bond H  = 103 kcal/mol

H – H (g) 
 2C (g) ;  bond H  = 80 kcal/mol

C – C (g) 
Note : (i)  bond H  is always positive i.e. energy is always required to break the bond between two atoms.
(ii) Whenever a bond is formed between two atoms in gaseous state, energy is always released.
(d) Heat of Phase change :

It is the amount of energy required to change the phase of a substance under the particular conditions
for the phase change.
H2O (s) 
 H2O () ;  fus H  = 6 kJ/mol at 273 K and 1 atm
H2O () 
 H2O (g) ;  vap H  = 40.8 kJ/mol at 373 K and 1 atm
CO2 (s) 
 CO2 (g) ; sub H = 108 kcal/mol at 195 K and 1 atm
Note : (i)  fus H  : Amount of heat required to melt one mole of a substance at a constant temperature
and 1atm pressure.
(ii)  vap H  : Amount of heat required to vaporize one mole of a substance at a constant
temperature and 1 atm pressure.
(iii) sub H : Amount of heat required to sublime one mole of a substance at a constant
temperature and 1 atm pressure.

(e) Heat of Atomization (  a H  ) :

It is the amount of energy required to break the bonds in a molecule (in gas phase) into gaseous
atoms.
Na (s) 
 Na (g) ;  a H  = 108 kJ/mol
H – H (g) 
 2H (g) ;  a H  = 435 kJ/mol
CH4 (g) 
 C (g) + 4 H (g) ;  a H  = 1665 kJ/mol
Note : (i) For a monoatomic molecule (i.e. atom) in solid phase,  a H  is also called as sub H  .
(ii) For a diatomic molecule,  a H  is also called as  bond H  .
(iii) For a polyatomic molecule, it is the enery required to break all the bonds to form gaseous atoms.
(f) Average Heat of Dissociation ( mean, bond H  ) :
It is the average amount of energy required to break one mole of bonds in a polyatomic
molecule (in gas phase) into gaseous atoms.
CH4 (g) 
 C (g) + 4 H (g) ;  a H  = 1665 kJ/mol
Note : In general, in a polyatomic molecule, the energy required to break a bond changes in the successive bond
dissociations. For example :
CH4 (g) 
 CH3 (g) + H (g) ;  bond H1
CH3 (g) 
 CH2 (g) + H (g) ;  bond H 
2
CH2 (g) 
 CH (g) + H (g) ;  bond H 3
CH (g) 
 C (g) + H (g) ;  bond H 
4
 1 
Here :  bond H1   bond H 2   bond H3   bond H 4 and  mean, bond H   a H
4

(g) Heat of Lattice(  lattice H  ) and Heat of Hydration(  hyd H  ) :
 lattice H  : It is the energy required to break one mole of an ionic compound into ions in their
gaseous atoms.
 Na+ (g) + Cl– (g)

NaCl (s)  ;  lattice H  = 787 kJ/mol
 hyd H  : It is the energy released when atoms (gaseous) in one mole of an ionic compound gets
hydated.
Na+ (g) + Cl– (g) (  NaCl ) 

 Na+ (aq.) + Cl– (aq.) ;
 hyd H  = –783 kJ/mol

Note :  lattice H  is always positive and  hyd H is always negative.
(h) Heat of Solution ( sol H  ) :
It is the change in enthalpy when one mole of a substance (solute) is completely dissolved in excess of
water.
 Na+(aq) + Cl–(aq)
NaCl(s) + aq  ; sol H  = 5 kJ
HCl(g) + aq 
 HCl(aq) ; sol H  = –x kJ

Note : (i) sol H  =  lattice H  +  hyd H (can be positive or negative)
(ii) Generally, when gases are dissolved, heat is evolved. In case of salts (solids), heat is absorbed
except when anhydrous salts are dissolved.
(i) Heat of Ionisation ( ionisation H  ) :
It is the amount of heat absorbed when one mole of a compound completely dissociates into ions in a
solution.
 H+(aq) + CN–(aq)
HCN(aq)  ; ionisation H  = + p
 NH4+(aq) + OH–(aq)
NH4OH(aq)  ; ionisation H  = + q

(j) Heat of Neutralisation (  neutralisation H  ) :
It is the amount of heat liberated when one gm-equivalent of acid completely neutralises by one gm-
equivalent of base. In water, all strong acids (HCl, H2SO4, HNO3) and strong bases [NaOH, Ca(OH)2,
etc] ionise completely.  neutralisation H  is constant for strong acid and base neutralization and is
equal to –13.7 kcal/mol = –57.27 kJ/mol.
Neutralisation can be treated as :
H +(aq) + OH–(aq)  H2O ()

 ;  neutralisation H  = –13.7 kcal/mol
Note : (i)  neutralisation H  for weak acids (HCN, CH3COOH, benzoic acid) and weak bases (NH4OH,
amines) is lower than that for strong acids and bases. The reason is that heat is absorbed in complete
ionisation of weak acids and bases (unlike in case of strong acids and bases where no heat is required
for ionisation).
(ii)  neutralisation H  for the reaction between HCl and NaOH in aprotic solvents (solvents which doesn’t
ionizes) e.g. benzene etc. is less than –13.7 kcal/mol because HCl is a polar covalent substance and
doesnt get ionizes in aprotic solvent so requires non-zero ionisation H  for neutralization.
(iii)  neutralisation H  for the reaction between HF and NaOH is –16.27 kcal/mol which is greater than
the expected value of –13.7 kcal/mol (obviously to be compared in terms of magnitude). The differ-
ence is due to a very high heat of hydration of flouride ion due to its small size.

Hess’s Law of Constant Heat Summation Section - 3
It states that change in enthalpy for any chemical reaction is constant, whether the reaction occurs
in one step (directly) or in several steps (indirectly).
OR
The enthalpy change in a reaction depends upon initial and final states and is independent of the
route followed to complete the reaction.
It is the direct consequence of law of conservation of energy. rH of overall reaction will be obtained by
“appropriate summation” of the changes in enthalpies of various intermediate steps.
Find the enthalpy change for formation of NO2(g).
1
N (g) + O2 (g) 
 NO2(g) ; f H = ?
2 2
Using given thermochemical equations, and applying Hess’s Law :
1 1
(i) N2 (g) + O2 (g) 
 NO (g) ; rH1  (f H) NO
2 2
1
(ii) NO (g) + O (g) 
 NO2 (g) ; rH2  (c H) NO  ( f H) NO2
2 2
Adding two equations, we get :
1
N (g) + O2 (g) 
 NO2 (g)  rH = rH1 + rH2
2 2
1
Find rH of reaction : H2 (g) + O (g) 
 H2O (g)
2 2
1
(i) H2(g) + O (g) 
 H2O () ; rH1= –68.3 kcal/mol  (f H)H 2O  (c H)H 2
2 2
(ii) H2O () 

 H2O (g) ; rH2 = 10.52 kcal/mol  ( vap H)H 2 O
From Hess’s Law : rH = rH1 + rH2 = (–68.3) + (10.52) = –57.78 kcal/mol

Illustration - 3Enthalpy of neutralisation of acetic acid by NaOH is 50.6 kJ/mol. Calculate H for ionisation
of CH3COOH. Given, the heat of neutralisation of a strong acid with a strong base is –57.3 kJ/mol.
SOLUTION :
The neutralisation of a strong acid by a strong base is represented as :
H+ (aq) + OH– (aq) 

 H2O () ;  Neutralisation H   57.3 kJ / mol
Now acetic acid is a weak acid, so its neutralisation is represented in two stages: First complete ionisation
of weak acid and then complete neutralisation of the fully ionised acid by the base.
1.  CH3COO– (aq) + H+ (aq) ;  Io n isatio n H   ?

CH3COOH (aq) 
2. H+ (aq) + OH– (aq) 

 H2O () ;  Neutralisation H   57.3 kJ / mol
Now adding the two equations to get the equation of neutralisation ;
 CH3COO– (aq) + H2O () ;  Neutralisation H   50.6 kJ / mol

CH3COOH (aq) + OH– (aq) 
From Hess’s Law :  Ionisation H   ( 57.3)  50.6   Ionisation H   6.7 kJ / mol
Illustration - 4 Find the heat of formation of ethyl alcohol from following data :
C (s) + O2 (g) 
 CO2 (g) ; rH = –94 kcal/mol
1
H2 (g) + O (g) 
 H2O () ; rH = –68 kcal/mol
2 2
C2H5OH () + 3O2 (g) 
 2 CO2 (g) + 3 H2O () ; rH = –327 kcal/mol
SOLUTION :
Always write the balanced thermodynamic equation for which rH is to be calculated.
1
2 C (s) + 3 H2 (g) +  C2H5OH () ; fH = ?
O (g) 
2 2
Given :
I. C (s) + O2 (g) 
 CO2 (g) ; rH1 = –94 kcal/mol  (f H)CO 2  (c H)C
1
II. H2 (g) + O (g) 
 H2O () ; rH2 = –68 kcal/mol  (f H)H 2O  (c H)H 2
2 2
 2 CO2 (g) + 3 H2O () ; rH3 = –327 kcal  (c H)C2 H5OH
III. C2H5OH () + 3O2 (g) 

Now adding appropriately to get the required equation (Using Hess’s Law) :
Operate : 2 (I) + 3(II) – (III) to get :
1
2 C (s) + 3 H2 (g) + O (g) 
 C2H5OH ()
2 2
From Hess’s Law : fH = 2(rH1) + 3(rH2) - rH3 = 2 (–94) + 3(–68) – (–327) = –65 kcal/mol
Illustration - 5 From the following data, calculate the standard enthalpy change for the combustion of
cyclopropane at 298 K :
The enthalpy of formation of CO 2 (g), H 2 O() and propene(g) are –393.5, –285.8 and 20.42 kJ mol–1
respectively.
The enthalpy of isomerisation of cyclopropane to propene is –33.0 kJ mol–1.
SOLUTION :
9
CH3CH = CH2(g) + O (g) 
 3CO2(g) + 3H2O() . . . . (i)
2 2
       9  
c H (Propene) = 3 f H(CO2 )  3 f H (H 2O)     f H(Propene)   f H O2 
 2 
= 3 (– 393.5) + 3 (– 285.8) – (20.42) = – 2058.32 kJ mol–1
To the above reaction, if we add the reaction :
isomerization H   33.0 kJ mol1
we get :

Hence, c H(cyclopropane)  (2058.32  33.0) kJ mol 1  2091.32 kJ mol 1

Heat of Reaction and Bond Energy Section - 4
Let us consider that the bond energy of AB molecule is x kcal/mol.

Bond Formation :  A – B ; rH = – x
A + B  (Bond formation is exothermic)
Bond Dissociation :  A + B ; rH = + x
A – B  (Bond dissociation is endothermic)
During a chemical reaction, atoms and molecules are rearranged to form new molecules. During
the course of chemical reaction, old bonds are broken (of reactants) and new ones are formed (of
products).
A given chemical reaction can be analysed energetically into two parts :
(i) Bond Breaking (endothermic, rH > 0)
(ii) Bond Formation (exothermic, rH < 0)
If rH1 is the enthalpy change during bond breaking (i) and rH2 is the enthalpy change during bond
formation (ii), then overall enthalpy change of the reaction (rH) is given by Hess’s Law:
rH = rH1 + rH2
As discussed, rH can be calculated using Hess’s law of constant heat summation or using :
rH = H Product  H Reactants .
rH can also be theoretically calculated using bond energies in the following manner :
(i) On the reactants side, calculate the energy required to break all the bonds. If there is an element in
Solid / Liquid state, also consider the energy required to convert it into gaseous state.
(ii) On the products side, calculate the energy released when products are formed. If there is an ele-
ments/compound in Solid/Liquid state, also consider the energy released when it is converted from
gaseous state to the required state.
(iii) Add total energy released and absorbed to get rH.
Illustration - 6 Find rH of the reaction : OF2 (g) + H2O (g) 

 O2 (g) + 2 HF (g) ;
Average bond energies of O–F, O–H, O = O, H–F are 44, 111, 118 and 135 kcal/mol respectively.
SOLUTION :
OF2 (g) + H2O (g) 
 O2 (g) + 2 HF (g) ; rH = ?
(i) Bond Breaking: (endothermic) : rH1
 O (g) + 2 F (g) ; rH = + 2 × 44
F – O – F (g)  [bond energy of O – F = 44]
 O (g) + 2 H (g) ; rH = + 2 × 111
H – O – H(g)  1 [bond energy of O – H = 111]
 rH1 = 2 × 44 + 2 × 111 = + 310 kcal.

(ii) Bond Formation: (exothermic) : rH2

O (g) + O (g) 
 O = O(g) ; rH = –118 [bond energy of O = O = 118]
2[H (g) + F (g) 
 H – F (g)] ; rH = – 2 × 135 [bond energy of H – F = 135]
 rH2 = –118 + (–2 × 135) = –388 kcal
Now using Hess’s Law ; rH = rH 1 + rH2 = 310 + (–388) = –78 kcal
Illustration - 7 Find f H of HCl (g) if bond energies of H2, Cl2 and HCl are 104, 58, 103 kcal/mol respec-
tively.
SOLUTION :
1 1
H2 (g) + Cl2(g) 
 HCl (g) ; f H = ?
2 2
Now analyse the given thermochemical equation in two parts :
(i) Bond Breaking [rH1] : Endothermic Reaction
H2(g) 
 2 H(g) ; rH = 104 kcal/mol
Cl2(g) 
 2 Cl(g) ; rH = 58 kcal/mol
1
[H (g) 
 2 H(g) ; 104] [as we need mole of each reactant]
2 2
1
[ Cl2(g) 
 2 Cl(g) ; 58]
2
1 1
 rH1 = × 104 + × 58 = 81 kcal
2 2
(ii) Bond Formation : (rH2) : Exothermic reaction
 HCl (g) ; r H = –103 kcal

H(g)+ Cl (g)  (Bond energy of HCl = 103 kJ/mol)
r H2 = –103 kcal
Now r H = f H = r H1 + r H2 (using Hess’s Law)
 f H = 81 + (–103) = –22 kcal/mol

Illustration - 8 Calculate rH for the following homogeous gaseous reaction :

CH3COCH3(g) + 2O2(g) 
 CH3COOH(g) + CO2(g) + H2O(g)
Use the data in kcal mol–1. bond C – H = 99 ; bond C – C = 83 ; bond C = O = 173 ;
bond O = O = 118 ; bond C – O = 84 ; bond O – H = 110
SOLUTION :
First calculate the energy required to break all the bonds in reactants side and to convert them into gaseous
atoms.
H O
| ||
(i) 4H(g) + 2C(g) + 2O(g) 
 H  C  C  O – H (g)
|
H
Energy released = 3Bond C – H + Bond C – C + Bond C = O + Bond C–O + Bond O–H
= 3 × 99 + 83 + 173 + 84 + 110 = 747 kcal

(ii) C (g) + 2O (g) 
 O = C = O (g)
Energy released = 2Bond C = O = 2 × 173 = 346 kcal
 Total energy released = 1313 kcal
 rH = 1169 + (–1313) = –144 kcal mol–1
(iii) 2H(g) + O(g) 
 H – O – H(g)
Energy released = 2Bond O – H = 2 × 110 = 220 kcal
Note : (i) While calculating rH using the bond energy concept, it is important to know the structure of the
molecules/compounds taking part in the reaction.
(ii) If the reaction would have been :
CH3COCH3(g) + 2O2(g) 
 CH3COOH(g) + CO2(g) + H2O()
then we also need to consider the energy released for the conversion of H2O(g) 
 H2O()
rH = –144 – 9.72 = – 153.72 kcal

Illustration - 9 Compute the heat of formation of liquid methyl alcohol, using the following data (in
kJ/mol) : Heat of vaporization of liquid methyl alcohol = 38.
Heat of formation of gaseous atoms from the elements in their standard states: H = 218; C = 715; O = 249.
Average bond energies : C – H = 415; C – O = 356; O – H = 463.
SOLUTION :
The given data is as follows :
(i) CH3OH() 
 CH3OH(g)  r H1Θ  38 kJ mol1
1
(ii) H 2 ( g ) 
 H( g )  r HΘ
2  218 kJ mol
1
2
(iii) C(graphite) 
 C(g)  r H3Θ  715 kJ mol1
1
(iv) O 2 ( g ) 
 O( g ) r HΘ
4  249 kJ mol
1
2
(v) CH(g) 
 C(g) + H(g)  r H5Θ  415 kJ mol1
(vi) CO(g) 
 C(g) + O(g) r HΘ
6  356 kJ mol
1
(vii) OH(g) 
 O(g) + H(g) r HΘ
7  463kJ mol
1
We have to calculate the enthalpy of formation of liquid methyl alcohol, i.e.,
1
(viii) C(graphite) + 2H2(g) + O (g) 
 CH3OH()  r H 8Θ  ?
2 2
First of all, we calculate the enthalpy of reaction :
(ix) CH3OH(g) 
 C(g) + 4H(g) + O(g) ;  r H 9Θ  ?
 H 
 | 
 CH3OH  H  C  O  H 
 | 
 r H 9Θ  3  r H 5Θ   r H Θ Θ
6  r H7  
H
 contains one C  O, one O  H 
 
 and three C  H bonds 
 r H 9Θ = (3415 + 356 + 463) kJ mol = 2064 kJ mol

–1 –1

The equation (viii) can be generated as follows :

Eq. (iii) + 4  Eq. (ii) + Eq. (iv) – Eq. (ix) – Eq. (i)
Hence, the enthalpy of reaction of equation (viii) is given as :
 r H8Θ   r H3Θ  4  r HΘ Θ Θ Θ
2   r H 4   r H9   r H1
= (715 + 4 218 + 249 – 2064 – 38) kJ mol–1 = – 266 kJ mol–1
Illustration - 10 The heat of formation of ethane is –19.5 kcal. Bond energies of H – H, C – H and C – C
bonds are 104.2, 99.0 and 80.0 kcal/mol respectively. Calculate the heat of atomisation of graphite.
SOLUTION :
f H of ethane (C2H6) = –19.5 kcal/mol
2 C (s) + 3 H2 (g) 
 C2H6 (g) ; f H = –19.5 kcal/mol
Let the heat of atomisation is x kcal/mol
Bond Breaking : (rH1) Bond Formation : (rH2)
2[C (s) 
 C(g); +x] 1[C (g) + C (g) 
 C – C (g) ; – 80]
3[H2 (g) 
 2 H (g) ; +104.2] 6[C (g) + H (g) 
 C – H (g) ; – 99]
rH1 = 2x + 312.6 rH2 = (80) + (6 × 99) = 674
From Hess’s Law : f H = r H1 + r H2
–19.5 = (2x + 312.6) – 674  x = 171 kcal.
Illustration - 11 Using the data given below (all values are in kcal/mol at 25°C), calculate the bond ener-
gies of C–C and C–H bonds.
c H Θ ethane   372.0 ; c H Θ propane   530.0 ; a H Θ  172.0 ;

C  Graphite 
 bond H Θ H  H  104.0 ;  f H Θ H O   68.0 ;  f H Θ CO   94.0

2 2
SOLUTION :
From the data given for heats of combustion for ethane and propane, we can calculate the heats of formation
of two compounds (C2H6 and C3H8) as follows :
(a) Writing the equation for combustion of ethane:
7
C2H6 (g) + O (g) 
 2 CO2 (g) + 3 H2O () ;  c H Θ   372.0
2 2

From definition of rH of a reaction : rH = HProducts – HReactants
The enthalpy of a compound is the enthalpy of formation of that compound at standard conditions (i.e.  f H Θ ).
 7 
Δ c H Θ =  2 Δ f HΘ CO  + 3 Δ f HΘ  H O    Δ f HΘ  C H   Δ f HΘ  O  
 2 2   2 6 2 2 
Note that f HΘ(O 2 ) = 0 (as enthalpy of formation of an element in standard state is taken as zero).
 –372 = 2 × (–94) + 3 × (–68) – f HΘ(C2 H6 )
 f HΘ(C2 H6 ) = –20 kcal/mol
(b) Writing the equation for combustion of propane :
C3H8 (g) + 5 O2 (g) 

 3 CO2 (g) + 4 H2O () ;  c H Θ   530.0
From definition of rH of a reaction : rH = HProducts – HReactants
 c HΘ  3 Δ f HΘ CO  + 4 Δ f HΘ H O    Δ f HΘ C H  + 5Δ f H Θ O  

 2 2   3 8 2 
  530  3    94   4  (68)  Δ f HΘ C H 

3 8
 Δf HΘ C H    24 kcal / mol

3 8
Calculations of bond energies :

Let the bond energy of C – C bond = x kcal mol–1 and the bond energy of C – H bond = y kcal mol–1
(a) For ethane, heat of formation is given as :
 f H Θ = – 20 kcal mol
–1
2 C(s) + 3 H2 (g) 
 C2H6(g) ;
Bond breaking (rH1) : Bond formation (rH2) :

2[ C(s)  C(g) ; + 172 ]
 1[ C (g) + C (g) 
 C – C (g) ; –x ]
3[ H2(g) 
 2H(g) ; + 104 ] 6[ C (g) + H (g) 
 C – H (g) ; –y ]
 rH1 = 2 × 172 + 3 × 104 = 656  rH2 = – (x + 6y)
  f H Θ = heat absorbed + heat released = rH1 + rH2

 – 20 = 656 – (x + 6y)  x + 6y = 676 . . . . (i)

(b) For propane, heat of formation is given as :
 r H Θ = –24 kcal mol

–1
3 C(s) + 4 H2 (g) 
 C3H8 (g) ;
Bond breaking (rH1) : Bond formation (rH2) :

3[ C(s) 
 C(g) ; +172 ] 2[ C(g) + C(g) 
 C – C(g) ; –x ]
4[ H2(g) 
 2H(g) ; +104 ] 8[ C(g) + H(g) 
 C – H(g) ; –y ]
rH1 = 3 × 172 + 4 × 104 = 932  rH2 = – (2x + 8y)
  f H Θ = rH1 + rH2
 – 24 = 932 – (2x + 8y)  x + 4y = 478 . . . . (ii)

Solving (i) and (ii), we get x = 82 and y = 99.
 Bond energy of C – C bond = 82 kcal mol–1 and C – H bond = 99 kcal mol–1
Born Haber’s Cycle Section - 5
The energy binding ions together in a crystal is called as lattice energy (  Lattice H Θ ). Lattice energy is
defined as the enthalpy change which occurs when one mole of an ionic compound dissociates into its ions
in gaseous state which means  Lattice H Θ is +ve i.e.,
 Na  ( g )  Cl ( g )
NaCl( s)   LatticeHΘ   790 kJ mol1
These crystal lattice energies cannot be measured directly. By applying Hess’s Law to a series of elemen-
tary processes starting with Na (s) and Cl2 (g) and ending with formation of NaCl(s),  Lattice H Θ can be
calculated. Such a sequence of reactions for ionic compounds is called as Born-Haber Cycle. The
concept is illustrated below by taking the formation of NaCl(s).
The heat of formation of sodium chloride can be calculated from bond energies very easily.
1
 f H Θ = – 411 kJ mol
–1
Na(s) + Cl (g) 
 NaCl(s)
2 2
The following sequences can give the above equation :
1. Sublimation of one mole of Na(s) :
Na (s) 
 Na (g) sub HΘ   109 kJ mol1

2. Dissociation of half mole of Cl2 :
1
Cl (g) 
 Cl (g)
2 2
1
 Bond H Θ  122 kJ mol1
2
(Bond energy of Cl2 is Bond HΘ
= 244 kJ/mole)
3. Ionisation of one mole of Na atoms :
 Na+ (g) + 1e–
Na (g) 
IE HΘ   496 kJ mol1

(First ionisation energy of Na atoms is 496 kJ/mole)
4. Addition of one mole of electrons to one mole of chlo
rine atoms:
Cl (g) + 1e– 
 Cl– (g)
 EA HΘ   348 kJ mol1
(Electron affinity of chlorine is 348 kJ/mole)

(Electron affinity is the energy released, so H is negative).
5. Condensation of gaseous ions to form one mole of solid NaCl :
This can not be calculated directly.
Na+ (g) + Cl– (g) 
 NaCl (s) r HΘ    Lattice HΘ
The summation of the above five reactions and their H values allows us to calculate the value of  Lattice H Θ .
1
f H Θ (–411) = sub HΘ (+109kJ) +  Bond HΘ (+122kJ) +  IE HΘ (+496kJ) + EA HΘ
2
(–348kJ) –  Lattice H Θ
  Lattice H Θ = +790 kJ/mol of solid NaCl.

Note : The crystal lattice is a measure of the stability of an ionic solid. The more negative its value, the more energy
is released in the hypothetical reaction in which a mole of ionic solid is formed from its constituent ions in the
gaseous state.

Illustration - 12 Find the electron affinity of chlorine from the following data (in kcal/mol).
Enthalpy of formation of LiCl is –97.5 ; Lattice energy of LiCl = 197.7 ; Dissociation energy of chlorine
= 57.6 ; Sublimation enthalpy of Lithium = 38.3 ; Ionisation energy of Lithium = 123.8
SOLUTION :
For a ionic compound of type LiCl :
1
 Lattice HΘ Θ Θ
LiCl   EA H Cl   f H LiCl   bond HΘ Θ Θ
Cl2   sub H Li   IE H Li
2
Θ 1
197.7   EA HCl  ( 97.5)   57.6  38.3  123.8
2
  EA H Θ
Cl   90.7 kcal / mol
Relation between rH and rU Section - 6
Enthalpy (H) and Internal Energy (U) are related as :

H = U + PV
 H = U + (PV)
or d H = d U + d (PV)
Now, for a reaction, we can write : rH = rU + PV
[Chemical reactions occur at constant T and P] - 12
Illustration
or rH = rU + ngRT
where n g   (n g ) products –  (n g ) reactants = Change in the number of gaseous moles
Illustration - 13 Find the sign of rH – rU for the following reactions :
(i) H2(g) + Cl2(g) 
 HCl(g) (ii) N2(g) + O2(g) 
 NO2(g)
7
(iii) PH3(g) 
 P4(s) + H2(g) (iv) C2 H 6 ( g )   CO2 ( g )  H 2O()
O2 ( g ) 
2

SOLUTION :
First, balance each reaction :
(i) H2(g) + Cl2(g) 
 2HCl(g)
(ii) N2(g) + 2O2(g) 
 2NO2(g)
(iii) 4PH3(g) 
 P4(s) + 6H2(g)
7
(iv) C2H 6 ( g )   2CO 2 ( g )  3H 2O()
O 2 ( g ) 
2
Now, Use : rH – rU = ngRT and n g   (n g ) products –  (n g ) reactants
 If ng > 0, rH – rU > 0 ;
If ng < 0, rH – rU < 0 ;
If ng = 0, rH – rU = 0
(i) ng = 2 – (1 + 1) = 0 (ii) ng = 2 – (1 + 2) = – 1
(iii) ng = (6 + 0) – 4 = 2
 7 5
(iv) ng = (2 + 0) –  1     [Note : For H2O(), ng = 0]
 2 2
Illustration - 14 The enthalpies of combustion of carbon and carbon monoxide in excess of oxygen at
298 K and constant pressure are –393.5 kJ/mol and –283.0 kJ/mol respectively. Calculate the heat of
formation of carbon monoxide at constant volume.
SOLUTION :
Heat change at constant pressure means enthalpy change (rH = qp)
1
Heat of formation of CO is written as : C (s) +  CO (g) ;  f H Θ  ?
O (g) 
2 2
Now we have :
I. C (g) + O2 (g) 
 CO2 (g) ;  c H1Θ  393.5 kJ / mol
1
II. CO (g) + O (g) 
 CO2 (g) ; c HΘ
2  283 kJ / mol
2 2

1
Adding appropriately (i.e., I – II), we get ; C (s) +  CO(g) ;  f H Θ
O (g) 
2 2
From Hess’s Law :  f H Θ   c H1Θ   c H Θ

2
 f HΘ = – 393.5 – (– 283) = – 110.5 kJ/mol
Now, calculation of the heat of formation at constant volume means that we have to calculate change in
internal energy (i.e. rU).
Using : rH = rU + PV [For a chemical reaction]
= rU + ngRT [ng = gaseous moles of products – gaseous moles of reactant]
 rU = rH – ngRT
Now putting the values :
1 1
n g  1   T = 298 K R = 8.314 J/K/mol.  f H Θ = –110.5 kJ/mol
2 2
1
  f U Θ = –110.5 – × 8.314 × 298 × 10–3 = –111.7 kJ/mol
2
Illustration - 15 Standard enthalpy of formation of C3H7NO2(s), CO2(g) and H2O() are –133.6, – 94.0
and – 68.3 kcal/mol respectively. Standard enthalpy of combustion of CH4(g) at 25°C is – 212.8 kcal/mol.
1 1
Calculate r H Θ for the reaction: 2CH4(g) + CO2(g) + N2(g)   C3H7NO2(s) + H2(g)
2 2
Also calculate heat of reaction at constant volume for combustion of C3H7NO2(s).
SOLUTION :
1 1
2CH4(g) + CO2(g) + N2(g) 
 C3H7NO2(s) + H (g) :  r H Θ  ?
2 2 2
To calculate  r H Θ of the above reaction, we need to find out the  f H Θ for CH4 as :
Given : CH4(g) + 2O2(g) 

 CO2(g) + 2H2O() :  c H Θ = – 212.8 kcal/mol
Using the definition of rH, we have :

 r HΘ  [f H Θ(CO2 )  2  f HΘ(H 2O) ]  [f H Θ(CH 4 )  2  f HΘO2 ] [Note : f H Θ(O2 )  0 ]
 – 212.8 = [– 94.0 + 2(– 68.3)] – f HΘ (CH 4 )
 f HΘ(CH ) = –17.8 kcal/mol

4
Θ
Now find the  f HΘ of the required equation using f H (CH ) .
4
 r HΘ  [f HΘ (C3H7 NO2 )  0]  [2  f HΘ(CH 4 )  f HΘ(CO2 ) ]
  r H Θ  ( 133.6)  2( 17.8)  ( 94.0)  4.0 kcal / mol

Now calculate
15 1 7
c HΘ (C3H7 NO2 ) : C3H 7 NO 2 ( s )   3CO 2 ( g )  N 2 ( g )  H 2O()
O2 ( g ) 
4 2 2
7
c HΘ (C3H7 NO2 ) = 3( 94.0)  ( 68.3)  ( 133.6)  387.45 kcal / mol
2
 1
Find  r UΘ   r HΘ  n g RT  387.45      2  10 3 (298)
 4
  1  5 
 387.6 kcal / mol  n g   3  2   4 
   
Illustration - 16 From Navogardo atoms of an element A, when half the atoms transfer one electron to
another atom, 405 kJ/mol of energy was found to be consumed. An additional energy of 745 kJ was further
required to convert all the A– ions to A+. Calculate the ionisation energy and the electron affinity of atom A
in eV.
SOLUTION :
Let I.E. be x eV/atom and E.A. be y eV/atom (magnitudes)
 A+ + e–
A  ; rH = I.E. = x A + e– 
 A– ; rH = E.A. = – y
405  103
I: Energy absorbed in eV =
1.6  1019
405  103 6.02  1023 6.02  1023

  x y . . . . (i)
1.6  1019 2 2

A–   A+
 A 
745  103
II : Energy absorbed in eV =
1.6  10 19
745  103 6.02  1023 6.02  1023

  x  y . . . . (ii)
1.6  1019 2 2
Solve for IE and EA using (i) and (ii), IE = 11.93 eV/atom and EA = 3.52 eV/atom (Magnitudes)
Illustration - 17 In order to get maximum calorific output, a burner should have an optimum fuel to
oxygen ratio which corresponds to 3 times as much oxygen as is required theoretically for complete
combustion of the fuel. A burner which has been adjusted for methane as fuel (with x litre/hour of CH4 and
6x litre/hour of O2) is to be readjusted for butane, C4H10. In order to get the same calorific output, what
should be the rate of supply of butane and oxygen ? Assume that losses due to incomplete combustion etc. are
the same for both fuels and that the gases behave ideally. Heats of combustion : CH4 = 809 kJ/mol;
C4H10 = 2878 kJ /mol.
SOLUTION :
First calculate the amount of energy required in the burner per hour using methane as follows :
809
 c HΘCH  809 kJ mol1  kJ / L (at 25C)
4 24.48
 1 mol CH4 ( 24.48 L at 25°C) on combustion produces 809 kJ
x
 x L/hr CH4 on combustion produces energy =  809 kJ / hr
24.48
Now, this much energy will be required by burning of butane and we can find its rate of consumptiom as :
2878
 c HΘ C H  2878 kJ mol1  kJ / L (at 25C)
4 10 24.48
x
 809
L
 Required Rate of combustion of propane  24.48  0.28 x L / hr
2878 hr
24.48
13
C4H10(g) + O (g)  4CO2(g) + 5H2O()
2 2
13
 1 mol CH4  mol O2 (theoretically)
2

 13 
  3   mol of O2 is required/mol of CH4 (practically) [Given]
 2
 39 
 rate of O2 per hour = (0.28x)     (5.48 x ) L O 2
 2 
Bomb Calorimeter
Calorimetry is study of heat transfer during physical and chemical processes. A calorimeter is device for
measuring energy transferred as heat. The most common device for measuring U is the adiabatic bomb
calorimeter, shown in figure (figure 1 & 2). The inner vesel or the ‘bomb’ (figure 2) and its cover are made
of strong steel coated inside with gold or platinum or some other non-oxidisable material. The cover can be
fitted tightly to the vessel by means of a metallid screwed down on a lead washer. A weighed amount of the
substance is taken in a platinum cup C which is supported on a rod R.
Stirrer
T
O2
Water
Bomb G
R Platinum cup
W
Figure 1 : The Bomb Calorimeter Figure 2 : The Bomb
A thin platinum wire W is connected between the rods R and G as shown. This serves to initiate the
combustion when heated electrically. The bomb is tightly closed and oxygen introduced through the inlet
tube T unit a pressure of about 20 – 25 atmospheres is attained. The bomb is then lowered in water placed
in a double jacketed and polished metallic calorimeter so as to minimise error due to radiation. The
arrangement ensures that there is no net loss of heat from the calorimeter to the surroundings (the bath) and
hence that the process is adiabatic. A mechanical stirrer is provided as shown. When the temperature of the
water become steady, the substance of inginited by calorimeter is noted after every minute by means of a
Beckmann thermometer graduate to read up to hundredth of a degree. The final temperature when cor-
rected for the radiation error in the usual way, minus the initial temperature, gives the rise of temperature.
The heat capacity of the calorimeter system, called the calorimeter constant, C, is obtained by burning a
known mass of a substance of known enthalpy of combustion. For this purpose, usually benzoic acid of high
grade purity is taken. Its qv which has been very carefully measured in taken as – 3226.7 kJ mol–1. Suppose

the thermal capacity of the calorimeter system including water is C and  is the change in temperature
produced by burning a quantity m of the given substance of molar mass M. Then, the constant volume heat
of combustion, qv of the substance is given by C  q  M/m. The enthalpy of combustion qp is then
obtianed with the help of the equation qp = qv + ngRT.
Illustrating the concepts :

(i) 0.50 of benzoic acid was subjected to combustion in a bomb calorimeter when the temperature of the
calorimeter system (including water) was found to rise by 0.55oC. Calculate the enthalpy of combus-
tion of benzoic acid. The T calorimeter constant was found to be 23.85 kJ K–1.
qv = C  q  M/m
= 23.85 kJ K–1  0.55 K  122 g mol–1 / 0.50 g
= 3200.7 mol–1
= – 3200.7 kJ mol–1 (Heat of combustion has alwas a negative sign)
15
C 6 H 5COOH(s)   7CO 2 (g)  3H 2O()
O 2 (g) 
2
We know that q p  q v  n g RT ; n  7  7.5  0.5
q p  3200.7 kJ mol 1  ( 0.5)(8.314 10 3 kJ K 1mol 1)(298K)
 3201.9 kJ mol 1
(ii) Explain why the following statement, made by a student doing an experiment on bomb calorim-
eter, is wrong : “H = U + PV. Since in the experiment, V = 0, hence, H = U.”
The error is due to the fact that the student has applied the equation H = U + PV, which holds at
constant pressure, to a process which occurs at constant volume.
We know that H = U + PV
 H = U + (PV) = U + PV + VP
For a constant pressure process, P = 0 so that H = U + PV
However, for a constant volume process, V = 0 so that H = U + VP
We many meantion here that a calorimeter for studying processes at constant pressure, called an
isobaric calorimeter is also available commercially. A simple example is thermally insulated vessel open
to the atmosphere ; the heat released in the reaction monitored by measuring the change in tempera-
ture of the contents. For a combustion reaction, an adiabatic flame calorimeter can be used
to measure T when a given amount of substance burns in oxygen.

Enthalpy of Polymerization :
The difference between the enthalpy of one mole of monomer and the enthalpy of the products of the
polymerization reaction. Addition polymerizations are exothermic, values ranging from about 35 to 100 kJ/
mol
Let us consider an example of polythene.
n  H 2 C  CH 2  
 ...........  CH 2  CH 2  CH 2  CH 2  .............
H (Per mole) = B.E. of Reactants – B.E. of Products
(B.E. of C = C + 4  B.E. of C – H) – ( 2  B.E. of C – C + 4  B.E. of C – H)

Same logic can also be used in following reactions as well
nN 2(g)  nH 2(g) 
 ( NH  NH 
) n (g)
n(H 3C  C  C  CH 3 ) (g) 
 ( CH 2  CH  CH  CH 2 
) n(g)
CALCULATING RESONANCE ENERGY Section - 7
Resonance energy, as we know, is the difference in energy between resonance hybrid and the canonical
form of the compound. It can be easily calculated using the following key points :
(i) If the resonance hybrid is more stable than the canonical forms, resonance energy is negative otherwise
positive.
(ii) Simply figure out, which of the resonance hybrid and the canonical form is more stable based on the
rH values as explained :
(a)  f H Θ : More negative is  f H Θ , more is the stability as this means when compound is formed,
energy is getting lost to attain lower energy than the reactants.
(b)  c H Θ or  Hydrogenation H Θ : More negative value in this case means less stability as more heat
released means this compound is more reactive.
Note : In (a), the compound under analysis is the product whereas in (b), that compound is the reactant.
(iii) Now, calculate H for the theoretical (canomical) and actual (resonance hybrid) compound and
calculate the difference between the two to get resonance energy.

Illustration - 18 The standard molar enthalpies of formation of cyclohexane() and benzene() at 25C are
156 and +49 kJ/mole respectively. The standard enthalpy of hydrogenation of cyclohexene() at 25C is
–119 kJ/mole. Use this data to estimate the magnitude of the resonance energy of benzene.
SOLUTION :
Given : C6H10 () + H2(g) 
 C6H12() ;  Hydrogenation H Θ = 119 kJ/mole
Find the actual heat of hydrogenation of benzene from Hess’s law as follows :
1. 6C(s) + 6H2(g) 
 C6H12() ;  f H Θ = 156 kJ/mole
2. 6C (s) + 3H2(g) 
 C6H6() ;  f H Θ = +49 kJ/mole
C6H6 () + 3H2(g) 

 C6H12() ;  Hydrogenation H Θ
 ( Hydrogenation H Θ ) = 156  49 = 205 kJ/mole

Actual
[Note :  Hydrogenation H  is always negative ]
 hypothetical heat of   heat of hydrogenation of 

Now,     cyclo hexatriene

 hydrogenation of benzene   
 heat of hydrogenation 
3   
 of cyclohexane 
= 3  (119) = 357 kJ/mole
Here, we have assumed that there are only 3 double bonds in benzene (kekule’s structure) and in
hydrogenating it, the energy obtained will be roughly 3 times of hydrogenating cyclohexene.
and
Clearly, heat of hydrogenation for theoretical benzene is more negative and thus, it is less stable. So,
Resonance energy should be negative (since actual benzene is more stable).
 Resonance energy = 357  (205) = 152 kJ/mole of benzene

Illustration - 19 Calculate the resonance energy of isoprene (C H ) from the data given.
5 8
Standard Heats of combustion of isoprene, carbon and water are 3186, 393.5 and 285.83 kJ/mole respec-
tively. Bond energies of C = C, C  C, C  H and H  H bonds are 615, 348, 413, 435.8 kJ/mole respectively.
Standard Heat of sublimation of graphite is 718.3 kJ/mole.
SOLUTION :
Calculate  f H Θ of isoprene from its heat of combustion (This will give the value for the actual isoprene
existing in nature).
5C (s) + 4H2 (g) 
 C5H8 (g) ; f HΘ = ?
1. C5H8 (g) + 7 O2 (g) 

 5 CO2 (g) + 4 H2O () ;  r H1Θ = 3186 kJ/mole
2. C(s) + O2 (g) 
 CO2 (g) ; rHΘ
2 = 393.5 kJ/mole
3. H2 (g) + 1/2 O2 (g)  H2O ()

 ;  r H 3Θ = 285.83 kJ/mole
Now operating 5(2) + 4(3)  1 to get the equation of heat of formation.
From Hess’s Law we have :
 f H Θ = 5 r H Θ Θ Θ
2  4  r H 3   r H1
  f H Θ = 5(393.5) + 4(285.83)  (3186)  (  f H Θ ) actual = 75.18 kJ / mole
 H 2C  C  HC  CH 2 
Now calculate heat of formation using the bond energies and structure of isoprene.  | 
 CH 3 
Note : Data calculations from the bond energy concept is always theoretical.
1. Bond Breaking : (H1)

5 [ C(s) 
 C(g) ; +718.3 ]
4 [ H2 (g)  2H ; +435.8 ]

 H1 = 5 × 718.3 + 4 × 435.8
= + 5334.7 kJ
2. Bond Formation : (H2)
8[ C + H 
 C  H ; 413 ]
2[ C + C 
 C  C ; 348 ]
2[ C + C   C = C ; 615 ]
 H2 = (8 × 413 + 2 × 348 + 2 × 615)
= 5230 kJ

From Hess’s Law : (  f H Θ )Theoretical = H1 + H2
(  f H Θ )Theoretical = 5334.7 + (5230) = 104.7 kJ
 Resonance Energy = 75.18  104.7 = 29.52 kJ

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes The Solid State
The Solid State
BASICS Section - 1
1.1 Introduction :
A matter is said to be solid when its constituent particles (atoms, molecules, or ions) are closely packed. A
solid is also defined as that form of matter which possesses rigidity and hence possesses a definite shape and
a definite volume. Unlike gases and liquids, whose fluidity is determined by the relative free motion of their
molecules, in solids, on the contrary, molecules or atoms or ions are not free to move but can oscillate
around their fixed positions due to strong inetermolecular or inter-atomic or inter-ionic forces. This confers
rigidity and long range order in solids.
1.2 Characteristics of Solids :

Some of the common properties of solids, which distinguish them from other two states of matter, are :
 Solids are rigid and have definite shapes.
 Solids have definite volume irrespective of the size or shape of the container in which they are placed.
 Solids are almost incompressible, having compressibility, which is approximately 106 times more than
gases.
 Many solids have a crystalline appearance and have definite pattern of angles and planes.
 Solids diffuse very slowly as compared to liquids and gases. Constituent particles are very closely
packed in solids permitting very little space for their movement.
 Solids have a much higher density (mass to volume ratio) than that of gases and liquids.
 Most solids become liquids when heated. Some undergo sublimation on heating. The temperature at
which a solid change into liquid is called the melting point and the process is called as melting. Due to
the varying natures of solids their melting temperature vary considerably.
1.3 Classification of Solids :

The properties that different solids have suggest that the behavior of the solids not only depend upon the
nature of the constituents, but also on their arrangement.
On the basis of the arrangement of their atoms or ions or molecules, solids are broadly classified into two
group :
1. Crystalline Solids
The substances whose constituents are arranged in definite orderly arrangement are called crystalline
solids. Many naturally occurring solid substances occur in the crystalline form. Some common examples
of crystalline solids are sodium chloride, diamond, sugar, etc.

The Solid State Vidyamandir Classes
2. Amorphous Solids
An amorphous solid is a substance whose constituent particles do not possess a regular orderly arrangement
e.g. glass, plastics, rubber, starch, and proteins. Though amorphous solids do not possess long range regularity,
in some cases they may possess small regions of orderly arrangement. These crystalline parts of an otherwise
amorphous solid are known as crystallites.
An amorphous solid does not posses a sharp melting point. It undergoes liquefication over a broad range of
temperature. When an amorphous solid is cut with the help of sharp edged knife, it results in an irregular cut.
Amorphous substances are also, sometimes, referred to as super cooled liquids because they possess
disorderly arrangement like liquids. In fact many amorphous solids such as glass are capable flowing. Care-
ful examination of the window panes of very old houses reveals that the panes are thicker at the bottom than
at the top because the glass has flown under constant influence of gravity
Comparative Study of crystalline and Amorphous Solids
Properties Cyrstalline solids Amorphous solids

The internal arrangement of particles is The internal arrangement of particles is
Crystal geometry
regular so they possess definite and regular ge- irregular. Thus they do not have any definite
ometry. They have long range order. geometry. They have short range order.
Melting Point They have sharp melting points. They do not have sharp melting points.
There is no regularity in the external form

There is regularity in the external form when crys- when amorphous solids are formed.
External form tals are formed. Crystalline solids give a regular Amorphous solids give irregular cut.
cut when cut with a sharp - edge knife.
Heat of Fusion They have characteristic heat of fusion. They do not have characteristic heat of
fusion.
Physical state Crystalline solids are hard and rigid and their Amorphous solid are comparatively soft and
shape is not distroted by mild distorting forces. not very rigid. These can be distorted by
bending or compressing forces.
Crystalline solids are anisotropic. This implies Amorphous solids are isotropic in nature.
Anisotropic or that physical properties such as refractive index This implies that various physical properties
(e.g. Canada Balsam), conductivity, thermal ex- are same in all the directions. This is because
Isotropic nature pansion etc are different in different directions. of random arrangement of particles.
This is due to orderly arrangement of particles
Example Crystals of NaCl, CsBr, CaF2 and ZnS Rubber, glass, plastic etc.

Note : Some substances adopt different structural arrangements under different conditions, Such
compounds are called as polymorphs. These different structures have different properties
such as melting point, density etc.
Example : Diamond and graphite are two different polymorphic forms of carbon.
1.4 Classificaion of Crystalline Solids :

On the basis of the nature of bonding, the crystalline solids have been classified into fourmain
categories viz., Covalent, Ionic, Metallic and Molecular solids.
Different Types of Solids
Type of Constituent Bonding/Attractive Examples Physical Electrical
Solid Particles Forces Nature Conductivity
Molecules Dispersion Dipole Argon, HCl

Molecular
interaction Hydrogen Soft Insulator
Bonding H 2O (Icc)
Paraffin wax
Metallic Positive metal Positive ions and Ductile

Conductor
ions (kernels) electrons (delocalized Ag, Cu, Mg & Malleable
and mobile electrons)
electrons
Hard Insulator
Covalent Atoms Covalent Bonding SiO2 , SiC
(Electron sharing) Diamond
Ionic Ions Conductor
Columbic or Hard &
NaCl, MgO (in molten & in
Electrostatic Forces Brittle
KCl, BaCl2 aqueous solution)

X-RAY STUDY OF CRYSTALS Section - 2
*2.1 X-Ray Diffraction :

X-ray diffraction (XRD) is a versatile, non-destructive technique that reveals detailed information about the
chemical composition and crystallographic structure of natural and manufactured materials.
It was suggested by M. Von Laue, in 1913, that it might be possible to diffract X-rays by means of crystals.
The reason for the suggestion was that the wavelength of X-rays was of about the same order (108 cm)
as the inter-atomic distances in a crystal. In fact, Bragg succeeded in diffracting X-ray from Sodium chloride
crystals. This observation has proved to be highly useful in determining structure and dimensions of crystals
as well as in the study of number of properties of X-rays themselves.
For example, experiments (X-ray diffraction method) show

that in a crystal of sodium chloride, the constituent Na+
and Cl- ions are present at alternate sites as shown :
Though shown in two dimensions this systematic long-range order is also found in three dimensions, with
each Na+ surrounded by six Cl- ions and vice versa. This order is due to strong coulombic forces of
attraction between Na+ and Cl- ions. Similar regular arrangements are found in other solids too.
In a crystalline solid, the constituent particles (atoms, ions or molecules) arranged in a regular order. An
interaction of a particular crystalline solid with X-rays helps in investigating its actual structure.
Crystals are found to act as diffraction gratings for X-ray and this indicates that the constituent particles in
the crystals are arranged in planes at close distances in repeating patterns.

A simple representation of the X-ray diffraction is shown as follows :
*2.2 The Bragg’s Equation :

W.H. Bragg pointed out that scattering of X-rays by crystals could be considered as reflection fromsuccessive
planes of atoms in the crystals.
The process was based upon the principle that a crystal may considered to be made up of a number of
parallel equidistant atomic planes, as represented by line AB, CD and EF in the adjacent figure.
Suppose two waves (Y and Z) of X-ray beams, which are in phase fall on the surface of the crystal. If the
ray Y get reflected from the first layer i.e., AB line and the ray Z is reflected from the second layer of atoms
i.e., CD line, then it is evident that as compared to the ray Y, ray Z has to travel a longer distance, equal to
QRS in order to emerge out of the crystal. If the waves Y and Z are in-phase (for intensity of the reflected
beam to be maximum) after reflection, the difference in distance travelled by the two ray must be equal to an
integral multiple of wavelength i.e., n  (for constructive interference).
Thus,
Distance QRS  n . . . . (i)
It is obvious from the figure that QR = RS = PR sin θ

Therefore QRS = 2 PR sin  . . . . (ii)

If the distance between the successive atomic planes is d
Then PR = d . . . . (iii)
So, from equations (i), (ii) and (iii) we have, n  2d sin θ

This is the Bragg’s Equation.
Thus, Bragg gave a mathematical equation to establish a relationship between wave length of the incident
X-ray, the distance between the layers and the angle of diffraction.
Here,   wavelength of X-ray used.
θ = Angle between incident X-ray and plane of the crystal. The diffracted beam makes an angle 2θ.
d = Distance between planes of the constituent particles in a crystal.
n = An integer (1, 2, 3, 4, etc.) which represents the serial order of diffracted beams.
For a given set of lattice planes, d has a fixed value. Therefore, the possibility of getting maximum reflection
(i.e., the possibility of getting reflected waves in phase with one another) depends upon θ. If θ is increased
gradually, a number of positions will be found at which the reflections will be maximum. At these positions,
n will have values equal to 1, 2, 3, 4, 5 etc. Generally, in experiments on X-ray reflections, n is set equal to
1. If  is known, it is possible to determine d, the distance between atomic planes in the crystal by determining
θ experimentally. Similarly, if interplanar distance are given, the corresponding wavelengths of the incident
beam of X-ray can be calculated.
Illustration - 1 A sample of a crystalline solid scatters a beam of X-rays of wavelength 70.93 pm at an

angle 2θ of 14.66. If this is a second order reflection (n = 2), calculate the distance between the parallel
planes of atoms from which the scattered beam appears to have been reflected. Use : sin 7.33  0.1276 
SOLUTION :
We knonw that : nλ = 2d sin θ
2θ = 14.66° or θ = 7.33°
λ = 70.93 pm = 70.93 × 1012 m
nλ 2 × 70.93 × 1012
Therefore, d= = m = 556.3 × 1012 = 556.3 pm
2sin θ 2sin 7.33°

Vidyamandir Classes
LATTICE & UNIT CELL Section - 3
Before discussing the periodic patterns of atomic arrangements in crystals, we need to look into arrangements
of points in space in periodically repeating patterns. This leads us to the concept of a space lattice. A space
lattice provides the framework with reference to which a crystal structure can be described.
3.1 Definition (Lattice) :

It is the periodic arrangement of the points such that the environment at any point is the same as at any other
point. Every point in lattice should have same surroundings.
As an example, consider a two-dimensional square array of points shown in figure. By repeated translation
of the two vectors a and b on the plane of the paper, we can generate the square array. The magnitudes of
a and b are equal and can be taken to be unity. The angle between them is 90 ; a and b are called the
fundamental translation vectors that generate the square array. To ignore end effects near the boundary,
we will assume that the array can be extended infinitely. If we locate ourselves at any point in the array and
look out in a particular direction that lies on the plane of the paper, the scenery is the same, irrespective of
where we are.
Consider the immediate surroundings of a point in the array. If we look due north or due east from this point,
we see another point at a distance of 1 unit. Along northeast, we see the nearest point at a distance 2 units
and long north-northeast, the nearest point is at a distance of 5 units. As this is true of every point in the
array, the array satisfies the definition given above and can be called a two-dimensional square lattice.

The main features of a Lattice :

(i) Lattice should be infinite.
(ii) Each point in a lattice is called lattice point.
(iii) Lattice points are joined by straight lines to represent the geometry of Lattice.
(iv) Lattice is different from a crystal. Infact, a Lattice gives to rise to a crystal when points are replaced by
particles such as atoms, ion or molecules.
Note : We can have square lattice, hexagonal lattice but pentagonal lattice is not possible because the interior
angle of a regular pentagon is 108o Which is not an integral factor of 360o.
3.2 Space Lattice or 3 –D Lattice :

An array of lattice points showing arrangement of constituent particles in different positions in three dimensional
space is known as space lattice of crystal lattice. i.e. the constituent particles of a crystalline solid are
arranged in a definite fashion in the three dimensional space. Mathematically, a three-dimensional space
lattice is generated by repeated transalation of three noncoplanar vectors a, b and c.
One such arrangement by representing the particles with points is shown below :
From the complete space lattice, it is possible to select a smallest three dimensional portion which repeats
itself in different directions to generate the complete space lattice. This is called a Unit Cell. In the above
example of the square lattice, the unit cell is the square obtained by joining four neighbouring lattice points,
as shown in figure on last page. Since every corner of this square is common to four unit cell meeting at that
corner, the effective number of lattice points in the unit cell is only one. Alternatively, the unit cell can be
visualized with one lattice point at the centre of the square and with none at the corners (see figure on
previous page)

3.3 Unit cell

The smallest three-dimensional portion of a complete space lattice, which when repeated over and again in
different direction produces the complete space lattice.
The size and shape of a unit cell is determined by the lengths of the edges of the unit cell (a, b and c) and by
the angles ,  and  between the edges b and c, c and a, and a and b respectively..
It we take into consideration, the symmetry of the axial distances (a, b, c) and also the axial angles between
the edges (,  and  ), the various crystals can be divided into seven crystal systems. These are also called
crystal habits.
3.4 Difference between Crystal and Lattice :

A space lattice is combined with basis/motif to generate a crystal structure.
Space lattice + Basis 

 Crystal Structure
The regular pattern of wagons below can be described by placing a lattice point at the same place in each
wagon. The arrangement of dots is the lattice, which has a given repeat distance. The motif is the wagon.
The pattern is recovered by stamping the motif on each lattice point.
The motif/basic can be single atom or groups of atoms. But in many elemental crystals, the basis is simple
and consists of one atom per lattice point. In such cases, the crystal is generated by just positioning one
atom of the element at each lattice point. For example, the crystal structure of chromium and copper are
generated as :
BCC space lattice + 1 Cr atom per lattice point 

 BCC crystal of Cr
FCC space lattice + 1 Cu atom per lattice point 

 FCC crystal of Cu
These crystals are called monoatomic crystals, to denote the fact that the basis is one atom per lattice
point. ABCC crystal means a monoatomic BCC crystal, unless otherwise stated.

In principle, an infinite number of crystal structure can be generated by combing different bases and different
lattice parameters with the same space lattice. In figure, three different base are combined with the simple
cubic lattice. In figure (a), the crystal is monoatomic, with just one atom at each lattice point. For clarity,
neighbouring atoms are shown separately. Figure (b) illustrates a molecular crystal, with a diatomic molecule
at each lattice point. The centre of the larger atom of the molecule coincides with a lattice point, while the
smaller atom is not at a lattice point. In molecular crystals, the basis is fully defined by giving the number and
types of atoms, the internuclear distance of separation between neighbours molecule and the orientation of
the molecule in relation to the unit cell. In figure (c), the corner atoms of the cube are of one type, but the
atom at the body centre is of different type. The basis is two atoms, the larger one in this case at a lattice
point and the smaller one positioned half-way along the body diagonal, at the body centre, which is not a
lattic point. In the crystal, of course, the unit cell can be shifted such that the body centre becomes a lattice
point and the body corners are no longer lattice points. This crystal should not be confused with monoatomic
BCC crystal, where the body corner and the body centre atom are of the same type.

Illustration - 2 Draw two dimensional Hexagonal Lattice. Try to visualize the possibility of pentagonal
two dimensional lattice.
SOLUTION :
Three regular hexagons intersect at one point. So, in this tow-dimensional lattice, this lattice point is shared
by three unit cells.
1
So, effective no. of lattice points per unit cell  6     1  1  3
 3
A regular pentagon has an interior angle of 108o. As 360o is not an integral multiple of 108o, pentagons
cannot be made to meet at a point bearing a constant angle to one another. Hence, a pentagonal lattice is not
possible. On the other hand, a square or a hexagonal two-dimensional lattice is possible as their internal
angles add up to give 360o.
Note : You are advised to read this section again after Section – 5 and then proceed further.

TYPES OF SYMMETRY IN CRYSTALS Section - 4

4.1 Definition
Crystals possess a regular, repetitive internal structure. The concept of symmetry describes the repetition of
structural features. Crystals therefore possess symmetry, and crystallography is basically concerned with
describing different types of symmetry. Broadly, two general types of symmetry exist. These consist of
translational symmetry and point symmetry. Translational symmetry describes the periodic repetition of a
structural feature across a length or through an area or volume. The concept of a lattice is directly related to
the idea of a translational symmetry. Point symmetry, on the other hand describes the periodic repetition of
a structural feature around a point. Reflection, rotation, and iversion are all point symmetries.
These are explained in detail as below :
(a) Reflection/plane of symmetry :

A reflection occurs when a motif on one side of a plane passing through the center of crystal is the mirror
image of a motif which appears on the other side of the plane. The motif is said to be reflected across the
mirror plane which divides the crystal. In other terms, it is an imaginary plane which passes through the
centre of crystal and divides it into two equal portions such that one part is exactly the mirror image of the
other. A cubic crystal like NaCl possesses, in all, nine planes of symmetry: three rectangular planes of
symmetry and six diagonal planes of symmetry.

(b) Rotational symmetry/ Axis of symmetry :

It arises when a structural element is rotated a fixed number of degrees about a central axis before it is
repeated. In other terms, it is an imaginary straight line about which, if the crystal is rotated, it will present the
same appearance more than once during the complete revolution.

The axes of symmetry are called diad, triad, tetrad and hexad, respectively, if the original appearance is
repeated twice (after an angle of 180o), Thirce (after an angle of 120o), four times (after an angle of 90o) and
six times (after an angle of 60o) in one rotation. These axes of symmetry are also called two-fold, three-fold,
four-fold and six-fold, respectively.
360
In general, if the same appearance of a crystal is repeated on rotating through an angle , of around an
n
imaginary axis, the axis is called an n-fold axis.

(c) Inversion symmetry/Centre of Symmetry :

If a crystal possesses inversion symmetry, then every line drawn
through the center of the crystal will connect two identical
features on opposite sides of the crystal. In other terms, it is
such an imaginary point within the crystal that any line drawn
through it intersects the surface of the crystal at equal distances
in both directions. A crystal always possesses only one centre
of symmetry.
4.2 Elements of symmetry :

The total number of planes, axes and centre of symmetry possessed by a crystal are termed as elements of
symmetry. A cubic crystal possesses a total of 23 elements of symmetry.
Planes of symmetry = (3 + 6) = 9
Axes of symmetry = (3 + 6 + 4) = 13
Centre of symmetry = 1
Total number of symmetry elements = 23
CRYSTAL SYSTEM AND BRAVAIS LATTICES Section - 5
On the basis of symmetry, viz., Translational, Rotational and Reflection, in total only fourteen 3-D lattices
are possible. These are called Bravais Lattices. These are categorized under 7 crystal systems. Before
going into their detail, lets take a look at the types of unit cells.
5.1 Types of Unit Cells :

Unit cells in which the particles are present only at the corners are called ‘Simple Unit Cells’ or ‘Primitive
Unit Cells’.
However it has been observed that the particles may be present not only at the corners but may also be
present at some other special positions with the unit cells. Such unit cells are called ‘Non-primitive Unit
Cells’ or Centred Unit Cells’.
There are different types of non - primitive unit cells as follows :
(a) Face centred unit cell

When the particles are present not only at the corner but also at the centre of each of the unit cell, is called
Face Centred Unit cell.

(b) Body centred unit cell

When in addition to the particles at the corner of the cube, there is one present at the body Centre position
of the unit cell, then the unit cell is called Body Centred Unit cell.
(b) End centred unit cell

Another type of unit cell, called End centered unit cell, is possible for orthorhombic and monoclinic crystal
types. In an end centered unit cell, there are lattice points in the face centers of only one set of opposite
faces, in addition to the lattice points at the corners of the unit cell.
It may be noted that all the four types of unit cells are not possible for each crystal system i.e., simple, face
centered, end centered and body centered.
A three-dimensional space lattice is generated by repeated translation of three non coplanar vectors a,b and
c. It so turns out that there are only 14 distinguishable ways of arranging points in three-dimensional space
such that each arrangement conforms to the definition of a space lattice. These 14 space lattices are known
as Bravais Lattices are according to the arrangement of the points in the different unit cells involved. They
belong to seven Crystal systems.
Crystal systme and their features with some examples



EFFECTIVE NUMBER OF ATOMS IN A UNIT CELL Section - 6
It can be determined by the simplest relation :

1. A point that lies at the corner of a unit cell is shared among eight unit cell and, therefore, only one-
eighth of each such point lies within the given unit cell.
2. A point along an edge is shared by four unit cells and only one-fourth of it lies within any one cell.

3. A face-centred point is shared by two unit cell and only one half of it is present in a given unit cell.
4. A body-centred point lies entirely within the unit cell and contributes one complete point to the cell.
ne n n n
Total number of atoms in unit cell = + f + i + e
8 2 1 4
When nc : Number of atom at the corners of the unit cell
nf : Number of atoms at six faces of the unit cell
ni : Number of atoms completely inside the unit cell
ne : Number of atoms at the edge centres of the unit cell
ATOMIC RADIUS & SHORTEST DISTANCE IN CUBIC SYSTEM Section - 7

7.1 Definition :
The atomic radius is defined as half the distance (centre to centre) between neighbouring atoms in a crystal.
It is expressed in terms of edge ‘a’ of the unit cell of the crystal.
7.2 Detailed View :

(a) Simple Cubic (SC)
1. Crystal System : Cubic
2. Lattice Points Occupied : Only all corners of cube are occupied and each corner atom is in
contact with adjacent corner atoms.

3. Arrangement of constituent particles in simple cubic.
Note : Neighbouring atoms are in contact with each other.
4. Top View of Unit Cell :
5. Relation between edge length of unit cell and radius of constituent particles.
Each corner atom is in contact with its adjacent corner atom such that
a
2R = a  R =
2
6. Rank of the unit cell (z) : Effective number of constituent particles per unit cell.
1 1
z = nc × = 8 × =1
8 8
7. Number of nearest neighbours or Co-ordination number.
(i) Number of nearest neighbours (NNs) :
It is number of neighbouring constituent
particles that are in close contact with
given constitueat particles.

(ii) Number of next nearest neighbours (NNNs)

It is neighbours at second shortest distance (NNNs = 12)
Four in every plane
NNs is at ‘a’ distance from ‘X’ (NNs = 3)
NNNs is at 2 a distance from ‘X’ (NNNs = 3)
NNNNs is at 3 a distance from X (NNNNs = 1)
In a simple cubic system for particle ‘X’
8. Packing Efficiency :
Packing efficiencey  volume occupied by all constituent

Volume of unit cell
For cubic unit cell
4 3 4 3 4
z× πr 1× πr 1 × πr3
Packing efficiency = 3 = 3 = 3 = 0.52
a3 a 3
 2r 3
(b) Face Centred Cubic (FCC)

1. Crystal system : Cubic
2. Lattic point occupied : Two types of lattice points are occupied and these are
(i) All corners (ii) All face centres

Note : FCC unit cell can be ideal FCC and pseudo FCC. In pseudo
FCC constituents at corner lattice points are different from
the face centre lattice points.
3. Arrangement of constituent particles in FCC unit cell.
4. Top view of unit cell
Note : Face centre constituent particle is in close contact with constituent particle at corners.
Face centre constituent of adjacent faces are in contact with each other.
5. Relation between radius of constituent particles and edge

length of unit cell
Closest contact is along face diagonal of cube. Each corner
of a particular face centre atom touches the face centre
atom such that :
a a
2R =  R= or 2a = 4R
2 2 2

a
Note : Each face centre touches other face centre atoms (at a distance of ) provided they are not the centres
2
of opposite faces.
6. Rank of the unit cell (z) : Effective number of constituent particles per unit cell.
1 1
Z= ×  No. of corner  + ×  No. of face centres 
8 2
1 1
= 8  6 1 3  4
8 2
7. Number of nearest neighbours (Co-ordination Number)
Consitituent particles at corners are nearest neighbours of the consitituent particle at face centre of the
FCC unit cell.
Horizontal plane showing NNs of particle under observation

Vertical plane showing NNs of particle under observation
Vertical plane showing NNs of particle under observation.
4 3 4
Z × πr 4 × πr3
8. Packing efficiency = 3 = 3 = 0.74
3 3
a  4r 
 
 2
Note : In single FCC unit cell there are total 14 constituent particles present at different lattice points.
2
(i) No. of nearest neighbours (NNs) at a distance from particles under observation are three.
2
(ii) No. of next nearest neighbor (NNNs) at a distance from particle under observation are three.
3
(iii) No. of next to next nearest neighbours (NNNNs) at a distance from particle under observation
2
are three.

Reference Atom/Constituent Particle is 1.
2a
 No of atoms at distance (NNs) are 3. [9, 10, 13]
2
 No. of atoms at distance a (NNNs) are 3 [2, 4, 5]
3
 No. of atoms at distance a (NNNNs) are 3 [11, 12, 14]
2
 No. of atom at distance 2 a are 3 [3, 6, 7]
 No. of atoms at distance 3 a is 1 [8]

Total No. of atoms for reference atom = 3 + 3 + 3 + 3 + 1 = 13
(c) Body Centred Cubic (BCC)

Each corner of the unit cell touches the body centre atom such
3 3
that 2R = a  R= a
2 4

VOIDS Section - 8
In close packing of spheres, there is always some empty space left. The empty space is called hole or void
or interstitial site. There are two main types of interstitial voids in closely packed structures :
(a) Tetrahedral voids (b) Octahedral voids
Tetrahedral void : When one sphere is placed upon the three other
spheres which are touching each other, tetrahedral structure results. The
name ‘tetrahedral void’ comes from the regular tetrahedron obtained by
joining the centres of four spheres. The four spheres leave a small space
between them which is smaller than the size spheres.
However, when the spheres are bigger in size, the
tetrahedral site becomes larger. In HCP and FCC, each
sphere is in contact with three spheres above and three
spheres below (see adjacent fig). Thus, there are two
tetrahedral sites associated with each sphere.
For example, in the FCC unit cell, the centres of the tetrahedral voids lie quarter - way and three - quarter
- way along the four nonparallel body diagonals of the cube (at a distance of 3a/4 form ever corner along
body diagonal). There are thus eight tetrahedral voids in the unit cell. As the effective number of atoms in the
unit cell is 4, this works out to a ratio 2 : 1 for the tetrahedral void to the atoms.
Figure show 8 Tetrahedral

voids per FCC unit cell :
Note : For HCP unit cell, refer to the Section - 10.
Octahedral void : An octahedral void is formed with three spheres on a close packed plane and three
more spheres on an adjacent close packed plane. Note that the three spheres of the adjacent plane are
positioned such that the centres of the three spheres are directly over the three triangular valleys surrounding
the central valley of the first plane, with no sphere over the central valley. The given figure is tilted view of the
octahedral arrangement, showing the square base with one sphere each on top and at the bottom.

The name comes from the regular octahedron (a polyhedron

with six corners and eight faces, the face being equal and
equilateral triangles) formed by joining the centres of the six
spheres. There is one octahedral void per sphere in the three
dimensional array.
For example, in the FCC unit cell, the centres of the octahedral voids fall at the body centre and the middle
1 
of the 12 cube edges. the effective number of octahedral voids per unit cell is then 1  1    12   4.
4 
As the effective number of atoms in the unit cell is 4, this work out to a ratio 1 : 1 for the octahedral void to
the atoms.
Figure shows 1 octahedral void at the body centre (with probability 1)

and 12 octahedral sites (with probability 1/4) are at edge centres in FCC unit cell.
(Note : Only required atoms are shown in figure)
Note : For HCP unit cell, refer to the Section – 10.
In general, if in a Close Packed crystal (CCP or HCP), there are N spheres (atoms or ions) in the packing,
then Number of Octahedral voids = N and Number Tetrahedral voids = 2N

Illustration - 3 A crystal is made of particles A and B. A forms FCC

packing and B occupies all the octahedral voids. If all the particles along
the plane as shown in figure are removed, then the formula of the crystal
would be :
(A) AB (B) A 5B 7 (C) A 7B 5 (D) None of these
SOLUTION : (A)
1 1 5
No. of A atoms Left  4    4     2  
8  2  2
corner
atoms   centerfaceatoms
1  5
No. of B atoms Left  4    2  1  1 
4  2
centeredgatoms centerbodyatoms
This simplest formula of crystal is AB
Illustration - 4 In a solid AB having rock salt structure, if all the atoms touching 1 body diagonal plane
are removed plane are removed (except at body centre), then the formula for the left unit cell is :
(A) A 7B 3 (B) A 5B 3 (C) A 5B 3 (D) A7/2B5/2
SOLUTION : (D)
‘B’ atoms are at corners and face centres

1  1  5
No. of B atoms left  4    4     2  
8  2  2
‘A’ are at edge centres and body centre
1  7
No. of ‘A’ atoms left  4    2  
4  2
The formula of the compound is : A7/ 2 B5/2
PQRS is the body diagonal plane

CO-ORDINATION NUMBER (C.N.) Section - 9
The number of atoms in a crystal which surrounds particular atom as its nearest neighbour atoms in its
neighbourhod is called co-ordination number.
Note : (i) For diatomic atoms, co-ordination no. of a cation is the no. of surrounding anions of vice – versa.
(ii) In crystals with directional bonds, co-ordination number is lower than that of crystals with non-directional
bond such as metals and ionic compounds.
The coordination no. of Monoatomic crystals is discussed below :

(A) Simple Cubic (SC)
No. of atoms surrounding the (touching) the body centre atom = 6
Hence, Co-ordination No. = 6
(B) Body Centred Cubic (BCC)

No. of atoms surrounding the (touching) the body centre atom = 8
Hence, Co-ordination No. = 8
(C) Face Centred Cubic (FCC)

No. of atoms surrounding (touching)
the face centre of any face = 12
Hence, co-ordination No. = 12.

PACKING OF CONSTITUENT PARTICLES IN CRYSTALS Section - 10

In the formation of crystals, the constituent particles, atoms or ions or molecules, may be different sizes and
so it may give different mode of packing of particles in the crystal. The actual mode of packing of the
particles in the crystal is determined experimentally by the X-ray diffraction method. However, in order to
understand the packing of the constituent particles in a crystal, it is assumed that these particles are hard
spheres of identical size. The packing of these spheres takes place in such a way that they occupy the
maximum available space and hence the crystal has maximum density. This type of packing is called closed
packing in crystals. The packing of spheres of equal size takes place as follows :
One Dimensional Packing :

When the spheres are placed in a horizontal row, touching each
other, an edge of the crystal is fromed.
Two dimensional Packing :

When the rows are combined touching each other, crystal plane is obtained. The rows can be combined in
two different ways :
(a) Square Packing : The particles when
placed in the adjacent row, show a
horizontal as well as vertical alignment
and form squares. This type of packing
is called Square Close Packing.
(b) Hexagonal Packing : The particles in every next row are placed in the depression between the
particles of the first row. The particles in the third row will be vertically aligned with those in the first
row. This type of packing gives a hexagonal pattern and is called Hexagonal Close Packing (HCP).
Note :(i) The second mode of packing (i.e., HCP) is more efficient as more space is occupied by the sphere in
this arrangement.
(ii) In Square Close Packing, a central sphere is in contact with four other spheres whereas in Hexagonal
Close Packing a central sphere is in contact with six other spheres.
Three Dimensional close packing :

In three dimension packing of spheres, the two dimensional close packed layers can be stacked in
two different arrangements :

(a) When the spheres of the second layer are placed on the spheres of the first layer and the spheres of
the third layer on the spheres of second layer and so on. In this form of packing, the spheres are
vertically aligned and the voids are also vertically overlapping. It results in an inefficient way of three
dimensional packing. This leads to simple cubic packing with a packing efficiency of 52% (It has been
discussed in section 14)
(b) When the second layer is placed in such a way that its spheres find place in the ‘a’ voids of the first
layer, then ‘b’ voids will be left unoccupied since under this arrangement no sphere can be placed in
them. Similarly there are two types of voids in the second layer. When both layers are considered
together, we have two type of voids marked as voids ‘c’ and voids ‘d’.
The voids ‘c’ are ordinary voids which lie
above the spheres of the first layer whereas
voids ‘d’ lie on the voids of the first layer and
hence are combination of two voids ; one of
the first layer and other of the second layer
with the vertex on one triangle upwards and
the vertex of the other triangle downwards
which leads to an octahedral void.
Figure shows the type of voids when two layers are considered
Now there are two way to build up the third layer :
(i) When a third layer is placed over to second layer in such a way that the spheres cover the tetrahedral
or ‘c’ voids, a three dimension closest packing is obtained where the spheres in every third of alternate
layer are vertically aligned (i.e., the third layer is directly above the first, the fourth above the second
layer and so on). Calling the first layer as layer A and second layer as layer B, the arrangement is
called ABAB………..pattern or Hexagonal Closed Packing (HCP). Molybdenum, Magnesium and
Beryllium crystallise in HCP structure.

Figure shows Hexagonal Closed Packing Figure shows ‘e’ is shared by sic unit cells
1  1 
Effective number of atoms per HCP unit cell    12     2   1  3  6
6  2 
Note : 11.51% of the total volume of the middle layer sphere extends
out of one side of the parallelepiped. Another 11.51% of
this sphere extends out of an adjacent face of the unit cell,
leaving 76.98% enclosed within the unit cell boundary. The
excluded portions are precisely matched by portions of two
other middle layer spheres extending from adjacent unit cells
into the first unit cell toward the center of the equilateral
triangle centered over the unoccupied hole in the bottom
layer [See figure (a) and (b)].
(ii) When the third layer is placed over the second layer in such a way that spheres cover the octahedral
of ‘d’ voids, a layer different from layers A and B is produced. Let us call it as layer C. Continuing
further a packing is obtained where the spheres in every fourth layer will be vertically aligned. This
pattern of stacking spheres is called ABCABC………..pattern or Cubic Close Packing (CCP). It is
similar to Face-Centred Cubic (FCC) packing.

Figure show ABCABC...........packing can be represnted in FCC unit cell
Note : In both HCP and CCP the coordination number is 12 because a sphere is in contact with 6 spheres in its
own layer. It touches three spheres in the layer above and three in the layer below.
Comparison of Various Type of Views of HCP & FCC Unit Cell :
Figure showing Comparison of Top view of unit cells

Figure showing comparison of Front view of unit cells
Illustration - 5 When over a 2 dimensional square packing same layers are kept in the way so that the
centres are aligned in all 3 dimensions, coordination number of each sphere is :
(A) 6 (B) 8 (C) 12 (D) 10
SOLUTION : (A)
The co-ordination number is 6. (“4 atoms” in the plane + 1 atom above + 1 atom below the particular atom).
Illustration - 6
In an FCC crystal, which of the following shaded
planes contains the given    type of arrangement of atoms ?
(A) (B) (C) (D)

SOLUTION : (A)

Illustration - 7 In hexagonal close packing of sphere in three dimensions.

(A) In one unit cell there are 12 octahedral voids and all are completely inside the unit cell
(B) In one unit cell there are six octahedral voids and all are completely inside the unit cell
(C) In one unit cell there are six octahedral void and of which three are completely inside the unit cell and
other three are from contributions of octahedral voids which are partially inside the unit cell
(D) In one unit cell there are 12 tetrahedral voids, all are completely inside the unit cell
SOLUTION : (B)
HCP  AB AB AB ………pattern repeat

For calculating voids between two layers A and B.
Total tetrahedral voids = 12 (represented by ' ' and ' ' ) out
of which 8 are completely inside  ' ' and  ' '  are shared by
other unit cells (each shared in 3 unit cells)
Total octahedral voids = 6 (represented by ' ' ). All are completely inside.
Illustration - 8
The co-ordination number of fcc structure for a metal in 12, since
(A) each atom touches 4 others in same layer, 2 in layer above and 6 in layer below
(B) each atom touches 4 others in same layer, 4 in layer above and 4 in layer below
(C) each atom touches 6 others in same layer, 5 in layer above and 1 in layer below
(D) each atom touches 8 others in same layer, 2 in layer above and 2 in layer below
SOLUTION : (B)

Illustration - 9 Which of the following statements is correct for a two-dimensional hexagonal close-packed
layer ?
(A) Each sphere is surrounded by six spheres (B) Each sphere is surrounded by six voids
(C) Each sphere has three voids (D) Each void is surrounded by three spheres
SOLUTION : (ABD)
(C) Effective number of atoms in a hexagonal unit
cell
1 
   6   1  1  3
3 
Effective no. of voids in a hexagonal unit cell = 6
Hence, each sphere has 2 voids
(A) Each sphere is surrounded by six spheres
(D) Each void is surrounded by 3 spheres
(B) Each sphere is surrounded by six voids
Illustration - 10 Calculate the c/a ratio for an ideally close packed HCP crystal.
SOLUTION :
The…ABA…type of stacking represents the HCP structure joining the centres of the three neighbouring atoms of
the middle plane to the centres of the atoms of the top and the bottom planes results in two tetrahedra with a
common base. The top and bottom atoms are centred at two lattice points, one above the other on the two
hexagonal basal planes of the unit cell. So, the distance between them is the unit distance along the c-axis. The
distance between any two adjacent atoms of a plane is unit distance along the a-axis. Unit of c is equal to twice the
normal from the apex of a tetrahedron to its base. Unit of a is equal to the side of the tetrahedron.
c 2PT
=
a RS
RU = RS2  SU 2 = a 2  a 2 /4 = 3a/2
2 a
RT = RU =
3 3
PT = PR 2  RT 2 = a 2  a 2 /3 = a 2 / 3
c 2 2
= = 1.633
a 3
Note : Your are advised to learn it as a result.

STACKING SEQUENCE Section - 11

11.1 Definition
It is the sequence in which closest packing
can exist. In stacking sequence, the same
layer can not repeat just after a layer i.e. A
after A is restricted.
If carefully observed, stacking sequence
has FCC, HCP and combination of FCC
and HCP such that all are closely packed
with packing efficiency of 74% (P.E. has
been discussed in Section – 14)
Illustration - 11
Tick the close – packing arrangements in the following :
(A) …… ABABABA …. (B) …… ABCABCABCA ….

(C) ….. ABABCBCABC ….. (D) …..ACCBCABCABC ….
SOLUTION : (ABC)
HCP, CCP and their combination (HCP + CCP) are the close – packed arrangement with packing efficiency
= 74%
IN-CHAPTER EXERCISE-B
1. Sapphire is aluminium oxide. It crystallises with aluminium ions in two-thirds of octahedral holes in
a closest packed array of oxide ions. What is the formula of aluminium oxide ?
NOW ATTEMPT IN-CHAPTER EXERCISE-B FOR REMAINING QUESTIONS

FAMILIES OF CRYSTALS Section - 12
These are discussed in detail as follows :

(i) Rock Salt (NaCl) type :
The chloride ions form a FCC lattice and sodium ions are present in octahedral voids i.e. at body centre and
edge centre of the chloride lattice.
Effective no. of Cl– per NaCl unit cell = 4 [Cl– being present at corners and face centres of the unit cell]
Effectie no. of Na+ per NaCl unit cell = 4 [Na+ being present in octahedral voids of the unit cell]

 Na   Cl
NaCl 
4 units 4 units 4 units
No. of NaCl formula units per FCC unit cell = 4
Figure shows the concept of reversibility in the case of NaCl crystal
Co-ordination no. of Na+ = 6 [Na+ is present in octahedral void formed by six Cl– ions]
Co-ordination no. of Cl– = 6 [Cl– is present is octahedral void formed by six Na+ ions
using reversibility principle]
(ii) Celsium chloride (CsCl) type :

The chloride ions form a SC lattice and cesium ions are present in the cubic void (or body centred
void)
Effective no. Cl– of ions per CsCl unit cell = 1 [Cl– being present at the corners of the unit cell]
Effective no. Cs+of ions per CsCl unit cell = 1 [Cs+ being present at the body centre of the unit
cell]
 Cs   Cl
CsCl 
No. of CsCl formula units per SC unit cell = 1

Co-ordination no. of Cs+ = 8 [Cs+ touches eight corner (Cl–) atoms of the unit
cell ]
Co-ordination no. of Cl– = 8 [Cl– touches eight corner (Cs+ ) atoms of the
unit cell using reversibility principle]

(iii) Zinc Blend (ZnS) type :

Lets first know about the structure of diamond. Diamond has FCC structure with four more carbon
atoms are found to be present in the alternate tetrahedral voids. So, effective no. of carbon atoms in
diamond cubic unit
1 1
8  6


1  4
 
8
8
cell   2  Alternate tetrahedral
FCC unit cell
The carbon atom in tetrahedral voids touches its 4 surrounding atoms (nearest neighbours), so the co-
ordination no. is 4.
Note : Carbon atoms in the FCC lattice do not touch at all (But carbon atoms which are present in the
tetrahedral voids touch the surrounding 4 atoms. So, centre to centre distance between two carbon
3a
atoms is 2r = where a is the length of the unit cell and r is the radius of the carbon atom.
4
Solids which follow the structure of diamond are called “Diamond cubic”
Zinc blende (ZnS) is a member of diamond cubic family where sulphide (S2–) ions form a FCC lattice
with zince (Zn2+) ions present in alternate tetrahedral voids i.e. 4 out of 8 tetrahedral voids are
unoccupied.
We have two tetrahedral voids per body diagonal out of which one is filled but in alternate fashion with
other boyd diagonls.

No. of S2– ions per ZnS unit cell = 4 [S2– being present at corners and face centres of the unit
cell]
No. of Zn2+ ions per ZnS unit cell = 4 [Zn2+ being present in 4 out of 8 tetrahedral voids of the
unit cell]
ZnS  Zn 2+  S2 
No. of ZnS formula units per FCC unit cell = 4
Co-ordination no. of Zn2+= 4 [Zn2+ is present in the tetrahedral void formed by 4S2- ions]
Co-ordination no. of S2-= 4 [One S2- supports 8 tetrahedrons out of which 4 are fillled with
Zn2+]
(iv) Fluorite (CaF2)

In the fluorite structure, calcium (Ca2+) ions form a FCC and Fluorite (F–) ions are present in all the
tetrahedral voids.
No. of Ca2+ ions per CaF2unit cell = 4 [Ca2+ being present at the corners and face
centres of the unit cell]
–
No. of F ions per CaF2 unit cell = 8 [F– being present in all 8 tetrahedral voids of the
unit cell]
 Ca   2F
CaF2 
No. of CaF2 formula units per FCC unit cell = 4

Co-ordination no. of F– = 4 [F– is present in the tetrahedral void formed by 4 Ca2+ ions]
Co-ordination no. of Ca2+ = 8 [One Ca2+ supports 8 tetrahedral voids and all are filled with F-]
(v) Antifluorite (Na2O) type : It is just opposite to the fluorite structure where role of cations and
anions is interchanged. So, oxide (O2–) ions form a FCC unit cell and sodium (Na+) ions are present
in all the tetrahedral voids
No. of oxide (O2–) ions per FCC unit cell = 4
No. of (Na+) sodium ions per FCC unit cell = 8
 2Na   O2 
Na 2O 
Co-ordination no. of Na+ = 4 Co-ordination no. of O2– = 8
Illustration - 12 a a a
Diamond has face-centred cubic lattice. There are two atoms at (0, 0, 0) and  , , 
4 4 4
coordinates. The ratio of the carbon-carbon bond distance to the edge of the unit cell is :
3 1 1 1
(A) (B) (C) (D)
16 4 4 2
SOLUTION : (A)
a a a
Distance between (0, 0, 0) and  , ,   2r
4 4 4
3a 2r 3
 2r    where 2r = bond distance
4 a 16

Illustration - 13 Which of the following statements is (are) correct for the diamond structure ?
(A) Each atom has 4 nearest neighbours and 12 next-nearest neighbours
(B) It is relatively empty
(C) The maximum proportion of the available volume which may be filled by hard spheres is only 0.34
(D) The maximum proportion of the available volume which may be filled by hard spheres is only 0.46
SOLUTION : (ABC)
Atom (carbon) lying in the tetrahedral voids touches the surrounding 4 atoms at a distance of 3a
4
a
And the face centre atom has 12 next nearest neighbours at a distance of
2
4 3
8  R
3 3a R 3
The packing efficiency (P.E.)  where 2R   
a3 4 a 8
32  3 3  3
Hence P.E. is :     0.34
3  8  64  16
Note : You will be able to understand P.E. in Section - 14.
RADIUS RATIO RULES Section - 13

Consider first the local packing geometry of one type of cation and one type of anion. The cation is assumed
to be the smaller ion. The number of anions surrounding a central cation is called the coordination number or
ligancy. The ligancy is function of the ion sizes and can be worked out from spaced filling geometrywhen the
following conditions corresponding to a stable configuration are satisfied simultaneously :
(a) An anion and a cation are assumed to be hard spheres always touching each other.
(b) Anions generally will not touch, but may be close enough to be in contact with one another in a limiting
situation.
(c) Cation should surround itself with as many anions as possible. Each ion tends to surround itself with as
many ions of opposite sign as possible to reduce the potential energy. This tendency promotes the
formation of close packed structures.
When the cation is very small compared to the anion, it is easily seen that only two anions can be neighbours
to the cation in order to satisfy all the above three conditions. Consider the configuration as shown in the
figure (i) below. Here, the three surrounding anions are touching one another and also the central cation.

The ratio of the cation to anion radius rc / ra for this configuration is 0.155, which can be worked out from
the simple geometry (see Illustration- 14). The triangular arrangement in (i) is one of the limiting situations.
The radius ratio is said to be a critical value because for value of rc / ra smaller than 0.155, the central
cation will rattle in the hole and not touch all the three anions at the same time, as illustrated in (ii). This
violates condion (a) above and leads to instability. When the radius ratio is less than 0.155, then only way to
satisfy all three conditions is to reduce the number of anions to 2. For values of rc / ra slightly greater than
0.155, all the anions touch the central cation but do not touch one another, as shown in (iii). All three
condtions of stability are still satisfied. This situation will prevail till the radius ration increases to 0.225, the
next higher critical value corresponding to tetrahedral (four) coordination. At rc / ra  0.225, the four
surrounding anions touch one another and also the central cation. This configuration is the same as that
obtained by fitting the largest possible sphere in the tetrahedral void of a close packed structure, (See
Illustration- 15).
A ligancy of five does not satisfy all the three conditions for stable configuration because it is always possible
to have six anions as an alternative to any arrangement that contains five anions, without a change in the
radius ratio. The critical condition for octahedral (six) coordination occurs at rc / ra  0.414, which is the
same as the size of the octahedral void in a close packed structure. Ligancies of 7, 9, 10 and 11 are again
not permissible.
The radius ratio ranges in which different values of ligancy are obtained are summarized in the given table. At
the end of the table, the limiting case of rc / ra  1 is identified with configurations of close packing of equal
sized spheres.

Illustration - 14 Find the critical radius ratio for triangular coordination.
SOLUTION :
The critical condition for triangular coordination is shown in the adjacent figure.
The three anions touch one another as well as the central
cation. From the simple geometry, we can write :
2
 R  r  cos 30  r  Rr  R
3
r 2
  1  0.155
R 3
Illustration - 15 Find the critical radius ratio for tetrahedral co-ordination.
SOLUTION :
The critical condition for tetrahedral co-ordination is shown in the adjacent figure. Than anions touch one
another as well as the central cation. From the simple geometry, we can write :
3 2
  2 R and h Rr where h  
4 3
3 2
   2R  R  r
4 3
r 3
  1  0.225
R 2
Note : The centre of tetrahedron is at distance of 3/4th of ‘h’ from the apex. Also, height of regular tetrahedron is
2 / 3 times is side of the tetrahedron.

Illustration - 16 Find the critical radius ratio for octahedral co-ordination.
SOLUTION :
The critical condition for octahedral co-ordination
is shown in the adjacent figure. The anions touch
one another as well as the central. From the simple
geometry, we can write :
 2r  2R  cos 45  2R
r
  2  1  0.414
R
Illustration - 17 Find the critical radius ratio for body-centered co-ordination.
SOLUTION :
The critical condition for cubic void shown in the
adjacent figure. The anions touch one another as well
as the central cation. From the simple geometry, we
can write :
a  2R and 3a  2R  2r
r
  3  1  0.732
R
The ligancy rules outlined above are obeyed in a number of cases. for example, in the NaCl crystal, the
radio r  / r   0.54, which lies between 0.414 and 0.732. As listed in the previous table, the predicated
Na Cl
ligancy is six. The octahedral geometry of six chlorine ions surrounding a central cation is experimentally
observed. In MgO, r /r  0.59 and again the octahedral coordination is observed. In CsCl,
Mg 2 O 2
r /r  0.73, it is difficult to predict whether a six – fold or an eight – fold coordination will occur. It
Cs  Cl 
so turns out that the eight coordination is observed. In this case, that is, every cesium cation is surrounded by
eight chlorine anions.
The Si – O bond in silica as well as in silicates is about 50% ionic and 50% covalent. Here, the central silicon
cation is surrounded by four oxygen anions located at the corners of a regular tetrahedron. This arrangement
satisfies both the ligancy rules (as rc / ra  0.29, then tetrahedral coordination is predicted from the previous
table, as well as the orientation relationships of (sp3) bonds).

The stability criteria listed above for predicting the ligancy may not always be valid. If directional characteristics
of bonding persist to any significant degree, the considerations based on the radius ratio alone will not lead
to the correct prediction of ligancy. In the above-discussed example of Si – O coordination, the radius ratio
criterion and the bond angle requirements happen to coincide. In ZnS, where the bond is more covalent than
ionic, the ligancy predicated from r /r  0.48 is octahedral. Yet the four-fold coordination
Zn 2 S2
characteristic of (sp3) bonding is what is observed.
In the formation of ionic crystals, the ligancy rules described above determine the local packing around a
cation. The long-range arrangement of ions in the crystal is dependent on the following factors :
(i) In the crystal, the overall electrical neutrality should be maintained, whatever be the net charge on a
local group of a cation and surrounding anions. For example, in NaCl, where a cation is surround by
six anions, the net charge on (NaCl6) is five. Evidently, this has to be neutralized in the long range
arrangement.
(ii) The ionic bond being nondirectional, the ions are packed as closely as possible in the crystal, consistent
with the local coordination.
When the cation charge is not more than two or at best three and when the radius ratio is in the range 0.414-
0.732, the crystal structure can be described as a FCC or HCP packing of anions with the cations occupying
all or part of the octahedral voids in the structure. The fraction of octahedral voids that are filled depends on
the number of cations to anions in the chemical formula. Thus, for the rock salt (NaCl) structure, adopted by
hundreds of binary ionic compounds, r  / r   0.54, and the anion packing is FCC with all octahedral
Na Cl
voids filled with sodium cations. Recall that there is one octahedral void per sphere in a close packed array.
A unit cell of NaCl crystal is shown in fig. below, with the large chlorine ions occupying the corner and
facecentred cubic positions and the sodium ions in the octahedral voids. The octahedral positions are at the
body centre and the midpoints of the cube edges. Note that, unlike in the monoatomic FCC crystal, the
chlorine ions do not touch one another along the face diagonal. This is so because the radius ratio of 0.54 is
greater than the size of the octahedral void in a close pakced structure, which is 0.414. The FCC close
packing is ‘opened up’ here to the extent necessary to accommodate the sodium cations in the octahedral
voids.

As the FCC positions and the octahedral void centre are interchangeable like the body centre and the body
corners in the BCC cell, the NaCl structure can also be described as two interpenetrating monoatomic
FCC cells, one corresponding to the anions and the other to the cations. The sum of the their radii, rc / ra
r r  a / 2, where a is the lattice parameter..
Na  Cl 
When rc / ra is in the range 0.7312 – 1, the eight – fold coordination is observed. CsCl with
r r  0.91 is a typical example of this structure. The cesium ions are at the body centre and the
Cs  Cl
chlorine ions are at the body corners. The space lattice is simple cubic, with a basis of one cesium ion plus
one chlorine ion per lattice point.
As an example of an ionic crystal with more than two types of ions, consider the crystal structure of spinels.
Spinels are compounds with two different cations A2+ and B3+ and oxygen as the anion, with general
formula, AB2O4. Here, the oxygen anions form the FCC packing, For every four oxygen anions, there are
four octahedral sites and eight tetrahedral sites. Out of these twelve, only three are needed to fill the cations
of the above formula. In the normal spinel structure, the A cations are in the tetrahedral voids and the B
cations are in the octahedral voids. Alternatively, half of the B cations can occupy the tetrahedral voids while
the remaining half of the B cations and all the A cations are randomly distributed in octahedral voids, resulting
in the inverse spinel structure. In both normal and inverse spinels, only half of the octahedral sites and 1/8 of
the tetrahedral sites are filled.
Note : When B2O3  Fe 2O3 , we have a series of compound calls ferrites, where different cations can be present
in varying proportions. Ferrites have the inverse spinel structure.
PACKING EFFICIENCY Section - 14
volume occupied by atoms

Packing Fraction = volume of unit cell
volume occupied by atoms

Packing Efficiency   100
volume of unit cell
We will discuss it for monoatomic and diatomic cases separately.
(A) Monoatomic unit cells :

For monoatomic unit cells, packing efficiency is given as :

 No. of atoms per unit cell    volume of one atom 

Packing Efficiency   100
volume of unit cell
(i) Simple Cubic (SC) (ii) Body Centred cubic (BCC)
4 3 4 3
1  r  2  r
P.E.  3  100 P.E.  3  100
3 3
a a
3a
Where 2r = a [a  length of unit cell] Where 2r  [a  length of unit cell]
2
3 3
4 1  8  3 3
P.E.     100   100  52% P.E.     100   100  68%
3 2 6 3  4  8
(iii) Face centred Cubic (FCC) (iv) Diamond Cubic (DC)

4 3 4 3
4  r 8  r
P.E.  3  100 P.E.  3  100
3 3
a a
a 3a
where 2r  [a  length of unit cell] where 2r  [a  length of unit cell]
2 4
3 3
16  1   32  3  3
P.E.      100   100  74%     100   100  34%
3 2 2 3 2 3  8  16
(v) Hexagonal Crystal Closed Packed (HCP)
4 3
 6 
r
P.E.  3 100
3 2
6 a c
4
2 2
where c a and 2r  a [a  length of unit cell]
3

P.E.   100  74%
3 2

(B) Diatomic unit cells :

For diatomic unit cells, packing efficiency is given as :
  no. of atoms of each kind    volume of atom of each kind   100

P.E. 
volume of unit cell
(i) Rock Salt (NaCl) type :

4 3 4
4  r   4   r3 
If AB crystallizes in the same way as NaCl, then P.E.  3 A 3 B  100
3
a
such that 2rA   2rB  a [a  length of unit cell]
Note : If nothing is mentioned, we consider the limiting case i.e. anions-anions are also contact at the same
time when caton-anion contact is always present. So, we can always have cation-anion contact equation
but anion-anion contact equation is possible for limiting case only.
(ii) Cesium Chloride (CsCl) type :

4 3 4
1 r   1  r3 
If AB crystallizes in the same way as CsCl, then P.E.  3 A 3 B  100
3
a
Such that 2rA   2rB  3a [a  length of unit cell]
(iii) Zinc Blende (ZnS) type :

4 3 4
4 r   4  r3 
If AB crystallizes in the same way as ZnS, then P.E.  3 A 3 B  100
3
a
3a
Such that rA   rB  [a  length of unit cell]
4
(iv) fluorite structure type :

4 3 4
4 r   8  r3 
If AB2 crystallizes in the same way as CaF2 , then P.E.  3 A 3 B  100
3
a
3a
Such that rA   rB  [a  length of unit cell]
4

r
Note : Here radius ratio rules will changes. Now, r lies in 0.225 – 0.414 as anion lies in tetrahedral void.

(v) Anti-fluorite structure type :

4 3 4
8 r   4  r3 
If A 2 B crystallizes in the same way as Na 2O, P.E.  3 A 3 B  100
3
a
3a
Such that r  r   [a  length of unit cell]
A B 4
DENSITY Section - 15
It is defined as the ratio of mass of the unit cell and volume of unit cell.
mass of atoms present in unit cell
Density 
volume of unit cell
 No. of atoms    Molecular weight in a.m.u.  1.67  1027 kg

 [For monoatomic crystal]
volume of unit cell
In general,
  No.of atoms of each kind    Molecular weight of each kind in a.m.u. 1.67  10 27 kg
Density 
volume of unit cell
 No. of fomula units    Molecular weight of compound   1.67  1027 kg

or Density 
volume of unit cell
Illustration - 18 Al crystallises in cubic shape unit cell and with edge length 405pm and density 2.7g/cc.
Predict the type of crystal lattice.
SOLUTION :
 No.of atoms    Molecular weight  1.67  10 27 kg
Density 
volume of unit cell
3 3  n   27  1.67  1027
2.7  10 kg / m   n4
3
 4.05  10 
10
Hence, the possible crystal lattice is FCC.

Illustration - 19 CdO has NaCl structure with density 8.27 g/cc. If the ionic radius of

O 2  is 1.24 A, determine ionic radius of Cd 2  .
SOLUTION :
 No.of formula units    Molecular weight of compound  1.67  1027 kg

Density 
volume of unit cell
3 3  4   128.41  1.67  1027 

8.27  10 kg / m   a  4.70 A
3
a
We have,  Cd
2 r 2 r
O 2  a

 r  1.24  2.35  r  1.11A
Cd 2 Cd 2
DEFFECTS IN CRYSTALS Section - 16

According to third law of thermodynamics, it is only at 0 K that true crystals pass perfect order ofarrangement
of atoms in pure crystals. But with rise in temperature, some deviations from complete order take place.
Presence of impurities also adds to disorder.
“Any departure from perfectly ordered arrangement of atoms/ions in a crystal is called imperfection or
crystal defect”.
These imperfections modify the properties of the crystal and also sometimes impart new properties to the
solids.
There are two types of imperfections :
 Electronic imperfections  Atomic or point imperfections
16.1 Electronic Imperfections
At zero K (absolute zero), electrons in covalent or ionic crystals (e.g., Si or NaCl) occupy the lowest
energy level. Above zero K in pure silicon or germanium, electrons are released thermally from the covalent
bonds. This leads to the presence of free electrons and electron deficient bonds called holes, which are
responsible for intrinsic conduction. These free electrons and the holes is solids give rise to electronic
imperfections.
(a) Hole : The electron deficient bond formed by the release of an electron.
(b) Intrinsic conduction : Conduction which is cause in crystal due to heating, leading to the formation
of free electrons and holes. e.g., crystal of Si or Ge.
(c) n : Concentration of electrons (e) (d) p : Concentration of holes (h)

16.2 Atomic or Pont imperfections

The defects which arise due to the irregularity in the arrangement of atoms or ions are called point defects.
Point defects in crystal may be classified into the following three types :
 Stoichiometric defects  Non-stoichiometric defects  Impurity defects
16.2.1 Stoichiometric Defect

If imperfections in the crystal are such that the ratio between the anions and cations remain same as represented
by the molecular formula, the defect is called a stoichiometric defect.
There are three types of stoichiometric defects :
 Schottky defect  Frenkel defect  Interstitial defect
(a) Schottky defect
In ionic crystals of the type A  B , equal number of

anions and cations are missing from the lattice sites so that
electrical neutrality is maintained. This type of defect is called
Schottky defect
Types of compound exhibiting Schottky defect

This type of defect is shown by highly ionic compounds which have
 High coordination number  Cations and anions of similar size
Examples : KCl, NaCl, AgBr, KBr and CsCl.
Consequences of Schottky Defect

 As the number of ions decrease, volume is the same, so density decreases.
 Crystals with Schottky defect conduct electricity to a small extent. This is because if an ion
moves from it lattice site the occupy a ‘hole’, it creates a new ‘hole’. In this way, a hole moves
across the crystal which as a result moves the charge in the opposite direction.
 Du tot the presence of holes, the stability (or lattice energy) of the crystal decreases.

(b) Frenkel Defect

If an ion is missing from its lattice site (causing a vacancy or a hole
there) and it occupies an interstitial site so that electrical neutrality
as well as stoichiometry of the compound are maintained. This
type of defect is called Frenkel defect. Since the size of cation is
generally smaller it is more likely that cations occupy interstitial
sites.
Types of compounds exhibiting Frenkel defect
This type of defect is present in those compound which have
 Low co-ordination number  Large difference in size of anion and cation e.g., AgCl, AgBr,
AgI and ZnS
Consequences of Frenkel Defect

 Solids with this defect conduct electricity to a small extent  The density of the solid
is unchanged
 The dielectric constant of the crystal increases.
 Due to the presence of holes, the stability of the cryastal decreases.
Note 1 : (i) The above two defects are intrinsic defects, or thermodynamic defects.
(ii) AgBr is a compound in which both Schottky and Frenkel defects are found because AgBr is
highly ionic but there is a great difference in the size of Ag  and Br  .
Note 2 : (ii) The number (n) of Schottky defects present in an ionic crystal containing N ions at temperature T
 E 
is given by : n  N exp    where E is the energy required to create these ‘n’ Schottky
 2kT 
defects and
k is Boltzmann constant  R / N0  1.38  1023 JK 1
(ii) Similarly, if Ni is the number of interstitial sites in an ionic crystal having N ions, the number ‘n’ of
Frenkel defects is given by :
1
 N 2  E 
n    exp    where E is the energy required to create these ‘n’ Frenkel defects.
N
 i  2kT 
(iii) It may be noted that number of Schottky & Frenkel defects increases exponentially with increase
in temperature.

(iv) In NaCl, there are approximately 106 Schottky pairs per cm3 at room temperature. In 1 cm3 ,
there are about 1022 ions and therefore there is one Schottky defect per 1016 ions.
(c) Interstitial Defects

Atoms (or ions), with occupy normally vacant interstitial
positions in a crystal, are called interstitials. The important
factor in determining the formation interstitials is the size
of the atom (or ion), because they are accommodated
into the voids.
16.2.2 Non-stoichiometric Defects

If an imperfection causes the ratio of cations and anions to become different from that indicated by the
ideal chemical formula, the defect is called non-stoichiometric.
These defects result in either excess of the metal atoms or excess of the non-metal. These can occur
as follows :
 Metal excess  Metal deficiency  Impurity defects
(a) Metal excess

This may occur in either of the following two ways
(i) By anion vacancies
A negative ion may be missing from its lattice site, leaving a hole, which is occupied by an electron
thereby maintain an electrical balance. The trapped electrons are called F –centers or color
centers because they are responsible for imparting color to the crystal. The defect is similar to
schottky defect and is found in crystals having schottky defects.
Example : NaCl when heated in Na vapor atmosphere,

the excess Na atoms deposit on the surface. Now Cl
diffuse to the surface where they combine with the Na
atoms, which lose the electrons. The electrons diffuse into
the vacant sites created. The electrons absorb some energy
from the white light and re-emit the yellow color to NaCl
crystal. Excess of Li in Li in LiCl give a pink color. Excess
of K in KCl make it violet.

(i) By the presence of extra cations in the interstitial sites

Extra cations occupying interstitial sites with electrons
present in another interstitial site to maintain electric
neutrality causes metal excess. This defect is similar to
Frenkel defect and is formed in crystals having Frenkel
defects.
Example : If ZnO is heated, it loses oxygen and turns
yellow.
 Zn 2   1 O2  2e 
ZnO 
2
The excess Zn 2  ions thus formed get trapped into the vacant interstitial sites and the electrons
in the neighboring interstitial sites. It turns yellow when hot and white when cold.
Note : Crystals with either type of metal excess defect act as semiconductors.
(b) Metal deficiency

This defect occurs when metals shown variable valency.
It occurs due to the missing of a cation whith higher charge
(e.g., +2 instead of +1) in the adjacent site.
Example : Transition elements, FeO, FeS and NiO.
16.2.3 Impurity Defects

These defects arise when foreign atoms are present at the lattice site (in place of host atoms) or at the
vacant interstitial sites. The formation of former depends upon the electronic structure of the impurity
while that of the latter on the size of the impurity.
(a) Introducing impurity defect in covalent solids

Group 13 elements such as Ga and Al and group 15 elements such as P and As can enter the crystal
structure of group 14 element Ge of Si substitutionally.
The Group 15 elements have one excess valence electrons as compared to Group 14 elements (Si or
Ge). Therefore after forming four covalent bonds, one electrons remains in excess which gives rise to
electrical conduction.
Group 13 elements have one valence electron less compared to Group 14 elements leading to electron
deficient bond a hole. Such holes can move across the crystal giving rise to electrical conductivity.
Group 14 elements doped with group 15 elements are called n-type semiconductors, where the
symbol ‘n’ indicating negative charge which flows in them. Group 14 elements doped with group 13
elements are called p-type semiconductors, the symbol ‘p’ indicating positive hole movement.

(b) Introducing impurity defect in ionic solids

In case of ionic solids, the impurities are introduced by adding
impurity of ions. If the impurity ions are in a different oxidation
state from that of the host ions, vacancies are created.
Example : If molten NaCl, containing a little of SrCl2 as

impurity, is allowed to cool, in the crystals of NaCl formed, at
some lattice sites Na  ions are substituted of Sr 2  ion. For
ever Sr 2  thus introduced, two Na  ions are removed to
maintain electrical neutrality.
Illustration - 20 If all the atoms touching 1 face plane are removed in a solid A B having rock salt type
structure, then the formula of the left compound and defect brought by this removal respectively is :
(A) AB, Frenkel defect (B) A2B, Frenkel defect
(C) AB, Schottky defect (D) A2B, Schottky defect

SOLUTION :
1  1 
Atoms at the corners and face centre are ‘B’ type atoms No. of B atom left  4    4     1  3
8  2 
‘A’ atoms are present at body centre with probability (share) = 1 and at edge centres with probability (share)
1

4
1 
Hence no. of A atoms left after removal will be 4    4   3
4 
Hence 3 “A type” and 3 “B type” atoms left. So, the formula is AB.
Note : As atoms are completely removed. Hence it is schottky type of defects.

Illustration - 21 The addition of CaCl2 Crystal to a KCl crystal
(A) lowers the density of the KCl crystal (B) raises the density of the KCl crystal
(C) does not affect the denstiy fo the KCl crystal (D) increases the Frenckel defects of the KCl crystal
SOLUTION :
Once Ca 2  lets two K  leave the crystal to maintain the electrical neutrality of the compound.
The Mass of two K  is greater than the mass of C2, hence density decreases.
PROPERTIES OF SOLIDS Section - 17
Properties of the solids depend mainly upon their structure and composition. Three main properties are
discussed below :
17.1 Electrical properties

Electrical conductivity varies from 108 ohm 1 cm 1 in metals to 1012 ohm 1cm 1 in insulators. Based
on their conductivity. Solids can be divided into three categories :
(a) Conductors
Solids through which electricity can flow to a large extent are called conductors. Depending upon the
type of charge carriers, the conductors are further classified as metallic and electrolytic conductors. In
metallic conductors, electrons are the charge carriers. In electrolytic conductors, ions are the charge
carries. Therefore electrolytic conductors conduct only when there are mobile ions i.e., in molten
state. However in solid state they conduct electricity only to a small extent, which is due to the
presence of defects (hole, electrons etc). e.g. , NaCl, KCl.
(b) Insulators
The solids which almost do not allow the electricity to pass through them are called insulators. e.g.,
S,P.
(c) Semiconductors
The solids whose conductivity lives between metallic conductors and insulators are called
semiconductors. The electrical conductivity of semiconductors is due to the presence of impurities
and defects. Their conductivity increases with increase in temperature as the defects increase with the
increase in temperature.
The magnitude of the electrical conductivity strongly depends on the number of electrons available to
participate in the conductor process.

In metals, the atomic orbitals form molecular orbitals, which are so close in energy to each other as to
form a band. If conduction band is not completely full or it lies very close to a higher unoccupied band,
then electrons can flow easily under an electric field thereby showing conductivity.
In case of semiconductors, the energy gap between valence band and the conduction band is small
and hence some of the electrons may jump from valence band to conduction band and the result is
some conductivity.
In case of insulators, the difference of energy between valence band and conduction band is so
large that electron transition doesn’t take place. Hence, no conductivity is shown. The in-between
region is called Forbidden zone.
17.2 Magnetic Properties of Solids

The magnetic properties of materials are a consequence of
magnetic moments associated with individual electrons. The
magnetic moment of an electron is due to its orbital motion
and also due to its spin around its own axis.
A moving electron may be considered to be a small current
loop, generating a small magnetic field, which has a magnetic
moment along the axis of rotation and the magnetic moment
due to electron spin is directed along the spin axis.
The fundamental magnetic moment is the Bohr Magneton  m B  , which is equal to 9.27  1024 Am 2 .
For each electron in an atom, the spin magnetic moment is   B (depending on the two possibilities of the
spin). The contribution of the orbital magnetic movement is equal to mi  B where mi is the magnetic
quantum number of the electron. Materials can be classified depending on their response to externalmagnetic
field.
(a) Diamagnetic Materials : Substances which are weakly repelled by external magnetic fields. This
property is shown only by those substances which contain fully-filled orbitals i.e., no unpaired electrons
are present e.g, TiO 2 , NaCl.

(b) Paramagnetic Materials : Substances which are attracted by the magnetic field but lose their
magnetism in the absence of the magnetic field. This property is shown by those substances whose
atoms, ions or molecules contain unpaired electrons eg., O 2 , Cu 2 
*(c) Ferromagnetic Materials : Substance which show permanent magnetism

even when the magnetic field is removed e.g,. Fe, Ni. The spontaneous alignment
of magnetic moments due to unpaired electrons in the same direction gives
rise to ferromagnetism.
*(d) Anti-Ferromagnetic Substances : Anti-ferromagnetic substances are
expected to possess paramagnetism or ferromagnetism on the basis of unpaired
electrons present in them but actually they possess zero net magnetic moment.
This is because the alignment of dipole is in a compensatory way so as to give
a net zero dipole moment, then we get anti-ferromagnetic substances e.g.,
MnO
*(e) Ferrimagnetic Substances : Ferrimagnetic substance are expected to possess large magnetism on
the basis of the number of unpaired electrons present in them, but actually have small net magnetic
moment. This is because the moments are aligned in parallel and anti-parallel directions in unequal
number resulting in a net dipole moment. e.g., Fe3O 4
Note : Ferromagnetic, Antiferromagnetic and Ferrimagnetic solids transform to the paramagnetic state at some
temperature due to randomisation of spins. Ferrimagnetic Fe3O 4 become paramagnetic at 850 K. It is also
observed that Ferromagnetic substances have a characteristic temperature above which no ferromagnetism
is observed. This is known as Curie temperature.
*17.3 Dielectric Properties of Solids

Insulators do not conduct electricity
because the electrons present in
them are held tightly to the individual
atoms or ions and are not free to
move. However when electric field
is applied, polarization takes place
because the nucleus is attracted
towards cathode and electron cloud
towards anode.
Such polar crystals show the following electrical properties.
(a) Piezoelectricity :
When these crystals are subjected to mechanical stress, electricity is produced due to displacement of
ions. The electricity thus produced is called piezoelectricity and the crystals are called piezoelectric
crystals. But if an electric field is applied to these crystal, there will be atomic displacement causing
mechanical strain.

(b) Pyroelectricity :
Some polar crystals when heated produce a small current or pyroelectricity.
(c) Ferroelectricity :
In some piezoelectric crystals the dipoles are permanently lined up even in the absence of an electric
field. However, on applying electric field the direction of polarization changes. e.g., BaTiO3 , Sodium
potassium tartrate (Rochelle Salt).
Note : All ferroelectric solids are piezoelectric but the reverse in not true.
(d) Anti-Ferroelectricity :
If there is no net dipole moment it is said to be an antiferroelectric crystal. This is because the dipoles
are alternately arranged. e.g., Lead zirconate (PbZrO3).
(e) Superconductivity :
When the electrical resistance of materials becomes almost zero, the material becomes superconductor.
The temperature at which the material shows superconductivity is called transition temperature. e.g.,
YBa 2 Cu 3 O7 at 90K.
EFFECT OF TEMPERATURE AND PRESSURE ON THE CRYSTAL STRUCTURE Section - 18

A number of metals have more than one crystal from. Iron, for example, is BCC at room temperature and
changes over to the FCC form at 910C. At 1410C, iron again changes over to the BCC form. In general,
at higher temperatures, the BCC crystal structure is to be expected as it allows larger vibrational amplitudes
for atoms, thereby increasing the entropy and lowering the free energy of the crystal. This is believed to be
the reason for a number of alkali metals adopting the BCC from at room temperature.
At ordinary temperature and pressures, chlorides, bromides and iodides of lithium, sodium and rubidium
and some halides of silver possess the NaCl structure with 6:6 co-ordination. On application of high pressure,
they transform to the CsCl structure with 8:8 co-ordination. On the other hand, CsCl on heating transforms
to the NaCl structure with 6:6 co-ordination.
IN-CHAPTER EXERCISE-D
1. Calcium crystallizes in a Face Centred Cubic unit with a = 0.556 nm. Calculate the density if
(a) it contains 0.1% Frenkel defects. (b) it contains 0.1% Schottky defects.
2. Sapphite is aluminium oxide. It crystallises with aluminium ions in two-thirds of octahedral holes in a
closest packed array of oxide ions. What is the formula of aluminium oxide ?
NOW ATTEMPT IN-CHAPTER EXERCISE-D FOR REMAINING QUESTIONS
Example - 1 Spinel is an important class of oxides consisting of two types of metal ions with the oxide ions
arranged in CCP pattern. The normal spinel has 1/8 of the tetrahedral holes occupied by one type of metal
ion and 1/2 of the octahedral holes occupied by another type of metal ion. Such a spinel is formed by Zn2+,
Al3+ and O2– with Zn2+ in the tetrahedral holes. If CCP arrangement of oxide ions remains undistorted in the
presence of all the cations, find the formula of spinel and fraction of the packing fraction of crystal :
SOLUTION :
No. of O2– ions = 4 r 3 r 2
2+
Now Zn is present in one of the tetrahedral where Al  0.414 , Zn  0.225 and
r 2 r 2
voids and two Al3+ are present in two out of O O
four octahedral voids for the electrical neutrality 2a  4r
O2 
of the crystal.
[Limiting case as structure is not distorted]
So, the formula of spinel is : ZnAl2O4
Hence P.E. = 77%
4 4 4
2  r3 3 1  r 3 2  4  r 3 2
P.E.  3 Al 3 Zn 3 O
3
a
Example - 2 Assume an FCC unit cell cube (edge length a) with one of its
corners
at the origin of cartesian coordinates. Find :
(i) the coordinates of tetrahedral and octahedral voids nearest
and farthest to the origin.
(ii) find the distance between two succesive tetrahedral voids.
(iii) the distance between two successive octahedral voids.
SOLUTION :
(i) co-ordinates of tetrahedral void nearest to co-ordinates of octahedral void nearest to origin
origin
 a  a   a
  0, , 0  ;  , 0 , 0  ;  0, 0, 
a a a  2  2   2
 , , 
4 4 4 co-ordinates of octahedral void farthest to origin
co-ordinates of tetrahedral void farthest a a a
  , a , a  ;  a, , a  ;  a, a, 
to origin 2   2   2
 3a 3a 3a 
  , , 
 4 4 4 
(ii) Distance between two successive tetrahedral (iii) Distance between two successive octahedral
voids voids = Distance between body centre and any
a
 Distance between P  a , a , a  and edge centre of the FCC unit cell i.e.
4 4 4 2
 3a a a  a
Q  , ,  i.e.
 4 4 4 2
Example - 3 The number of Schottky defects (n) present in an ionic crystal containing N ions at tempera-
ture T is given by n = Ne–E/2KT, where E is the energy required to create ‘n’ Schottky defects and K is Boltzmann
constant. If the mole fraction of Schottky defect in NaCl crystal at 2900 K is X (Given : H of Schottky defect
= 2 eV and K = 1.38  10–23 JK–1 , e = 1.608 × 10–19 ), then calculate – ln (X).
SOLUTION :
The number of schottky defects (n) is given as Mole fraction of defect is given as :
n = Ne–E/2KT . . . . (i) n n
N NA N e E/ 2KT
No. of moles of ions = X  X
NA n N n e  E/ 2KT  1
 1
N NA NA N
 No. of moles of schottky defects = [Using (i)]
NA
19
Substitute the value of E = 2  1.608  10 J
to get : –nX ~ 4
Example - 4 Sulphide of cobalt metal has a cubic structure with four formula units per unit cell. If density

is 4.269g/cc and edge length of unit cell is 6.93A, determine mass of sulphur required to produce 1.5 kg of
this compound.
(Molecular weight of Co = 58.94 and S = 32 amu)
SOLUTION :
3 (4)  M  1.67  1027 kg The possible compound is Co2S3

4.269  10 
(6.93  1010 )3 [i.e. CoS + CoS2]
Molecular weight (M) = 212.69  2Co3 3S2  ;

Co 2S3  
L et compound be Cox Sy 1mole 3moles
 58.94x + 32y = 212.69 1.5 1.5

 103 moles 3   103 moles
213.89 213.89
Hence mass of sulphur required = 0.673 kg
Example - 5 FeO crystallizes in NaCl type of crystal lattice. The crystals however are always non-sto-
ichiometric and deficient in iron. Some cationic sites are vacant and some contain Fe3+ ions but the combina-
tion is such that structure is electrically neutral. The formula approximates to Fe0.95O.
(i) What is the ratio of Fe2+ to Fe3+ ion in the solid ? (ii) What percentage of cation sites is vacant ?
SOLUTION :
(i) The compound is Fe0.95O  Fe95O100 Fe 2  85 17
Hence,  
Let compound has x% of Fe2+ and Fe3 10 2
(95 – x)% of Fe3+ such that
(ii) No. of Vacant sites = 100 – 95 = 5%
2x  3(95  x)  2  100  0  x = 85
[Structure is neutral]
Example - 6 What fraction of the Ca atoms lies on the surface of a cubic crystal that is 1.0cm in length,
if the radius of Ca atoms is 96pm and it crystallizes in Body Centered Cubic arrangement.
SOLUTION :
As Ca atoms crystallizes in body centred cubic, Surface area of one face of crystal = 10–4 m2
we have : Surface area of one face of unit cell = a2
4  96 No. of square faces visible at one face of crystal
3 a  4R  a  pm
3 104
=  2.03  1015
 a = 221.7 pm 10 2
(2.217  10 )
Volume of unit cell
No. of atoms = 1  2.03  1015
3 12 3 3
= a  (221.7  10 ) m  10.9  1030 m3
Volume of crystal = (10–2)3 = 10–6 m3
[ one atom per face of unit cell
106 1 
No. of unit cells =  9.17  1022   4  1 ]
10.9  1030 4 
 No. of atoms = 2  9.17  1022 2.03  1015

Ratio =  1.11  108
22
[ two atoms per unit cell] 2  9.17  10
Example - 7 Ar crystallizes in Face Centered Cubic arrangements and density of solid and liquid Ar is
1.59g/cc and 1.42g/cc respectively. Find the percentage of empty space in liquid Ar.
SOLUTION :
Density of solid Argon = 1.59 g/cc, 74 100
density of liquid Argon = 1.42 g/cc Volume of solid argon in crystal  cc
100 1.59
Let the solid argon crystal be 100 gm
Volume of liquid argon in crystal is given as :
100
Volume of argon crystal (solid ) cc x 100 74 100
1.59     x = 66.08 %
100 1.42 100 1.59
Empty space = 33.92 %
Note : You could also have simply solved using P.E. = constant
density
Example - 8 Cadmium oxide crystallizes in NaCl type of crystal lattice. The compound is however
usually non-stoichiometric with approximate formula CdO0.95. The defect arises as some cationic positions
are occupied by neutral Cd atoms instead of Cd 2+ ions and equivalent numbers of anionic sites are vacant.
(Molecular weight of Cd = 112.41 amu)
(i) What percentage of anionic sites is vacant ?
(ii) What is the density of non-stoichiometric solid : (a = 470 pm.) ?
(iii) If the edge length of the unit cell is 470 pm, what would be the density of the perfect solid ?
SOLUTION :
(i) % of anionic sites vacant = 5 %
95 4  [112.41  0.95  16]  1.67  10 27

(ii) No. of oxide ions =  4 Density  kg / m3  8.21 g / cc
100 3
 4.7  1010 
(4)  (128.41)  1.67  1027
(iii) Density = kg / m3  8.26 g / cc
(4.7  1010 )3
Example - 9 When heated above 916C, iron changes its crystal structure from Body Centred Cubic to
Cubic Closed Packed structure. Assuming that the metallic radius of the atom does not change, calculate the
ratio of density of the Body Centered Cubic crystal to that of the Cubic Closed Packing crystal.
SOLUTION :
2  M  1.67  1027
Density of iron in BCC  kg Also, 3a  4r
Volume of unit cell
2  M  1.67  1027
d BCC 
 3
 4r/ 3 
Density of iron in FCC
4  (Molecular weight)  1.67  1027 4  M  1.67  1027

 kg  d FCC 
3
Volume of unit cell  4r 
 
 2
d BCC 23 3
Also, 2a  4r   0.9185
d FCC 42 2
P.E.
Note : You could also have simply solved using = constant
density
Example - 10 The unit cell length of NaCl is observed to be 0.5627nm by X-ray diffraction studies. The
measured density of NaCl is 2.164 g/cc. Correlate the difference of observed and calculated density and
calculate the percentage of missing Na+ and Cl– ions.(Molecular weight of NaCl compound = 58.5 amu)
SOLUTION :
4  58.5  1.67  1027 d cal

d calc.  dobs  x
10 3
(5.627  10 ) 4
kg / m3  2.193g / cc 2.164
  4  x  x  3.947
dobs < dcalc implies some of the sites are vacant 2.193
Hence, missing sites = 4 – 3.947 = 0.053
x  58.5  1.67  1027
d obs  kg/m3 0.053
10 3 % of missing sites = 100  1.325%
(5.67  10 )
4
Example - 11 In an atomic Face Centered Cubic, all the lattice positions are occupied by A and the body
centred octahedral hole is appropriately occupied by B, without disturbing the Face Centered Cubic of A.
Calculate packing fraction of this solid.
SOLUTION :
No. of A atoms = 4, No. of B atoms = 1  3 3 3
4  
4rA  2  1 rA  
Hence packing fraction=  
4 4 
3
4 rA 1  rB3 3 3
Packing fraction = 3 3 
2 2 rA 
3
a
  3
2a  4rA and 2  rA  rB   a
12 2 
4  
2  1   0.75

rB
rA  rB  2 rA 
rA
  2 1 
Example - 12 A metallic element has simple cubic arrangement where edge length = 288 pm, density = 7.5
g cm–3 . Find the number of atoms in 100g of the metal.
SOLUTION :
(Number of atoms )  (Molecular weight)  1.67  1027 kg
d
Volume of unit cell
(1)  M  1.67  1027 kg

7.5  103 kg / cm3   M  107.28
(2.88  108 )3 cm3
g 100
No. of atoms =  6.023  1023   6.023  1023  5.6  1023
M 107.8
Example - 13 Find the concentration of cation vacancies in a lattice of NaCl which has been dopped with
–3
10 mole % of SrCl2 .
SOLUTION :
10–3 mole % of Sr Cl2 10–3 moles of Sr Cl2 in Note that for Sr2+ to occupy the place of Na+
100 moles of NaCl 10–5 moles are present in the crystal, it has to remove two Na+ leaving
in 1 mole of NaCl Hence 10–5 moles of Sr2+ onehole
are present [to balance the charge].
 Sr 2  2 Cl ]
[Use stoichiometry : SrCl2 
1mole 1mole 2moles = 10–5 × (6.023 × 1023) = 6.023 × 1018
No. of atoms = (No. of moles) 6.023  1023 So, no. of cation vacancies = no. of Sr2+ present.
No. of atoms in 10–5 Sr2+
Example - 14 The molar volume of KCl and NaCl are 37.46 mL and 27.94 mL respectively. Find the ratio
of the unit cube edges of the two crystals. (Assume both have same packing efficiency)
SOLUTION :
volume of 6.023 × 1023 formula units of KCl Similarly volume of unit cell of NaCl crystal
= 37.46 ml 100 27.94
   4 mL
volume of 4 formula units of x NA
37.46
KCl   4 ml
NA volume of unit cell |KCl a3 37.46
 KCl 
3
volume of unit cell |NaCl a NaCl 27.94
volume occupied by KCl formula units
x 1/3
  volume of unit cell a KCl  37.46 
100     1.113
a NaCl  27.94 
 volume of unit cell of KCl crystal
100 37.46
= x  N  4 mL
A
Example - 15 Calculate the void space in closest packing of n spheres of radius 1 unit, n spheres of radius
0.414 units and 2n spheres of radius 0.225 units.
SOLUTION :
It resembles face centered cubic situation : 2a  4 1  a2 2

n
Also, No. of unit cells =
4
n 4 3 4 3 4 3
Volume of atoms =  4   (1)  4   (0.414)  4  2   (0.225)   4.58n
4 3 3 3 
n 3
Volume of crystal =    a  4 2n
4
4.58 n
 Percentage of space occupied = 4 2 n  100  81 %
Hence, void space = 19 %

ANSWERS TO IN-CHAPTER EXERCISE

B 1. Al2O3
D 1. 1.554 g/cc, 1.55 g/cc
SOLUTIONS TO IN-CHAPTER EXERCISE - B

2
1. Two third of octahedral voids are occupied by aluminium implies aluminium proportion =  4 and no. of
3
oxide ions = 4.
So, the formula is Al8/3O4  Al2O3
SOLUTIONS TO IN-CHAPTER EXERCISE - D
1. (a) Frenkel defects do not change the density of the crystal.
4  40  1.67  1027 kg
Density   1.554g / cc
(5.56  1010 )3 m3
(b) Density
 0.1 
4  4   40  1.67  1027 kg
 100   1.55g / cc
= 3
 10  3
 5.56  10  m
 
70 Answers & Solutions Self Study Course for IITJEE with Online Support
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Self Study Course for IITJEE with Online Support Concept Map 71
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Solutions
Solutions
Theory of Solutions
BASICS Section - 1
A solution is defined as homogenous mixture of two or more substances (called as components), the
relative proportion or composition of which may vary between certain limits.
The component in small quantity is called as solute and the component in excess is called as solvent. A
solution consisting of two components is known as binary solution and of three components is known as
ternary solution.
The solutions may be gaseous, liquids and solids. The most common type of solution is liquid solution (gas
in liquid, liquid in liquid, solid in liquid). In all, we can divide solutions into nine different classes as
follows :
Types of Solutions Solute in Solvent Examples
Gas in Gas air, mixture of all gases
Gaseous Solutions Liquid in Gas water in air, bromine in chlorine, acetic acid in nitrogen
Solid in Gas Naphthalene in methane, iodine in air, camphor in air
Gas in Liquid CO2 in water, HCl in benzene
Liquid Solutions Liquid in Liquid Alcohols in water, bromine in CS2 or in CCl4
Solid in Liquid Sugar in water, iodine in CCl4, lead in mercury, NaCl

in water
Gas in Solid Hydrogen in palladium
Solid Solutions Liquid in Solid Mercury in Thallium
Solid in Solid Co in Ni, gold in silver, PbCl2 in PbBr2, all alloys
Note : In general, the physical state of a solution is the physical state of solvent.
There are various ways in which one can express the concentration of a solution. We have already learnt
about these in Stoichiometry - 1. These are Strength (g/L), Molarity (mol/L), Normality (gm-eq/L), mole
fraction, mass fraction and molality (mol/kg).

Solutions Vidyamandir Classes
1. Solubility of Gases
The solubility of a gas in a liquid is determined by several factors.
In addition to the nature of the gas and the liquid, solubility of the
gas depends on the temperature and pressure of the system. The
solubility of a gas in a liquid is governed by Henry’s Law which
states that the solubility of a gas in a liquid is directly propor-
tional to the pressure of the gas. Dalton, a contemporary of the
Henry, also concluded independently that the solubility of a gas in
a liquid solution is a function of the mole fraction of the gas in the
solution as a measure of its solubility, then :
Mole fraction of the gas in a solution is proportional to the partial pressure of the gas above the
solution.
P = KH  where KH is Henry’s law constant and is the mole fraction of the gas in the solution.
It is obvious that the higher the value of KH at a given pressure, the lower is the solubility of the gas in the
liquid. The KH value for both N2 and O2 increases with increase of temperature indicating that solubility of
gases decreases with increase of temperature. It is due to this reason that aquatic species are more comfort-
able in cold waters rather than warm waters. Dissolution of gas in liquid is accompanied by release of heat
i.e. the dissolution of gas is exothermic reaction.

The Henry’s law constant for the solubility of N2 gas in water at 298 K is 1.0  105 atm. The mole
fraction of N2 in air is 0.8. The number of moles of N2 from air dissolved in 10 moles of water at 298
K and 5 atm pessure is :
(A) 4.0  10–4 (B) 4.0  10–5 (C) 5.0  10–4 (D) 4.0  10–6
SOLUTION : (A)
As per Henry’s law :
p N2  K H ( N 2 )in solution
5
n N2 n N2
 ( N 2 )in solution  4  10  n N 2  n H 2O

nH2 O
Now, p N 2  pTotal  ( N 2 )in air  5  0.8  4 atm
 ( N 2 )in solution  4  105  n H 2O  4  104
 4  105  ( N 2 )in solution

2 Vapour Pressure of a Solution
Consider a pure liquid in a container covered with a lid. The molecules of liquids at the surface escape
(vapourisation) and fill the space available to them. After sometime, equilibrium is established between the

vapour and the liquid phases. The pressure exerted by the vapours in such a state (vapour  liquid) of
equilibrium is known as vapour pressure of a liquid.
Now if some solute (B) is added to such a solvent (A) to make a solution, two possibilities arises:
(i) If the solute is volatile (solid or liquid) (ii) If the solute is non-volatile (solid or liquid).
(i) When solute is volatile : The surface molecules of both solute and solvent escape (vapourise) and fill
the vacant space. The vapour phase now consists of vapours of solute (B) and vapours of solvent (A). At
vapour liquid equilibrium, the pressure exerted by the vapours of solute and solvent is known as vapour
pressure of the solution.
Raoult’s Law
The partial vapour pressure of a component in such type of solution is given by Raoult’s Law. It states that
the partial vapour pressure of each component in the solution is directly proportional to its mole fraction.
Let A and B be the mole fractions of solvent (A) and solute (B) molecules in the solution and PA and PB be
the partial vapour pressures of A and B respectively. Then according to Raoult’s Law :
PA  A and PB  B
From the results of various experiments, it has been observed that :
PA  PA0  A and PB  PB0  B where PA0 and PB0 are vapour pressures of pure A and B.
Now the total vapour pressure (PTotal) of the solution is given by Dalton’s Law of partial pressures as
follows :
PTotal = PA + PB  PTotal  PA0  A  PB0  B

For a solution of different compositions made from A and B, the plot of PA, PB against A and B is shown
as follows :
In the graph :
Two dotted lines 1 and 2 show variations in partial pressure with

increasing mole fraction and the solid line 3 gives the total vapour
pressure PTotal exerted by the solution as a whole at any composition.
P PA
Note :  A(Liquid phase)  A ,  V 
0 A  Vapour phase  PA  PB
PA

Note : The solutions which obey Raoult’s Law at all compositions of solute in solvent are called as Ideal Solutions.
The plot of partial pressure (P) vs mole fraction () of such solution is typical and in general like the graph
shown here.
Illustration - 1 At a certain temperature, the vapour pressure of pure ether is 646 mm and that of pure
acetone is 283 mm. Calculate the mole fraction of each compnent in the vapour state if the mole fraction of
ether in the solution is 0.50.
SOLUTION :
In the given solution, both ether and acetone PA PA0 A
are volatile, so from Raoult’s Law, we can have V
A  vapour 
 
PTotal PTotal
vapour pressure of solution (PTotal).
Let A : ether and B : acetone. 646  0.5
  0.695
464.5
PTotal  PA  PB  PA0  A  PB0  B
PB PB0 B
 PTotal  646  0.5  283  0.5 V
B vapour 
 
PTotal PTotal
 464.5 mm
283  0.5
Now mole fraction in vapour state is given as   0.305
464.5
follows :
(ii) W hen solut e is non-volat ile : In such a solution, the surface molecules of only solvent will escape and
contribute to the vapour phase i.e. there is no contribution from solute in the vapour phase. The vapour
pressure of such a solution is equal to the partial vapour pressure of solvent molecules (= PA).
PTotal  PA0  A  PB  PA0  A ( PB  0).

For binary solution : A + B = 1  A = 1  B
PA0  PA
  B
PA0
0
The expression PA  PA is called as Relative Lowering of Vapour Pressure for a solution usually
PA0
p
expressed as .
p0

Another form of Raoult’s Law can now be stated as :

Relative Lowering of vapour pressure for a solution containing non-volatile solute is equal to the
mole fraction of the solute.

4.375 g of a substance when dissolved in 36.0 g of water, lowered its vapour pressure by 0.5 mm at
a given temperature. The vapour pressure of water at this temperature is 25.0 mm. Calculate the
molecular weight of solute.
SOLUTION :
P = 0.5 mm, using the formula for lowering of vapour pressure :
P nB gB / MB
 B  
PA0 n A  n B gA / M A  gB / MB
0.5 4.375 / M B
   MB = 109.38 gm/mol
25 36 / 18  4.375 / M B
Illustration - 2 Assuming ideal behaviour, calculate the vapour pressure of 1.0 molal solution of a non-
volatile molecular solute in water at 50oC is 0.122 atm.
SOLUTION :
1000
0  A 
Psolution  PA  P A  A (Raoult’s Law) mMA  1000
By using the relation between molality and 1000 1000
 A    0.982
mole fraction, we have : 1  18  1000 1018
 B 1000 1   A 1000
m     Psolution  PA0A  0.122  0.982
A MA A MA
 0.120 atm
Illustration - 3 The vapour pressure of pure water 25oC is 23.76 torr. What is the paour pressure of 100
gm of water to which 100 gm of C6H12O6 (glucose) has been added ?
SOLUTION : 100
Psolution  PA  P 0 A  A  Psolution  23.76  18
100 100
gA 
18 180
nA MA
 Psoluion  PA0  PA0
n A  nB gA g  MGlucose 180 gm / mol;PA0  23.76 torr 
 B  
MA MB
 Psolution  21.6 torr

Illustration - 4 At 298 K, the vapour pressure of pure liquied n-butane is 1823 torr and vapour pressure of
pure liquid n-pentane is 521 torr and form nearly and ideal solution.
(a) Find the total vapour pressure at 298 K of a liquid sution containing 10% n-butane and 90% n-
pentane by weight.
(b) Find the mole fraction of n-butane in solution exerting a total vapour pressure of 760 torr.
(c) What is the composition of vaporus of two components (mole fraction in vapour state) ?
SOLUTION :
10 / 58
(a)  n  butane   0.122 (b) Let mole fraction of n-butane = y
10 / 58  90 / 72
 mole fraction of n-pentane  1  y
n  pentane  1  0.122  0.878
Using Raoult’s Law, we have:
From Raoult’s Law :
760  y 1823  1  y  521
PTotal  PA0  A  PB0  B
 y  0.183
PTotal  0.122  1823  0.878  521
(c) The mole fraction in vapour state :
 PTotal  679.84 torr
0.122  1823
 vn  butane   0.327
679.84
0.278  521
 nv  pentane   0.673
679.84
 vvapour is alos called as vapour fraction
3. Formation of Ideal Solutions :

When solute B is added to a solvent A, an ideal solution is formed if molecular interactions A-A and B-B are
same and there is no change in the type of molecular interaction when A and B are mixed to form a solution.
This means that in solution, A–B interactions are almost same as A-A and B-B interactions.
It has been observed that liquid pairs which are generally similar in size and structure form ideal solutions.
For example, bromo-ethane and chloro-ethane, n-hexane and n-heptane, benzene and toluene, CCl4and
SiCl4 form nearly an ideal solution.

Criteria for formation of Ideal Solutions :

 They must obey Raoult’s Law at all concentrations and at all temperatures.
 The heat of solution should be equal to zero, i.e., Hsolution = 0.
 There should be no change in the volume of solution on mixing, i.e., neither there is any contraction
nor there is any expansion or Vsolution = 0.
Like gases, most of the solutions deviate from ideal behaviour and are called as Non ideal solution or Real
Solutions.
Real solutions do not obey Raoult’s Law over entire range of composition. It is observed that by progres-
sive dilution, all solutions tend to reach a state where they behave ideally.
4. Formation of Non-ideal Solutions :

 Solutions which show higher experimental values of pressure
(PTotal) than those calculated from Raoult’s law are said to
show positive deviation from Raoult’s law e.g. solution of
cyclohexane and ethonal.
 Solutions which shown lower experimental values of
pressure (PTotal) than those calculated from Raoult’s law
are said to show negative deviation from Raoult’s law e.g.
solution of chloroform and acetone.
Note : The cause for these deviations lies in the nature of interactions at the molecular level. On mixing two dissimilar
substances, their molecular environment will change.
Suppose the two components that are mixed to form a non-ideal solution are A and B.
A positive deviation is exhibited when interaction between A – B is weaker than that between A – A and B
– B. This means that on mixing, molecules of A (or of B) will find it easier to escape than if these were as
pure components. This will cause an increase in the vapour pressure resulting in a positive deviation. Mol-
ecules of ethanol and acetone are hydrogen bonded. On adding acetone to pure ethanol, these molecules
get in between the host molecules (ethanol) breaking the hydrogen bonds of host molecules. This changes
the intermolecular interaction pattern and becomes the cause for ethanol and acetone solution to behave
non-ideally and show a positive deviation from Raoult’s law.
A mixture of chloroform and acetone forms a solution with negative deviation from Raoult’s law. This is
because chloroform molecules are able to form hydrogen bond with acetone molecules as shown below :
This decreases the escaping tendency of molecules for each component
and consequently, the vapour pressure decreases resulting in negative de-
viation from Raoult’s law.

Note :  Solutions showing positive deviations boil at relatively low temperature than calculated value as well
as have Vmixing = + ive and Hmixing = + ive. On the other hand, solutions showing negative
deviations boil at relatively high temperature than calculated value as well as have Vmixing = ive
and Hmixing = ive.
+ive : positive ; –ive : negative.
 Raoult’s law is also not valid when solute shows dissociation or association nature in given solvent.
Some examples of Ideal solutions are :

(i) n-Hexane and n-heptane (ii) Chlorobenzene and Bromo benzene
(iii) Ethyl Bromide and Ethyl Chloride (iv) CCl4 and SiCl4
(v) Ethyl Bromide and Ethyl Iodide (vi) Benzene and Toluene
Example of solutions showing positive deviation :
(i) Benzene and Ethyl alcohol (ii) CS2 and acetone
(iii) Chloroform and ethanol (iv) n-hexane and ethanol
(v) Benzene and acetone (vi) CCl4 and benzene
(vii) CCl4 and CHCl3 (viii) CCl4 and C6H5CH3
(ix) H2O and Methanol (x) H2O and Ethanol
Solutions showing negative deviation :
(i) Chloroform and Acetone (ii) Chloroform and Benzene
(iii) Chloroform and Diethyl ether (iv) Acetic acid and Pyridine
(v) H2O and HCl (vi) Acetone and Aniline
(vii) H2O and HNO3

5. Azeotropes
Some liquids on mixing form azeotropes which are binary
mixtures having same composition in liquid and vapour phase
and boil at a constant temperature. There are two types of
azeotropes called as minimum boiling azeotrope and
maximum boiling azeotrope, respectively. Solutions of ethanol
and water show such a large deviation from Raoult’s law that
there is a maximum in the vapour pressure curve and hence a
minimum in the boiling point diagram as shown in figure ()
There are also solutions that show large negative deviation from ideality and, therefore, have a minimum in
their vapour pressure curves. This leads to a maximum on the boiling point diagram. HNO3 (68%) and H2O
(32%) form examples of this class of the azeotrope.
Note : Components in a Azeotrope cannot be separated by distillation as they have same composition in liquid and
vapour phase, because when azeotrope is boiled, the resulting vapour has same ratio of constituents as
original mixture. Also called as constant boiling boiling mixture.
6. Vapour pressure of mixture of two immiscible volatile liquid :

When a volatile liquid is added to another volatile liquid, which are completely immiscible with each other,
each liquid will behave independent to the other and will exert its own vapour pressure. The more dense
liquid (A) will from lower layer and less dense liquid (B) will be forming upper layer. The total vapour
pressure of the system will be the sum of vapour pressure of both the volatile liquids.
 PTotal  PA  PB  PA  PB
The total vapour pressure of the system remain constant as long as both the volatile liquids are present and
will not depend on the relative amounts of the two liquids.
The boiling point of a liquid system is the temperature at which its vapour pressure becomes equal to the
external atmospheric pressure. Since the total vapour pressure of a mixture containing immiscible volatile
liquids is greater than that of either of the pure constituents, thus the mixture will boil at a temperature, which
is lower than the boiling point of either of the pure constituents. The boiling point of the liquid mixture will
remain constant as long as the two layers are present, as the total vapour pressure is independent of the
relative amounts of the two constituents.
Note : This forms the basis of steam distillation, in which one of the volatile liquids is water.
This composition of the vapour above the liquid mixture can be calculated using Dalton’s law of partial
pressures. Thus,
PA  PA  PTotal  A
' ... (i) and
PB  PB  PTotal 'B .... (ii)

' '
Where  A and  B represents the mole fraction of a A and B in the vapour phase. Let nAand nB are
the mole of A and B, respectively in the vapour phase.
Dividing equation in the (ii) by (i),
nB
'
PTotal  B PB 'B n  nB n PB WB  M A
   A  B or 
'
PTotal  A PA 'A nA nA PA M B  WA
n A  nB
WB P  M B
  B
WA PA  M A
Thus, the masses of the constituents in the vapour (distillate) will be proportional to their respective molar
mass and vapour pressure.
COLLIGATIVE PROPERTIES OF SOLUTIONS Section - 2
As we dilute a solution, its behaviour moves towards ideality. The properties of dilute solutions depend
solely on the number of particles of the solute dissolved in the solvent and have nothing to do with the
chemical behaviour of the solute. These properties in face depend upon the nature of solvent. In our discussion,
we will take solute to be non-volatile and non-associating or dissociating and solvent to be volatile.
The colligative properties that we are going to study are :
1. Relative Lowering of Vapour Pressure 2. Elevation in Boiling Point
3. Depression in Freezing Point 4. Osmotic Pressure
Note : Colligative properties are the properties of only dilute solutions because they are supposed to behave as
ideal solutions.
1. Relative Lowering of Vapour Pressure :

When a non-volatile solute (B) is dissolved in a liquid, the vapour pressure (PTotal) of the solution becomes
lower than the vapour pressure of pure solvent.
From Raoult’s Law : Vapour pressure of the solution is given by :
PTotal  PA (PA  partial vapour pressure of the solvent in solution)  PB  0

 PTotal  PA  P0A  A

where P0A = vapour pressure of pure A and  A  mole fraction of A.
For Binary Solution : A  B  1   A  1  B
P 0A  PA
 P  PA  P 0A 1   B    B
P 0A
P 0A  PA ΔP nB n
Relative Loweing of Vapour Pressure =   B or  B   B
P 0A P 0A n A  nB nA
For dil. soluition: n A  n B  n A
2. Elevation in Boiling Point :

The vapour pressure of a solution is lower than that of pure solvent
(on adding non-volatile solute). Now, the boiling point (BP) of a
liquid is the temperature at which its vapour pressure becomes equal
to 760 mm of Hg column (atmospheric pressure). Hence, the BP of
a solution will always be higher than that of the pure solvent.
Let Tb be the elevation in boiling point, then

Tb = T0b  Tb Tb : boiling point of solution ; T0b : boiling point of pure solvent
Kb : molar boiling point elevation constant or ebullioscopic constant of solvent
m: molality of the solution
From the definition of molality, we have :
 gB 
n  M 
ΔTb  K b  B  1000  OR ΔTb  K b  B  1000 
 gA   gA 
 
 

Note : According to Trouton’s rule, the ratio, of the molar heat of vaporization of a liquid to its normal boiling
point (in Kelvins) is approximately the same for all the liquids :
ΔH vap
 88 J / K / mol
Tb
Enthalpy change and entropy change in various phase change processes.
3. Depression in Freezing Point :

Freezing point is a temperature at which a solid and a liquid state of a substance have the same vapour
pressure. Since the vapour pressure of a solution is less than that of pure solvent, the freezing point of the
solution will be lower than that of pure solvent.
Let ΔTf be the depression in freezing point, then
Tf  T0f  ΔTf Tf : freezing point of solution
T 0f : freezing point of pure solvent
We have ΔTf  K f m
where K f : mollal freezing point depression constant

or cryoscopic constant of solvent
m : molality of the soluition
From the definition of molality, we have :

 gB 
n  M 
ΔTf  K f  B  1000  OR ΔTf  K f  B  1000 
 gA   gA 
 
 

Note : [1] The values of Kb and K f which are functions of the nature of the solvent can be ascertained from the
R (Tb )2 R (T f )2
following relations : Kb  and Kb 
1000H vap / M solvent 1000H fus / M solvent
[2] During freezing of solution only solvent molecules separate out from the solution.
Here the symbols R and Msolvent stand for universal gas constant and molar mass of the solvent, respectively
Tb and Tf denote the boiling point and freezing point of the solvent, respectively in Kelvin. Further,,
ΔH vap and ΔH fus represent change in enthalpies for the vaporisation of the solvent and fusion of the
pure solid solvent, respectively and are to be taken per gram of the solvent.
10
For H 2O  l  , ΔH vap  10 kcal mol1  kcal gm 1  540 cal gm 1
18
1.44
For H 2O  s  , ΔH (fus)  1.44 kcal mol1  kcal gm 1  80 cal gm 1
18
4. Osmotic Pressure :
When a semi permeable membrane (a material with extremely small holes in it so that it allows only
solvent molecules to pass through it) separates a solvent from a solution, solvent molecules tend to pass
from the solvent side into the solution.
Also, if the solutions of different concentrations are separated by semi permeable membrane, the solvent
molecule pass from dilute solution into the more concentrated solution. This movement of solvent molecules
through a semi permeable membrane is called as osmosis.
The excess pressure (external pressure) which must be applied to a solution to prevent the flow of solvent
molecules into it through the semi permeable membrane (as a result of osmosis) is called as osmotic pres-
sure.
Laws of Osmosis :
Van’t Hoff studied the phenomenon of osmosis in detail and showed that the dilute solutions behave very
closely to ideal gases. He studied the effects of concentration and temperature on osmotic pressure.
Effect of Concentration :
At constant temperature, osmotic pressure (P or ) of a solution is directly proportional to the concentra-
tion of solution.
i.e.   C (C : concentration in mol/L)
or Osmotic pressure varies inversely as the volume of solution that contains one mole of a solute at a
given temperature.
1
i.e.  
V

Effect of Temperature :
Osmotic pressure varies directly as the absolute temperature (T).
  T
Combining the two expessions :

V=nRT (R : gas constant and n : moles of solute)
or = C R T (C = n/V)
The equation  V = nRT is remarkably similar to the ideal gas law (PV = nRT).
Isotonic Solutions
Two or more solutions having equal osmotic pressure under given conditions are called isotonic solutions.
For such cases :
1 = 2
Hypertonic Solutions :
They contain a high concentration of solute relative to another solution (e.g. cell’s cytoplasm). When a cell
is placed in a hypertonic solution, the water diffuses out of the cell, causing the cell to shrink.
Hypotonic solutions :
They contain a low concentration of solute relative to another solution (e.g. the cell’s cytoplasm). When a
cell is placed in a hypotonic solution the water diffuses into the cell, causing the cell to swell.
Calculation of Molecular Mass from Colligative Properties

All of four colligative properties are used to determine the molecular masses of non-volatile solute (espe-
cially organic solutes).
1. Vapour Pressure Lowering :

ΔP nB n
 B   B
PA0 nA  nB nA
gB
ΔP MB gBMA PA0
   MB 
0 gA gA ΔP
PA
MA

2. Elevation in Boiling Point :
 gB 
M   gB 
ΔTb  K b  B  1000   MB  Kb   1000 
 gA   g A ΔTb 
 
 

The boiling point of a solution made by dissolving 12.0 gm of glucose in 100 gm of water is 100.34C.
Calculate the molecular weight of glucose. Kb for water = 0.52C/m.
SOLUTION :
Using the relation for molecular weight of a solute from elevation in boiling point, we have :
 gB 
MB  Kb   1000 
 g A ΔTb 
 12 
 M B  0.52   1000 
 100  0.34 
 M B  183.5 g / mol
3. Depression in Freezing Point :
 gB 
M   gB 
ΔTf  K f  B  1000   M B  Kf   1000 
 gA   g A ΔTf 
 
 
4. Osmotic Pressure :
gB g B RT
V  nRT  RT  MB 
MB V

Illustration - 5 Blood freezes at 272.44 K and a solution of 3.0 gm of Urea in 250 gm of water freezes at
272.63 K. Calculate osmotic pressure of blood at 310 K. (Assume density of blood at 310 K to be 1 g/cc)
SOLUTION :
In this question, first calculate Kf of water from Urea solution.
 gB 
M 
Tf  K f  B  1000 
 gA 
 
 
Tf 0.37
 Kf   Kf  1.85  ΔTf  273  272.63  0.37 K 
 gB   3 
M   60 
 B  1000    1000 
 gA   250 
   
 
Now determine the molality of blood by using :
 Tf = Kf m
Now,  Tf = 273  272.44 = 0.56C
Tf 0.56
m   0.303
k f 1.85
Note : Colligative properties are defined for dilute solutions. Assume molarity molality.
 Molarity = molality = 0.303

Now using :  = c RT
  = 0.303  0.0821  310 = 7.7 atm
Illustration - 6 Calculate the freezing point depression and boiling point elevation of a solution of 10.0
gm of urea (MB = 60) in 50.0 gm of water at 1 atm. pressure. Kb and Kf for water are 0.52 C/m and 1.86 
C/m respectively.
SOLUTION :
Depression in freezing point = Tf and Elevation in boiling point = Tb

 gB   10 
M   
Tf  K f  B  1000   1.86  60  1000   6.2C
 gA   50 
   
 
g
 B   10 
M   60 
Tb  K b  B  1000   0.52   1000   1.7C
 gA   50 
   
 
Note : Freezing point (Tf) = T0f – Tf = 0 – 6.2 = – 6.2C
Boiling point (Tb) = T0b + Tb = 100 + 1.7 = 101.7C
Illustration - 7 The boiling point elevation constant for benzene is 2.57C/m. The boiling point of benzene
is 80.1C. Determine the boiling point of a solution formed when 5.0 gm of C14H12 is dissolved in 15 gm of
benzene.
SOLUTION :
Using the result :
 gB   5 
M   
Tb  K b  B  1000   2.57  180  1000   4.76 C
 gA   15 
   
 
Tb = T0b + Tb [T0b = Boiling point of pure solvent]
= 80.1 + 4.76 = 84.86 C
Illustration - 8 What mass of sugar, C12H22O11 (M0 = 342) must be dissolved in 4.0 kg of H2O to yield a
solution that will freeze at –3.72°C. (Take Kf = 1.86°C/m)
SOLUTION :
 Tf = 3.72 C, Msugar = 342 Tf g A M B
 gB 
1000 K f
 gB 
M  3.72  4 103  342
 gB   2736 gm
Tf  K f  B  1000  1000 1.86
 gA 
 
 

ABNORMAL MOLECULAR MASS (van’t Hoff Factor) Section - 3
It has been observed that molecular masses of non-volatile solutes calculated from colligative properties
(observed molecular masses) are sometimes not accurate i.e., these do not agree with actual values (normal
molecular masses). This is attributed to following reasons :
1. Solution may not behave as an ideal solution. (i.e. it may not be dilute solution).
2. Association of molecules of solute.
3. Dissociation of molecules of solute.
Association
There are certain organic molecules (like acids) which forms dimers (or trimers) in non-aqueous solutions.
In solution of such solutes, there exist single, double and larger associated molecules. Hence the effective
number of molecules decreases and as a result all colligative properties are less than that calculated on the
basis of single molecule. So the molecular masses calculated by using colligative properties will be higher
than actual. For example ; acetic acid in benzene, benzoic acid in benzene and chloro-acetic acid in
naphthalene.
Dissociation
Inorganic acids and ionic solutes undergo dissociation in aqueous medium. They form catinon and anions in
the solutions. For example when KCL is dissolved in water, it exists as K+ and Cl– ions in solution. As a
result, the number of effective solute particles increases and therefore, the colligative properties of such
solutions are much higher than those calculated on the basis of undissociated single molecule. As a result, the
molecular mass calculated in such case will be lower than the actual value.
Van’t Hoff Factor (i) :
Observed osmotic effect

i=
Normal osmotic effect
The colligative property implies osmotic effect implies osmotic pressure (), vapour pressure lowering
(P/PTotal), elevation in B.P. (Tb) and depression in freezing point (Tf).
1
Osmotic effect 
Molecular Weight
Normal Molecular Weight  Note : "Observed " means "Experimental" 

 i=
Observed Molecular Weight  " Normal means "Theoretical" 
 
or We can write  colligative   i  

colligative 

 property observed  property  normal
P
 Tb = i (Kb m) ; Tf = i (Kf m) ;  = i (CRT) ;  0  i B
PA

Degree of Association :
It is the fraction of total number of molecules of solute which combines to form bigger molecules.
Let n moles of solute (X) associate from one mole of it.
  X 
nX  n
Let x be the degree of association.
  X 
nX  n
Initially 1 0
In solution 1  x x/n
Total moles (or molecules) in the solution = 1  x + x/n
As osmotic effect is proportional to the number of moles (or molecules)
Observed osmotic effect 1  x  x / n

 i= 
Normal osmotic effect 1
Normal Molecular Weight 1  x  x / n

or i= 
Observed Molecular Weight 1
Note : Number of solute particles decreases during complex formation.
Illustration - 9 Acetic acid associates in benzene to form a dimer. 1.65 gm of acetic acid when dissolved in
100 gm of benzene raised the B.P. by 0.36 °C. Calculate the Van’t Hoff factor and degree of association of
acetic acid.
(Kb for benzene = 2.57 C/m)
SOLUTION :
Calculation of Van’t Hoff factor :
First calculate molecular mass from elevation in boiling point.
 gB   1.65 
MB  K b   1000   2.57   1000   117.8
 g A Tb   100  0.36 
Normal Molecular Weight 60

 i= = = 0.509
Observed Molecular Weight 117.8

Calculation of degree of association :

Let x = degree of association
2 CH3COOH 
 (CH3COOH)2
1 0
1x x/2
Total moles = 1  x/2
Total Moles 1  x / 2
i= 
Initial Moles 1
1 x / 2
 0.509 
1
 x = 0.982
Degree of Dissociation :
It is defined as the fraction of total number of molecules which dissociates into free ions.
Let us take 1 mole of KCl and x be its degree of dissociation, then we have
KCl 
 K+ + Cl–
Initially 1 0 0
In solution 1x x x
Total moles in solution = 1  x + x + x = 1 + x
Observed colligative property 1  x

 i= 
Normal colligative property 1
Normal Molecular Weight 1 x

 i= 
Observed Molecular Weight 1
Find van’t Hoff factor of :

(a) CH3COOH in H2O, (b) CH3COOH in benzene
SOLUTION :
(a) CH3COOH in water dissociates (as a weak acid) :  CH3COO  H 
CH3COOH 
 i>1

(b) CH3COOH in benzene (i.e. non-polar solvent) associates to form a Dimer.
O HO
|| |
CH 3  C  OH  O  C  CH3  i<1
Illustration - 10 Van’t Hoff factors of aqueous solution of X, Y, Z are 1.8, 0.8 and 2.5. Which of the following
statement (s) is (are) correct ?
(A) B.P. : X < Y < Z (B) F. P. : Z < X < Y
(C) Osmotic Pressure : X = Y = Z (D) V.P. : Y < X < Z
SOLUTION : (B)
Obseved colligative property  i  Normal
colligative Property
(A) Elevation in B.P. follows the order : Y < X < Z (C) Osmotic Pressure follows the order : Y < X < Z
 P. following the order : Y < X < Z
(B) Depression in F.P. follows the order : (D) Relative lowering in the vapour pressur follows :
Y < X < Z (Tf  Tt0  ΔTf ) Y<X<Z
 F.P. Following the order : Z < X < Y V.P. follows the order : Z < X < Y
Illustration - 11 A 0.1 M solution of potassium sulphate, K2SO4 is dissolved to the extent of 90%. What
would be its osmotic pressure at 27 C ?
SOLUTION :
Using the result :  =iCRT Total moles = 1  x + 2x + x = 1 + 2x
Calculation of i :
1  2 x 1  2  0.9
i   2.8
K2SO4 
 2K+ + SO4 2
1 1
1 0 0  = 2.8  (0.1  0.0821  300) = 6.90 atm
1–x 2x x

Illustration - 12 When dissolved in benzene, a compound C38H30 partially dissociates by the following
 2 C H . 25.6 gm of C H is dissolved in 400 g of benzene, the freezing point is
equation : C38H30  19 15 38 30
lowered by 0.680°C. What % age of C38H30 molecules have dissociated ? (Kf = 4.9)
SOLUTION :
Tf = i Kf m Total moles = 1  x + 2x = 1 + x
Total Moles 1  x
T f 0.68 i= 
i  Initial Moles 1
 gB   25.6 
M   486  1000 
K f  B  1000  4.9   1 x
400  1.0538  x = 0.0538
 gA    1
   
   % age dissociation = 5.38 %
= 1.0538
Consider :  2 C H
C38H30  19 15
1x 2x
Illustration - 13 Calculate osmotic pressure of a solution containing 0.01 moles of NaCl and 0.03 moles of
Glucose in 500 ml at 27C.
SOLUTION :
Ceffective= iNaCl ( 2)  C NaCl  iGlucose ( 1)  CGlucose
 0.01 0.032 
= 2  1  M = 0.1 M
 500 /1000 500 /100 
  = Ceff. RT = 0.1  0.082  300 atm = 2.46 atm
Illustration - 14 Dry air is passed through a solution containing 20g of an organic non-volatile solute in
250 ml of water. Then the air was passed through pure water and then through a U-tube containing anhydrous
CaCl2 . The mass lost in solution is 26 g and the mass gained in the U-tube is 26.48 g. Calculate the molecular
mass of the organic solute.
SOLUTION :
The loss in mass is due to absorption of vapours of solvent in dry air and due to absorption by
anhydrous CaCl2 [ if solvent is water ]. Loss in mass  pressure of vapours of solvent /solution.

Loss in mass of solvent P0  P


Gain in mass of U- tube P0
Loss in mass in solution = 26g ; Gain in mass of U-tube = 26.48 g
Therefore, loss in mass in solvent = 0.48 g
0.48 P 0  P mole fraction of solute in the solution

 
26.48 P0
0.48 n solute n solute
 
26.48 n solute + n solvent n solute + 250 / 18
250  0.48
 n solute 
18(26)
20  18  26
 M solute   78
250  0.48
IN-CHAPTER EXERCISE-C
1. Arrange the following solutions as directed.

(a) (i) 0.001 m NaCl, (ii) 0.001 m urea, (iii) 0.001 m MgCl2 ,
(vi) 0.001 m CH 3COOH
Increasing order of boiling points
(b)( (i) 0.1 M ethanol, (ii) 0.1 M Ba3 ( PO4 ) 2 , (iii) 0.1 M Na2 SO4
Increasing order of freezing points
(c)( (i) 0.1 M glucose, (iii) 1% urea solution, (iii) 0.1 M common salt
Increasing order of osmotic pressure
(d) (i) NaNo3 , (ii) BaCl2 , (iii) K3[ Fe(CN )6 ],

(iv) C6 H12O6 , (v) CH 3COOH
Increasing order of van’t Hoff Factor

Example - 1 A 0.025 M solution of a monobasic acid has a freezing point of –0.06C. Find the value of
Ka of this acid. Kf of water = 1.86 K/m. Assume that molarity is equal to molality.
SOLUTION :
Calculate Van’t Hoff factor using the relation : Total Moles 1  
i= 
Tf = i Kf m Initial Moles 1
Taking m  M  i = 1 +  = 1.29   = 0.29
Tf 0.06 HA 

 H+ + A
 i   1.29
K f m 1.86  0.025
c  c c c
Van’t Hoff factor is given as :
[H  ] [A  ] (c) c 2
 +   Ka   
HA  H + A [HA] c  c 1  
1  
0.025  (0.29)2
   2.96  103
1  0.29
Note : In dilute solutions of weak acids (or weak bases), do not use K a  C  2 as 1    1.
Example - 2 Vapour pressure of benzene at 30°C is 164.88 mm of Hg. When in 3 moles of benzene, 6 gm of
acetic acid was dissolved, the solution has a vapour pressure of 162.04 mm of Hg. Calculate :
(a) Van’t Hoff factor (b) the degree of association of acetic acid in benzene at 30°C.
SOLUTION :
Using the relation for lowering in vapour pressure Hence, acetic acid associates in benzene
and considering the van’t Hoff factor (i), we have
 (CH COOH)
2 (CH3COOH) 
P 3 2
 i B 1  /2
PA0
 i = 1  /2
(164.88  162.04)  0.1 
 i.    = 2 (1  0.533) = 0.932
164.88  0.1  3 
 i = 0.533 (i.e., i < 1)
Example - 3 1.0 gm of monobasic acid when dissolved in 100 gm of pure water lowers the freezing
point by 0.168°C. 0.2 gm of the same acid when dissolved and titrated required 15.1 ml of N/10 base. Determine
the degree of dissociation of the acid. Kf of water is 1.86 K/m.
SOLUTION :
Calculate the molecular mass (observed from 0.2 0.1  15.1 (meq of acid = meq of

colligative property) using the relation : M /1 1000
 gB  base)
M B  Kf   1000   M = 132.45
 g A Tf 
M actual 132.45
 1  i   1.19
  1.86   1000  M0 110.6
 100  0.168 
HA  H+ + A
 MB = 110.6
1  
Now calculate the actual molecular mass
 i = 1 +  = 1.19
fromneutralisation experiment.
  = 0.19
Example - 4 The molar volume of liquid benzene (density = 0.877 g/cc) increases by a factor of 2750 as
it vapourises at 20C and that of liquid toluene (density = 0.867 g/cc) increases by a factor of 7720 at 20C.
A solution of benzene and toluene at 20C has a vapour pressure of 46.0 torr. Find the mole fraction of
benzene in the vapour above the solution.
SOLUTION :
78 RT 0 RT
molar volume of benzene = ml PB0  ; PT  ; PTotal  PB B  PT T
0.877 VB VT
92 46  RT   RT 
molar volume of toluene = ml  760  B  V   T  V 
0.867
 B  T
At 20C, volume of vapour of benzene and Substitute for VB and VT and T = 1 – B
toluene
 B = 0.452
78
VB =  2750 = 244.58 L Now find the vapour fraction of benzene.
0.877
VT =
92
 7720 = 819.19 L PB0  B 0.452  RT 
0.867 V
B      0.734
PTotal 46 / 760  VB 
Example - 5 12.2 g of benzoic acid is dissolved in (i) 1 kg acetone (Kb = 1.7 K kg mol–1)
and (ii) 1 kg benzene (Kb = 2.6 K kg mol–1).
The elevations of boiling points are 0.17C and 0.13C, respectively.
(a) What are the molar masses of benzoic acid in the two solutions ?
(b) What are the structures of benzoic acid in the two solutions ?
SOLUTION :
Let M be the molar mass of benzoic acid in the 1.7  12.2
solution. The molality of the solution is M Benzoic Acid  g mol1
0.17
n 12.2g  / M  122 g mol1
m= B 
gA 1kg
(b) Benzene solution
Since Tb = Kb m, we get :
(a) Acetone solution

0.13 K  2.6 K kg mol 1 
12.2 g / M Benzoic Acid 

0.17 K  1.7 K kg mol 1  
 1kg


12.2 g / M Benzoic Acid  2.6  12.2

1kg
 M Benzoic Acid  g mol1
  0.13
 244 g mol1
The actual molar mass of benzoic acid (C6H5COOH) is 122

g mol–1. This means benzoic acid is present as a monomer in
acetone solution while it dimerises in benzene solution. The
structure of dimerised benzoic acid is ()
Example - 6 Match the following if the molar mass of X, Y and Z are the same.
Solvent Tb/ °C Kb/kg K mol–1
X 127 0.73
Y 27 0.53
Z 253 0.98
SOLUTION :
RTb2 H vap
Since Kb  , we have [ is taken to be constant as per Trouton’ss
1000H vap / Msolvent
Tb
rule]
RTb
Kb   K b  Tb
 H vap 
1000   / M solvent Thus, we have
 Tb 
Kb (X) = 0.73 kg K mol–1 ; Kb (Y) = 0.53 kg K
 (constant) Tb
mol–1 ; Kb (Z) = 0.98 kg K mol–1
Example - 7 Following are equimolal aqueous solutions :

(a) 1m urea (b) 1m KCl (c) 1m MgCl2 (d) 1m Na3PO4
Arrange them in increasing (i) boiling point, (ii) freezing point, (iii) osmotic pressure, (iv) vapour pressure.
SOLUTION :
 While analysing the colligative properties, if the (ii) Freezing point of solution
density of the solution is not given, take the
Tf = T0f – (Tf)
Molarity of the solution same as Molality and
vice-versa. Tf = i (Kf m)
 In such type of questions, always assume 100% Thus, greater the value i, greater the value of
dissociation for the ionic solutes until and unless Tf but
specified. Thus, greater the value i, greater the value of
Tf but smaller the value of freezing point.
Solute Ionisation i
D<C<B
(A) Urea No 1 (iii) Osmotic pressure ()
–
(B) KCl K+ + Cl 2  = i CRT
(C) MgCl2 Mg2+ + 2Cl– 3 Thus, greater the value i, larger the value of os-
motic pressure.
(D) Na3PO4 3 Na   PO34 4 A<B<C<D
(iv) Vapour pressure of solution
(i) Boiling point of solution
P P nB n
Tb = T0b + (Tb)  i B or i i B
PA0 PA0 nA  nB nA
Tb = i (Kb m)
 The greater the value of i, greater the value of
Thus, greater the value of i, greater the value of
P. Hence, smaller the value of vapour pressure
Tb and boiling point of solution.
of solution.
A<B<C<D
D < C < B <A
Example - 8 The steam distillation of chlorobenzene is observed to occur at a temperature of

90.6C , when the total pressure is 1 atm. Assuming complete immiscibility of these liquids, calculate the mass
of chlorobenzene in 0.1 kg of distillate. The vapor pressure of water at 90.6C is 539.9 Torr..
SOLUTION :
WC
For a mixture of two immiscible liquids, the total  
pressure is given by Pchlorobenzene nC MC
  

Pwater nW WH 2O

PTotal  Pchlorobenze 
 Pwater
M H 2 O

760  Pchlorobenze  538.9


Pchlorobenzene WC  M H 2O
 Pchlorobenze  221.1 Torr  

Pwater WH 2O  M C
 V ... (i)
Pchlorobenze  chlorobenzene  PTotal
 
 Where M C and M H 2O represents molar
and Pwater   water (V)  PTotal .... (ii)
mass of chlorobenzene and water respectively
Divinding equation (i) by (ii) gives,
and WC and WH 2 O denotes weight of
V 
chlorobenzene Pchlorobenzene chlorobenzene and water the vapour phase,

V
water

Pwater respectively.

nC Pchlorobenzen  WH 2O  M C
 WC 


Pchlorobenzene n  nW PH  M H 2O
or  C 2O

Pwater nW
nC  n W Let the mass of chlorobenzene in the distillate
be x g, then mass of H2O would be
where nC and nw represents the number of moles
(100 - x) g.
of chlorobenzene and water in the vapour phase,
respectively. 221.1  100  x   112.5
 x 
538.9  18
x  71.94 g
THINGS TO REMEMBER
1. Henry’s law : PGas  K H  in solution Solubility of Gas  as T  and as P  .
° ° P° 
2. Raoult’s law : (For ideal solutions) PTotal  PA  A  PA  B ;  vA  A A ;  vB  1  A
v
PTotal
where  A  mole fraction of A in solution  B  mole fraction of B in solution
v
A  mole fraction of A in vapour state  vB  mole fraction of B in vapour state
(i) Ideal solution : Vmixing  0; H mixing  0; A B interactions are similar to A A and
B B interactions.
(ii) Solution showing +ive deviation : Vmixing  0; H mixing  0; A  B interactions are weaker
than and B B interactions.
(iii) Solutions showing  ive deviation : Vmixing  0; H mixing  0; A  B interactions are stronger
than A  A and B B interactions.
3. Colligative Properties :  For dilute solutions.

 Depends only on the number of solute particles and independent of
their nature.
Normal molecular mass
i= or i = Observed colligative property
Observed molecular mass Normal colligative property
PA°  PTotal P
(i)  i  B = Relative lowering of vapour pressure
PA° PA°
(ii) Tb  iKb m ; Tb  Tb  Tb
(iii) T f  iK f m ; T f  T f  T f
(iv)   Ceff RT [Ceff   iCi ]

[Osmosis : Solvent molecules move from dilute to concentrated through Semi-Permeable membrane.]
SOLUTIONS TO IN-CHAPTER EXERCISE-C
1. (a) B.P. is higher if Tb is higher which in turn depends on meffective ( = i meffective)
0.001 m urea < 0.001 m CH3COOH < 0.001 m NaCl < 0.001 m MgCl2
(b) F.P. is higher if Tf is lower (depends on meffective)
 0.1 M Ba3(PO4)2 < 0.1M Na2SO4 < 0.1M Ethanol
(c) Osmotic Pressure is higher if Ceffective is higher.
0.1M Glucose < 1% urea ( 0.167 M) < 0.1 M NaCl
(d) NaNO3 : i = 2 K3[Fe(CN)6] : i = 4
CH3COOH (Weak acid) : 1 < i < 2; BaCl2 : i = 3 C6H12O6 : i = 1
30 Solutions Self Study Course for IITJEE with Online Support

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Chemical Kinetics
Chemical Kinetics
This branch of chemistry deals with the study of rates of chemical reactions and the mechanism by which
they occur.
While studying reaction rates, one deals with :
(a) How fast (or slow) the reactants get converted into products
(b) The steps or paths through which the products are formed (reaction mechanism)
BASIC Section - 1
Rate of a Reaction :
In general, for a reaction : A 
 B, the behaviour of the concentration of the reactant and product, as the
reaction proceeds, is shown graphically.
From the graph, it is clear that the concentration of the reactant decreases and that of the product increases
as the reaction proceeds and the rate of the change of the concentration of the reactant as well as that of the
product is also changing.
Rate of a reaction can, now, be defined in two ways :
[A] [B]
1. Average Rate of reaction (ravg) given by : ravg  
t t
where Δ[A] and Δ[B] represents the change in the concentrations of ‘A’ and ‘B’ respectively over a time
interval Δt.
The average rate of the reaction between a time interval (t2 – t1 = Δt) can be determined from the above
graph by locating the concentration of ‘A’ or ‘B’ on this graph at the time instants t2 and t1 as shown.
If [A]2 and [A]1 are the concentrations of the reactant ‘A’ at the time instants t2 and t1, then :
 [A]  [A]1 
ravg    2 
 t 2  t1 

Chemical Kinetics Vidyamandir Classes
 [B]2  [B]1 
Similarly from the plot of ‘B’ as a function of ‘t’, we have : ravg   t  t 
 2 1 
Note : The above expressions for ravg is equivalent to the slope of the line joining the points (t2, [A]2 ) and (t1, [A]1)
or (t2, [B]2) and (t1, [B]1) as shown.
2. Instantaneous Rate of reaction (rinst.) can be calculated from ravg in the limit Δt 
 0 and is represented
as :
d[A] d[B]
rinst   
dt dt
Note :  The above expression for rinst. is equivalent to the slope of the tangent from the plot of the concentration
of A’ or ‘B’ at any time instant ‘t’.
 The rate of the reaction (rinst.or ravg) is always calculated as a positive quantity.
 The rate of the change of the concentration of the reactant will be a negative quantity since its
concentration is decreasing with time.
 The rate of the change of the concentration of the product will be a positive quantity since its concentration
is increasing with time.
 The magnitude of the rates of the change of the concentration of reactants and products will be equal
in this case, as one mole of ‘A’ gives one mole of ‘B’ in the above reaction.
 The rate of a reaction at any temperature depends on the concentration of the reactants and sometimes
on the concentration of some foreign substances (e.g a catalyst) being used in the reaction as well. The
representation of this dependence of the rate of the reaction on the concentrations is known as rate
law and this rate law is determined experimentally.
 The above expression for rinst. is called as differential rate law.
In general for a reaction :

mA + nB 
 pC + qD
The rate of reaction can be expressed as follows :

1 d[A] 1 d[B] 1 d[C] 1 d[D]
Rate     
m dt n dt p dt q dt
The rate of formation of NO(g) in the reaction 2NOBr(g)   2NO(g) + Br2(g) is found to be
4
1.6  10 M/s. Find the rate of overall reaction and rate of consumption of NOBr.

d[NO]
We have : = 1.6 × 10–4 M/s.
dt
1 d[NOBr] 1 d[NO] 1 d[Br2 ]
Now, Rate of overall reaction = –   = 0.8 × 10–4 M/s
2 dt 2 dt 1 dt
d[NOBr]
Rate of consumption of NOBr = = –1.6 × 10–4 M/s
dt
Order of a Reaction :
By performing a reaction in actual in laboratory and carefully examining it, it is possible to express the rate
law as the product of concentrations of reactants each raised to some power.
For example consider the reaction :
P + 2Q   R
The differential rate law is written as :

d[P] 1 d[Q]
Rate   
dt 2 dt
Also, Rate can be expressed as Rate = k [P]m [Q]n
where k is called as rate constant or velocity constant or specific reaction rate.
k is a characteristic of a reaction at a given temperature. It changes only when the temperature changes.
The powers m and n are integers or fractions. m is called as order of reaction with respect to P and n is
called as order of reaction with respect to Q.
The overall order of reaction = m + n
Note : The values of m and n are calculated from the experimental data obtained for a reaction and the powers m
and n are not related to the stoichiometric coefficients of the reactants.
Units of k :
In general, the rate law for a nth order reaction can be taken as :
dc  dc n
  kc n  Note: rinst.   dt  kc 
dt  
where k : rate constant ; c : concentration and n : order of reaction
dc / dt
 k=
cn
 Units of k  (mol/L)1 – n (time)–1

For a ‘zero’ order reaction (n = 0) :

Units of k  (mol/ L)1 (time)–1
 Units are : mol/L/sec, mol/L/min, ... etc.
For a first order reaction (n = 1) :

Units of k  (time)–1
 Units are : sec–1, min–1, hrs–1 etc.
For a second order reaction (n = 2) :

Units of k  (mol/ L)–1 (time)–1
 Units are : L/mol/sec, L/mol/min, .... etc.
Illustration - 1 From the rate laws for the reactions given below, determine the order with respect to
each species and the overall order:
– +
(i) 2HCrO4 + 6I– + 14H   2Cr3+ + 3I2 + 8H2O (ii) H2O2 + 2I– + 2H+  I2 + 2H2O
– –
Rate = k [HCrO4 ][I ]2[H+]2 Rate = k [H2O2][I–]
SOLUTION :
(i) The order of the reaction with respect to [HCrO4–] is 1; with respect to [I–] is 2 and with respect to [H+]
is 2. The overall order of the reaction is 1 + 2 + 2 = 5
(ii) The order of the reaction with respect to [H2O2] is 1 and with respect to [I–] is 1. The overall order of
the reaction is 1 + 1 = 2
Note :  In (i) the stoichiometric coefficient of I– is 6 whereas the power coefficient (n) in the rate law is 2.
 Reaction (i) may not take place in a single step. It may not be possible for all the 22 molecules to be
in a state to collide with each other simultaneously. Such a reaction is called a complex reaction.
 A complex reaction takes place in a series of a number of elementary reactions.
Illustration - 2 For a reaction 2 NO(g) + 2 H2(g) 

 N2(g) + 2 H2O(g) ; the following data were
e
obtained.
[NO](mol/L) [H2](mol/L) Rate(mol/L/s)
1. 5 × 10–3 2.5 × 10–3 3 × 10–5
2. 15 × 10–3 2.5 × 10–3 9 × 10–5
3. 15 × 10–3 10 × 10–3 3.6 × 10–4
(a) Calculate the order of reaction.
(b) Find the rate constant.
(c) Find the initial rate if [NO] = [H2] = 8.0 × 10–3 M

SOLUTION :
Assuming rate law can be expressed as follows :
rate = k [NO]x [H2]y
By analysing the data :
From observations 1 and 2, we see that [H2] is constant and when [NO] is tripled, the rate is also tripled.
 rate (r)  [NO]  x=1
From observations 2 and 3, we see that [NO] is constant ; when [H2] is increased four times, the rate also
increases four times.
rate  [H2]  y=1
 r = k [NO] [H2O]
 The order of reaction w.r.t NO and H2 is 1 and the overall order of reaction is 1 + 1 = 2.
Initial rate = k [NO] [H2] = 2.4 × (8 × 10–3)2 = 1.536 × 10–4 mol/L/s.
nth ORDER REACTIONS Section - 2
Zero Order Reactions :

The rate law for zero order reactions (n = 0) is written as :
dc
d t = –k . . . . .(i)
Clearly, zero order reactions are those, whose rates are not affected by change in concentrations of reactants
(i.e., independent of concentration). The rates of such reactions only depend upon temperature. Most of
photochemical reactions are zero order reactions. Other examples are : decomposition of HI over the
surface of gold and NH3 over tungsten.
Equation (i) can be rearranged and integrated to get the variation of the concentration of the reactants as a
function of time.
Ct t
 dc    k dt  [Ct – C0] = –k [t – 0]
C0 0
 C t  C0 
Thus, k =– . . . . .(ii)
t
where C0 = Initial concentration of the reactant
and Ct = Concentration of the reactant at any time instant ‘t’ after the reaction started

 From the above expression, it is clear that if we plot Ct as a function of time (t) then it will be a straight
line with a negative slope = –k and Y– Intercept of C0.
 One can also define, Half Life (t1/2) which is equal to the time taken for the reactant’s concentration
to drop to 50% of its initial value.
C0
Putting Ct = 0.5 C0 in equation (ii), we get t = t1/2 =
2k
Thus, for a Zero order reaction, half life is directly proportional to initial concentration of the reactant.
Note : The equation obtained on integrating the differential rate law is known as Integrated Rate Law.
For example : equation (ii) is the Integrated Rate Law for the Zero Order Reaction.
First Order Reactions :

The differential rate law for a first order reaction A 
 B; is given as :
dc
= –k c . . . . . .(i)
dt
This equation can be rearranged and integrated as follows to get the integrated rate law for a first order
reaction :
Ct t
dc C
    k dt  ln 0  kt
c Ct
C0 0
C
or 2.303 log10 0  kt . . . . .(ii)
Ct
[ln is the Natural Log (base ‘e’)  loge]
Sometimes, it is important to remember the log10 for the following values :
log10 2 = 0.301 log10 3 = 0.477 log10 4 = 0.602
log10 5 = 0.699 log10 6 = 0.778 log10 7 = 0.845
Also, remember that lnx  loge x = 2.303 log10 x
2.303log10 2 0.693
Putting Ct = 0.5 C0 in equation (ii), we get t = t1/2 =
k k
Thus, for a first order reaction half life is independent of the initial concentration of the reactant.
For the reaction A 
 B (following first order)
Initial conc. C0 0
After time ‘t’ Ct  C0 – x x

The integrated rate law can also be written as :

C0 1
2.303 log10  kt or 2.303 log10  kt
C0  x 1 
x
where x is the concentration of the reactant consumed and  is the degree of dissociation = C
0
Features of a First Order Reaction :

1. A first order reaction must follow above form of rate law for all time instants.
This means if we are given value of C0 and values of x at different time instants [i.e (C0 – x) as
value of reactants after t], the values of k can be calculated for different time instants by using the
above first order law. If the reaction for which the data were given is a first order reaction, then all
values of k will approximately equal to each other.
2. The time for half reaction for a first order reaction is independent of initial concentration of reactants.
3. The concentration of reactants in a first order reaction decreases exponentially with time (see figure)
[Ct = C0e–kt from (ii)]
Note that plot of log10 Ct vs t is linear. It is important to note that equation of this straight line is of the
form :
y = m x + b. Comparing it with Ist order rate law as follows :
C0
k t = 2.303 log10
Ct
 k 
 log10C t    t  log10C0 is the equation of line.
 2.303 
 k 
Note that slope of the line =   and Y-intercept (OA) = log10 C0
 2.303 
 Rate constant of a first order reaction can also be calculated by measuring the concentration of the
reactant at two time instants (if the initial concentration is not known).
If C1 and C2 are the reactant’s concentrations at two time instants ‘t1’ and ‘t2’ respectively, then we
have :

C
2.303 log10 0  kt1 . . . . .(iii)
C1
C
and 2.303 log10 0  kt 2 . . . . .(iv)
C2
Subtracting (iv) from (iii), we get :

C
2.303 log10 1  k  t 2  t1  Thus, k can be evaluated.
C2
Ct 1
 After Ist half life : Ct = C0/2  
C0 2
2
Ct 1
nd
After 2 half life : Ct = C0/2 2
  
C0 2
n
Ct 1
 After nth half life :    (where n = t/t = No. of half lives)
C0 1/2
2
Note : The differential rate law can be integrated for a nth order reaction as follows :
dc
Using : = –k cn [Provided that all the reactants are present in the same molar concentrations]
dt
Ct t
dc 1  1 1 
     k dt   n 1  n 1   kt . . . . .(v)
C0
cn 0
(n  1)  C t C0 
The above equation is the integrated rate law for a nth order reaction.
Also, linear plot can be obtained for 1 / c nt  1 vs t. (n  1)
1  2n 1  1
Putting Ct = 0.5C0 in equation (v), we get t = t1/2=   . . . . .(vi)
(n  1) C0n 1 k
1
From the above expression, it is clear that t1/2 
Cn0 1

Order of a reaction (n) can also be obtained by measuring the half life (t1/2) of a reaction at different values
of initial concentration (C0) of the reactant molecules.
 If C01, C02 are the initial concentrations of the reactants and (t1/2)1, (t1/2)2 are the corresponding half
lives, then using (vi), we get :
 t1/2 1  C02 n 1
=
 t1/2 2  C01 
 t1/ 2 1
log10
 t1/ 2 2
Taking log on both sides, we get : n=1+ C 
log10  02 
 C01 
Illustration - 3 The half life of first order decomposition of nitramide is 2.1 hour at 15C.
NH2NO2 (aq) 
 N2O(g) + H2O(l)
If 6.2 gm of NH2NO2 is allowed to decompose, find :
(a) time taken for nitramide to decompose 99%
(b) volume of dry N2O gas produced at this point at STP.
SOLUTION :
(a) Using first order kinetics, we have :
C0
kt = 2.303 log10 C
t
0.693  100   0.693 

  t  2.303 log10   k    t = 13.96 hours
2.1  00  99   t1/2 
(b) 6.2 gm of NH2NO2  0.1 mol

NH2NO2(aq.) 
 N2O(g) + H2O()
Moles at t = 0 0.1 mol

Moles at t = 13.96 hrs 0.1– 0.99 × 0.1 0.99 × 0.1
 Moles N2O = 0.099
 VN 2 O at STP = 0.099 × 22.4 L = 2.217 L at STP

Molecularity
As already discussed, the order of a reaction is an experimental concept. The theoretical aspect of chemical
kinetics is molecularity.
A complex chemical reaction is understood in terms of various indirect steps called elementary processes.
The study of a reaction in terms of elementary processes is called as reaction mechanism. Now various
elementary steps occur at different rates. The slowest elementary process in the reaction mechanism is
called as rate determining step.
Molecularity is defined as the number of ions or molecules or atoms taking part in an elementary process of
the reaction mechanism.
In the rate determining step, when one molecule takes part, it is said to be a unimolecular reaction ; two
molecules take part, it is said to be a bimolecular reaction ; three molecules take part, it is said to be a
termolecular reaction.
Unimolecular :
1. Cyclopropane 
 propene
2. O3 (g) 
 O2 (g) + O (g)
3. N2O5 (g) 
 N2O4 (g) + 1/2 O2 (g)
Bimolecular :
1. NO (g) + O3 (g) 
 NO2 (g) + O2 (g)
2. 2HI (g) 
 H2 (g) + I2 (g)
Termolecular :
1. 2 NO (g) + O2 (g) 
 2 NO2 (g)
Note :  For a reaction : A 

 B in the rate law : rate = k [A]m [B]n
Neither the order of reaction (m + n) nor the molecularity of a reaction can be predicted from
stoichiometric coefficient of a balanced reaction. The order of reaction is always to be determined
experimentally and molecularity is determined theoretically after studying the reaction mechanism.
However as a theoretical idea sometime, we can have an approximate order of reaction equal to
molecularity (i.e., the number of molecules taking part in slowest elementary step for complex
reactions).
 Order of a reaction can be fraction also. For example consider the following reaction:
(i) H2 (g) + Br2 (g) 
 2 HBr (g)
rate = k [H2] [Br2]1/2 (determined experimentally)

1 3
order of reaction = 1  
2 2

(ii) CH3CHO (g)  CH4 (g) + CO (g)

rate = k [CH3CHO]3/2 (determined experimentally)
3
order of reaction =
2
Also note that sum of stoichiometric coefficient (1 + 1 = 2) is not equal to the order of
reaction.
Pseudo First Order Reactions :

The molecularity of acidic hydrolysis of sucrose and esters is 2, whereas their order is 1. In both the
reactions water is in excess so that its concentration remains constant throughout the reaction. The rate of
reaction therefore depends only on the concentration of sucrose and ester in two reactions respectively.
So the reactions in which the molecularity is 2 or 3 but they conform to the first order kinetics are known
as pseudo first order reactions OR pseudo unimolecular reactions.
C12H22O11 + H2O + H+ 
 C6H12O6 (glucose) + C6H12O6 (fructose)
CH3COOC2H5 (ester) + H2O + H+ 

 CH3COOH + C2H5OH
(In both the reactions, H+ ion acts as a catalyst)
Illustration - 4 The rate law for the decomposition of gaseous N2O5,
1 d [ N 2O5 ]
N2O5(g)   2NO2(g) + 2 O2 (g) is observed to be : r   dt
 k[ N 2O5 ]
A reaction mechanism which has been suggested to be consistent with this rate law is
eqK

N2O5(g)  
 NO2(g) + NO3(g) (fast equilibrium)
k
1  NO (g) + NO(g) + O (g)
NO2(g) + NO3(g)  2 2 (slow)
k
2  2NO (g)
NO(g) + NO3(g)  2
(fast)
Show that the mechanism is consistent with the observed rate law.
SOLUTION :
r = k1 [NO2] [NO3] . . . . .(i)

and from the fast equilibrium step,
[NO 2 ][NO3 ]
K eq 
[N 2O5 ]
Thus, [NO2] [NO3] = K [N2O5] . . . . .(ii)

Using (ii) in (i), we get :

r = k1Keq [N2O5] = k [N2O5] where k = k1 Keq
This shows that the mechanism is consistent with the observed rate law.
Illustration - 5 The termolecular reaction 2NO(g) + H2(g)   2NOH(g) is found to be third-order

2
obeying the rate law r = k[NO] [H2]. Show that it is consistent with either of the following mechanisms :
eqK
(i) 
2NO (g)  
 N2O2 (g) (fast equilibrium)
k
N2O2 (g) + H2 (g)   2NOH (g) (slow)

K eq
(ii) 

2NO (g) + H2 (g)  NOH2 (g) (fast equilibrium)
k
NOH2 (g) + NO (g)   2NOH (g) (slow)
SOLUTION :
(i) Since the slow step is the rate determining step, hence
r = k’ [N2O2] [H2]
[N 2O2 ]
K eq  or [N2O2] = Keq [NO]2
[NO]2
 r = k Keq [NO]2 [H2] = k [NO]2 [H2] where k = kKeq
(ii) Proceeding as in (i) above, we have

r = k [NOH2] [NO]
[NOH 2 ]
K 'eq  or [NOH2] = Keq [NO][H2]
[NO][H 2 ]
 r = kKeq [NO]2 [H2] = k [NO]2 [H2] where k = kKeq

Methods of determining the order of a reaction

The following methods are commonly used for determining the order of a reaction :
1. Use of differential rate expressions :
We know that for an nth order reaction, r = k cn
Taking log on both sides, we have : log10 r = log10k + n log10c
Thus, if we plot log10 r as a function of log10c, it should be a straight line with a slope ‘n’.
 The order of the reaction can be evaluated.
2. Use of integrated rate laws :
This method can be used both analytically and graphically.
In the analytical method, a certain order of the reaction is assumed and rate constant of the reaction is
calculated from the given date. The constancy of the ‘k’ values obtained suggests that the assumed order of
the reaction is correct. If not, we assume a different order for the reaction and again calculate the values of
‘k’ using the new rate expression. This is essentially a trial and error method.
In the graphical method, if the plot of log c versus t is a straight line then the reaction is of first order. Similarly,
the integrated expression for second order can be utilized to ascertain if the reaction order is 2 and so on.
3. Half life method :
Provided that all the reactants are present in the same molar concentrations, we have already derived the
expression for calculating the order of a reaction given by :
 t1/ 2 1
log10
 t1/ 2 2
n=1+
C 
log10  02 
 C01 
where C01, C02 are the initial concentrations of the reactants and (t1/2)1, (t1/2)2 are the corresponding half
lives
4. Isolation method :
Sometimes, the kinetics of a reaction are studied in successive experiments by keeping the concentrations of
all but one reactant in excess so that the result gives the order with respect to the reactant whose concentration
is changing significantly. The synthesis of HI (g) from H2 (g) and I2 (g) is pseudo first order with respect to
H2 (g) in the presence of large excess of I2 (g) and also pseudo first order with respect to I2 (g) in the
presence of large excess of H2 (g). Hence, overall the reaction is of second order.

ANALYSIS OF SOME IMPORTANT FIRST-ORDER REACTIONS Section - 3
Analysis of some important first-order reactions :

1. Decomposition of Hydrogen peroxide ( H2O2 )
2 H 2O 2 () 
 2 H 2O()  O 2 (g)
The rate of this first order reaction is measured by titrating a fixed volume of H2O2 (undecomposed) against
a standard solution of KMnO4. Here KMnO4 acts as oxidising agent and H2O2 as reducing agent. The
volumes of KMnO4 used for H2O2after regular intervals of time are as follows.
Time instants t=0 t1 t2 t3 t4 t5
Vol. of KMnO4 V0 V1 V2 V3 V4 V5
Volume of KMnO4 at t = 0 corresponds to volume of H2O2 initially present.  C0  V0

Volume of KMnO4 at time instants t1, t2 , t3 ,. . . corresponds to volume of H2O2 remaining
after t1, t2, t3,. . .  Ct  Vt
V0
Now it being a first order reaction, follows first order kinetics, so kt  2.303 log10
Vt
Now using the above expression, if we calculate the values of k for different time intervals t1 , t2 , . . .
(for actual numerical data), the values of k should be same if the reaction follows first order kinetics.
2. Decomposition of ammonium nitrite (NH4NO2) and benzene diazonium chloride

(C6H 5N=NCl)
 2 H 2O()  N 2 (g)
NH4 NO2 (s) 
C6H 5  N  N  Cl() 
 C6 H5  Cl()  N 2 (g)
The rate of both the reaction is studied (measured) in similar manner. The volume of nitrogen (N2) is collected
after a regular interval of time as follows :
Time instants t=0 t1 t2 t3 t4 t
Vol. of N2 0 V1 V2 V3 V4 Vt
At t = 0, clearly the volume of N2 = 0

Time instant t =  means the end of a reaction i.e., when whole of NH4NO2 or C6H5 – N = N – Cl is
decomposed.

 At t = , V corresponds to the initial volume of NH4NO2 or C6H5 – N = N – Cl .

(Note that the ratio of stoichiometric coefficient for both N2 : NH4NO2 or N2 : C6 H5 N = NCl is 1 : 1).
 C0  V
At t = t1 , t2 , t3 , . . . . , the volume of N2 corresponds to concentration of product formed i.e., equal to x.
 x  Vt
V
 C0 – x  V – Vt  kt = 2.303 log10
V  Vt
3. Hydrolysis of esters (CH3COOC2H5)
CH3COOC2H5 (ester) + H2O + HCl (H+) 

 CH3COOH + C2H5OH
The reaction rate is measured by titrating the acid (CH3COOH) produced against a standard alkali solution.
Note that when a test sample is prepared from the reacting mixture, there are two acids : one is mineral acid
H+ (HCl or any other) and second is CH3COOH produced. So volume of alkali used gives titration value
for both acids. The data is collected in the following manner.
Time instants t=0 t1 t2 t3 t4 t
Vol. of NaOH V0 V1 V2 V3 V4 V
At t = 0, V0 is the volume NaOH used to neutralise the mineral acid present (H+) being used as catalyst.
(At t = 0, no CH3COOH is yet produced)
At t =  (i.e. at the end of hydrolysis), V is the volume of NaOH used to neutralise whole of CH3COOH
plus vol. of HCl present. At t =  , volume of CH3COOH corresponds to volume of ester taken initially.
 C0  V – V0 (as V0  vol. of HCl)
At t = t1 , t2 , t3 , . . . . , V1 , V2 , V3 , . . . . corresponds to vol. of HCl plus vol. of CH3COOH being

produced.
 x  Vt – V0
 C0 – x  (V – V0) – (Vt – V0)  C0 – x  V – Vt
V  V0
 kt = 2.303 log10 V  V
 t

4. Kinetics of some reactions can be studied by measuring optical rotation of reaction mixture at different
interval of time.
(i) Inversion of Cane Sugar (C12H22O11)
C12H22O11 + H2O + H+ 
 C6H12O6 (glucose) + C6H12O6 (fructose)
The rate is measured by measuring the change in the angle of rotation (optical activity) by a polarimeter.
Sucrose is dextro-rotatory, glucose is dextro-rotatory and fructose is leavo-rotatory. The change
produced in rotatory power in time t gives a measure of x, the quantity of sucrose decomposed in that
time. The total change in the rotatory power produced at the end of the reaction gives the measure of
C0, the initial concentration of sucrose.
If r0, rt and r represent rotations at the start of reaction, after time t and at the end of reaction
respectively, then
 C0  r0 – r and x  r0 – rt
 C0 – x  rt – r 
r0  r
 kt = 2.303 log10 r  r
t 
(ii) Consider the following first order reaction on which A, B and C are optically active compounds which
rotate the place polarized light in the clockwise or anticlockwise direction.
A(soln.)  B(soln .) + C(soln.)
Time 0 t 
Total rotation in degrees r0 rt r
Let the specific optical rotations of A, B and C per unit concentration be, ra , rb and rc (including +ve
or –ve sign).
Let the initial concentration of A be C0 and the decrease in concentration till time t be x.
A(soln .)  B(soln .) + C(soln .)
At time = 0 C0 0 0
At time = t C0  x x x
At time =  0 C0 C0
1 Co
Such that k = In
t Co x
Optical rotation at time = 0, ra C0 = r0 .…(i)

Optical rotation at time = t, ra (C0  x )  x rb  x rc = rt .

ra C0  x(rb + rc  ra ) = rt
r0  x (rb + rc  ra ) = rt .…(ii)
Optical rotation at time  , C0 (rb + rc ) = r .…(iii)
From equation (ii)
rt  r0
x .…(iv)
(rb + rc  ra )
1
Since constant involved in x is (r + r  r ) , the same constant must appear in expression of C0 .
b c a
Thus, subtracting equation (i) from equation (iv), we get :
r  r0
C0 = .…(v)
(rb + rc  ra )
Subtracting equation (iv) from equation (v)
r  r1
C0  x 
(rb  rc  ra )
1 r r
 k  ln  0
t r  rt
5. In first-order reactions involving gases, sometime measuring the pressure of the reaction mixture is very
good method for measuring reaction rates.
For example consider decomposition of arsine gas (AsH3).
3
AsH3 (g) 
 As (s) + H (g)
2 2
The rate of reaction is measured as the increase in pressure of the reaction mixture. Note that there is an
increase in number of moles of the gaseous products to the right, so as the reaction proceeds, there will be
an increase in pressure of contents (P  n).
Let the initial pressure of AsH3(g) is P0, if x is the decrease in pressure of AsH3(g) after time t.
3
AsH3(g)  
 As (s) + H 2 (g)
2
C0  initial pressure P0 0 0
3
Ct  partial pressure P0 – x 0 x
2
Arsenic is solid, so P(As) = 0

After time t, let Pt be the total pressure, then

3x
Pt = P(AsH3) + P(H2) = (P0 – x) +
2
x
 Pt = P0 +  x = 2 (Pt – P0)
2
Now C0  P0
P0
and Ct  P0 – x  P0 – 2 (Pt – P0)  3P0 – 2Pt  kt = 2.303 log10
3 P0  2 Pt
On similar pattern, please try to write the expression for Ist order rate law for following first-order
reactions. (in terms of Po and Pt )
1
1. N2O(g) 
 N2(g) + O (g)
2 2
2. (CH3)3C – O – O – C(CH3)3 (g) 
 2 (CH3)2C = O(g) + C2H6(g)
ACTIVATION ENERGY (Ea) Section - 4
A mixture of magnesium and oxygen does not react at room temperature. But if a burning splinter is introduced
to the mixture, it burns vigorously. Similarly a mixture of methane and oxygen does not react at room
temperature, but if a burning match-stick is put in the mixture, it burns rapidly. Why it happen like this, that
some external agents has to be introduced in order to initiate the reaction ?
According to the theory of reaction rates “ for a chemical reaction to take place, reactant molecules
must make collisions among themselves ”. Now in actual, only a fraction of collisions are responsible
for the formation of products, i.e., not all collisions are effective enough to give products. So the collisions
among reactant molecules are divided into two categories :
Effective collisions and In-effective collisions
Effective collisions are collisions between the molecules which have energies equal to or above a certain
minimum value. This minimum energy which must be possessed by the molecules in order to make an
effective collision (i.e., to give a molecule of products) is called as threshold energy. So it is the effective
collisions which bring about the occurrence of a chemical reaction.
Ineffective collisions are the collisions between the molecules which does not posses the threshold energy.
These can not result in a chemical reaction.

Now most of the times, the molecules of reactants do not possess the threshold energy. So in order to make
effective collisions (i.e., to bring about the chemical reaction), an additional energy is needed to be absorbed
by the reactant molecules. This additional energy which is absorbed by the molecules so that they achieve
the threshold energy is called as energy of activation or simply activation energy. It is represented as Ea.
Note :  The progress of the reaction can studied in a graph with energy of the reacting system. You can find
H and Ea from graph below.
 All the colliding molecules must collide at a proper orientation for a collision to be effective, other than
“sufficient energy” factor. A reaction having more number of reactants (high molecularity) is expected
to be slower because it is less probable that all the reactant molecules, with energy greater than
activation energy collide simultaneously at proper orientation.
A reaction which needs higher activation energy is slow at a given temperature.

1
For example : NO(g) + O (g) 
 NO2(g) is faster at ordinary temperature whereas the following
2 2
reaction :
1
CO(g) + O (g)   CO2(g) is slower at the same temperature as the value of Ea for the second
2 2
reaction is much higher.
Arrhenius Equation :
Arrhenius proposed the following equation for the determination of activation energy (Ea) at a given
temperature T.
k  e E a / RT  k  A e E a / RT
where Ea = activation energy, A = frequency factor and k = rate constant
Simplifying the equation :
Ea
log10 k   log10 A
2.303 RT

Now a plot of log10 k or n k vs 1/T will be a straight line whose equation is given above. If k1 is the
value of the rate constant at T1 K and k2 is the value of rate constant at T2 K for a reaction whose energy
of activation is Ea , then
k1  A e Ea /RT1  k2 Ea  T2  T1 
 Divide and take loge on both sides to get : log10   
and k 2  A e Ea / RT2  k1 2.303RT  T1T2 
This equation is called as Integrated Arrhenius equation.

This equation is very useful in determining the value of Ea of
a reaction by knowing the values of k1 and k2 at different
temperatures T1 and T2.
Note :  For most of the reactions, a 10° C rise near the room temperature, the rate constant is almost
k35 C
2
doubled i.e. k .
25 C
This can be explained by the fact that the number of molecules possessing energy greater than the
threshold energy increases tremendously as shown by the shaded area (a–b–f–e–a) in the figure.
 The fraction of molecules having internal energy greater than or equal to Ea is equal to e E a /RT .
This shows that as temperature increases, the number of molecules crossing this energy barrier
increases tremendously, accounting for the increase in the rate constant.

 Rate constant ‘k’ can also be increased by reducing ‘Ea’ to ‘Eac’ through the addition of a catalyst in
the system.
k1  Ae E a / RT and k 2  Ae  E ac / RT
k E  E ac
 log10 2  a
k1 2.303RT
(k 2 ) f (E a ) f  (E ac )f
Note : log10  . . . .(i)
(k1) f 2.303 RT
(k 2 )b (E a ) b  (E ac ) b
and log10  . . . .(ii)
(k1 )b 2.303RT
(k 2 )f (E a )f  1 1 
log10     . . . .(iii)
(k1 )f 2.303R  T1 T2 
(k 2 )b (Ea )b  1 1 
log10     . . . .(iv)
(k1 )b 2.303R  T1 T2 
where (Ea)f and (Ea)b are the activation energies of the reaction in forward and backward reaction, and
(Eac)f and (Eac)b are the activation energies of catalysed reaction in forward and backword reaction.
Illustration - 6 The activation energy of the reaction : A + B   products is 105.73 kJ/mol. At 40C,
the products are formed at the rate of 0.133 mol/L/min. What will be rate of formation of products at 80C ?
SOLUTION :
Let the rate law be defined as
Using Arrhenius equation, find k at 40C.
At T1 : r1 = k1 [A]x [B]y
At T2 : r2 = k2 [A]x [B]y k2 E a  T2  T1 
log10 k  2.303 R  T T 
1  1 2 
 k2 
 r2 = r1  k 
 1

k 2 105.73 103  40  k2
 log10   100
k1 2.303  8.31  313  353 
  k1
k2  r2 = 0.133  100 = 13.3 mol/L/min

  2.0
k1
Illustration - 7 The activation energy of a non–catalysed reaction at 37C is 200 kcal/mol and the
activation energy of the same reaction when catalysed decreases to only 60.0 kcal/mol. Calculate the ratio of
rate constants of the two reactions.
SOLUTION :
kc 1
 log10 k  2.303 R T  E a  E ac 
k 1
 log10 c  (200 103  60 103 )
k 2.303  2  310
Illustration - 7 log10 k c  98.0

k
kc
  1098
k
Note : Decrease in the activation energy in forward and backward direction by the addition of catalyst is same. i.e.
(Ea)f – (Eac)f = (Ea)b – (Eac)b .Thus rate constant in forward and backward directions increases by same
kf
  kf
factor. Since, for a reaction A   B : K eq  , adding catalyst will not alter Keq of the reaction.
kb kb
IN-CHAPTER EXERCISE - B
1. Show that for a first order reaction, the time required to complete 99.9 % of the reaction is 10 times
that required for the half of the reaction.

FACTORS AFFECTING RATE OF REACTIONS Section - 5
Factors affecting Rate of Reactions

The rate of reaction depends upon following factors :
1. Concentration :
In general the rate of a reaction is directly proportional to the concentration of reactants, i.e., the rate
increases as the concentration of reactant(s) increases. For gaseous reaction, rate is proportional to the
partial pressures of reactant(s).
2. Nature of Reactants :
 The rate of reactions in which complex molecules are taking part is slower than those in which simple
molecules take part. A chemical reaction involves the rearrangement of atoms (i.e., breaking and
reforming of bonds), hence the rearrangement of molecules involving many bonds is rather slow
process and consequently the rate of a reaction is slower.
 Physical state of reactants also play key role in determining reaction rates. The greater is the surface
area of a solid surface, the faster is the rate of reaction involving solid molecules. For example, the
burning of wood is slower than the burning of a pulverized wood (due to increased surface area).
3. Effect of Catalyst :
The catalyst in general enhances the rate of reactions with out actually taking part in the reaction. The
catalyst is used up during the reaction but at the end of reaction it is recovered as such. The phenomenon of
increase in the rate of a reaction with the help of a catalyst is known as catalysis. Catalysts generally lower
the activation energy which enables more reacting molecules to cross the energy barrier and hence increased
rate of reaction.
4. Effect of Temperature :
The rate of a reaction increases by increasing the temperature. It is quite clear from Arrhenius equation
 k  A eE / RT  , that for small rise in temperature rate of reaction increases tremendously (increase in
a
exponential). In fact it is one of most significant factors that affects the rate most strongly. A 10C rise
in temperature, for most of the reactions, doubles the rate of reaction. On increasing the temperature,
the number of molecules possessing activation energy increases (i.e, effective collisions) by a large quantity,
as compared to the total increase in molecular collisions.

RADIOACTIVE DECAY Section - 6
It is a process in which an unstable nucleus spontaneously looses energy by emitting ionizing particles and
radiation. This decay results in an atom of one type (called the parent nuclide) transforming to an atom of
a different type (called the daughter nuclide). This is a stochastic (random) process i.e. it is impossible to
predict when a given atom will decay, but if a large number of similar atoms are given, the decay rate is
predictable. The substances which undego radioactivity are called as radioactive substance. It was discovered
by Henry Becquerel for atoms of Uranium. Later it was discovered that many naturally occurring compounds
of heavy elements like radium, thorium etc also emit radiations. At present, it is known that all the naturally
occurring elements having atomic number greater than 82 are radioactive. e.g. radium, polonium, thorium,
actinium, uranium, radon etc.
The S.I. unit of activity is becqueral (B.q). One Bq is defined as one decay per second. Other unit of
acticvity is Curic (Ci) and is related to Bq as : 1 Ci  3.7  1010 Bq
Type of decay :
Following are the decay generally occurring in nature :
(i)   decay : In this decay, a helium nucleus (42 He) is emitted.
  particles are He nuclei. they carry a charge of 2e and mass equal to (roughly) 4m p . They
have less penetrating power but high ionizing power and they can be deflected by electric and
magnetic fields.
An   decay is represented as :
A A 4 4
Z X  Z  2Y  2 He (  particle)
Parent Daughter
nucleus nucleus
238 234
e.g. 92 U  90 Th  24 He
If the above reaction is spontaneous i.e. Q-value (or disintegration energy) is positive, it can also be
represented as :
238 234
92 U  90 Th  42 He  Q
where Q  m 238
92 U  90
m 238 m

Th  24 He  931.5 MeV
and m A X represents mass of the nuclide ZA X in amu (or  )

Z
(ii)   decay : In this decay, a nucleus spontaneously by emitting an electron (e  ) or a positron
( e  mass equal to me and charge +e). They can be deflected by electric and magnetic fields.
They have low ionising power but high penetrating power.

Type of  decay :
(a)  
 decay : An e 01e is emitted by the nucleus as :
A
ZX  ZA 1 Y  10 e  v (anti  neutrino)
In this decay, a proton transforms into a neutron within the nucleus emitting a e  :
1
on  11 p  01 e  v
32 32
e.g. 15 p  16 S  01e  v
(b)

0

  decay : A positron e  1e is emitted by the nucleus as :
A
Z X  ZA 1 Y 10 e  v(neutrino)
In this decay, a proton transforms into a neutron within the nucleus emitting a e :
1 1
1 p  0n  10 e  v
The symbols v and v represents neutrino and anti-neutrino, these are neutral particles with zero rest
mass they travel with speed of light, and they very weakly interact with matter.
Application of Radioactivity and Radioisotopes :

Radioisotopes find numerons uses in different areas. Some important applications of radioisotopes are as
follows :
(i) Tracers : By incorporating a small amount of a radioisotope in a reaction system, one can trace
the course of the reaction. Such a sample of radioisotope is called tracer. Since all the isotopes of an
element are chemically equivalent, the monitored path of the isotope will indicate the path of the
reaction. Consider the following esterification reaction :
By labelling the oxygen atom of methanol with 18O and then using it in the esterification, it can be
proved that the starred oxygen comes from the alcohol and not from the acid as the ester is found
enriched with 18 O isotope. The use of 14 C as a radioactive tracer using labelled compound is well
known. The dynamic nature of chemical equilibria has been established by the use of labelled
compounds.

(ii) Age of Minerals Rocks : It involve determination of either a spaces formed during a radioactive
decay or of the residual activity of an isotope which is undergoing decay. The former may be
illustrated by helium dating. Helium present in uranium mineral has almost certainly been formed
from   particles.
A gram of uranium in equilibrium with its decay products produces approximately 107 g of helium
per year. So if the helium and uranium contests of a mineral are known, the age of the mineral can be
estimated.
238 which has a half life of
The lather can be illustrated by considering a rock containing 92 U
238
4.5  109 years. We have seen that in the uranium decay series, 92 U after a series of decay give
206
the stable isotope 82 Pb as the end product. Asuming that initially the rock did not contain any lead,
238
we can determine the age of the rock by measuring the ratio of 92 206
U and 82 Pb and using the
equation :
N t = N 0e kt
where N 0 and N t are the amounts of uranium present initially (t = 0) and after the lapse of time t,
respectively and k is the decay constant.
(iii) Radiocarbon Dating : Radiocarbon (14

6 C ) dating of historical wooden derived objects is based
on knowledge that the cosmic ray intensity has been practically constant for thousands of years.
14 is formed in the upper atmosphere by the action of cosmic radiation on
6 C
14
7 N  10 N  14 1
6 C  1H
The 14C so produced is eventually converted into carbon dioxide, which is turn is incorporated
into plants and trees by the process of photosynthesis and then finds way into animals which eat
plants. Because of the natural plant-animal cycle, an equilibrium is set up and all living matter
contains the same small proportion of as it contains the same small proportion of as it occurs in
the atmosphere. Once the plant or animal dies, the uptake of carbon dioxide by it ceases and the
level of in the dead begins to fall due to the decay which undergoes.
14 14
6C7n  01 
The half life (t1/ 2 ) period of 14C is 5770 years. A comparison of the  - activity of the dead
matter with that of the carbon still in circulation enables measurement of the period of isolation of the
material from the living cycle. The method, however, ceases to be accurate over period longer than
two or three half life periods of 14C . The proportion of 14C to 12 C in living matter 1:1012.

Illustration - 8 The beta activity of 1g of carbon made from green wood is 15.3 counts per minute. If the
activity of 1 g of carbon derived from the wood of an Egyption mummy case is 9.4 counts per minute the
same conditions, how old is the wood of the mummy case ?
SOLUTION :
0.693 0.693
k= = = 1.20×104 yr 1
t1/2 5770
N0 kt
log =
N t 2.303
1.20×104 × t N 15.3
= log 0 = log
2.303 Nt 9.4
2.303 15.3
Hence t = 4
log
1.20×10 9.4
t = 3920 years.
Illustration - 9
One of the hazards of nuclear explosion is the generation of Sr 90 and its subsequent
incorporation in bones. This nuclide has a half life of 28.1 year. Suppose one microgram was absorbed by a
new born child, how much Sr 90 will remain in his bones after 20 years.
SOLUTION :
Given t1/ 2 = 28.1year, m = 106 g, t = 20 year, m = ?
°
2.303 m
 t= log °
 m
2.303× 28.1 106

 20 = log
0.693 m
 m = 6.1×107 g
Illustration - 10 0.1 g atom of radioactive isotope X A ( half-life 5 days ) is taken. How many number of
Z
atoms will decay during eleventh day?
SOLUTION :
N = 0.1 g atom and t = 10 days and t1/ 2 = 5 days
°

2.303 N 0.693 2.303 0.1

= log °  = log
t N 5 10 N
 Amount left after 10 days = 0.0250 g atom
Similarly if t = 11 days
0.693 2.303 0.1
= log
5 11 N
 Amount left after 11 days = 0.0218 g atom
 Amount decayed in 11 day  0.0250  0.0218
 3.2×103 g atoms
= 3.2× 6.023×1023 ×103 atoms = 1.93×10 21 atoms
Nuclear Stability :
 It has been found out that for a nuclei to be stable ratio of
neutrons to protons (n/p ratio) should lie in the range 1 to
1.5.
 On plotting the graph of no. of neutrons to no. of protons,
the stable nuclei lie in a well defined belt, called stability
belt.
 The nuclei with atomic number upto 20 (Z = 20, n = 20 i.e. upto 40

20 Ca ) have n/p ratio close to 1 i.e.
plot is linear with slope equal to 45 . With increase in atomic number, the graph becomes curved
whose slope increases gradually. Which means that as no. of protons increase, more no. of neutrons
are required to held them together.
 The nuclei with n/p ratio lying above or below the stability belt are unstable. They undergo positron
emission or K-capture or lose  or   particles so that their n/p ratio falls within the stability belt.
 With increase in atomic number beyond 20, a nuclide (below the stability belt) decays by  
( N  1)
emission or K-electron capture so that n/p ratio increase to so as to go up into the stability
(Z  1)
belt.
 Above the stability belt, the nuclide being neutron-rich decays by  , emission so that n/p ratio
( N  1)
decreases to so as to come down into the stability belt.
( Z  1)

 When the atomic number increases beyond 82, the stability is attained by   emission. The greater
importance of this emission lies in the fact that number of protons decreases and so the proton-proton
repulsion decrease.
Hence the stability increases.
Note :  It has been observed that the maximum number of stable nuclei are those which contain even number
of protons and even number of neutrons. The remaining stable nuclei contain either odd number of
protons or odd number of neutrons. The number of stable nuclei containing odd number of protons
and odd number of neutrons is the least.
e.g. there are only 4 nuclei (H, Li, B and N ) having odd number of both protons and neutrons.
No. of n No. of p No. of such nuclei

even even 160
even odd 56
odd even 52
odd odd 4
 A free neutron is unstable. However, a neutron is stable inside a nucleus due to the presence of
protons. Protons exert a repulsive force on each other and they need a “glue” to stay together in a
nucleus which is provided by neutrons through nuclear force.
Nuclear Fission & Fusion :

(a) Nuclear Fission
The breaking of a heavy nucleus into two or more fragments of comparable masses, with the release of
tremendous energy is called as nuclear fission. The most typical fission reaction occurs when slow moving
neutrons strike 92U 235 . The following nuclear reaction takes place :
235
92 U  0 n1  56 Ba141 36 Kr 92  30 n1  200MeV
 If more than one of the neutrons produced in the above fission reaction are capable of inducing a
fission reaction (provided U 235 is available), then the number of fissions taking place at successive
stages goes increasing at a very brisk rate and this generates a series of fissions. This is known as
chain reaction. The chain reaction takes place only if the size of the fissionable material ( U 235 ) is
greater than a certain size called the critical size.
 It the number of fission is a given interval of time goes on increasing continuously, then a condition
of explosion is created. In such cases, the chain reaction is known as uncontrolled chain reaction.
The forms the basis of atomic bomb.

 In a chain reaction, the fast moving neutrons are absorbed by certain substances known as
moderators (like heavy water), then the number of fissions can be controlled and the chain reaction is
such cases is known as controlled chain reaction. This forms the basis of a nuclear reactor.
(b) Nuclear Fusion
The process in which two or more light nuclei are combined into a single nucleus with the release of
tremendous amount of energy is called as nuclear fusion. Like a fission reaction, the sum of masses before
the fusion (i.e. of light nuclei) is more than the sum of masses after the fusion (i.e. of bigger nucleus) and
this difference appears as the fusion energy. The most typical fusion reaction is the fusion of two deuterium
nuclei into helium.
2
1 H 2  2 He4  21.6 MeV
1H
For the fusion reaction to occur, the light nuclei are brought closer to each other (with a distance of
1014 m ). This is possible only at very high temperature to counter the repulsive force between nuclei.
Due to the is reason, the fusion reaction is very difficult to perform. The inner core of sun is at very high
temperature, and is suitable for fusion, In fact the source of sun’s and other start’s energy is the nuclear
fusion reaction.
Laws of Radioactive Decay :

The laws of Radioactive decay are as follows :
 The disintegration of a radioactive substance is random and spontaneous.
 Radioactive decay is purely a nuclear phenomenon and is independent of any physical and chemical
conditions.
 The radioactive decay follows first order kinetics, i.e., the rate of decay is proportional to the number of
undecayed nuclei in a radioactive substance at any time t. If d/N be the number of nuclei disintegrating in
dN
time dt, the rate of decay is given as .
dt
dN
From first order kinetic rate law :  N
dt
where  is called as decay or disintegration constant.
dN
Rate of decay (R) i.e. Number of nuclei decaying per unit time is defined as 
dt
dN
 R (t )  
dt
Let N 0 be the number of nuclei at time t = 0 and N t be the number of nuclei after time t, then according
to integrated first order rate law, we have:

Nt  N 0 e t
N N
 t  n 0  2.303 og 0 and R(t)   N 0 e t  N where R0 is the decay rate at
Nt Nt
t 0
 The half life (t1/2 ) period of a radioactive substance is defined as the time in which one-half of the radioactive
substance is disintegrated. If N 0 be the number of nuclei at t  0 , then in a half life t1/ 2 , the number of
nuclei decayed will be N 0 .
N0
Nt  N 0 e t …(i)   N 0 et1/2 …(ii)
2
n
Nt  1 
From (i) and (ii)    n : number of half lives  t
N0  2  t1/ 2
0.693
The half life (t1/2 ) and decay constant () are related as : t1/ 2 

 The mean life () of a radioactive substance is equal to the sum of life times of all atoms divided by the
number of all nuclei and can be calculated as follows :
No. of nuclei decaying between time t and t  dt are equal to dN = R(t) dt
 dN  N 0 e t dt
The life of these nuclei is thus  N 0 e t dt  t


Total life of all nuclei   tN 0et dt 1
 Average life () =   0 
Total nuclei N0 
Illustration - 11 At a given instant there are 25% undecayed radio-active nuclei in a sample. After 10
seconds the number of undecayed nuclei reduces to 12.5% Calculate (i) mean-life of the nuclei, and (ii) the
time in which the number of undecayed nuclei will further reduce to 6.25%.
SOLUTION :
25.0%  12.5%
0.693 1
 time taken is one half life  t1/ 2  10 sec or  or   0.1sec
t1/ 2 
12.5%  6.25%
 time taken is one half life  t  10sec

Illustration - 12 A radioactive sample of 238U decays to Pb through a process for which the half-life is
238 9
4.5  109 years. Find the ratio of number of nuclei of the Pb to U after a time of 1.5 10 years.
Given (2)1/3  1.26.

SOLUTION :
n
Nt  1  t 1.5  109 1
   where n   
N0  2  t1/ 2 4.5  109 3
1/3
Nt  1  1
   
N0  2  1.26
238
U  Pb
t 0 x 
t t x y y
x y (N )
  1.26   t Pb  0.26
x y x  y ( Nt )U
Illustration - 13 210 decays with a-particle to 82 Pb 206 with a half life of 138.4 days. If 1.0 g of
84 Po
210 is placed in a sealed tube, how much helium will accumulate in 69.2 days ? Express the answer in
84 Po
3
cm at STP..
SOLUTION :
t1/ 2  138.4 days, t  69.2 days

t 69.2 1
 No. of half-lives n   
t1/ 2 138.4 2
Amount of Po left after 69.2 days  1
 g  0.707 g
(2)1/2
 Amount of Po used in 69.2 days  1  0.707  0.293g
210
 Now 84 Po  82Pb 206  2 He 4
 210 g Po on decay will produce = 4 g He
4  0.293
 0.293 g Po decay will produce   5.581 103 g He
210
5.581103  22400
 Volume of He at STP   31.25 cm3
4

Illustration - 14 208
In nature a decay chain series starts with 90 Th 232 and finally terminates at 82 Pb .A
thorium ore sample was found to contain 8  105 ml of He at STP and 5 107 g of Th 232 . Find the age of
ore sample assuming that source of He to be only due to decay of Th232 . Also assume complete retention of
232
He with in the ore. [t1/ 2 of Th  1.39  1010 years ].
SOLUTION :
232
90 Th  82 Pb 208  6 2 He 4  41 e0
 6  22400 ml He is formed by 232 g thorium decay
232  8 105
 8  108 ml He is formed by  g thorium decay  1.38 107 g
6  22400
After time t, amount of thorium  5  107 g
At t = 0, amount of thorium in the sample  5  107  1.38  107  6.38 10 7 g
2.303 m 2.303  1.39  1010 6.38 10 7

Now, t  log   log  4.89  109 years
 m 0.693 5  107
Illustration - 15 An experiment requires minimum  activity produced at the rate of 346   particles per
99
minute. The half life period of 42 Mo99 which is a emitter is 66.6 hrs. Find the minimum amount of 42 Mo
required to carry out the experiment in 6.909 hours.
SOLUTION :
To carry out experiment, Activity at the last minute of 6.909th hour = 346 dpm.
2.303 A
Now, t  log
 At
2.303  66.6  A 
6.909  log   
0.693  346 
 A  6.909  0.693
log      0.03121
 346  2.303  66.6
 A  346  1.0745  371.77

371.77
Now, A   N

 N   66.6  60  35728.5  60  2143710
0.693
99
Amount of Mo required to carry out experiment in 6.909 hour   2143710  3.52  1016 g
23
6.023 10

ADVANCED KINETICS Section - 7
1. Parallel / Side Reactions (Elementary Reactions) :
d[A]  d[A] 
Rate of consumption of ‘A’ in A 
B :   k1[A]  Rate of Re action  k1 [A]   
dt 1  dt 1 
d[A]
Similarly, Rate of consumption of ‘A’ in A 
C :   k 2 [A]
dt 2
d[A] d[A] d[A]

 Overall (net) rate of consumption of ‘A’ =  
dt dt 1 dt 2 = –k1[A] – k2[A]
d[A]
 = – (k1 + k2)[A] = –koverall [A] . . . . (i)
dt
 The Overall reaction is also of the same order (here, Ist order) with koverall = k1 + k2
Check yourself that solution of (i) is :
[A] [A]0 e(k1  k2 ) t
d[B] d[C]
Also, from the rate equation :   k1[A] and   k 2 [A]
dt dt
Substituting the value of [A] (t) in the differential equation for [B] and [C] and integrating, we get :
t
k1[A]
[B]  [B]o   k1[A]0 e (k1  k 2 )t dt  [B]0 
(k1  k 2 )

1  e (k1  k 2 )t 
0
t
k 2 [A]
and [C]  [C]o   k 2 [A]0 e (k1  k 2 )t dt  [C]0 
(k1  k 2 )

1  e (k1  k 2 )t 
0
[B] k1
Also, if [B]0 and [C]0 = 0, we get : [C]  k
2

k1 = 10–3s–1 and k2 = 2 × 10–3s–1. Find the overall half life of the reaction.
SOLUTION :
koverall = k1 + k2 = 3 × 10–3s–1
0.693 0.693
t1/ 2   s  231 sec . [Note : Reactions are of first order].
koverall 3  103
2. Consecutive Reactions (Elementary Reactions) :
k
1  B 
2 k
A  C
d[A]
  k1[A] . . . .(i)
dt
d[B]
  k1[A]  k 2 [B] . . . .(ii)
dt
d[C]
  k 2 [B] . . . .(iii)
dt
On solving the above differential equations, we get :
[A]  [A]0 e  k1t . . . .(iv)
k1
[B]  [A]0
k 2  k1

e k1t  e  k 2 t  . . . .(v)
 k e k 2 t  k e k1t 
[C]  [A]0  1  1 2  . . . .(vi)
 k 2  k1 
 
Note : [A] + [B] + [C] = [A]0 [Assuming [B]0 = [C]0 = 0]

d[B]
[B] is maximum when 0
dt
 k1[A] = k2 [B]max. . . . . (vii)
d[B]
Using (v),   k1e k1t  k 2e  k 2 t  0  k e k1t  k e  k 2 t
dt 1 2
1 k
 t n 2
k 2  k1 k1
1 k2
Thus, at t = k  k  n k , [B] is maximum.
2 1 1
Illustration - 16 k  0.1 s 1 k 1 / 30 s 1
1
A  2
 B  C
Find the time at which concentration of B is maximum. Also, find the concentration of A, B, and C at this
instant. Take [A]0 = 1M
SOLUTION :
1 k2 1 0.1
[B] is maximum at t = k  k  n k  0.1  1/ 30  n 1 / 30  15  n 3 sec.
2 1 1
[A] t = 15 n3 = [A]0 e  k1t

1.5 1
= 1 e 0.115 n 3  e n (3 )
 31.5  M
3 3
 d[B] 
When [B] is max : k1[A] = k2 [B]max.   0
 dt 
1 1 1 1
   [B]max .  [B]max.  M
10 3 3 30 3
Also, [A] + [B] + [C] = [A]0

1 1 4
[C] = 1   1  M
3 3 3 3 3

3. Reversible Reaction (Elementary Reactions) :

k

1
A B
k2
d[A]
Net rate of consumption of ‘A’ = = –k1[A] + k2 [B]
dt
Also, [A] + [B] = [A]0  [B] = [A]0 – [A]
d[A]
 = – k1[A] + k2 ([A]0 – [A])
dt
d[A]
= – (k1 + k2) [A] + k2 [A]0
dt
d[A]
At equilibrium, = 0  k1 [A]eq = k2 [B]eq
dt
[B]eq k1
 eq [A]  k
K 
eq 2
Try yourself : Find [A]t = ? and [B]t = ?

Example - 1 The vapour pressure of two miscible liquids ‘A’ and ‘B’ are 300 and 500 mm of Hg respectively.
In a flask, 10 mol of ‘A’ is mixed with 12 mol of ‘B’. However, as soon as ‘B’ is added, ‘A’ starts polymerising
into a completely insoluble solid.This polymerisation follows first-order kinetics. After 100 minutes, 0.525
mol of a solute is dissolved which arrests the polymerisation completely. The final vapour pressure of the
solution is 400 mm of Hg. Estimate the rate constant of the polymerisation reaction. Assume negligible
volume change on mixing and polymerisation, and ideal behaviour for the final solution.
[Given, log1011 = 1.04]
SOLUTION :
We have :
PA0  300 mm Hg and PB0  500 mm Hg

nA0 = 10 mol and nB0 = 12 mol
Let the amount of A after 100 min is reduced to nA.
At this stage :
nTotal = nA + nB + nSolute = nA + 12 + 0.525
Mole fractions of A and B in the solution will be
nA 12
A  and B 
n A  12.525 n A  12.525
Since PTotal = PA0  A = PB0  B , , we get
nA 12
400  300   500 
n A  12.525 n A  12.525
Solving for nA, we get :

nA = 9.90 mol
nA   An
For the first-order kinetics, we have :
[A]0
kt  2.303log10
[A]t
10
or k(100 min)  2.303log10
9.9
 k =1.00  10 min = 1.67  10–6 s1
–4 1
Example - 2 A first order reaction : A   B requires activation energy of 89 kJ/mol. When 20% solution
of A was kept at 27C for 40 minutes, 25% decomposition took place. What will be the percent decomposition
in the same time in a 30% solution maintained at 37C ? Assume that the activation energy remains constant
in this range of temperature.
SOLUTION :
Note : It does not atter whether you take 20%, 30%, 40% or 70% of ‘A’ because first order reaction is independent
of the initial concentration of reactant.
At 27C, 20% of A decomposes 25%

C0 1 1
 kt = 2.303 log10 C = 2.303 log10 1  =  n 1  [ = 0.25]
t
100
 k(40) =  n
75
1 4
 k (at 300 K) = n min 1
40 3
Using Arrhenius equation find k at 310K.
k 310 E a  T2  T1 
log10 k   
300 2.303 R  T1T2 
3
log10 k 310  89 10  310  300   0.5
k 300 2.303  8.31  300  310 
 k(at 310 K) = k(at 300K)  10
Now calculate % decomposition at 310K using first order kinetics.
C0
kt = 2.303 log10 C
t
1
 k  40 = n
1 
1  1 4 
 n   n   10   40  0.91
1    40 3 
1 0.91
 log10   0.40
1   2.303
1
 2.5   = 0.6
1 
  = 0.6  60.0 % decomposition of A at 310 K.
Example - 3 A certain reaction A + B   products ; is first order w.r.t. each reactant with
k = 5.0 × 10–3 M–1s–1. Calculate the concentration of A remaining after 100s if the initial concentration of A
was 0.1 M and that of B was 6.0 M. State any approximation made in obtaining your result.
SOLUTION :
C
A + B 
 products Using, 2.303 log10 0A  k 0 t
C tA
Given : Rate = k [A][B] (2nd Order reaction)
Now, since [B] >> [A], [B] can be assumed to 0.1
 2.303 log10  k0 t = 3
remain constant throughout the reaction. Thus, C tA
the rate law for the reaction, becomes : 0.1
Rate  k0 [A]  log e 3
C tA
where k0 = k [B] = 5.0 × 10–3 × 6.0 s–1
[ loge x = 2.303 log10 x]
= 3.0 × 10–2 s–1
 C tA  10e 3  5  10 3 M
Thus, the reaction is now of first order [Pseudo
first order]. Check your approximation :
k [B]change = x = 0.1 – 5 × 10–3

Note : A + B 
 products
= 0.095 M
0.1M 6.0M
0.1 – x 6.0 – x 0.095
% [B]change = × 100% = 1.58%
6
Example - 4 The gas phase decomposition of N2O5 to NO2 and O2 is monitored by measurement of
total pressure. The following data are obtained.
Ptotal (atm) 0.154 0.215 0.260 0.315 0.346

Time (sec) 1 52 103 205 309
Find the average rate of disappearance of N2O5 for the time interval between each interval and for the total
time interval. [Hint : Integrated rate law is NOT to be used].
SOLUTION :
2N2O5 (g) 
 4NO2 (g) + O2 (g)
Initial Pressure (at t = 0) P0 0 0
At t = t P0 – 2x 4x x
1
Now : PTotal = (P0 – 2x) + 4x + x  x= (P – P 0)
3 Total
PN 2O5 = P0 – 2x = (5P0 – 2PTotal) = Pt
2
Thus, PN 2 O5  (Pt1 – Pt2) where Pt2 and Pt1 are the total pressures at time instants t2 and t1 (t2 > t1)
3
respectively
PN 2O5
Ptotal (atm) Time (sec) = Avg. Rate of disappearance of N2O5 (atm/sec.)
t
0.154 1
2 (0.154  0.215)
= –7.97 × 10–4
3 (52  1)
0.215 52
2 (0.215  0.260)
= – 5.88 × 10–4
3 (103  52)
0.260 103
2 (0.260  0.315)
= – 3.59 × 10–4
3 (205  103)
0.315 205
2 (0.315  0.346)
= – 1.99 × 10–4
3 (309  205)
0.346 309
Example - 5 In an ore containing Uranium, the ratio of U238 to Pb206 nuclei is 3. Calculate the age of
the ore, assuming that all the lead present in the ore is the final stable product of U238. The half life of U238 is
4.5  109 years.
SOLUTION :
Note : The radio active decay follows first order kinetics. Here, we take N0  C0 and Nt  Ct and   k
The first order rate equation for radioactive decay is :
N0 0.693
 t  2.303 log where  = t
Nt 1
2
N0 = initial nuclei (at t = 0)
Nt = final nuclei (at t)
 = decay constant or disintegration constant
U238 
 Pb206
N0  x 0
Nt  x – y y
N0 x
 
Nt x  y
x
Using t = 2.303 log10
xy
xy x 4
Given : 3  
y xy 3
2.303 4
 t=  4.5  109 log10
0.693 3
 t = 1.85  109 years.
Example - 6 The nucleidic ratio of 1H3 to 1H1 in a sample of water is 8.0 × 10–18 : 1. Tritium undergoes
decay with a half life period of 12.0 years. How many tritium atoms would a 10.0 gm of such sample contain
36 years after the original sample is collected ?
SOLUTION :
The ratio of tritium atoms to that of H–atoms
will be same as the ratio of moles of T-atoms  
  N T O  NT2O  2
to that of H–atoms, since 1 mole of T2O  2  40 
mole of T atoms and 1 mole of H2O  2 mole =  1018  6 1023   2
 9 
of H atoms.
= 5.33 × 106 atoms
Calculate the initial number of tritium atoms.
10 gm = mass of T2O + mass of H2O 36
No. of half lives   3
12
= n T 2 O  22  n H 2 O  18 ( x)
 
 8 1018 n H 2O  22  n H 2 O  18 1
x
1
Use : N t  N 0    N 0  
3
2 2
 n H 2O  18
1
10 5   5.33  106 atoms
 n H 2 O   8
18 9 = 6.66 × 105 atoms
5 18 40
 n T2O   8 10  1018
9 9
Example - 7 Dimethyl ether decomposes according to the following reaction :

CH3 – O – CH3 (g)   CH4 (g) + CO(g) + H2 (g)
At a certain temperature, when ether was heated in a closed vessel, the increase in pressure with time was
noted down.
Time (min) 0 10 20 30
Pressure (mm Hg) 420 522 602 678
(i) Show that the reaction is first order. (ii) Compute the pressure of CO (g) after 109 minutes.
SOLUTION :
CH3 – O – CH3 (g)  CH4 (g) + CO (g) + H2 (g) (all are gases)
time CH3 – O – CH3 CH4 CO H2
t=0 C0  P0 0 0 0
t=t Ct  P0 – x x x x
 Pt = P0 + 2x
1
 x= (P – P0)
2 t
C0 P 2 P0
  0 
C t P0  x 3P0  Pt
Now find k1, k2 and k3 using the first order kinetics
2 P0
kt = 2.303 log10
3P0  2Pt
2.303 2 (420)
k1 = log10 = 0.0129 min–1
10 3(420)  522
2.303 2 (420)
k2 = log10 = 0.0122 min–1
20 3(420)  602
2.303 2 (420)
k3 = log10 = 0.0123 min–1
30 3(420)  678
As k1  k2  k3 , the reaction is first order.

1
kaverage = (k1 + k2 + k3) = 0.0127 min–1
3
0.693
 t1/ 2   54.56 min
k
109
No. of half lives = 2
54.56
2
1 420
 (Pt )CH3OCH3  P0   
2 4
= 105 mm Hg = P0 – x
 x = PCO = 420 – 105 = 315 mm Hg
Example - 8 The decomposition of N2O5 according to following reaction is first order reaction :
2N2O5(g) 
 4 NO2(g) + O2(g)
After 30 min. from start of the decomposition in a closed vessel, the total pressure developed is found to be
250 mm of Hg and on complete decomposition, the total pressure is 500 mm of Hg. Calculate the rate
constant of the reaction.
SOLUTION :
2N2O5(g) 
 4NO2(g) + O2(g)
t=0 P0 0 0
t=t P0 – 2x 4x x
t= – 2P0 P0/2
P0 : initial presure ; Let Pt : pressure at 30 min and
P : pressure at the end of decomposition
1 1 5
 Pt = P0 + 3x  x= (P – P0) and P = 2P0 + P0 = P0
3 t 2 2
2 2
 P0  P  × 500 = 200 mm Hg
5 5
For the first order kinetics
C0
kt = 2.303 log10 C
t
C0 : initial concentration ; Ct : final concentration
C0 P0 1 50
Now C  P  2x and x  (250  200) 
t 0 2 3
C0 200 6
  
Ct 200  2  50 5
3
1 6
 k  2.303 log10  6.08  10 3 min 1
30 5

THINGS TO REMEMBER
1. k
mA  nB 
 pC  qD
m 1 d  A 1 d  B 1 d C 1 d  D
 Rate of reaction = k  A   Bn    
m dt n dt p dt q dt
where k depends only on T.
 Units of k = (mol/L)1 – n (time)–1
2. k
A 
B
2n  1  1 1
nth order reaction : Half life  t1/ 2    t1/ 2 
 n  1 kC0n  1 C0n  1
1  1 1 
and     kt
 n  1  C nt  1 Cn0  1 
k
3. First order reaction : A  B
C C0 1
kt  2.303 log10 0  2.303 log10  2.303 log10
Ct C0  x 1 
0.693
Half life  t1/2   (independent of initial concentration of the reactant)
k
x
1 t
C t  C0   where x  = No. of half lives
2 t1/ 2
4.  Arrhenius Equation : k  Ae Ea / RT
where A = Arrhenius factor OR Pre-exponential factorand Ea = Activation energy
 k can be increased by increasing T OR reducing Ea (addition of catalyst)
k Ea  1 1 
(i) Temperature effect : log10 2    
k1 2.303R  T1 T2 
(ii) Catalyst effect : log10 k 2  E a  E ac

k1 2.303 RT
SOLUTIONS TO IN-CHAPTER EXERCISE-B
2.303 C0 2.303 3  2.303

1. t 99.9 %  log10  log10 1000 
k C0  0.999 C0 k k
2.303log10 2 t 99.9% 3
t1/ 2     10
k t1/ 2 log10 2
Self Study Course for IITJEE with Online Support Things to Remember & Solutions 45
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Illustration - 1

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Vidyamandir Classes Electrochemistry - I
Electrochemistry - I
(Electrochemical Cells)
BASICS Section - 1
Electrochemisrty deals with the inter-conversion of electrical energy and chemical energy. This part of
Electrochemistry will deal with the conversion of chemical energy into electrical energy (Electrochemical
Cells).
Electrochemical Cells :
Consider the following redox reaction :
Zn(s) + Cu2+(aq) 
 Cu(s) + Zn2+(aq)
In the above reaction , Zn displaces copper ions (Cu2+) from aqueous solution. This reaction can be achieved
very easily in practice. Put a Zn rod into a solution of CuSO4 (containing Cu2+ ions). It is observed that blue
colour of CuSO4 solution disappears after sometime. What happens actually ? Zn loses 2e–s per atom and
Cu2+ ions in the solution accepts them. Cu2+ ions from solution in this manner are deposited out in form of
solid Cu and Zn goes into the solution as Zn2+ (colourless). The reaction can well be understood in terms of
two half reactions :
Oxidation :  Zn2+(aq) + 2e–
Zn(s) 
Reduction : Cu2+ (aq) + 2e– 

 Cu(s)
Note : (i) In this reaction, Zn atoms are directly giving electrons to the copper ions.
(ii) Another aspect of this reaction is that it is an exothermic reaction. This means decrease in energy of
the reacting system takes place which appears as heat.
Now, we can make the same reaction take place even if the copper ions and zinc rod are not in direct
contact. If we put the Cu2+ ions and Zn rod in two separate containers and connect the two by a conducting
metallic wire and introduce an inverted U shape instrument (called as salt-bridge), then electrons will still be
transferred through the connecting wires. The electrons from Zn rod travel to Cu2+ ions through the con-
necting wires and the same reaction takes place.

Electrochemistry - I Vidyamandir Classes
In such an arrangement, the solution does not get heated up. The loss in energy now appears as the potential
difference which is used to do the work in transferring the electrons from Zn to Cu2+ ions. Such an arrangement
is called as electrochemical cell or Galvanic cell or Voltaic cell. The potential difference which drives the
electrons from Zn to Cu2+ ions, is called as electromotive force (E.M.F.) of a cell.
An electrochemical cell (shown in diagram) mainly consists of two compartments : left hand electrode
(LHE) and right hand electrode (RHE). In LHE, oxidation takes place and is called as anode. In RHE,
reduction takes place and is called as cathode.
Anode is generally of that metal (or substance) which readily loses electrons (i.e., oxidised easily). A rod of
that metal is prepared and put into one of its solution in LHE to get anode. In RHE, a rod of metal that loses
electrons less easily as compared to the metal of LHE (in the diagram, Zn is taken in LHE and Cu is taken
in RHE) is prepared and put into one of its solution to get cathode. LHE and RHE are also known as two
half-cells. Now the electrons move from anode (LHE) to cathode (RHE) and hence a current flow is
maintained in the external circuit.
The two half cells are connected by a inverted ‘U’ shaped tube called as salt-bridge. The salt-bridge
contains solution of strong ionic salts like NaCl, NaNO3, KNO3 and KCl, etc., (salts of most reactive alkali
metals) soaked in a colloidal solution of agar-gel which allows only the movement of ions of salts, not water.
The role of a salt-bridge is very important as it allows the continuous discharge of the cell (i.e., the supply of
voltage from cell). The salt-bridge keeps the two solutions (i.e., in LHE and RHE) electrically neutral to
each other. In the Zn-CuSO4 cell, in left hand cell as Zn loses electrons, excess of positive charge (in form
of Zn2+ ions) is collected near LHE and as Cu2+ ions gets discharged (accepting electrons from Zn) in right
hand cell, excess of negative charge (in form of SO 24  ions) is accumulated near RHE. Now the salt-bridge
provides positive charge to RHE (in form of K+, Na+ ions) and negative charge to LHE (in form of Cl–,
NO3– etc) and thus bringing about the neutrality of two solutions. If this does not take place, a reverse
potential difference is created in the two compartments and thus breaking the continuous supply of voltage
(current), which is the purpose of the cell.
The efficiency of a cell is determined by the tendency of LHE to loose electrons and the tendency of RHE
to accept electrons. A measure of cell efficiency is called as electromotive force (EMF) or the voltage or the
difference in potentials of two electrodes. EMF is defined as the difference in the potential across LHE and
RHE due to which electrons from anode travel to cathode.
EMF value of a cell made up of such two half-cells is a constant provided that the concentration of electro-
lyte, temperature and the pressure (if gases are involved) remains constant. It means that EMF values do
change with concentration, temperature and pressure. EMF values are hence standardised at a temperature
of 25°C (298 K), a pressure of 1 atm (if gases are involved) and at concentrations of 1.0 M for all solutes
prevent as electrolytes. EMF value under these conditions is called as standard EMF and is denoted as E0.
EMF of a cell is measured as the difference of potentials of anode and cathode. The potential of a half-cell
or EMF of a half-cell (i.e., a cathode or anode) is called as electrode potential. It is defined as the tendency
of an electrode either to get oxidised or to get reduced i.e., to loose or gain electrons. electrode potentials
are of two types :

Oxidation Potential :
It is the tendency of an electrode to get oxidised, i.e., to loose electrons.
Reduction Potential :
It is the tendency of an electrode to get reduced, i.e., to accept electrons.
Electrode potentials at standard conditions (1 atm, 298 K and 1.0 M) are called as standard electrode
potentials.
Note :  Anode is the negatively charged electrode in electrochemical cell and positively charged in electrolytic
cell (to be discussed later) but it will always be the oxidation electrode (electrode on which oxidation
take place).
 Cathode is the positively charged electrode in electrochemical cell and negatively charged in electrolytic
cell (to be discussed later) but it will always be the reduction electrode (electrode on which reduction
takes place).
 We can also define cathode and anode electrodes as :
Anode : Electrode at which current enters.
Cathode : Electrode at which current leaves.
 An important property for an ionic salt to act as a salt bridge is that ionic mobility (ease with which
ions move in solution) of both cations anion should be similar. Also, it should not react with the
contents of either anode or cathode.
Types of Electrodes :
1. Metal in contact with its ions :
Metal (M) in contact with its ion (Mn+) is represented as M/Mn+ when it acts as oxidation electrode
(anode) and Mn+/M when it acts as reduction electrode (cathode). Whether a given electrode acts as
anode or cathode depends upon the other electrode with which it forms an electrochemical cell. So,
it is necessary to define both oxidation and reduction potentials for an electrode.
M / Mn+ is written as :
 Mn 
M(s)  (1.0 M)  ne  (oxidation electrode)
and its potential is called as oxidation potential and at standard state is represented as E0(M/Mn+).
Mn+ / M is written as :
M n  (1.0 M )  ne  
 M (s) (reduction electrode)
and its potential is called as reduction potential and at standard state is represented as E0(Mn+/M).
Note : Symbol “/” denotes the phase seperation between the two substances.

2. Gaseous electrode :
Gases like H2(g) can loose electrons to form H+ ions and hence can
act as anode and also H+ ion can add up electrons to form H2 (g)
and hence can act as cathode. Similarly gases like Cl2 (g) can add
electrons to form Cl ions and Cl ions can loose electrons to form
Cl2(g). The concentration of electrolytes is the value for [H+] ions
and we take pressure of gas in atm. A hydrogen electrode is made
by passing H2 (g) at 1 atm near an electric conductor made up of
platinum (for conduction of e–s) dipped in an aqueous solution
containing H+ ions (generally HCl) as shown in figure.
Electrode representation : Pt, H2/H+

or H+/H2, Pt
Its electrode potentials are represents as :
1
E (H 2 / H  ) :  H  (aq.)  e 
H 2 (g)  (oxidaion potential)
2
1
E(H  / H 2 ) : H  (aq.)  e 
 H 2 (g) (reduction potential)
2
1
E0 (H 2 / H  ) :  H  (1M)  e 
H 2 (1 atm)  (standard oxidation potential)
2
1
E0 (H  / H 2 ) : H  (1M)  e 
 H 2 (1atm) (standard reduction potential)
2
Similarly, Cl2/Cl– electrode is prepared by passing Cl2 gas and taking HCl (aq) or KCl (aq) as electrolyte.
3. Redox Electrodes :
In this type of electrode, an inert wire (e.g. Platinum) is placed in a solution (electrolyte) containing ions of an
element in more than one oxidation states. e.g. Pt wire dipped in an electrolyte of Fe2+ and Fe3+ ions. The
electrode (inert material wire) acts as a source / sink for electrons.
Electrode representation : Pt/Fe3+ , Fe2+
Electrode reaction : As cathode : Fe3+ (aq.) + e– 
 Fe2+ (aq.)
As anode : Fe2+ (aq.) 

 Fe3+ (aq.) + e–
Another example : Pt/ MnO 4 , Mn 2+ , H +
As cathode : MnO 4 (aq.)  8H  (aq.)  5e  

 Mn 2  (aq.)  4H 2 O   

Redox electrodes can also be made using substances that exist in two different oxidation states. Quinhydrone
is an equimolar mixture of benzoquinone (Q) and hydroquione (H2Q)
Electrode representation : Pt/H2Q, Q, H+
Electrode reaction : As anode :
Note : If two substances are in same solution then in the cell or electrode representation, they are separated by
comma (‘,’).
4. Calomel Electrode :
It consists of mercury covered with mercurous chloride (calomel) in contact with a solution of KCl :
Electrode representation : Hg / Hg2Cl2 / Cl–
Electrode reaction :  2 Hg ( ) + 2Cl– (aq.)

As cathode : Hg2Cl2 (s) + 2e– 
As anode :  Hg2Cl2 (s) + 2e–

2 Hg () + 2Cl– (aq.) 
Most common calomel electrode is the saturated catomel electrode (SCE) in which the concentration of
0
KCl is at its saturation (about 3.5 M). ESCE  0.24 V (w.r.t. SHE)
5. Silver - Silver Chloride Electrode :

It consists of a pure silver wire in a solution of KCl saturated with solid silver chloride.
Electrode representation : Ag/AgCl/Cl–
Electrode reaction : As cathode:  Ag(s) + Cl–(aq.)

AgCl(s) + e–  E0Reduction  0.222 V
As anode :  AgCl(s) + e–

Ag(s) + Cl–(aq) 
If saturated KCl solution, E0reduction become 0.197 V (w.r.t. SHE)
6. Mercury - Mercurous Sulphate Electrode :

In this electrode, the metal is mercury, the sparingly soluble compound is mercurons sulphate (Hg2SO4) and
the source of SO42– anions is H2SO4 or K2SO4. It represented as :

Electrode representation : Hg / Hg2SO4 / SO42–
Electrode reaction :  2 Hg( ) + SO42– (aq.)

As cathode : Hg2SO4(s) + 2e– 
E0Reduction  0.616 V (w.r.t. SHE)
As anode : 2 Hg( ) + SO42– (aq.) 

 Hg2SO4(s) + 2e–
Note : [1] Calomel electrodes, Silver - Silver Chloride electrodes and Mercury - Mercurons Sulphate electrodes
are secondary reference electrodes. Silver - Silver electrodes and calomel electrodes are the most
commonly used (practically) as a reference electrode rather than SHE / NHE due to practical difficulties
associated with its (SHE) used and maintenance.
[2] The potential of metal - metal ion electrode and metal-metal insoluble salt-slat anion electrode is same
while their standard potentials are not same. Statndard potential are related by the following equation.
2.303RT
E  E  log K sp (MX) [Refer example - 4]
X  / MX / M M  /M F
7. Amalgam electrodes :
This is the modified version of Metal / Metal - ion electrode in which metal strip is replaced by metal
amalgam.
e.g. Na (in Hg at c1 M) / Na+ (c2 M)
Electrode Potentials :
It is impossible to measure the absolute EMF’s (electrode potentials) for half electrodes. This is done by
arbitrarily selecting one half cell and setting its electrode potential as ‘0’ volts. The electrode potentials of
other half cells can then be measured by combining them with the standard reference electrodes in a cell
arrangement.
The reference electrode against which all other half cells are generally measured is the hydrogen electrode
half-cell at a concentration of H+ ions equal to 1.0 M and H2(g) at 1 atm pressure kept at 25°C (298 K). It
is also known as SHE (standard hydrogen electrode) or NHE (normal hydrogen electrode). Its potential is
taken as ‘0’ volts.
E0(H2 / H+) = 0 = E0(H+ / H2)
Now other half cells can be divided into two categories : One which will act as anode and other which will
act as cathode in a cell arrangement with SHE. Each type of cell arrangement will give an EMF value which
will be actually the EMF value of known electrode as EMF value of SHE is ‘zero’ volts (whether SHE acts
as anode or cathode).
For example : Cu electrode (half cell) acts as cathode with SHE, i.e., as :
Cu 2  / Cu : Cu 2  (aq) (1.0M )  2e  
 Cu (s) .

The experimental measurement of EMF value for this cell arrangement give 0.34 volts. Since Cu electrode
shows reduction with SHE, the given value of EMF represents the reduction potential of Cu half-cell.
E0 (Cu2+ / Cu) = 0.34 volts
The oxidation potential of Cu half-cell is just the negative of this value.

E0 (Cu/Cu2+) = – 0.34 volts [Note : Ereduction = – Eoxidation]
Note : Reduction potential is taken as a standard potential i.e. if electrode potential is given (and nothing is mentioned
whether it is oxidation or reduction), it is taken as the reduction potential, by default.
Rules for assigning sign (+ve or –ve) to electrode potentials :

1. The oxidation potential of half-cell (or an electrode) is given a positive sign if the given electrode acts
as anode in a cell arrangement with SHE and its reduction potential is given a negative sign with the
same magnitude. For example : oxidation potential of active metals like Na, Mg, Al, Zn, Fe etc. is
given a positive sign.
2. The reduction potential of half-cell (or an electrode) is given positive sign if the given electrode acts as
cathode in a cell arrangement with SHE and its oxidation potential is given a negative sign with the
same magnitude.
For example : reduction potential of less active metals like Cu, Ag etc is given a positive sign.
Note : Electrode potential measured in this manner are called as standard hydrogen scale potentials.
0 ):
Standard EMF of a Cell ( Ecell
E0cell can be defined in two ways as :
 
(i) E 0cell  standard reduction potential  standard reduction potential 
 of cathode of anode 

E0cell  E0reduction 
cathode
0

 Ereduction
anode

 
(ii) E0cell = standard oxidation potential  standard oxidation potential 
 of anode of cathode 

E0cell  E0oxidation 
anode
0

 Eoxidation 
cathode

Construction of a cell and writing cell representation :

It is clear that an electrochemical cell will be developed by two half-cells. If you arbitrarily select two half-
cells for the purpose of constructing a galvanic cell, then always act in following manner :
Compare the reduction potentials of two electrodes. The electrode whose reduction potential has greater
positive value is made the cathode and the other electrode is made the anode.
Note : (i) Constructing the cell in this manner will always give a positive EMF otherwise sometimes if an elec-
trode is chosen wrongly, the EMF comes out to be negative. In that case, you should reverse the
electrodes i.e., make anode the cathode and vice-versa.
(ii) It is now standardised to use the definition of EMF in terms of standard reduction potential.

E 0cell  E 0reductioncathode

 E 0reduction
anode

Cell Representation :
The cell representation of a cell is written as :
LHE | | RHE | | : represents salt-bridge
In general, if two electrodes at standard conditions are :
M/Mx+ and N/Ny+
and let E0(Mx+ / M) < E0 (Ny+ / N).
So M / Mx+ is the anode and N / Ny+ is the cathode. [ Electrode having higher reduction potential has to
be cathode.]
LHE  M(s) / M x  (1.0 M) and RHE  N y  (1.0 M) / N
M(s) / M x  (1.0M) || N y  (1.0M) / N(s) is the cell representation for a cell at standard state.
If the cell is not at standard state, then let c1 be the concentration of anode and c2 be the concentration of
cathode. In that case, cell representation will be :
M(s) / M x  (c1M) || N y+ (c 2 M) / N(s)
Analysis of a given cell representation :

Analyse : M(s) / Mx+ (c1 M) || Ny+(c2M)/N(s)
(i) Anode : M(s) /Mx+(c1M)
Half-cell reaction :  M x (c1 )  xe

M(s)  [oxidation]
(ii) Cathode : Ny+(c2M) / N(s)
Half-cell reaction : N y (c 2 )  ye 

 N(s) [reduction]

Overall Reaction : y M(s)  x N y  (c2 M) 

 yM x  (c1M)  xN(s)
[Balance the num ber of e–s transfered at Cathode and Anode]
Electrochemical Series :
In this series, the standard reduction potential measured on hydrogen scale are arranged in increasing order.
Half Cell Electrode reaction Reduction

Potentials (volts)
Li+ / Li Li+ (aq.) + e– 

 Li (s) – 3.04
K+ / K K+ (aq.) + e 
 K(s) – 2.93
Ca2+/Ca Ca2+(aq.) +2e– 

 Ca(s) – 2.87
Na+ / Na Na+ (aq.) + e– 

 Na(s) – 2.71
Mg2+ / Mg Mg2+ (aq.) + 2e 

 Mg(s) – 2.37
Pt, H2 / H H2 (g) + 2e  –

 2H (aq.) – 2.25
Al3+ / Al Al3+ (aq.) + 3e 

 Al(s) – 1.66
Oxidising Power decreases
Reducing Power increases

Mn2+/Mn Mn2+ (aq.) + 2e– 
 Mn(s) – 0.91
OH / H2 , Pt 2H2O () + 2e–  –

 H2(g) + 2 OH (aq.) – 0.83
Zn2+ / Zn Zn2+ (aq.) + 2e– 

 Zn(s) – 0.76
Cr3+ / Cr Cr3+ (aq.)+ 3e– 

 Cr(s) – 0.74
Fe2+ / Fe Fe2+ (aq.) +2e– 

 Fe(s) – 0.44
Cr3+ / Cr2+, Pt Cr3+ (aq.) + e– 

 Cr2+(aq.) – 0.41
Cd2+ / Cd Cd2+ (aq.) + 2e– 

 Cd(s) – 0.40
Co2+ / Co Co2+ (aq.) + 2e– 

 Co(s) – 0.28
Ni2+/Ni Ni2+ (aq.) + 2e– 

 Ni(s) – 0.25

I– / AgI / Ag AgI(s) + e– 
 Ag(s) + I (aq.) – 0.15

Sn2+ / Sn Sn2+ (aq.) + 2e– 

 Sn(s) – 0.14
Pb2+ / Pb Pb2+ (aq.) + 2e– 

 Pb(s) – 0.13
Fe3+ / Fe Fe3+ (aq.) + 3e 

 Fe(s) – 0.04
H+ / H2 , Pt 2 H+ (aq.) + 2e 
 H2(g) 0.00
Br / AgBr / Ag AgBr(s) + e–  –

 Ag(s) + Br (aq.) 0.10
Cu2+ / Cu+, Pt Cu2+ (aq.) + e  +

 Cu (aq.) 0.16
Sn4+ / Sn2+, Pt Sn4+ (aq.) + 2e– 

 Sn2+(aq.) 0.15
SO42–/H2SO3 SO42– (aq.) + 4H+ + 2e– 

 H2SO3 (aq.) + H2O() 0.17
Cl / AgCl/ Ag AgCl(s) + e 

 Ag(s) + Cl  (aq .) 0.22
Cl / Hg 2Cl2 / Hg  Pt  Hg2Cl2  s   2e  

 2 Hg     2 Cl  aq. 0.27
Oxidising Power decreases
Reducing Power increases

Cu2+ / Cu Cu2+ (aq.) + 2e– 
 Cu(s) 0.34

Pt, O 2 / OH  O2(g) + 2H2O() + 4e 
 4 OH (aq.) 0.40
Cu+ / Cu Cu+ (aq.) + e 

 Cu(s) 0.52
I2/I, Pt 1/2I2(s) + e  
 I (aq.) 0.54
Pt, O2 / H2O2 O2(g) + 2H+ (aq.) + 2e– 

 H2O2 (aq.) 0.68
Fe3+ / Fe2+, Pt Fe3+ (aq.) + e–  2+

 Fe (aq.) 0.77
Hg22+ / Hg (Pt) 1/2Hg22+ (aq.) + e– 

 Hg(s) 0.79
Ag+ / Ag Ag+ (aq.) + e 

 Ag(s) 0.80
Hg2+ / Hg22+ 2Hg2+ (aq.) + 2e–  2+

 Hg2 (aq.) 0.92
NO3– / NO, Pt NO3– + 4H(aq.) + 3e– 

 NO(g) + 2H2O() 0.97
Pt, Br2 / Br– Br2 () + 2e–  

 2 Br (aq.) 1.09
MnO2 / Mn2+ MnO2(s) + 4H+(aq.) + 2e–  2+
 Mn (aq.) + 2H2O() 1.23

H+ / O2 / Pt O2(g) + 4H+(aq.) + 4e– 

 2 H2O() 1.23
Cr2O72– /Cr3+ Cr2O72– (aq.) + 14H+ (aq.) + 6e–  3+

 2Cr (aq.) + 7H2O() 1.33
Cl2 / Cl 1/2 Cl2 (g) + e  

 Cl (aq.) 1.36
Au3+ / Au Au3+ (aq.) + 3e 

 Au(s) 1.40
MnO4/ Mn2+, H+/Pt MnO4 (aq.) + 8H+ (aq.) + 5e 

 Mn2+ (aq.) + 4H2O() 1.51
Ce4+ / Ce3+, Pt Ce4+ + e 

 Ce3+(aq.) 1.72
H2O2 / H2O H 2 O2 ()+ 2H+ (aq.) + 2e– 

 2H2O() 1.78
Co3+ / Co2+, Pt Co3+(aq.) + e 

 Co2+ (aq.) 1.81
O3 / O 2 O3 (g) + 2 H + (aq.)  2 e 
 O 2 (g) + H 2O() 2.07
Pt, F2 / F–  2F– (aq.)

F2(g) + 2e–  2.87
 Lower the reduction potential, higher will be the tendency of forming positive ions. This is related to
reactivity of metals. The order of reactivity of metals is : Li > K > Ca > Na > Mg > Al
 In this series oxidising character decreases and reducing character increases, e.g., the reducing char-
acter follow the order : Na > Mg > Zn > Fe > Ni > Cu > Ag
Illustration - 1
(a) If E0 (Ag+/Ag) = 0.8 V and E0 (H+/H2) = 0 V, in a cell arrangement using these two
electrodes, which will act as anode and cathode ? Also find the E0cell.
(b) Construct a cell using given electrodes at 25C. Find its standard EMF.
E0 (Zn2+/Zn) = –0.76 V and E0 (Cu2+/Cu) = 0.34 V
SOLUTION :
(a) Note that reduction potentials are given. Com-  
E0cell  E0reduction
cathode

 E0reduction 
anode
paring the two values, clearly
E0(H+/H2) < E0(Ag+ / Ag)
E0cell = 0.8  0 = 0.8 V
 Hydrogen electrode will acts as anode and
silver electrode will act as cathode. The cell (b) Note that E0(Zn2+/Zn) < E0(Cu2+ / Cu)
representation of the cell will be :
 Zinc electrode will act as anode and Cop-
Pt, H2 (1 atm.) / H+ (1.0M) || Ag+ (1.0 M)/Ag(s) per electrode will act as cathode.

The cell representation of the cell is :

Zn(s)/Zn2+ (1.0M) || Cu2+ (1.0M) / Cu(s) E0cell = 0.34  (0.76) = 1.1 V

E 0cell  E 0reduction 
cathode

 E 0reduction 
anode
Illustration - 2 The dry cell (flash light battery) used to power flashlights, clocks, radios etc . follows
following reaction : Zn(s) + 2 MnO2(s) + 8 NH4+ 

 Zn2+ + 2 Mn3+ + 8 NH + 4 H O
3 2
(a) Write anode and cathode reactions.
(b) 0 of the dry cell if the electrode potential of cathode ( 0

Calculate the Ecell Ereduction ) varies between
0
+ 0.49 V and + 0.74 V and of anode ( Ereduction ) is –0.76 V..
SOLUTION :
Anode :  Zn2+(1.0 M) + 2e– ; E 0reduction = – 0.76 V

Zn(s) 
Cathode : 2MnO2(s) + 8NH4+ (aq.) + 2e– 

 2Mn3+ (aq.) + 8 NH3 (g) + 4 H2O()
E 0reduction of cathode varies between + 0.49 to +0.74 V
For E0cathode = 0.49 V
 
E 0cell  E 0reduction
cathode
 
 E 0reduction
anode = 0.49  (0.76) = 1.25 V
For E0cathode = 0.74 V
0
Ecell = 0.74  (–0.76) = 1.50 V
0
 Ecell cell varies between 1.25 V to 1.50 V..
Note : A given electrode potential is to be taken as Reduction Potential. [as reduction potential is to be consid-
ered, “by default”.]

Illustration - 3 For each of the following cells :

(a) Write the equation for cell process. (b) Find E0 for each cell.
(c) Explain the significance of any negative answers in part (b).
1. Fe/Fe(NO3)2 (1.0M) || Zn2+(1.0 M)/Zn(s)
2. Pt,Cl2(g) / KCl(1.0M) || KCl(1.0M)/Hg2Cl2(s)/ Hg ( )

3. Cd/Cd2+(1.0M) || AgNO3(1.0M/Ag(s)
E0(Fe) = –0.41 V ; E0(Cd) = –0.40 V ; E0(Zn) = –0.76 V
E0(Cl– / Cl2) = – 1.36V ; E0(Ag) = + 0.80V ; E0 (Hg / Hg2 Cl2) = +0.27V
SOLUTION :
Cell Reaction : Hg2Cl2(s) 
 Cl2(1.0 atm)
Use:  
E0cell  E 0reduction
cathode + 2Hg(s)
E0cell = 0.27  (1.36) = 1.36 V

 E0reduction 
anode
Negative EMF value means that the cell will not
1. Anode :  Fe2+(1.0M) + 2e–
Fe(s)  work in the manner shown i.e., Cl/Cl2 as an-
ode and Hg2Cl2 as cathode. So reversing (in-
Cathode : Zn2+(1.0M) + 2e– 
 Zn(s) terchanging) the anode and cathode i.e., mak-
ing Hg2Cl2 (i.e., Hg/Hg2Cl2) as anode and Cl2/
Cell Reaction : Fe(s) + Zn2+ (1.0M) 
 Cl as cathode can make the cell work.
Fe2+(1.0M) + Zn(s) 3. Anode :  Cd2+ (1.0 M) + 2e–

Cd(s) 
E0cell = 0.76  (0.41) =  0.35 V
Cathode : Ag + (1.0M) + e– 
 Ag (s)
Negative EMF value means that the cell will not
work in the manner shown i.e., Fe as anode and Cell Reaction : Cd(s) + 2Ag+(1.0M) 

Zn as cathode. So reversing (interchanging) the
anode and cathode i.e., making Zn as anode and Cd2+(1.0M) + 2Ag(s)
Fe as cathode, can make the cell work.
E0cell = 0.8  (0.4) = 1.20 V
2. Anode :
EMF value is positive, hence cell will function
2 Cl (1.0M) 
 Cl2 (1.0 atm) + 2e– with Cd as anode and Ag as Cathode.
Cathode :
Hg2Cl2(s) + 2e 

2 Hg () + 2Cl(1.0 M)

Illustration - 4 For the reduction of NO3 ion in an aqueous solution, E° is +0.96 V. Values of E° for
some metal ions are given below :
V2+ (aq) + 2e– 

 V(s) E° = – 1.19 V . . .(i) Fe3+(aq) + 3e– 
 Fe(s) E° = –0.04 V . . .(ii)
Au3+(aq) + 3e– 
 Au(s) E° = 1.40 V  Hg ()
. . .(iii) Hg2+(aq) + 2e–  E° = + 0.86 V . . .(iv)
The pair(s) of metals that is oxidized by NO3 in aqueous solution is (aree) :
(A) V and Hg (B) Hg and Fe (C) Fe and Au (D) Fe and V
SOLUTION : (ABD)
E 0Re duction of (i), (ii) and (iv) is lesser than
NO3  e  
? E 0Reduction  0.96 V E 0Re duction for NO .
3
Check the reduction potential of the given metals So, NO3 will be able to oxidise V, Fe and Hg.
and compare it with that of NO3 reduction. So, pairs are V and Fe, V and Hg, Fe and Hg.
Illustration - 5 The following electrochemical cell has been set up :

Pt (1) | Fe3+ , Fe2+ (a = 1) || Ce4+, Ce3+ (a = 1) | Pt (2)
If an ammeter is connected between the two platinum electrodes, predict the direction of flow of current. Will
0
the current increase or decrease with time ? ( E  1.61V ; E 0  0.77 V )
Ce 4 / Ce3 Fe3 / Fe 2
SOLUTION :
For the electrochemical cell :
The net cell potential is :
Pt (1)  Fe3+, Fe2+ (a = 1) | | Ce4+, Ce3+
(a = 1) | Pt (2) E 0cell  (E 0reduction ) cathode  (E 0reduction )anode
The electrode reactions are as follows. = 1.61 V – 0.77 V = 0.84 V
Right half cell : Ce4+ + e– 

 Ce3+ Since E0cell is positive, the cell reaction will be
(Reduction) spontaneous.
Left half cell :  Fe3+ + e

Fe 2+  The current in the circuit will flow from Pt (2)
(which serves as cathode) to Pt (1), which serves
(Oxidation) as anode. With the passage of time, EMF of the
cell will decrease and so is the current in the
Cell reaction : Ce4+ + Fe2+ 
circuit.
Ce3+ + Fe3+

Note : Current in an electrochemical cell flows from cathode to anode where as the electron flow from anode to
cathode.
NERNST EQUATION Section - 2
Effect of concentration on EMF of half-cells and on EMF of a cell

(a) For an electrode M(s)/Mn+ (c M) c : concentration of electrolyte
(i)  Mn+ (c M) + ne–, then its oxidation

If it acts as oxidation electrode (i.e., as anode) : M(s) 
potential E(M/Mn+) at 25C is given as :
2.303 RT
E (M / M n  )  E(M / M n  )  l og10 Qoxidation
nF
0.059
E (M / M n  )  E(M / Mn  )  l og10 Qoxidation at 25C . . . . (i)
n
(n : number of e(s) transferred & F = charge on 1 mole electrons = 96500 C)
where Qoxidation : reaction coefficient of oxidation half reaction and is given as :
aM n  
 M n
Qoxidation   where [ ] denotes concentration ; ‘a’ denotes activity
aM M 
(ii) If it acts as reduction electrode (i.e., as cathode) : Mn+ (c M)+ ne– 

 M(s), then its reduction
n+
potential E(M /M) at 25C is given as :
2.303 RT
E (M n  / M)  E(M n  / M)  l og10 Qoxidation
nF
0.059
E (M n  / M)  E (Mn  / M)  l og10 Q reduction  at 25C  . . . . (ii)
n
where Qreduction. : reaction coefficient of reduction half reaction and is given as :
aM M
Qreduction  
a M n  
M n  
We can see that E(Mn+/M) =E(M/Mn+)

(b) For EMF of the cell : M(s)/Mx+ (c1 M) | | Ny+ (c2 M) / N(s)
(i) Anode :  Mx+(c1 M) + xe–

M(s)  [oxidation]
(ii) Cathode : Ny+(c2 M) + ye– 

 N(s) [reduction]
Overall reaction : yM(s) + xNy+ (c2 M) 

 yMx+ (c1 M) + xN(s)
EMF (Ecell) of such a cell at 25C is given is :
0.059
Ecell  E0cell  log10 Qcell . . . . (iii)
n cell
where Qcell : reaction coefficient of overall reaction ; E0cell : standard E.M.F. of the cell ;
ncell : Number of e– transfer in the cell reaction.
y y
Qcell 
 a M x   a N 
x M x 
 
(aN = aM = 1 for solids)
x x
 a M   a N y 
y N y 
 
y
M x  
0.059  
E cell  E 0cell  log10
n cell x
N y 
 
Illustration - 6 Find the reduction potentials of the following electrodes :

(a) Pt, H2 (1 atm) / HCl (0.1 M), (b) Pt, H2 (2 atm) / H2SO4 (0.01 M)
SOLUTION :
1
(a) Writing half-cell reaction :
H 2 (1atm)   H  (0.1M)  e
2
 H 
0.059
 + 0 +
E (H2/H ) =E (H2 / H ) – log10  
1 1/ 2
p  H2 
0.059  0.1
 E(H2/H+) = E0(H2/H+) – log10
1 (1)1/ 2
 E (H2/H+) = 0.059 V [ E 0(H2 / H+ ) = 0 V]  E(H+/ H2) = – 0.059 V
Note : In the expression of Q, we put the value of partial pressure (for gases) in atmospheric units (atm.).

1
(b) Writing the half-cell reaction :  H  (0.02M)  e
H 2 (2atm) 
2
0.059 [H  ]
 E (H2/H+) = E 0(H2 / H+ )  log10
1 PH 2
0.059 0.02
 E (H2/H+) = 0  log10 [ E0(H2 / H+ ) = 0 V]
1 2
 E (H2/H+) = 0.109 Volts  E 0(H+/H2) = – 0.109 V
Illustration - 7 For the cell : Zn(s)/Zn2+(x M)  Ag+(y M)/Ag(s)

(a) Write Nernst Equation to see how Ecell vary with concentration of Zn2+ and Ag+ ions.
(b) Find Ecell for [Zn2+] = 0.01 M and [Ag+] = 0.05 M. [E0 (Zn2+/Zn) = – 0.76 V E0 (Ag+/Ag) = 0.80]
(c) For what value of Q will the cell EMF be :
(i) 0.97 V (ii) 0.0V
SOLUTION :
First writing the two half-reactions :
(a) Anode :  Zn2+(x M) + 2e–

Zn(s) 
Cathode : Ag+(y M) + e– 
 Ag (s)
The cell reaction is :
Zn(s) + 2Ag+(yM) 
 Zn2+(xM) + 2Ag(s)

E 0cell  E 0reduction 
cathode

 E 0reduction 
anode = 0.80  (0.76) = 1.56 V
Now writing Nernst Equation :
0.059 [Zn 2  ]
E cell  E 0cell  log10 (Activity of Ag(s) and Zn(s) = 1)
n cell [Ag  ]2
0.059 0.118
 E 0cell  E cell  log10 [Zn 2  ]  log10 [Ag  ]
n cell n cell
 E0cell will decrease when [Zn2+] increases and [Ag+] decreases.

(b) If [Zn2+] = 0.01 M and [Ag+] = 0.05 M
0.059 0.01
 Ecell  1.56  log = 1.54 V
2  0.052
(c) (i) Ecell = 0.97 V ; E 0cell = 1.56 V
0 0.059 0.059
 Ecell  E cell  n log10 Qcell  0.97  1.56  log10 Qcell
cell 2
2  0.59
 log10 Q cell   20  Qcell = 1020
0.059
(ii) Ecell = 0.0 V ; E0cell = 1.56 V
0.059 0.059
0
 E cell  E cell  log10 Qcell  0.0  E 0cell  log10 Qcell
n cell 2
2  1.56 1  1 
 log10 Qcell =  52.88  53  0.15  log 10 10 53  log  log 10   10 53 
0.059 2  2 
 Qcell = 7.07  1052 [approximately]
Illustration - 8 The solution of CuSO4 in which copper rod is immersed is diluted to 10 times, the reduction
electrode potential will :
(A) Increase by 0.030 V (B) Decrease by 0.030 V
(C) Increase by 0.059 V (D) Decrease by 0.059 V
SOLUTION : (B)
Cu2+(aq.) + 2e 
 Cu(s)
0 0.059  1 
Initially : E  E
Cu 2  /Cu 1 Cu 2  /Cu

2
log10 
 [Cu 2  ] 
 1
(Using Nernst equation.)
0 0.059  1 
After Dilution : E 
Cu 2 / Cu 2
E
Cu 2  /Cu

2
log10 
 [Cu 2  ]
 2


(Using Nernst equation.)

0.059  [Cu 2 ] 
 E  
Cu 2 /Cu 2
 E 
Cu 2 /Cu 1

2
log10 
 [Cu 2  ]
2  = 0.059 log  1  = – 0.03 V
 2
10  
 10 
 1 
 Reduction potential of the electrode decreases by 0.03 V
Illustration - 9 For the cell : T | T + (0.001M) || Cu2+ (0.1M) | Cu, Ecell can be increased by :
(A) increasing [Cu2+] (B) increasing [T +] (C) decreasing [Cu2+] (D) decreasing [T+]
SOLUTION : (AD)
First write the cell reaction :
2T(s) + Cu2+(0.1 M) 
 2T+ (0.001 M) + Cu(s)
0.059
Using : E cell  E 0cell  log10 Qcell
n cell
0.059  [T ]2 
E cell  E 0cell  log10  
2  [Cu 2  ] 
 
 0.059
0
= E cell  0.059 log10[T ]  log10[Cu 2  ]
2
 Ecell can be increased by decreasing [T+] or increasing [Cu2+]
Condition of equilibrium (Ecell = 0.0 V)

When Ecell = 0.0 V, i.e., no potential difference is obtained between the terminals of cell (battery), the cell
reaction in such a state is said to be in equilibrium. So in such cases, when Ecell = 0, Q = Keq. = equilibrium
constant.
0.059
Ecell  E 0cell  log10 Qcell
n cell
0.059
 0.0  E 0cell  log10 K eq
n cell
0.059 2.303RT RT
 E0cell  log10 K eq  log10 K eq  nK eq
n cell n cell F n cell F
Note : Refer to the illustration-7, part (c), when Ecell = 0 volts.

 Qcell = Keq = 7.07 × 1052

Illustration - 10 If excess of Zn is added to 1.0 M solution of CuSO , find the concentration of Cu2+ ions at
4
equilibrium. The standard reduction potentials of Zn and Cu at 25C are –0.76 V and +0.34 V.
SOLUTION :
We know that at equilibrium, Ecell = 0.0 V and Let x be the concentration of Cu2+ at equilibrium.
the reaction coefficient Q = Keq. So first let us
Zn Cu2+ Zn2+ Cu
calculate the value of Keq. as follows :
Initial conc.  1.0 0 0

E = E 0reduction
0

Cathode
0

– E reduction
Anode
 Final conc.  1x x x
(Zn is in excess, so [Zn]= )
E0 = 0.34  ( 0.76) = 1.10 V
0.059 [Zn 2  ] x 1
Now using E0cell  log10 K eq K eq.    [ x  1]
n cell [Cu 2  ] 1 x 1  x
[At equilibrium] (Look at the value of equilibrium constant. Too high)
E 0cell  n cell 1 1

1.10  2  1 x    5 1038 M
log10 K eq   K eq 2.0 1037
0.059 0.059
= 37.288  37.30 = log10 1037 + log102  [Cu2+]eq = 1–x = 5 × 10–38 M
 Keq  2.0  1037
Note that aZn(s) = aCu(s) = 1
Now writing the reaction at equilibrium :
Zn(s) + Cu2+ (aq.) 


Zn2+ (aq.) + Cu(s)
Illustration - 11  2Fe2+ + I3–. The

Calculate the equilibrium constant for the reaction: 2Fe3+ + 3I 
standard reduction potentials in acidic conditions are 0.78 V and 0.54 V respectively for Fe3+/ Fe2+ and I3– /
I couples.
RT
[Use : 2.303 = 0.06 at 298 K ]
F
SOLUTION :

The given reaction is : 2Fe3+ + 3I–  The electrodes reactions are :

2Fe2+ + I3 Anode : 3I 
 I3 + 2e–
Cathode : Fe3+ + e–  Fe2+



 E 0cell  E 0 3 2  E 0 (2) (0.24 V)

Fe / Fe I / I3  log10 Keq. = (0.06 V) = 8.0
= 0.78 V – 0.54 V = 0.24 V
 Keq. = 108
Using the expression :
0
n E
log10 Keq. = cell cell (at 298 K) [ncell = 2]
0.06
CONCENTRATION CELLS Section - 3
By difference in concentration of a given electrode, we can construct a cell from only one type of electrode
as follows :
Let us take an electrode M/Mn+ and take two different concentrations of it.
M(s) / M n  (c1 ) and M(s) / M n  (c 2 )
A cell made by using these two electrodes is called as concentration cell. Its cell representation is given as :
M(s) / M n  (c1 ) || M n  (c 2 ) / M(s)
The two half-cell reactions are written as :
Anode :  M n  (c1 )  ne 
M(s) 
Cathode : M n+ ( c2 )  ne 
 M(s)
Overall reaction : Mn  (c 2 ) 
 M n  (c1 )
0.059
Using : Ecell  E 0cell  log10 Qcell
n cell
[M n  (c1 )]
Now, clearly E0cell = 0 volts and Qcell  [For a concentration cell : E0cell = 0 (always )]
[M n  (c 2 )]
0.059 [M n  (c1 )]
E cell   log10
n cell [M n  (c 2 )]
Note : For a concentration cell made by using hydrogen electrodes, derive the EMF of cell in terms of pH of two
electrodes. (Try yourself)
 1 (p H 2 )anode 
Ecell = 0.059  pH anode  pH cathode  log10 
 2 (p H 2 )cathode 


Illustration - 12 Find the EMF of the concentration cell formed by coupling the following electrodes :
(a) Pt, H2(1 atm) / HCl(0.1 M) (b) Pt, H2 (2 atm)/H2SO4 (0.01 M)
SOLUTION :
 1 (pH 2 )anode 
Using Ecell  0.059  pH anode  pH cathode  log10 
 2 (p H ) cathode

 2 
Assume electrode (a) to be anode :
 1 1
E cell  0.059 1  log10 0.02  log10  Volts = – 0.05 Volts
 2 2
Note : Ecell is negative which means that electrode (a) is cathode and electrode (b) is anode.
Illustration - 13 A cell contains two hydrogen electrodes. The negative electrode is in contact with a solu-
tion of 10–6 M H+ ions. The EMF of the cell is 0.118 V at 25C. Calculate the concentration of hydrogen ions
at the positive electrode.
SOLUTION :
The negative eletrode is taken as anode and the positive electrode is as taken as cathode. Let the concen-
tration of H+ ions at positive electrode (i.e., at cathode) is x M. Also, assume pH2  1atm at anode and
cathode.
1
Anode :  H+ (1 × 106 M) + 1e
H 2 (1atm) 
2
1
Cathode : H+ (x M) + 1e 
 H 2 (1atm)
2
 H+ (1 × 106 M)
Overall reaction : H+ (x M) 
 1 (pH 2 )anode 
Using : Ecell  0.059  pH anode  pH cathode  log10 
 2 (pH 2 )cathode 

 0.118 = 0.059 (6 – pHcathode + 0)
 pHcathode = 4  [H+]cathode = 10–4 M

E.M.F. vs WITH TEMPERATURE Section - 4
Free Energy
Let n faraday charge be taken out of a cell of emf E, then work done by the cell will be calculated as :
Work = Charge × Potential
Work done by the cell is equal to the decrease in the free energy.
G = nFE
Similarly, maximum obtainable work from the cell at standard condition will be :
Wmax = nF E0cell where E0cell = standard emf of standard cell potential
G = nF E0cell
Variation of E.M.F. (Ecell) with Temperature

The temperature coefficient of e.m.f. of the cell is written as :
 d ( G) 
 G   H+ T   . . . .(i)
 dT Const. Pressure
[This equation is known as Gibbs - Helmholtz equation. Learn this as a result]
 d( nFE cell ) 

  nFE cell   H  T 
dT    G   nFE cell 
 P
 dE cell   H E cell
  dT   nFT  T . . . .(ii)
 P
 d 
Enthalpy change : From eq. (i) : H  G  T   G  
 dT P
  dE  
  H   nF  E cell  T  cell   . . . .(iii)
  dT P 
Entropy change : Compare with equation : G = H – TS with (i)
 d   dE 
 S   ( G)   nF  cell 
 dT P  dT P

Illustration - 14 For the standard electromotive force of the cell : Fe | Fe2+(aq) || Cd2+ (aq) | Cd
If the temperature co-efficient of emf is –0.125 VK–1, the value of S at 25°C would be :
(A) –20.125 kJ K–1 (B) –24.125 kJ K–1 (C) –26.125 kJ K–1 (D) –22.125 kJ K–1
SOLUTION : (B)
dEcell S
Using : 
dT nF
 dE 
 S   cell   nF = – 0.125 × 2 × 96500 = – 24.125 KJ K
–1
 dT 
Illustration - 15 The Edison storage cell is represented as : Fe (s) / FeO (s) || KOH (aq) || Ni O (s) / NiO(s)
2 3
The half cell reactions are :

Ni2O3 (s) + H2O (l) + 2e 
 2NiO (s) + 2OH (aq.) ; E = + 0.40 V
 Fe (s) + 2OH (aq.)

FeO (s) + H2O (l) + 2e  ; E = – 0.87 V
(a) What is cell reaction ?
(b) What is the cell EMF ? How does it depend on the concentration of KOH ?
(c) What is the maximum amount of energy that can be obtained from one mole of Ni 2O3 ?
SOLUTION :
   
FeO(s) / Fe(s) will be anode
E 0cell  E 0reduction  E 0reduction
and Ni2O3(s)/NiO(s) will be cathode. cathode anode
= 0.4 – (–0.87) = 1.27 volts

(a) C : Ni2O3 (s) + H2O (l) + 2e 
 2NiO (s)
As KOH does not effect cell reaction, so EMF
+ 2OH
does not depend on concentration of KOH
A : Fe (s) + 2OH   FeO (s) + H2O (l) (c) Energy obtained from the cell = magnitude of
+ 2e free energy (G)
So cell reaction will be :
G = nF E0cell
Fe (s) + Ni2O3 (s) 
 FeO(s) + 2NiO (s)
 amount of energy = 2  96500  1.27
(b) In the cell reaction, all the species are solid, so
= 245.11 kJ.
their activities will be equal to unity.
Hence Ecell = E0cell

Illustration - 16 Find the standard electrode potential of MnO /MnO . The standard electrode potentials
4 2
of MnO4/ Mn2+ = 1.51 V and MnO2/Mn2+ = 1.23 V
SOLUTION :
Use : –G = nFE0
 MnO2 + 2 H2O , E0req. = ?

MnO4 + 4H+ + 3e– 
 G 0req.   3FE0req.
Given :
(i) MnO4 + 8H+ + 5e 

 Mn2+ + 4 H2O G1 = 5(F) (1.51)
(ii) MnO2 + 4H+ + 2e 

 Mn2+ + 2 H2O –G2= 2(F) (1.23)
(i) – (ii) gives the required equation
 G 0req.  G10  G 02 (G is a state function)
 3FE0req. =  5F (1.51)  [2F (1.23)]
 E0req.  1.7 V
Illustration - 17 E.M.F. of following cell is 0.265 V at 25C and 0.26 V at 35C. Calculate heat of the
reaction taking place at 25°C. Pt , H 2 ( g ) / HCl ( aq.)|| Cl  ( aq.) / AgCl ( s ) / Ag ( s )
SOLUTION :
L.H.S.  2H   aq.  2e

H 2  g  
R.H.S. 2AgCl  s   2e 

 2Ag  s   2Cl  aq.
H2  g   2AgCl  s   
 2H(aq.) 
 2Ag  s   2Cl(aq.)
  dE  
Use :  H   nF  E cell  T  cell  
  dT P 
Put n = 2, F = 96500 C
d E cell 0.260  0.265
  5.0  104 , E cell = 0.265 V (at 298 K)
dT 308  298
to get : H = –79.9 kJ.

BATTERIES Section - 5
There are two types of batteries.

1. Primary Batteries 2. Secondary Batteries
Primary Battery (Dry Cell) :

In this type of battery, the reaction occurs only once and battery then becomes dead after use over a period
of time and cannot be then re-used. It is also called as a primary voltaic cell. It has a cathode consisting of
carbon (graphite) rod surrounded by a paste consisting of MnO2 and powdered graphite and an anode of
zinc. The electrolyte is a moist paste of NH4Cl. The electrode reactions are :
Anode :  Zn2+ + 2e
Zn 
Cathode : 2 MnO2 + 2NH4+ + 4H2O + 2e– 

 2 Mn(OH)3 + 2 NH4OH
The cell potential is 1.6 V.
Another type of dry cell is Mercury cell which is suitable for the low current devices like hearing aids and
watches, etc., consists of Zn  Hg amalgam as anode and a paste of HgO and carbon as the cathode. The
electrolyte is a paste of KOH and ZnO. The electrode reactions for the cell are :
Anode : Zn (Hg) + 2OH 

 ZnO (s) + H2O + 2e
Cathode : HgO + H2O + 2e 
 Hg (l) + 2OH
The overall cell reaction is: Zn (Hg) + HgO (s) 

 ZnO (s) + Hg ()
The cell potential is approximately 1.35 V and remains constant during its life as the overall reaction does
not involve any ion in solution whose concentration can change during its life time.
Alkaline dry cell is also similar to ordinary dry cell. It contains potassium hydroxide. The reactions in alkaline
dry cell are:
Anode : Zn + 2OH  
 Zn(OH)2 + 2e
Cathode : 2MnO2 + 2H2O + 2e 
 2MnO(OH) + 2OH

The overall cell reaction is: Zn + 2MnO2 + 2H2O 

 Zn(OH)2 + 2MnO(OH).
The cell potential is 1.5 volts.
Secondary Battery or Reversible Galvanic or Voltaic Cell :

(Lead Storage Battery) :
A galvanic cell (or Voltaic cell) supplies a certain voltage. By imposing a higher voltage than the E.M.F. of
cell (external voltage), one can reverse the cell reactions i.e. anode becomes cathode and the cathode
becomes anode. The reversible lead storage battery is a typical example of it.

In a typical lead storage battery, the anode plates are made of lead, while the cathode plates are grids of
lead packed with lead dioxide. A solution of sulphuric acid (H2SO4) surrounds the plates and acts as
electrolyte. The half-cell reactions when the battery is being used up are :
Anode : Pb(s) + SO42   PbSO4(s) + 2e


Cathode : PbO2 + SO42 + 4H+ + 2e 

 PbSO4 + 2H2O
Overall cell reaction is : Pb  PbO2  4H   2SO42  

 2PbSO 4  2H 2 O ECell = 2.041 V
The battery is chargeable (reversible) since lead sulphate (product of both anode and cathode reactions)
sticks to the plates. From cathode reaction, we see that as the battery is used up, the sulphuric acid is used
up. Now we can determine the charge on the battery by measuring the concentration of H2SO4 in the cell.
When the density of solution is between 1.25 g/m and 1.30 g/m, the cell is considered as fully charged.
When its value goes down below 1.20 g/m, the battery is in need of charge. By applying external current we
can charge the battery again. The charging follows following reactions :
Anode :  PbO2 + SO42 + 4H+ + 2e

PbSO4 + 2H2O 
Cathode : PbSO4(s) + 2e 

 Pb(s) + SO42
Overall cell reaction is : 2PbSO4  2H 2O 

 Pb  PbO2  2H 2SO4
After many repeated charging and discharging cycles, some of the Lead sulphate falls to the bottom of the
container, the sulphuric acid concentration remains low and the battery cannot be recharged fully.
Another important secondary cell is the nickel-cadmimum cell which has longer life than the lead storage cell
but more expensive to manufacture. The discharging follows following reactions :
At Cd electrode : Cd + 2OH– 
 Cd(OH)2 + 2e–
–
At Ni electrode : Ni(OH)3 + e– 
 Ni(OH)2 + OH
The overall reaction during discharge is:
Cd (s) + 2Ni(OH)3 (s) 

 CdO (s) + 2Ni(OH)2 (s) + H2O (l)
Note :  Ni – cd cell has a cell potential of 1.2 V which changes a little as it discharges.
 Specific gravity of alkaline electrolyte remain same. So, it is not a guide to its change of state.

Otehr examples of rechargeable (secondary) cell are :

(i) Nickel - Metal hydride (NiMH) (ii) Lithium ion (Li - ion)
(iii) Lithium ion polymer (Li - ion polymer) (iv) Iron - nickel
Fuel Cell :
Fuel cells are another means by which chemical energy may be converted into electrical energy. The main
disadvantage of a primary cell is that it can deliver current for a short period only. This is due to the fact that
the quantity of oxidising agent and reducing agent is limited. But the energy can be obtained indefinitely from
a fuel cell as long as the outside supply of fuel is maintained. One of the examples is the hydrogen-oxygen
fuel cell. The cell consists of three compartments separated by a porous electrode. Hydrogen gas is intro-
duced into one compartment and oxygen gas is fed into another compartment. These gases then diffuse
slowly through the electrodes and react with an electrolyte that is in the central compartment. The electrodes
are made of porous carbon and the electrolyte is a resin containing concentrated aqueous sodium hydroxide
solution. Hydrogen is oxidized at anode and oxygen is reduced at cathode. The overall cell reaction pro-
duces water. The reactions which occur are :
Anode : 2H2 (g) + 4OH (aq) 

 4H2O () + 4e
Cathode : O2 (g) + 2H2O () + 4e 

 4OH (aq)
The overall cell reaction is: 2H2 (g) + O2 (g) 

 2H2O ()
The cell runs continuously as long as the reactants are supplied. Fuel cells produce electricity with an
efficiency of about 70% compared to thermal plants whose efficiency is about 40%. There has been tre-
mendous progress in the development of new electrode materials, better catalysts and electrolytes for
increasing the efficiency of fuel cell. These have been used in automobiles and space crafts. Fuel cells are
pollutions free and in view of their importance in future a variety of fuel cells have been fabricated and tried.

Example - 1 Calculate the reduction potential of an electrode which was originally 0.1 M MnO4 and
0.5 M H+ and has been treated with 50% of the Fe2+ required to reduce all the MnO4 to Mn2+.
(E  2  1.51V )
MnO4 / Mn
SOLUTION :
MnO 4 + 8H+ + 5e– 
 Mn2+ + 4H2O
t0 0.1 M 0.5 M

(Concentration)
t  t final
 After 50% Fe2   0.1  0.5 × 0.1 0.5  0.05 × 8 0.05 M
  = 0.05 M = 0.1M
 treatment 
 E
0.059
Using : E  log10 QRe duction
MnO 4 / Mn 2 MnO 4 / Mn 2 n
[Mn 2  ]
 E
0.059
E  log10
MnO 4 /Mn 2  MnO 4 / Mn 2 5 [MnO 4 ][H  ]8
.059 0.05
 1.51  log10 = 1.42 volts
5 0.05  (0.1)8
Example - 2 Calculate the EMF of the following cell at 25C.
Pt, H2 (1 atm) / H+ (0.09 M) | | OH  (0.075 M) / H2 (1 atm), Pt (Kw of H2O = 1 × 1014)

SOLUTION :
Note that in this question, instead of H+ ions in pHAnode = – log10 0.09 = 1.05
RHE, OH– are given. Now, calculate [H+] from
concentration of OH in the solution. Use : Ecell = 0.059 (pHAnode – pHCathode)
pHcathode = 14 – pOHcathode = 0.059(1.05 – 12.87) = – 0.70 V
= 14 + log10(0.075) = 12.87
Note : The given cell is a Hydrogen concentration cell.
Example - 3 Calculate the reduction electrode potential at 25C of Cr2O72–/Cr3+ electrode at pOH =
11 in a solution of 0.01 M both in Cr3+ and Cr2O72 . E 0 1.33V . If this electrode is coupled with
Cr2O72 / Cr 3
a hydrogen gaseous electrode at pH = 3, find the emf of the spontaneous cell.
SOLUTION :
Writing balanced equation for Cr2O72  / Cr 3 electrode :
Cr2O72 + 14H+ + 6e– 

 2Cr3+ + 7H2O
pOH = 11  [H+] = 10–3 M
Using Nernst Equation :
0.059
ECr O 2 /Cr3  ECr O2 /Cr 3  log10 Q reduction
2 7 2 7 n
0.059 [Cr 3 ]2
 E  E  log10
Cr2 O72 /Cr 3 Cr2 O 27  / Cr 3 n [Cr2 O7 2  ] [H  ]14
0.059 [0.01]2
 E Cr O 2 /Cr3  1.33  log10  0.94V
2 7 6 [0.01] [103 ]14
Also, find the electrode potential of hydrogen electrode using Nernst Equation :
2H+(10–3M) + 2e– 
 H2 (1 atm)
0.059 1
E H / H  E 0   log10
2 H / H2 2 [H  ]2
0.059 1
E H / H  0  log10  0.177V
2 2 
[10 3 ]2
 The hydrogen electrode will serve as anode and Cr2O72/Cr3+ will serve as cathode
So, Ecell = (E reduction )Cathode  (E reduction )Anode = 0.94 – (–0.177) = 1.06 V
Example - 4 Find the Ksp of AgCl The standard electrode potential of Ag/AgCl/Cl is 0.22 V and Ag+/
Ag is 0.8 V.
SOLUTION :
The given electrode Ag/AgCl/Cl is visualized as : At equilibrium, Ecell = 0 V and Q = Ksp
 Ag(s) + Cl(aq.)
AgCl(s) + e–  0.059
 E0cell  log10 K sp
It is now coupled with silver electrode as anode n cell
Cathode : AgCl(s) + e–  
 Ag(s) + Cl (aq.) E 0  Ag / AgCl / Cl    E 0  Ag  / Ag 
Anode :  Ag+(aq.) + e–
Ag(s)  0.059
 log10 Ksp
 Overall cell reaction is : 1
0.22  0.8

 Ag+(aq.) + Cl (aq.)
AgCl(s)   log10 Ksp    9.85
0.059
At saturation (i. e. at equilibrium), the above reac-  Ksp = 1.4  10–10
tion gives the solubility of AgCl.
Example - 5 The standard reduction potential of Ag+/Ag electrode at 298 K is 0.80 volts. Ksp of AgI =
1.0  10–16. Find the electrode potential of Ag+/Ag in a saturated solution of AgI. Also, calculate standard
reduction potential of I –/AgI/Ag electrode.
SOLUTION :
First calculate the concentration of Ag+ in a satu- Ag+ + e 
 Ag
rated solution of AgI.
E(Ag  / Ag)  E (Ag  / Ag) 
 Ag (aq.)  I (aq.)
AgI(s)   
0.059 1
log 10
Let [Ag+] =x 1 [Ag  ]
 Ksp of AgI = [Ag+] [I] = x2
 E(Ag+/Ag) = 0.80 – 0.059 log10
 [Ag  ]  x  K sp  1.0  10 16 

1.0  10 8
–8
= 1.0  10 M
E(Ag+/Ag) = 0.33 volts
Now, calculate the reduction potential of silver
electrode at [Ag+] = 10–8 M For E of I/AgI/Ag, visualize the electrode as:

AgI + 1e 
 Ag + I
Now couple this electrode with Ag/Ag+ as an- Atequilibrium :

ode
 E0cathode  E0anode = 0.059 log10 Ksp [AgI]
+ 
Anode : Ag 
 Ag + 1e
 E0cathode  E0anode + 0.059 log10 Ksp [AgI]
  
Cathode : AgI  e 
 Ag  I
= 0.8 + 0.059 log10 10–16 = – 0.17 V
+ –
AgI 
 Ag + I
Example - 6 Find the solubility product of a saturated solution of Ag2CrO4 in water at 298 K if the emf
of the cell : Ag | Ag+ (saturated Ag2CrO4 solution) | | Ag+(0.1M) | Ag is 0.177 V at 298 K.
SOLUTION :
The given cell is :
Ag | Ag+ (sat. Ag2CrO4 solution) | | Ag+ (0.1M) | Ag If x is the solubility of Ag2CrO4 in solution, then :
[Ag+] = 2x and [CrO42–] = x
Anode : Left half-cell Ag(s)  (Ag+)
 L + e–
 Ksp = [Ag+]2[CrO42–] = (2x)2(x) = 4x3
Cathode : Right half-cell (Ag+)R +e– 
 Ag(s) or x = (Ksp/4)1/3
Cell reaction (Ag+)R  +  [Ag+]L = 2x = 2(Ksp/4)1/3 = (2Ksp)1/3

 (Ag )L
Using Nernst Equation, we get : Substituting the values in Nernst Equation, we have
:
RT [Ag  ]L 1/3
E cell  0  ln RT (2K sp )
F [Ag  ]R E cell   ln
F [Ag  ]R
( E0cell = 0 for concentration cells)
(2K sp )1/3
 0.177 V = – (0.059 V) log10
[Ag+]R = 0.1 M. Let [Ag+]L = 2x molar. (0.1)
In the left half-cell, the concentration of Ag+ will be  1/3 
related to the solubility product of Ag2CrO4 as 
log10 
2K sp     0.177   3
follows: 0.1  0.059
 
 2Ag+(aq) + CrO 2–(aq)
Ag2CrO4(s)  1/3
4

 2Ksp   103  K sp  5  1013
0.1
Example - 7 The standard potential of the following cell is 0.23 V at 15C and 0.21 V at 35C:
Pt, H2 (g) | HCl (aq) || KCl (aq) | AgCl (s) | Ag (s)
(i) Write the cell reaction.
(ii) Calculate H and S for the cell reaction by assuming that these quantities remain unchanged in the
range 15C to 35C.
(iii) Calculate the solubility of AgCl at 25C.
Given: The standard reduction potential of the Ag+(aq)|Ag(s) couple is 0.80 V at 25C ;
RT
2.303 at 25°C = 0.06 V
F
SOLUTION :
The given cell is : Pt , H2(g) | HCl(aq) || KCl(aq) | AgCl(s) | Ag(s)
(i) The cell reactions are as follows.
Right cell: 2AgCl  s  +2e 

 2Ag  s  +2Cl  aq   Reduction 
Left cell:  2H +  aq  +2e 
H 2  g    Oxidation 
Cell reaction:  2Ag(s) + 2H+(aq) + 2Cl–(aq)
2AgCl(s) + H2(g) 
0 –1
(ii) G15 º C = nF Ecell = (2) (96500 C mol ) (0.23 V)
= 44390 J mol–1
G035 º C = nF Ecell = (2) (96500 C mol–1) (0.21 V)
= 40530 J mol–1
0 –1
Now, G15 º C = H – (288 K) S = –44390 J mol
and G035 º C = H – (308 K) S = – 40530 J mol–1
[Using G = H– TS and assuming H and S at 298 K and temperature inde-
pendent i.e. H15°C = H° and H35°C = H°]
Solving for H and S, we get,
H = –99974 J mol1 and S = – 193 J K–1 mol1

(iii) The value of G at 25C is calculated as follows :
G = H  (298 K) S = – 99974 J mol–1 – (298 K) (293 J K–1 mol–1)
= – 42460 J mol–1
The value of E 0 
at 25C will be :
Cl | AgCl | Ag
0
Ecell 
G 0cell


 42460 Jmol1  = 0.22 V
nF  2   96500Cmol
1

 E0   E0   0.22 V
Cl / AgCl/ Ag H /H 2
 
 E0   0.22 V  E 0  0V
Cl / AgCl/ Ag  H / H2 
For determination of Ksp, constructing the cell :
Ag/Ag+ || Cl– /AgCl/ Ag
Anode : Ag  Ag+ + 1e–
Cathode : AgCl + le  
 Ag  Cl
 Ag+ + Cl

Cell Reaction : AgCl 
RT
Now using the expression : E 0cell  E    E   ln K sp (at equlibrium)
Cl / AgCl/ Ag Ag / Ag F
 0.22 V  0.80 V = (0.06 V) log10 Ksp
 0.22  0.80  V
 log10 Ksp =  10.0
 0.06 V 
 Ksp = 1.0  10–10
Example - 8 Two Daniel cells contain the same solution of ZnSO4 but differ in the CuSO4 solution. The
emf of the cell containing 0.5 M CuSO4 is higher than the other cell by 0.06 V. Calculate the concentration of
CuSO4 in the other cell.
 2.303 RT 
Use :  0.06 
 F 
SOLUTION :
The reaction occurring in a Daniell cell is : Zn(s) + Cu2(aq) 

 Zn2+(aq) + Cu(s)
RT [Zn 2  ]
The EMF of the cell is given as : Ecell  E0cell  ln
2F [Cu 2  ]
For the two cells, we have :
RT  [Zn 2  ]1  
 Ecell 1  E 0cell  ln   
2F  [Cu 2  ]1   RT  [Cu 2 ]2 
  Ecell 2   Ecell 1  ln  2  
RT  [Zn 2 ]2   2F  [Cu ]1 
0
 Ecell 2  E cell  ln  
2F  [Cu 2  ]2  
= 0.06 [Taking [Cu2+]2 = 0.5 M]
 0.5 
 log10  2  [Cu2+]1 = 0.5 × 10–2 = 5 × 10–3 M
 [Cu 2  ] 
 1
Example - 9 During the discharge of a lead storage battery, the density of sulphuric acid fell from 1.294
g/ml to 1.139 g/ml. Sulphuric acid of density 1.294 g/ml was 39% H2SO4 by wt. while acid of density 1.139 g/
ml contains 20% acid by wt. The battery holds 3.5 L of acid and the value remained practically same through
the discharging. Calculate the number of amp/hr for which the battery must have been used. The charging
and discharging reactions are :
PbO2 + SO42 + 4H+ + 2e 

 PbSO4 + 2H2O (discharging)
PbSO4 (s) + 2e– 

 Pb (s) + SO42 (charging)
SOLUTION :
Note that density of sulphuric acid has decreased, i.e discharging of battery takes place.
First write both the reaction for discharging.
Anode :  PbSO4(s) + 2e

Pb(s) + SO42 
Cathode : PbO2 + SO42 + 4H+ + 2e 

 PbSO4 + 2H2O
Overall reaction : Pb(s) + 2H2SO4 + PbO2  2 PbSO4(s) + 2H2O


 For the consumption of 2 molecules of H2SO4, 2e– are transferred
 For the consumption of 2 moles of H2SO4, 2 moles of e– s are transferred
 2 mole of H2SO4  2F of electricity
(Note : 1F  Charge on 1 mole of electrons)
Now let us calculate the decrease in moles of H2SO4 from the data given.
Volume of solution = 3.5 L = 3500 ml
Let the mass of H2SO4 before discharging = mi
And the mass of H2SO4 after discharging = mf
39
 mi =  
 3500   1.294  1766.3 gm
 100 
 20 
 mf =   3500   1.139  797.3 gm
 100 
 m (the decrease in mass) = 1766.3  797.3 = 969 gm
 m 970
 moles of H2SO4 consumed    9.89
98 98
Now 1 mole of H2SO4  1 F of charge
 9.89 moles  1  9.89 F of charge  9.89  96500 = 954385 C of charge
Q 954385
Now Q = I t  I  I  265 amp
t I  60  60
Example - 10 Determine the degree of hydrolysis and hydrolysis constant of aniline hydrochloride in M/
32 solution of salt at 298 K from the following cell data at 298 K. :
+
Pt | H2(1 atm) | H+ (1M) || C6H5 N H 3 Cl–(M/32) | H2 (1 atm), Pt. Ecell = – 0.177V
SOLUTION :
Note : Given cell is a Hydrogen Concentration cell.  h = 32 × 10–3 = 0.032
Ecell = 0.059 (pHAnode – pHCathode)
 K
= 0.059 (0 – pHCathode) = 0.059 log10 
h
C6 H5 N H3  H2O 
 C6 H5 NH2  H3O

[H+]Cathode
t=0 c
= – 0.177 t = teq c – ch ch ch
 [H+] Cathode =
10–3M
ch.ch 103.103
Kh    3.31105
 c  ch 1
Note : Aniline Hydrochloride : C6 H5 N H 3 Cl  103
32
[salt of SA – WB]
 [H+]Cathode = 10–3 = ch
1
(c = M ; h = degree of hydrolysis)
32
Example - 11 Calculate the quantity of electricity delivered by a Daniel cell initially containing 1L, 1M
Cu 2+ ion and Zn 2+ ion which is operated until its potential drops to 1.041 V.
(E 0   0.76 V ; E 0   0.34 V )
Zn 2  / Zn Cu 2  / Cu
SOLUTION :
Cell Reaction : Zn (s) + Cu2+(aq.) 

 Zn2+(aq.) + Cu(s)
t 0
1 1
(concentration )
t = teq 1 –x 1+x
0.059 [Zn 2  ]
Using Nernst equation : E cell  E
cell  log10
n cell [Cu 2  ]
 E  0.34  ( 0.70)  1.1V 

0.059 [Zn 2  ]  cell 
1.041 = 1.1  log10  n 2  write half  
2 [Cu 2  ]  cell  cell reactions  
 
0.059 [Zn 2  ]
 0.059 = log10
2 [Cu 2  ]
1x 1 x 99
 log10 2  100  x
1 x 1 x 101
Moles of Cu2+ (initially) = 1 × 1L = 1
99 2
Moles of Cu2+ (left) = 1 – x = 1  
101 101
For each ion of Cu2+ to Cu, 2e–s are transferred.
99
Thus, no. of electrons transferred = x × 96500 = × 2 × 96500 C = 189178.2 C
101
Example 12 - 14 Read the following passage :

Tollen’s test is used for detection of aldehydic group in organic compounds like glucose. The test is as follows
: An aqueous solution of AgNO3 is added to an aqueous slolution of glucose in a test tube. When concentrated
ammonia is added, silver is deposited. This is a redox reaction as Ag+ is reduced to Ag and glucose is oxidized
to gluconic acid. The following half-cell reactions and the standard half-cell potentials are given :
Ag+ + e– 
 Ag 0
Ered  0.8V
 C6H12O7 +2H+ + 2e–

C6H12O6 + H2O  0
Eox   0.05V
[Ag(NH3)2]+ + e– 
 Ag + 2NH3 0
Ered  0.37 V
Given : 2.303 RT/F = 0.0592 V, F/RT = 38.90 V–1 at 298 K
Example - 12 The logarithm of the equilibrium constant (lnK) of the reaction is :
 C H O + 2H+ + 2Ag

C6H12O6 + 2Ag+ + H2O  6 12 7
(A) 66.1 (B) 29.2 (C) 58.4 (D) 116.8

SOLUTION : (C)
Create cell as :
Cathode : Ag+ + e– 
 Ag E 0reduction  0.8V
E 0reduction  0.05V
Anode :  C6H12O7 + 2H+ + 2e–
C6H12O6 + H2O 
2Ag + + C6 H12O6 + H 2O 
 2Ag + C6 H12O7 + 2H +
When the reaction reaches equilibrium, Qcell = Keq and Ecell = 0
0 F
Using : n K eq  E cell .n cell . = 0.75 × 2 × 38.90 = 58.35 (E 0cell  0.8  0.05  0.75 V)
RT
Example - 13 On the addition of conc. NH , the pH of the solution rises to 11. Ignoring any changes in
3
the concentration of glucose and gluconic acid, identify which of the half-cell electrodes will be sensitive to
pH and the corresponding change in half-cell potential (E) relative to the standard half-cell potential (E0)
(A) 0 by an amount 0.65 V (B)

an increase of Eox over Eox 0 by an
an increase of Ered over Ered
amount 0.65 V
(C) 0 by an amount 0.65 V

decrease of Eox over Eox (D) 0 by an amount
decrease of Ered over Ered
0.65 V
SOLUTION : (AD)
0.0592
Consider : 
0
E ox  E ox  log10 [H  ]2
2
 C6H12O7 + 2H+ + 2e–
C6H12O6 + H2O  [Take other compounds activity to be unity]
E 0ox   0.05V 0
 E ox  E ox  0.0592 pH
Using Nernst Equation : 0
 E ox  E ox = 0.0592 × 11 = 0.65 V
0 2.303RT
E ox  E ox  log10 Qoxidation  There is an increase in E ox over E 0ox by
nF
0.65 V or decrease in E red over E 0red by
0.65 V
Note : Only glucose electrode will be sensitive to pH changes as other electrodes do not depend on [H+].
Example - 14 The reaction does not proceed efficiently without addition of NH . Moreover, addition of
3
any other base is not recommended. Which of the following statements about the role of NH3 must be incor-
rect ?
(A) Ag(NH3)2+ is weaker oxidizing agent than Ag+
(B) NH3 complex Ag+ efficiently
(C) In absence of NH3, silver salts of gluconic acid would precipitate.
(D) NH3 alters the standard electrode potential of the glucose / gluconic acid electrode.
SOLUTION : (D)
0
(A) E0  0.37 V and E  0.8 V

[Ag(NH3 )2 ] / Ag Ag  / Ag
 Ag+ has a stronger tendancy to get reduced than [Ag(NH3)2]+. So, Ag+ is a stronger oxidising agent
than [Ag(NH3)2]+.
(B) NH3 forms highly stable complex with Ag+.

(C) NH3 keeps most of Ag+ in solution in the form of [Ag(NH3)2]+. So, gluconate ion gets a very less chance
to form silver salt of gluconic acid.
(D) Standard electrode potential of the glucose / gluconic acid electrode is fixed and does not change with the
addition of NH3 in the solution.
Example - 15 (a) Calculate rG0of the reaction : Ag  (aq )  Cl  (aq) 

 AgCl ( s )
Given : fG0(AgCl) = –109 kJ/mol ; fG0 (Cl–) = –129 kJ/mol ; fG0(Ag+) = 77 kJ/mol
0 and find K
Represent the above reaction in the form of a cell. Also, calculate Ecell .
SP[AgCl]
(b) 6.539 × 10–2 g of metallic Zn was added to 100 mL of saturated solution AgCl. Calculate
[ Zn 2  ]
log10
[ Ag  ]2
Given that Ag   e 
 Ag E0 = 0.80 V
Zn 2   2e  
 Zn E0 = – 0.763 V
Also find how many moles of Ag will be formed. [Given : KSP[AgCl] 10–10]
SOLUTION :
(a) Ag  (aq.)  Cl  (aq.) 

 AgCl(s)
 r G 0   f G (AgCl)
0
 f G 0    f G 0  = – 109 – (–129) – 77 = – 57 kJ/mol
(Cl ) (Ag )
Cathode : Ag  (aq)  e  
 Ag(s)
Anode : Ag(s)  Cl  
 AgCl(s)  e 
Ag (aq)  Cl(aq)


 AgCl(s)
0 0 0 3
Using :  r G   n F E cell   1  96500 E cell   57  10  E 0cell = + 0.59 volts
1 E 0cell . n cell 0.59  1 1

Using : log10    10 [ Note : K eq.  ]
K sp[AgCl] 0.059 0.059 KSP[AgCl]
 Ksp [AgCl]  10–10
(b) Cathode : Ag   e  
 Ag E 0red  0.8 V
Anode :  Zn 2   2e
Zn  E0red   0.763V
2Ag   Zn 
 2Ag  Zn 2  
E 0cell  E0 
reduction cathode

 E0 
reduction anode
= 0.8 – (– 0.763) = 1.563 V

Initially 10–5M 0.01 M
  [Zn 2  ]   E 0cell . n cell 1.563  2

At equilibrium : log10  K eq      53
  [Ag  ]2   0.059 0.059
 
[Zn 2  ]
 K eq   1053 (i.e. whole of Ag+ is almost consumed.)
 2
[Ag ]
Mmoles of Ag formed = Mmole of Ag+ used = 10–5 × 100 = 10–3

 Moles of Ag formed =10–6
Electrochemistry - II Vidyamandir Classes
Electrochemistry - ll
The process in which an electric current causes a chemical change (conversion of electric energy to chemical
energy) is called as electrolysis. There are mainly two ways in which analysis is done in electrolysis :
(i) Qualitative Analysis : Study of possible products formed at cathode and anode during electrolys is.
(ii) Quantitative Analysis : Study of amount /moles /volume of the products formed at cathode and
anode during electrolysis.
QUANTITATIVE ANALYSIS Section - 6
To understand the process of electrolysis more clearly, first let us consider

electrolysis of molten salts (e.g., NaCl) and then aqueous solution of salts
in an electrolytic cell shown.
Molten NaCl (an electrolyte) means free sodium ions (Na+) and chloride
ions (Cl), so it conducts current with the help of ions. As electric current is
passed in the cell, Cl ions are attracted to anode (+ve electrode) and Na+
ions to cathode (ve electrode). Both ions are discharged at respective
electrode as follows :
Anode : 2 Cl 
 Cl2  g   2e  [Oxidation]
Cathode : Na   e  
 Na  s  [Reduction]
Overall Reaction : 2 Na   2Cl 

 2 Na  s   Cl2  g 
This type of cell is also called as electrolytic cell. The basic difference between an electrolytic cell and a
galvanic (or voltaic) cell is that a voltaic cell produces electricity; an electrolytic cell consumes electricity.
The importance of electrolytic cell is that they are widely used in isolation and purification of various elements
and gases.
Products of electrolysis depends mainly on the following factors :
(i) Electrode potential of various possible reactions (deposition or liberation) at cathode or anode.
(ii) Over potential of gases w.r.t. the electrode (material) at which they are liberating.
(iii) Concentration of the ions (to be oxidised or reduced) in the solution.
(iv) Type of electrodes [reacting or non-reacting (e.g. Pt, C (graphite))]
Now, we will discuss the products formed at cathode and anode for the most of the solutions as follows :

Vidyamandir Classes Electrochemistry - II
1. Aqueous NaCl solution :

Note : When electrode is not mentioned, assume it to be Pt.
In aqueous solution of NaCl, Na+, Cl, H+ (from water) and OH– (from water) ions are free to move for the
conduction of electric current. When electric current is passed, Na+ and H+ ions are attracted to cathode
and Cl and OH– ions to anode.
The solution now contains four ions Na+, Cl (from NaCl), H+, OH– (from water) and there is a race
amongst them for their discharge at their respective electrodes.
The following electrode reactions are possible :
Cathode : Na+ (aq.) + e– 

 Na (s) E   2.71V
Na  / Na

2H 2O()  2e 
 H 2 (g)  2OH  (aq.) E H 2O/ H 2   0.83 V
Anode : 2 Cl (aq.) 

 Cl2  g   2e E   1.36 V
Cl /Cl2
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
Overall Reaction : 2NaCl(aq .) + H 2O( ) 

 2 NaOH (aq .) + H 2(g) + Cl2(g)
In this electrolysis, H2 at cathode and Cl2 at anode are given off. Now, question is, why Na+ ions and
OH ions are not discharged ? The reason lies in the reduction potential values. Clearly,
E  EH 2O/ H 2
Na  / Na
 Although Cl– has a lesser tendency to discharge (oxidize) [Cl– will be at Anode where oxidation takes
place] as compared to OH– (Cl– lies below OH– in the Electrochemical series) at anode still OH– will
not be discharged (oxidize) due to the concept of Overpotential (Extra potential required to initiate
a reaction at a required rate). Formation of O2 from H2O is kinetically very slow (i.e. low rate). Thus,
OH– ions will remain in the solution.
 The aqueous solution of NaCl will become alkaline (due to the presence of OH– ions) after the
electrolysis.
 In case of electrolysis of NaX (aq.) (where X– is Br–, I–), X2 will be liberated at anode. Using NaF,
 
O2 gas will be liberated at anode instead. Also, E Br  / Br   1.09 V and E I / I   0.54 V
2 2

but E F /F   2.87 V
2

2. Aqueous CuSO4 solution :

Possible reactions at :
Cathode : Cu 2  (aq.)  2e  
 Cu  s  E   0.34 V
Cu 2 / Cu
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode :  O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
2SO24  (aq.) 
 S2O82  (aq.)  2e  E   2.01V
SO24  /S2 O82 
Overall Reaction : 2H 2O()  2Cu 2  (aq.) 

 2Cu(s)  O2 (g)  4H  (aq.)
In this electrolysis, Cu at cathode and O2 at anode are produced. Also, the aqueous solution of CuSO4 will
become acidic (due to the presence of H+ ions) after the electrolysis.
3. Aqueous Na2SO4 solution :
Cathode : Na  (aq.)  e  
 Na(s) E   2.71V
Na  / Na
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode : 2SO24  (aq.) 

 S2O82  (aq.)  2e  E   2.01V
SO24  /S2 O82 
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
Clearly, at cathode, Na+(aq.) ions will not be deposited due to their lower reduction potential than H2O.
Similarly, SO2–
4 will not be oxidised due to their lower oxidation potential than H2O.
Thus, electrolysis of Na2SO4/K2SO4/CaSO4/MgSO4/Li2SO4 etc. is actually equivalent of electrolysis of

H2O.
4. Aqueous NaCl solution(very dilute) :

 Na(s) E   2.71V
Na  / Na
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2 O/ H 2   0.83 V

Anode : 2Cl (aq.) 

 Cl2 (g)  2e E   1.36 V
Cl /Cl2
 O2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23 V
When NaCl is highly dilute, there is a very less chance of Cl– (due to their less availability) getting oxidised.
So, instead H2O will get oxidised.
Note : 2Cl (aq.) 

 Cl2 (g)  2e
0.059 pCl2 0.059

E   E   log10  E   log10 pCl2  0.059 log10 [Cl  ]
Cl /Cl2 Cl /Cl2 2  2 Cl /Cl 2
[Cl ] 2
Thus, E decreases as [Cl–] decreases making the oxidation of H2O more favorable.
Cl  /Cl 2
5. Aqueous NaCl solution (using Hg electrodes) :

 Na(s) E   2.71V
Na  / Na
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode : 2Cl (aq.) 

 Cl2 (g)  2e E   1.36 V
Cl  /Cl2
 O2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
When Hg electrodes are used instead of Pt, Na+(aq.) gets deposited which furthur reacts with Hg to form
Sodium-Amalgam.
Na(s)  Hg(s) 
 NaHg(s)
Thus, when NaCl(aq.) is electrolyzed using Hg as electrode sodium amalgam is formed at cathode and
Cl2 (g) is evolved at anode.

6. Aqueous CuSO4 solution (using Cu electrodes) :
Cathode : Cu 2  (aq.)  e 
 Cu(s) E  0.34 V
Cu 2  /cu
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2 O/ H 2   0.83 V
Anode : 2SO24  (aq.) 

 S2O82  (aq.)  2e E   2.01V
SO 24 /S2O82 
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V

 Cu 2  (aq.)  2e
Cu(s)  E  0.34 V
Cu /Cu 2 
Thus, when Cu is electrolysed using Cu electrodes, Cu is dissolved (at Cu anode) and Cu is deposited (at
Cu cathode).
Note : [Cu2+] in solution remain constant during electrolysis.

 This technique is used in refining of Cu.
7. Aqueous AgNO3 solution (using Ag electrodes) :

Cathode : Ag  (aq.)  e   E  0.8 V

 Ag(s) Ag  / Ag
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode :  O 2 (g)  4H  (aq.)  4e 

2H 2O()  EH 2 O/O2   1.23V
NO3 (aq.) 
 (No reaction)
 Ag  (aq.)  e  E   0.8 V
Ag(s)  Ag  / Ag
Thus, when aq. AgNO3 is electrolysed using Ag electrodes, Ag is dissolved (at anode) and Ag is deposited
(at cathode).
 [Ag+] in the solution remains constant during electrolysis.
8. Aqueous H2SO4 solution:

1
Cathode : H   aq.  e  
 H 2 (g) E 0V
2 H / H2
Anode : 2SO24  (aq.) 

 S2O82  (aq.)  2e  E   2.01V
SO4 2 /S2O82 
 O2 (g)  4H  (aq.)  4e

2H 2O()  EH 2 O/O2   1.23V
In actual practice, SO42– ions can be oxidised to S2O82– if either of the following conditions are satisfied :
(A) High current density (B) High [SO42–] (i.e. highly conc. H2SO4 solution]

9. A q u e o u s N iSO 4 solution:
Cathode : Ni 2  (aq.)  2e  
 Ni(s) E   0.25 V
Ni 2 / Ni
2H 2O()  2e 
 H 2 (g)  2OH  (aq.) EH 2O/ H 2   0.83 V
Anode : 2SO24  (aq.) 

 S2O82  (aq.)  2e  E   2.01V
SO 24 /S2O82 
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
In practice, it has been observed that H2 gas also gets liberated at cathode along with Ni.
10. Aqueous RCOONa solution (Kolbe’s Electrolysis):

Cathode : Na   aq.  e  
 Na(s) E   2.71V
Na  / Na
2H 2O()  2e 
 2OH  (aq.)  H 2 (g) EH 2O/ H 2   0.83 V
Anode : 2RCOO  (aq.) 

 R  R(g or )  2CO2 (g)  2e 
 O 2 (g)  4H  (aq.)  4e 
2H 2O()  EH 2 O/O2   1.23V
QUANTITATIVE ANALYSIS Section - 7
Faraday’s Law of Electrolysis (a quantitative analysis of electrolysis)

Faraday proposed following two laws for the quantitative analysis for the product of electrolysis :
Ist Law :
It states that “the amount of any substance that is deposited or liberated at an electrode is directly proportional
to the quantity of electricity passing through the electrolytic cell”.
The amount of electricity means quantity of charge (Q) in coulombs. If I is the current in amperes (A) and t
is the time in seconds, then Q = I t.

If w is the amount of substance liberated or deposited, then

wQ
w=ZQ Z : electrochemical equivalent of a substance
 w=ZIt
IInd Law :
It states that “when a given quantity of electricity is passed through different electrolytes, the amounts of
different substances produced at the electrodes are directly proportional to the respective equivalent weights”.
For two substances A and B in two different electrolytic cells ;
w A EA

w B EB
Experimentally it is seen that 1 gm eq. of a substance is deposited by passing 1 Faradays of electricity.

Magnitude of charge carried by 1 mole of electrons is 96487 C (6 × 1023 × 1.6 × 10–19 = 96487 C). It is
also known as one faraday i.e., 1F = 96500 C. [96500 C is the widely accepted value of 1 F].
It can also be seen by combining Ist and IInd Laws as follows :
wQ (Ist Law)
wE (IInd Law)
QE 1 1  w Q
 w     
F  F 96500  E F
No. of gram equivalents = No. of Faradays of electricity
 1 gm eq = any substance = 1 F of electricity
Now there are three approaches to solve a problem.
Q It
First calculate the number of faradays of electricity by using : No. of faradays  
F 96500
(i) Now by using the definition : 1 gm. eq. of any substance  1 F of electricity passed
 g
Calculate the number of gm. eq. and by using the definition of gm.eq.  gm.eq   , determine the
 E
amount of substance deposited.
(ii) Using anodic and cathodic reactions as follows :
Let us consider a typical cathode reaction : Mn+ + ne– 

 M

 n (e–s)  1 molecule of M  1 ion of Mn+

 N0 (n e–s)  N0 molecule of M (N0 : Avogadro number)
 N0 (n e–s)  1 mole of M  1 mole of Mn+
 n F  1 mole of M  1 mole of Mn+ (charge of N0 electrons  1 F = 96500 C)
So in this approach, first write anodic and cathodic reactions and derive the mole Vs faraday relation.
For example : Al3+ + 3e 

 Al  3F  1 mole of Al  1 mole of Al3+ ions
2Cl 
 Cl2 + 2e  2F  1 mole of Cl2  2 mole of 2Cl ions
(iii) Using the combined relation obtained from Ist and IInd Laws :
w=ZIt
EIt
 w
96500
Illustration - 18 In the electrolysis of aq. CuSO , a current of 2.50 Amp is allowed to flow for exactly 3.0
4
hr. How many grams of Cu and lts of O2 are produced at 25oC and 1 atm. pressure?
SOLUTION :
In the electrolysis of aqueous solution, following  2F  1 mole of Cu
reactions will take place :
 0.28 F  1/2  0.28 moles of Cu
Cathode : Cu2+ + 2e– 
 Cu (s)  1/2  0.28  63.5 gm
 8.9 gm of Cu have been deposited
Anode :  O2 + 4H+ + 4e
2H2O 
Now from anode :
(Sulphate ions and H+ ions remain in the solution
to given an acidic solution)  O2 + 4H+ + 4e–
2H2O 
Now from cathode : Cu2+ + 2e– 
 Cu (s)  4F  1 mole of O2
 2F  1 mole of Cu  0.28 F  1/4 × 0.28 = 0.07 moles of O2
It 2.5  3  3600 Now using gas equation : PV = nRT
No. of faradays = 
96500 96500
nRT 0.07  0.0821  298
= 0.28 F V   1.71 L Of O 2
P 1

Illustration - 19 Calculate the quantity of electricity required to reduce 12.3 gm of nitrobenzene to aniline
if the current efficiency for the process is 50%. If the potential drop across the cell is 3.0 V, how much energy
is consumed ?
SOLUTION :
Writing the half cell reaction for the reduction of nitro-benzene as follows :
C6H5NO2 + 6H+ + 6e– 

 C6H5NH2 + 2H2O
 1 mole of C6H5NH2 6 F of charge
0.6  100
Now, moles of nitro-benzene = 12.3/123 No. of Faradays required =
50
= 0.1 moles
= 1.2 F = 1.2 × 96500 C
 0.1 mole  0.6 F
Now potential difference = 3V
Hence, 0.6 F of electricity are used to reduce
The energy (E) consumed is given by :
12.3 gm of nitro-benzene if the current efficiency
is 100 %. But it is given that current efficiency is E = charge × potential difference
50 %, so
 E = (1.2  96500 × 3) = 347400 J
= 347.4 kJ
Illustration - 20 A potassium salt of ternary acid of Molybdenum (at. mass = 96) has the formula K MoO .
2 n
When an acidified solution of K2MoOn is electrolysed, O2 gas is liberated corresponding to a volume of 0.112
L at STP & 0.32 gm of Mo is deposited. Find the formula of salt.
SOLUTION :
The given situation in the question is possible 0.32
 0.02   x=6
only if MoO 2n  ion gets dissociated to M 0x 96 / x
which moves towards cathode. Mox+ + 6e–   Mo0
No. of faradays passed  gmeq of O2  gmeq  oxidation state of Mo = 6
of Mo
In K2MoOn, we have 2 (+1) +6 + n (2) = 0
4F  1 mole of O2  n=4
0.112  molecular formula is K2MoO4
 gmeq of O2 = 4   0.02
22.4
 gmeq of Mo = 0.02
g
= gmeq of Mo
E

Example - 16 During an electrolysis of conc. H2SO4, perdisulphuric acid (H2S2O8) and O2 form in
equimolar amount. The moles of H2 that will form simultaneously wil be :
(A) thrice that O2 (B) twice that O2 (C) equal to that O2 (D) half of that O2
SOLUTION : (A)
This is a special case of electrolysis where two So, if x moles of O2 are being produced,
products are being obtained at anode : electricity being passed at anode is :
At anode : 4x (For O2) + 2x (3For S2O82–) = 6x F
At cathode :
4OH– 
 O2 + 2H2O + 4e– . . . . (i)
2H+ + 2e– 
 H2 . . . . (iii)
2– 2– –
2SO4  S2O8 + 2e
 . . . . (ii)
2 F electricity  1 mole H2 is produced
1 mole O2 requires 4 F electricity and 1 mole S2O82–
 6x F electricity  3x mole H2 is produced
(  H2S2O8) requires 2 F electricity.
 Moles of H2 produced at cathode = 3
moles of O2 produced at anode.
Example - 17 Assume that impure copper contains iron, gold and silver as impurities. In the purification
of copper, after passing a current of 142 amperes for 482.5 seconds, the mass of anode decreased by 22.6 gm
and that of cathode increased by 22.0 gm. Estimate % of iron and copper originally present.
SOLUTION :
Note : Silver and gold form the anode mud. Also, Now, No. of faradays passed at cathode
Impure Cu forms anode while pure Cu is made as = Gm eq of Cu deposited
cathode in the refining of impure Cu.
22
At Impure Cu electrode ( anode in the Cu  0.69 = No. of fardays passed at anode.
63.5 / 2
purification), both iron and Cu will go into the solution.
So, mass of iron and Cu dissolved in solution is 22.6 It 142  482.5
Total faradays passed = 
gm. 96500 96500
At cathode (pure Cu electrode), mass of Cu = 0.71 (at anode and cathode )
deposited is 22.0 gm. So, amount of Cu in 22.6 gm
Thus, faradays taken upby Fe at at anode
dissolved at anode is 22.0 gm.
= 0.71 – 0.69 = 0.02
Thus, 22.6 – 22.0 = 0.6 gm contains Fe, Au and
Ag.
 Fe2+ + 2e–
Fe 
 2F electricity  1 mole Fe
0.02 22
 0.02 electricity  Mole Fe % Cu in the original sample  ×100%
2 22.6
 0.01 × 56 gm Fe = 97.3%
0.56 gm Fe 0.56
and % Fe in the original sample  × 100%
22.6
= 2.4%
Example - 18 If 6.43 × 105 Coulombs of electricity are passed through an electrolytic cell containing
NaClO3 . 245 gm of NaClO4 are produced at the anode at the end of electrolysis. Determine the anode
efficiency.
SOLUTION :
Anode efficiency
actual wt.of any substance deposited

 100 4  96500
theoretical wt.deposited  Anode efficiency =  100
6.43  105
or Anode efficiency
 Anode efficiency = 60.03 %
actual No. of faradays used up Alternative Method :
  100
total No. of faradays used
First calculate the theoretical amount of NaClO4
produced by passing 6.43 × 105 C.
Let us write anode reaction first :
 2 F  1 mole of NaClO4
 
ClO3 
 ClO4
6.43  105 1 6.43  105
Balancing by ion electron method :  F 
96500 2 96500
ClO3 + H2O 
 ClO4 + 2H+ + 2e moles of NaClO4
 2F  1 moles of NaClO4 1 6.43  105

   122.5
 1 mole of NaClO4  2 F of charge 2 96500
= 408.12 gm of NaClO4
245 245
 moles of NaClO4  2  =4F But in actual only 245 gm of NaClO4 are produced
122.5 122.5
(some of the current is lost as heat and against the
So for the production of 245 gm of NaClO4, 4F of resistance to flow of ions).
electricity i.e., 4×96500 C of charge is actually
consumed. But we are given that a total of 6.43 × 245
 Anode efficiency =  100 = 60.03 %
105 C of electricity is passed through the cell, so 408.12
some of the charge is wasted.
Note :Electro-synthesis
It is a method of producing chemical compounds through non-spontaneous reactions carried out by electrolysis.
The above example is an illustration of electro-synthesis. Similarly, by electrolysing a solution of MnSO4 in
H2SO4, MnO2 may be produced at anode.
Mn2+ + 2H2O   MnO2(s) + 4H+ + 2e–

 2F  1 mol of MnSO4  1 mol of MnO2
Example - 19 During the electrolysis of water, a total volume of 33.6 mL of hydrogen and oxygen gas
was collected at STP. Find the amount of electricity that passed during electrolysis.
SOLUTION :
From two electrode reactions, it clear that hydrogen
Cathode : 2H+ + 2e– 
 H2
and oxygen are evolved in the mole ratio of 2 : 1,
 2F  1 mole of H2  22400 mL hence their volumes will also be in the same ratio.
or 1F  0.5 mole of H2  11200 mL  volume of H2 = 2/3 (33.6) = 22.4 mL
As 2F  22400 mL H2
Anode : 4OH 
 O2 + 4e– + 2H2O
 0.002 F of charge is passed through the
 4F  1 mole of O2  22400 mL electrolytic cell.
or 1F  0.25 mole of O2  5600 mL  amount of electricity = 0.002  96500 C
= 193.0 Coulombs.
Example - 20 A current of 1.0 A is passed for 96.5 sec through a 200 mL solution of 0.05 M LiCl solution.
Find :
(a) the volume of gases produced at STP. (b) the pH of solution at the end of electrolysis :
SOLUTION :
No. of faradays passed  0.5 × 10–3 × 22400 ml H2 at STP
It 1.0  96.5  11.2 ml H2 STP
   103 F
96500 96500
Anode : 2Cl   Cl2 + 2e–
Cathode : 2H+ + 2e– 
 H2 [O2 will be not be liberated due to over potential]
(Li+ will remain in solution)  2F  1 mole of Cl2
 2F  1 mole of H2 or 1  10–3 F  0.5  10–3 moles of Cl2
or 1  103 F  0.5  10–3 mole of H2  0.5  10–3 × 22400 ml Cl2 at STP

 11.2 ml Cl2 at STP
In solution, Li+ and OH are left. Since H2O produces equal no. of H+ and OH– ions,
mmoles of OH– ions left in excess = 10–3
To calculate the pH of solution, first calculate the
mmoles of H+ ions electrolysed. 103

 [OH ]   5  103 M
 mmoles of H+ ions electrolysed = Meq. 200 /1000
of H+ ions electrolysed = No. of faradays [Neglect OH– from dissociation of H2O]
passed
 pOH = – log10 (5 × 10–3)
–3
= 10 F
= 3 – log10 5 = 2.3
 pH = 14 – pOH = 14 – 2.3 = 11.7
Example - 21 An acidic solution of Cu2+ salt containing 0.4 gm of Cu2+ is electrolysed until all the copper
is deposited. The electrolysis is contained for seven more minutes with the volume of solution kept at 100 ml
and the current at 0.965 amp. Calculate the volume of gases evolved at STP during the entire electrolysis.
SOLUTION :
Writing electrode reactions : Cathode : 2H2O + 2 e 
 H2 + 2OH
Cathode : Cu2+ + 2e 

 Cu(s)  O2 + 4H+ + 4 e
Anode : 2H2O 
Numbers of faradays passed in 7 minutes are
Anode : 2H2O   O2 + 4H+ + 4e calculated as follows :
At Cathode : 2F  1 mole of Cu(s)
It 0.965  7  60
No. of faradays = 
0.4 0.4 96500 96500
 moles of Cu  2  = 0.0125 F
63.5 63.5
= 4.2 mF
At Anode : 4F  1 mole of O2(g)
At Cathode : 2F  1 moles of H2(g)
1 4.2 m F  1/2 × 0.0042 = 2.1 × 10–3 moles of H2
 0.0125 F   0.0125
4
At Anode : 4F  1 mole of O2(g)
= 3.13  103 moles of O2 4.2 mF  1/4 × 0.0042 = 1.05×103 moles of O2(g)
After all the copper ions are deposited as copper, During entire electrolysis, moles of all gases produced
electrolysis is continued for 7 minutes (for what ?).
Now electrolysis of water is carried out to produce = moles of O2 (with Cu) + (moles of H2 + moles of
H2(g) and O2(g) at cathode and anode respectively O2)
as follows : = 3.13 × 103 + (2.1 × 103 + 1.05 × 10–3)
= 6.28 × 10–3
Volume of all gases at STP
= (6.28 × 103) × 22400 ml = 140.67 ml
Example 22 - 23 Read the following passage :

A student prepare 2L buffer solution of 0.3 M NaH2PO4 and 0.3 M Na2HPO4. The solution is divided in half
between the two compartment (each containing 1 L buffer) of an electrolysis cell, using Pt. electrodes. As-
sume that the only reaction is the electrolysis of water and electrolysis is carried out for 200 min with a
constant current of 0.965 A.
 
 Assume that pK a( H PO  )  7.2
 2 4 
Example - 22 pH at anode is :
(A) 7.2 (B) 6.83 (C) 7.57 (D) 7.0
SOLUTION : (C)
 0.12 Felectricity  0.12 mole H+ consumed

 0.12 mole OH– left in excess
0.12
 After 200 min, [OH–] =  0.12M
1
Now, these OH– ions will react H 2 PO 4 with ions

( Acid).
H 2 PO4  OH 
 HPO42   H 2O
No. of faradays passed during electrolysis
0.3 M 0.12 M 0.3 M
It 0.965  200  60
=   0.12 0.18 M - 0.42 M
96500 96500
[Salt]
At cathode : 2H+ + 2e– 
 H2  pHsolution  pK a  log10
[Acid]
 1 F electricity  1 mole H+ consumed
0.42
 7.2  log10  7.57
0.18
Example - 23 pH at cathode is :
(A) 7.2 (B) 6.83 (C) 7.57 (D) 7.0
SOLUTION : (B)
At anode : 4OH– 
 O2 + 2H2O + 4e–
 1 F electricity  1 mole OH– consumed
 0.12 F electricity  0.12 mole OH– consumed  0.12 mole H+ left in excess
0.12
 After 200 min, [H+–] =  0.12M
1
Now, these H+ ions will react HPO 24  with ions ( Salt).
HPO24   H  
 H 2 PO4
0.3 M 0.12 M 0.3 M

0.18 M - 0.42 M
[Salt] 0.18
 pHsolution  pK a  log10  7.2  log10  6.83
[Acid] 0.42
Note : In a buffer solution of H 2 PO4 / HPO 42  , H 2 PO4 will act as an acid and H P O 24  will act as a salt and this
will behave as an acidic buffer.
Read the following passage :

Chemical reactions involve interaction of atoms and molecules. A large number of atoms/molecules (approxi-
mately 6.023 × 1023 ) are present in a few grams of any chemical compound varying with their atomic/
molecular masses. To handle such large numbers conveniently, the mole concept was introduced. This con-
cept has implications in diverse areas such as analytical chemistry, biochemistry, electrochemistry and radio-
chemistry. The following example illustrates a typical case, involving chemical/ electrochemical reaction,
which requires a clear understanding of the mole concept.
A 4.0 molar aqueous solution of NaCl is prepared and 500 mL of this solution is electrolysed. This leads to the
evolution of chlorine gas at one of the electrodes (atomic mass : Na = 23, Hg = 200; 1 Faraday = 96500
coulombs).
Example - 24 (i) The total number of moles of chlorine gas evolved is :

(A) 0.5 (B) 1.0 (C) 2.0 (D) 3.0
(ii) If the cathode is a Hg electrode, the maximum weight (g) of amalgam formed from this solution is :
(A) 200 (B) 225 (C) 400 (D) 446
(iii) The total charge (coulombs) required for complete electrolysis is :
(A) 24125 (B) 48250 (C) 96500 (D) 193000
SOLUTION : (i)-(B), (ii)-(D), (iii)-(D)
Mole of NaCl in the solution = 4 × 0.5 = 2
At anode : 2Cl– 
 Cl2 + 2e–
Moles of Cl– in the solution to be electrolysed = moles NaCl = 2
1
 Moles of Cl2 produced = 2  = 1 2 F electricity  2 × 96500 C 193000 C
2
At cathode : Na+ + e– 
 Na (when Hg electrode)
Na + Hg 
 NaHg (Sodium Amalgam)
 1 F electricity  1 mole Na
 2 F electricity  2 mole Na  2 moles NaHg 2 × (23 + 200) = 446 gm
Electrochemistry - III Vidyamandir Classes
Electrochemistry - III
(Electrolytic Conductance)
In this chapter, we will deal with the Conductance of electricity (charge) through Electrolytic solutions
(Electrolytic Conductance).
BASICS Section - 8
Electrical conductors (materials/substances which conduct electricity) are of two types :
(i) Metallic or Electronic Conductors : Conductors which transfer electric current by transfer of electrons,
without transfer of any matter, are known as metallic or electronic conductors. These materials contain
electrons which are relatively free to move. The passage of current through these materials has no observable
effect other than a rise in their temperature.
(ii) Electrolytic Conductors : Conductors like aqueous solutions of acids, bases and salts in which the flow
of electric current is accompanied by chemical decomposition are known as electrolytic conductors. With
the increase in temperature, the resistance decreases unlike in metallic conduction.
(a) The substances whose aqueous solutions allow the passage of electric current and are chemically
decomposed are termed electrolytes. Solutions of NaCl, KCl, CH3COOH etc. are examples of
electrolytes.
(b) The substances whose aqueous solutions do not conduct electric current are called non-electrolytes.
Solutions of cane sugar, glycerine, alcohol, etc., are examples of non-electrolytes.
Conductance
The conductance (G) is the property of the conductor (metallic as well as electrolytic) which facilitates the
flow of electricity through it. It is equal to the reciprocal of resistance (R), i.e.
1 1
Conductance (G) =  . . . . (i)
Resistance R
 It is expressed in the unit called reciprocal ohm (ohm1 or mho) or siemens (S) (S.I. unit).
The term Conductance can be further classified in the following ways :
(i) Conductivity () :

The resistance of any conductor varies directly as its length () and inversely as its cross-sectional
area (A), i.e.,
 
R  or R =ρ . . . . (ii)
A A

Vidyamandir Classes Electrochemistry - III
where  is called the resistivity or specific resistance (This name is now outdated as per IUPAC
convention)
If  = 1 cm and A = 1 cm2, then R = 
The resistivity () is, thus, defined as the resistance of one centimeter cube of a conductor.
The reciprocal of resistivity () is termed the conductivity or it is the conductance of one centimeter
cube of a conductor. It is denoted by the symbol  (abbreviation for “Kappa”). Thus,
1
κ=
ρ
Conductivity () is also called as specific conductance (Outdated as per IUPAC convention).
From equation (ii), we have :
A 1  1
ρ= . R or = .
 ρ A R
  
κ= ×G  = cell constant and is denoted by G* 
A  A 
or Conductivity () = Conductance (G)  cell constant (G*)
Note :  The unit of conductivity () is ohm1 cm1 or S cm–1.

 Conductivity can also be defined as the conductance of one centimeter cube of a conductor.
 For the conductance measurement of a solution,  is the distance between the electrodes and A is the
area of the electrodes.
 G* is difficult to calculate using /A. It is calculated more precisely by using a solution having known
values of  at some concentration [Calibration Technique].
(ii) Molar conductance (Ùm)

The molar conductance is defined as the conductance of all the ions produced by the ionisation of 1 g
mole of an electrolyte when present in V ml of solution. It is denoted by m.
Molar conductance (m) =   V
where V is the volume in ml containing 1 gm mole of the electrolyte.
If c is the concentration of the solution in g mole per litre, then :
1000
m = κ × where c is the concentration of the solution in M
c

Its units are ohm1 cm2 mol1 or S cm2 mol1
Also, if AxBy is an electrolyte dissociating as :  xA y   yBx 

A x By 
  m A x By  x   m (A y )  y   m (B x  )
For example :  m Al (SO )  2  m 3  3  m

2 4 3 (Al ) (SO 42  )
(iii) Equivalent Conductance (eq)

One of the factors on which the conductance of an electrolytic solution depends is the concentration
of the solution. In order to obtain comparable results for different electrolytes, it is necessary to take
equivalent conductance.
 It is defined as the conductance of all the ions produced by one gram equivalent of an electrolyte
in a given solution. It is denoted by eq.
At concentration c (in gm-equivalent/L i.e., normality), equivalent conductance is denoted by
eq.
 eq 

1000  conductivity ohm 1cm 1   1000  
c  or Normality N
If ‘V’ is the volume in ml containing 1 gm equivalent of the electrolyte, the above equation can be
written as :
eq =   V
Its units are ohm1 cm2 equiv1 or S cm2 equiv1.
Also, Equivalent conductance
Molar conductance Molecular mass

= where x   n  factor
x Equivalent mass
Also, if AxBy is an electrolyte dissociating as :  xA y   yB x 

A x B y 
eq   eq  eq
(A x B y ) (A y  ) (B x  )
For example : eq Al2 (SO 4 )3   eq (Al3 )   eq (SO 2 )

4

Illustration - 21 Resistance of a decimolar solution between two platinum electrodes 0.02 m apart and
4cm2 in area was found to be 40 ohms. Calculate : (a) cell constant (b) conductance (c) conductivity
SOLUTION :
(a) Cell constant (G*)
(c) Conductivity () = G.G* = 50 × 0.025 S/m
 0.02
=  m 1  50m 1
A 4  104 =1.25 S/m
1 1
(b) Conductance (G) =  S  0.025S
R 40
Illustration - 22 The resistance of 0.1 M solution of a salt (type : AB) is found to be 2.5 × 103 ohm. The
equivalent conductance of the solution is (Cell constant = 1.15 cm–1) :
(A) 4.6 (B) 5.6 (C) 6.6 (D) 7.6
SOLUTION : (A)
Use :
1000 4.6 104 1000
= G.G* eq  
N 0.1
1  1 = 4.6 S cm–1 eq–1.
 G  R 
= 1.15 = 4.6 × 10–4
2.5 103
Illustration - 23 The conductivity of 0.02 M KCl solution at 25C is 2.78  103 ohm1 cm1. The resistance
of this solution at 25C when measured with a particular cell was 250 ohms. The resistance of 0.01 M CuSO4
solution at 25C measured with the same cell was 8330 ohms. Calculate the molar conductivity of the copper
sulphate solution
SOLUTION :
Conductivity( ) of KCl 1
Cell constant (G*) = and Conductance of KCl (G) =
Conduc tan ce(G) of KCl R
2.78  103
 Cell constant(G*) = = 2.78 × 10–3 × 250 cm–1
1/ 250
For 0.01 M CuSO4 solution :
Conductivity () = Cell constant (G*)  conductance (G)
1

 2.78  103  250   8330
ohm 1cm 1
1000  2.78 103  250  1000

Molar conductance (^m) = Conductivity ()    = 8.3 ohm1 mol–1 cm2
c  8330 
  0.01

EFFECT OF DILUTION Section - 9
Effect on conductance
(i) Conductance of a solution increases with increase in the number of solute molecules/ions and decreases
with decreases in the number of solute molecules/ions.
(ii) Conductance of a solution increases with dilution as the interactions between the molecules/ions
decreases due to increase in the average distance between the molecules/ions.
Effect on degree of dissociation

(i) Strong electrolytes : There is almost no change in the degree of dissociation (as it is already close
to unity).
(ii) Weak elect rolyt es : With dilution, degree of dissociation increases rapidly and thus, the number of
molecules increases.
Effect on Molar and Equivalent conductance

Both m and eq increases with dilution as conductance increases with dilution.
For strong electrolytes, the increase in m and eq is relatively small as increase in the number of molecules/
ions is very small.
For weak electrolytes, the increase in m and eq is large and rapid as ‘’ increases with dilution.
Effect on Conductivity
On dilution, number of molecules/ions per ml of the solution decreases. Since, coductivity is defined as the
conductance of one ml of the solution, conductivity decreases with dilution (due to decrease in the
conductance).
Infinite Dilution
When addition of water doesn’t bring about any further change in the conductance of a solution, this situation
is referred to as Infinte Dilution.
(a) Strong Electrolytes : When infinite dilution is approached,
the conductance of a solution of strong electrolyte approaches
a limiting value and can be obtained by extrapolating the curve
between m and c as shown: (Note: the behavior/variation
is linear)
The molar conductivity of strong electrolytes is found to vary with concentration as :

 m   0m  b c where b is a constant depending upon the type of electrolyte (e.g.
AB, A2B etc. ), the nature of the solvent and the temperature.

This equation is known as Debye HuckelOnsages equation and is found to hold good at low
concentrations.
(b) Weak Electrolytes : When infinite dilution is approached,

the conductance of a solution of weak electrolyte increases
very rapidly and thus, cannot be obtained through
extrapolation. Also, the variation between m and c is not
linear at low concentrations.

Note : (i) lim  m  m and lim eq  eq
c 0 c 0
(ii) Conductance of a weak electrolyte at infinite dilution can be calculated by using Kohlrausch’s’s law of
Independent Migration of Ions.
Ionic Conductance
Conductance of an ion in the solution in inversely proportional to its size in the solution.
e.g. Li+ ion has a very high charge to size ratio due to which it gets hydrated to a large extent, when dissolved
in water. Thus, Size of Li+ (aq.) >> Size of Li+(g).
Note :  r r r but r r r
K + (g) Na  (g) Li  (g) K + (aq) Na  (aq) Li  (aq)
^ ^ ^
 m K + (aq) m Na  (aq) m Li  (aq)
 A heavily hydrated ion has to drag water molecules along with it when it moves in a solution which
makes it less mobile (or less conducting).
 Size of H+ (g) and OH– (g) ions are extremely small yet they have a very high conductance value in the
solution (as opposed to what you might have expected). Infact, H+ ion has the highest ^m at any
temperature followed by OH– ions. This is due to the mechanism by which they travel in the aqueous
solution.
H H H H
| | | |
H+ moves in the solutions as shown : H  O  H  O  H 
 H  O H  O  H
 
Illustration - 24 Arrange the following compounds in the orders of increasing conductionce. HCl, LiCl,
NaCl, KCl.
SOLUTION :
Note that anion (Cl–) is same in all the given Since,  m H +   m K +   m Na    m Li 
compounds. So, look for the conductance values
of cations only. So,  m HCl   m KCl   m NaCl   m LiCl

KOHLRAUSCH’S LAW OF INDEPENDENT MIGRATION OF IONS Section - 10
As per Kohlrausch’s Law of Independent Migration of Ions “At infinite dilution, when dissociation is complete,
each ion makes a definite contribution towards molar conductance of the electrolyte irrespective of the
nature of the ion with which it is associated and the value of molar conductance at infinite dilution for any
electrolyte is the sum of contribution of its constituent ions, i.e., anions and cations”.
As per Kohlrausch’s law, at infinite dilution, the conductance of any ion is independent of its association with
the other ion in the electrolyte i.e. 0m (K+) will be same in infinitely diluted solution of KCl or KBr or
KNO 3 .
Illustration - 25 The equivalent conductance of sodium chloride, hydrochloric acid and sodium acetate at
infinite dilution are 126.45, 426.16 and 91.0 S cm2 equiv1, respectively, 25C. Calculate the equivalent
conductance of acetic acid at infinite dilution. If the equivalent conductance of N/100 solution of acetic acid
is 3.9 S cm2 eq–1, calculate the degree of dissociation of acetic acid at this dilution.
SOLUTION :
According to Kohlrausch’s law, 0eq CH COONa  0  0  91.0 . . . (i)

3 eq CH3COO eq Na 
Similarly, we have :
eq HCl      426.16 . . . (ii)

eq H  eq Cl
0eq NaCl  0   0  126.45 . . . (iii)

eq Na eq Cl
Adding Equations (i) and (ii) and subtracting (iii),
we get :   0 0   0 0   0 0 
             eq Na    eq Cl 
 eq CH3COO eq Na   eq H eq Cl   
= 91.0 + 426.16 – 126.45
 0 0 
   eq CH COO   eq H    390.7
 3 
 0eq CH COOH  390.7 Scm 2 equiv1

3
eq 3.9
Also,   0   0.01  1%
eq 390.7
0
Note : eq Cl has been taken as same in equation (ii) and (iii). This is from the direct result of Kohlrausch’s law..

Applications of Kohlrausch’s law :

(i) Solubility Product of a Sparingly Soluble Salt :
If solute is sparingly soluble in a given solvent, its concentration is taken as its solubility in the saturated
solution.
1000  conductivity 1000  
Thus, 0m  
c c
0m can be computed using Kohlrausch’s law:
Thus, c can be computed and can be used to calculate the solubility product.
For example : For Al(OH)3 : KSP = [Al3+](3(OH]–)3
= (c) (3c)3  KSP = 27c4
(ii) Degree of dissociation :
At any dilution, the equivalent conductance is proportional to the degree of dissociation. Thus,
 eq Equivalent conductance at a given concentration

Degree of dissociation ()  
 0eq Equivalent conductance at infinite dilution
m Molar conductance at a given concentration

 
 0m Molar conductance at infinite dilution
Illustration - 26
The conductivity of a saturated solution of water chloride is 2.30  10–6 mho cm1 at

25C. Calculate the solubility of silver chloride at 25C if    61.9 mho cm mol
2 1
and
 2 1 m Ag
  76.3 mho cm mol
mCl  .
SOLUTION :
Let the solubility of AgCl be x gram mole per 0m AgCl  61.9 + 76.3 = 138.2 mho cm2 mol1
litre (i.e., mole/L). [Note : NAgCl = MAgCl]
Using : 1000  2.30  106
 138.2 
x
1000  specific conductance 1000  
0m   2.30  103
c x  x  1.66  105 mol / L
138.2
Now find the equivalent conductance of AgCl
at infinite dilution.  Solubility in gm/L = 1.66  10–5  143.5
= 2.38  10–3
0m AgCl  0   0 
m Ag m Cl

(iii) Ionisation constant of weak electrolytes :

Let AB be a weak electrolyte of concentration c.

AB  A+ + B–
At t = 0 c 0 0
At equilibrium c – c c c
[A  ][B ]
Thus, Equilibrium Dissociation Constant = K d 
 AB
cα  cα cα 2
Kd =  . . . (i)
c – cα 1  
Kd
For weak electrolytes,  << 1  Kd  c2  =
c
As concentration decreases, degree of dissociation increases.
  rq
Now,   0m  0
m eq
2 2
    eq 
m
c 0  c 0 
    eq 
Putting this value of  in (i) we get : Kd   m    
. . . (ii)
m  eq
1 0 1 0
m  eq
Equation (ii) is known as Ostwald equation.
Illustration - 27 Resistance of a solution (A) is 50 ohm and that of solution (B) is 100 ohm, both solutions
being taken in the same conductivity cell. If equal volumes of solutions (A) and (B) are mixed, what will be the
resistance of the mixture, using the same cell ? Assume that there is no increase in the degree of dissociation
of (A) and (B) on mixing.
SOLUTION :
1
Let us suppose 1 and 2 are the specific Also, conductance =
conductance of solutions ‘A’ and ‘B’ respectively R
and cell constant is ‘y’. 1
 For (A) : 1  y
We know that : 50
Specific conductance = Conductance  cell 1
constant and For (B) :  2  y
100

When equal volumes of (A) and (B) are mixed, 1 y y  1

the volumes becomes double. Then,    y
2  50 100  R

  2
Specific conductance of mixture = 1 1 1 1
2    R = 200/3
100 200 R
1   2 1 = 66.66 ohm
  y
2 R
Illustration - 28 The solubility product of sparingly soluble AgBr(s) is 12 × 10–14 mol2 dm–6. Calculat the
conductivity in units of 10–7 Sm–1 of saturated solution of AgBr upon addition of 1 × 10–7 mol dm–3 aqueous
AgNO3. The limiting ionic molar conductivity of Ag+, Br–, and NO3– at infinite dilution are 6 × 10–3,
8 × 10–3 and 7 × 10–3 S m2 mol–1, respectively. [Conductivity of pure water = 350 × 10–7 S m–1] (Neglect any
effect due to concentration dependence of conductiance)
(A) 39 (B) 55 (C) 15 (D) 405
SOLUTION : (D)
2
 mol 
KSP AgBr = 12  1014  2
 12  1014 M 2
 dm 
When 10–7 AgNO3 is added into the saturated solution of AgBr :
 Ag   NO3
AgNO3 
107 M 107 M
 Ag   Br 
AgBr 
[where x : Solubility of AgBr in the presence of 10–7 M AgNO3]
xM xM
At equilibrium :
KSP AgBr = [Ag+][Br–] = (x + 10–7) . x = 12 × 10 –14
 x2 + 10–7 x – 12 × 10 –4 = 0
Solve to get : x = 3 ×10–7 M
 At equilibrium, [Ag+] = x + 10–7 = 4 × 10–7 M = 4 × 10–4 mol m–3 ; [Br–] = x = 3 × 10–7 M
= 3 × 10–4 mol m–3
[NO3–] = 10–7 M = 10–4 mol m–3 [Using : 1 M 1000 mol m–3]

Total conductivity of solution =  Ag    Br    NO   H 2O

3
= ^0
 . [Ag  ]  ^ 0  . [Br  ]  ^ 0 
. [NO3 ]   H 2O
m (Ag ) m (Br ) m (NO3 )
= 6 × 10–3 × 4 × 10–4 + 8 × 10–3 × 3 × 10–4 + 7 × 10–3 × 10–4 + 350 × 10–7

= 405 × 10–7 S m–1
CONDUCTOMETRIC TITRATIONS Section - 11
Measurement of conductance of resulting solution form an acid and base titration may used to calculate the
equivalence point if there is a regular change in the conductance and sharp change at the equivalence point.
CASE : I Strong Acid (HCl) vs. Strong Base (NaOH) :
Region I : Initially the solution has the conductance due to the presence of H+ and Cl– ions. As NaOH
is added, following reaction takes place :
(H   Cl )  (Na  OH  ) 
 (Na   Cl  )  H 2O
 
Initially Finally
Thus, highly conducting H+ ions are replaced by lower conducting Na+ ions, resulting in a
decrease in the conductance of solution. As more and more NaOH is added (till the equivalence
point), conductance goes on decreasing.
Region II : Just after the equivalence point, as more NaOH is added, now there are more ions
(Noneutralisation)
(Na+ + Cl–) + (Na+ + OH–)

So, conductance will increase due to the presence of more number of ions in the solution.

As we can see that equivalence point, there is a sharp change in the curve definition and we can easily
calculate the equivalence point.
CASE : II Weak Acid (CH3COOH) vs Strong Base (NaOH) :
Region I : As more NaOH is added, it will directly react with CH3 COOH to form highly ionizable salt,
CH3COO– Na+. So, conductance will start increase (slowly as CH3COO– and Na+ have
low conductance)
Region II : Just after equivalence point, there will be an increase in the number of ions.
(Na++CH3OO–) + (Na+ + OH–)
So, conductance will increase sharply (OH– ions have highly conductance) and we can easily
find the equivalence point required through the titration.
Case : III Strong acid (HCl) vs Weak Base (NH4OH) :
Follows similar discussion as in case II.

Illustration - 29 An aqueous solution of X is added slowly to an aqueous solution of Y as shown in List I.

The variation in conducitivity of these reaction is given in List II. Match List I with List II.
List l List ll
[P] (C2 H5 )3 N  CH3 COOH 1. Conductivity decreases and then increases.

X Y
[Q] KI  0.1M   AgNO 3  0.01M  2. Conductivity decreases and then does not change much
X Y
[R]  CH3COOH   KOH 3. Conductivity increases and then does not changes much
X Y
[S] NaOH  HI 4. Conductivity does not change much and then increases
X Y
SOLUTION :
1. EtN in CH3COOH solution
When Et 3 N solution is added to CH 3COOH. '  ' of CH3COOH will increase, so through H  ions
ions will be consumed by Et 3 N, the overall number of ions in the solution will increase and hence conductivity

increase initially. Once almost all of CH 3COOH is consumed, a lot of and Et 3 N H will be
present in the solution and now further addition Et 3 N doesn’t cause much change in the total number of
ions as Et 3 N will not be able to extract H  ion from H 2O (because their will be suppression due to

already present Et 3 N H ions) and hence conductivity will almost remain the same.
2. Kl solution in AgNO3 solution
Initially : Ag    
KI aq
(a)  NO3  aq    AgI  s    K aq  NO3 aq
 aq     
 Number of ions remain the same  Conductivity does not change much.
(b) After all Ag  ions have been precipitated out, then the conductivity will increase because we are adding a
more concentrated solution and consequently number of ions per unit volume will increase.
3. CH3COOH in KOH
 CH COOH  aq 
(a) Initially : K (aq)  OHaq  
3
 H 2O     K aq  CH3COOaq 
 
 Number of ions remains the same, but number of OH  ions decrease  Conductivity
decrease.

(b) After all of OH  ions have been consumed, then further addition of CH 3COOH will not have much effect
as CH 3COOH will not break up much, as its dissociation will be suppressed by the already present
ions.
4. NaOH in Hl
NaOH
(a) Initially : H   I   H 2O     Na aq  Iaq 
 
 Numner of ions remains the same, but number of H  decrease  Conductivity decreases.
(b) After all the H  ions have been consumed, then further addition of a strong electrolyte NaOH (which will

give O H ions in the solution will increase conductivity..
ANSWER : [P-3] [Q-4] [S-1]
IN-CHAPTER EXERCISE - C
1. Given the following molar conductivities at 25C ; HCl , 426  cm mol  ;
NaCl , 126  cm mol  ; NaC (sodium crotonate) 83  1 cm 2 mol 1. What is the ionization
constant of crotonic acid ?
The conductivity of a 0.001 M crotonic acid solution is 3.83  105 1cm 1.
NOW ATTEMPT IN-CHAPTER EXERCISE-C FOR REMAINING QUESTIONS

Electrochemistry Vidyamandir Classes
THINGS TO REMEMBER
1. In an electrochemical cell, cathode is the electrode with higher reduction potential or lower oxidation
potential.
°

°
Also, Ecell = E reduction cathode   E°reduction anode
2. Electrode potential of an electrode or cell varies with concentration, partial pressure of the species involved
and temperature.
 2.303RT 0.059 
E reduction  E °reduction    at 25° C  log10Qreduction
 nF n 
°  2.303RT 0.059 
and Ecell = Ecell   n F  n at 25°C  log10Qcell
 cell cell 
3. For a concentration cell, E°cell = 0
 1 (p H 2 )anode 
For a hydrogen concentration cell, Ecell = 0.059  pH Anode  pHcathode + log10 
 2 (p ) 
H 2 cathode 

4. Gibbs Helmholtz equation :
 d ( G )    dE  
G  H  T   H  ncell F T  cell   Ecell 
 dT T   dT  P 
 dE 
and S  ncell F  cell 
 dT P
5. In electrolysis, cations move towards cathode and anions move towards anode and the “chance” of their
deposition/liberation depends on their electrode potential, concentration, overpotential etc.
6. Faraday’s law : W = ZIt . . . . (i)
WA WB
 . . . . (ii)
E A EB
It
No. of Faradays supplied  = No. of gm eq. of the substance deposited/liberated at the electrode.
96500
7. Molar/ equivalent conductance and degree of dissociation of a electrolyte increases with dilution whereas
conductivity decreases with dilution.
 
G .G*   ; m  1000  ; eq.  1000 
C C
8. Molar/equivalent conductance of a strong electrolyte increases linearly with dilution whereas the change is
very rapid for weak electrolytes at high dilutions.
To calctrolytes the molar/equivalent conductance of a weak electrolyte at infinite dilution, use Kohlrausch’s
law of independent migration of ions.
 eq
Also,   m  
 m eq
9. For a smaller ion in gaseous state i.e. larger ion in aqueous, molar conductance is a small value. However,
H + and OH  ions are exceptions with high molar conductance values.
IN-CHAPTER EXERCISE-C
C 1. 1.11 10 5
SOLUTIONS TO IN-CHAPTER EXERCISE-C
1. Let crotonic acid be HC

0HC   0NaC   0HCl   0NaCl = 83 + 426 – 126 = 383
3.83  105  103 38.3

cHL   38.3    0.1
0.001 383
C 2 0.001  .12
Ka    1.11  105
1 1  0.1
Self Study Course for IITJEE with Online Support Answers & Solutions 3
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Co-ordination Compounds
Co - ordination Compounds
BASICS Section - 1
I. Molecular or Addition Compounds

When a solution made by mixing two or more simple stable compounds in simple molecular (stochiometric)
proportions is allowed to evaporate, crystals of new substances may separate out. These substances are
termed as molecular or addition compounds. Some common examples are :
KCl + MgCl2 + 6H2O 

 KCl.MgCl2.6H2O
carnalite
Fe(CN)2 + 4 KCN   Fe(CN)2 . 4 KCN (or K4[Fe(CN)6] )

Potassium ferrocyanide
The molecular or addition compounds are of two types :
(a) Double Salts or Lattice Compounds :
(i) The addition compounds which are stable only in crystalline state and lose their identity in solution
form are called double salts.
(ii) When dissolved in water, these salts dissociate completely to give all the ions as are given by the
compounds from which these were formed.
K 2SO 4  Al2 SO 4 3  24 H 2O  K 2SO 4 . Al 2  SO 4 3 .24 H 2 O

Potash Alum
solution
 2K   aq   4SO 24   aq   2 Al3  aq 
(iii) The molar conductivity of such a solution would correspond to all the ions as given by the constituent
compounds.
(b) Co-ordination Complexes (or Compounds) :

(i) The addition compounds which do not lose identity even in solution form (i.e., they are stable in solid
as well as dissolved state) are called complex compounds.
(ii) In solution form, these compounds do not furnish all the ions which are given by the constituent
compounds.
solution
2 KCN + Ni (CN)2 
 K2[Ni(CN)4]   2K+ (aq) + [Ni(CN)4]2–

Co-ordination Compounds Vidyamandir Classes
(iii) The molar conductivity of such a solution would correspond to fewer ions as given by the constituent
compounds. In above example, the addition compound of KCN and Ni(CN)2 does not give Ni2+
and CN ions in aqueous solution and hence the molar conductivity of such a solution is because of
two K+ ions and one [Ni(CN)4]2– ion and not because of two K+ ions, one Ni2+ ions and four CN–
ions.
II. Co-ordination Compounds and Complex Ions :
Co-ordination compounds are the compounds in which the central metal atom is linked to a number of ligands
(ions or neutral molecules) by co-ordinate bonds i.e. by donation of lone pairs of electrons by these ligands to
the central metal atom.
If a such a compound carries positive or negative charge, it is called a complex ion, e.g. [Fe(CN)6]4,
[Cu(NH3)4]2+. Hence co-ordination compounds may also be defined as those compounds which contain
complex ions, e.g., K4[Fe(CN)6], [Cu(NH3)4]SO4, etc. In general, a complex ion is represented as [MLn]x
where M is the metal ion, L represents ligands, n is the co-ordination number of metal ion and x is the net
charge on the complex.
There are following four types of complexes :
(i) Cation as complex ion, (carrying a net positive charge) e.g., [Co(NH3)6]3+ in [Cr(NH3)6]Cl3.
(ii) Anion as complex ion, (carrying a net negative charge) e.g., [Fe(CN)6]3 in K3[Fe(CN)6].
(iii) Cation and anion both as complex ion. For e.g., [Pt(Py)4] [PtCl4].
(iv) Neutral complex (A complex carrying no net charge) e.g., [Ni(CO)4] etc.
The formation of a complex ion involve following two things :
(i) Ligands should have atleast one lone pair of electrons which can be donated to central metal atom or ion.
(ii) The central atom or ion should have vacant orbitals so as to accommodate the electrons donated by the
ligands.
TERMINOLOGY OF CO-ORDINATION COMPOUNDS : Section - 2
1. Centre of Coordination (Central atom/ion or Acceptor atom/ion) :

The cation or neutral atom to which one or more ligands neutral molecules or anions are attached or co-
ordinated is the centre of co-ordination.
The central, atom/ion must have empty orbitals as it acts as an acceptor and thus has to accommodate
electron pairs donated by the donor atom of the ligand. This explains why the transition metal having
empty d-orbitals, form co-ordination compounds very readily.
For example in the complexes [Ni(NH3)6]2+ and [FeCN)6]3–, Ni2+ and Fe3+ respectively are the central
ions.

2. Ligands :
Any atom, ion or molecule which can donate alteast a pair of electrons to the central atom to form acoordinate
bond (or dative linkage) is called as ligand or coordinating group. Further in a ligand, the particular atom
which actually donates the electron pair is called the donor atom.
The ligands act as Lewis bases as they donate one or more electron pair to the central metal atoms or ions
which act as Lewis acids by accepting electrons.
Types of Ligands :
Ligands can be of following types depending on the denticity of the ligand i.e the number of donor atoms
present in a ligand. (Precisely, denticity of a ligand is the maximum number of donor atoms present in the
ligand which can be utilised to coordinate (or ligate) with the central atom simultaneously).
(i) Monodentate or unidentate Ligands : They have one donor atom, i.e. they supply only one electron
pair to the central atom. e.g. F–, Cl–, Br–, H2O, NH3, CO, SCN–, NO–, NH3, H2O etc.
(ii) Polydentate ligands or Multidentate ligands : These ligands coordinate using two or more donor
atoms. Structures of some bidentate or didentate, terdentate, tetradentate ligands have been shown below:
 Bidentate ligands :

 Terdentate ligands :
 Hexadentate ligand :
Note :Polydentate ligands have flexible character. It is not necessary that all the donor atoms present in the polydentate
ligands should form co-ordinate bonds with central metal atom or ion. For example, ethylenediaminetetraacetate
ion (EDTA) which is hexadentate ligand can also function as pentadentate or tetradentate ligand with certain
metal ions. Sulphate ion (SO 24  ) , can act both as monodentate as well as bidentate as shown :
Ambidentate Ligands : There are certain ligands which have two or more donor atoms in forming complexes
only one donor atom is attached to metal ion. Such ligands are called ambidentate ligands or in other words
these are the ligands which can ligate through two different atoms present in it. Examples of such ligands are
the NO2–, CN–, SCN– ions. NO2– ion can coordinate to a central metal atom/ion either through nitrogen or
the oxygen atoms as depicted below :

M  NO2– Nitro M  ONO– Nitrito

M  CN– Cyano M  NC– Isocyano
M  SCN– Thiocyanato M  NCS– Isothiocyanato
Chelation : When coordination of two or more donor atoms from a polydentate ligand to a single central
atom/ion takes place forming a closed or cyclic ring structure, it is called chelation and the ligand a chelating
ligand. The close ring compound thus formed is called chelate (or metal chelate).
Some Important Characteristic of Chelates :
(a) Chelating Effect : Chelating ligands form more stable complexes than the monodentate analogs. The complex
ion/compound have such ligands does not dissociate easily.
(b) Formation of Rings : Generally the chelate complexes with 5 or 6 membered rings are more stable. Out of
these, 5 membered rings are very stable when they involve saturated ligands, e.g., ethylenediamine, which
contains five membered stable ring structure. On the other hand 6-membered ring structures acquire
maximum stability when they involve unsaturated ligands containing conjugate double bonds.
(c) Steric Hindrance : Ligands with large groups form unstable rings than the ligands with smaller groups due to
steric hindrance.
(d) The complex compound having maximum number of rings formed with the ligands is most stable. For
example, a complex [M(en)3]3+ is less stable than a complex [M(EDTA)]– because in the former there
are 3 rings while in the latter has 5 rings.
(e) Entropy effect : The stability of the chelate complex is explained on the basis of entropy effect. To elaborate,
let us take an example of ethylene diamine ligand (en). When one end of ‘en’ is coordinated the probability
of coordination of the other end is high because this end is bound to stay close to the central atom/ion. This
shows that it is easier to form a chelate ring than forming coordinate bonds with two independent molecules.
Thermodynamically, the increased stability due to chelation can be attributed to an increase in the degree
of freedom of the system. A large change in entropy but only small heat of reaction generally accompany
the chelation process.
3. Co-ordination Number (C.N.) : The number of atoms (of the ligands) that are directly bound to the central
metal atom/ion by coordinate bonds is known as the co-ordination number of the central atom/ion. It is
actually the number of sigma bonds which the ligands form with the central metal atom/ion. Pie bonds, if
formed between the ligands and the central metal/ion, are not counted for this purpose.

Co-ordination Number of Complexes

Complexes Ligands C.N.
[Ag(NH3)2]+ NH3 2
[HgI3]– I 3
[PtCl4]2–, [Ni(CO)4] Cl, CO 4
[Fe(CO)5], [Co(CN)5]3 CO, CN 5
[Co(NH3)6]3+, W(CO)6 NH3, CO 6
[Mo(CN)7]3– CN 7
[W(CN)8]4– CN 8
[Co(en)3]3+, [Fe(C2O4)3]3– en, C2O42– 6
[Co(H2O)2(NH3)4]3+ H2O and NH3 2+4=6
4. Co-ordination entity (sphere) :

The central metal atom/ion & the ligands that are directly attached to it, enclosed in a square bracket, are
collectively called as co-ordination sphere (or entity). The ionisable groups are written outside the bracket
and are called counter ions. The co-ordination sphere behaves as a single unit because the ligands
present in the co-ordination sphere are held tightly by the metal ion. Any ion present outside this sphere is
separated from the complex, when compound is dissolved in the water. Eg : In the following compounds
[Cr(NH3)6]Cl3, K4[Fe(CN)6], K2[PtCl4], [Ni(CO)4], K2[Ni(CN)6] the respective coordination entities
are : [Cr(NH3)6]3+ ; [Fe(CN)6]4– ; [PtCl4]2– ; [Ni(CO)4] ; [Ni(CN)4]2– ; and the counter ions are Cl–,
K+, K+, (no counter ion) and K+.
5. Co-ordination polyhedron :
The spatial arrangement of the ligand atoms which are directly attached to the central metal atom or ion,
in definite direction thereby giving a definite geometry to the complex ion or compound, is called coordination
polyhedron around the central atom or ion. The most common coordination polyhera are octahedral,
square planar and tetrahedral.

6. Oxidation number of central atom :

It is is defined as the charge that the central metal ion would carry if all the ligands are removed alongwith
electron pairs. It is calculate as follows :
Example : K4[Fe (CN)6]
K4[Fe (CN)6]  4 K+ + [Fe (CN)6]4–
Charge on complex ion = – 4
Let charge on Fe = x,
Now charge on cynide ion (CN–) = –1
 x + 6  (–1) = –4
 x = +2
Hence oxidation no of Fe = +2 (or II)
Complexes Central metal ion Ligands Oxidation Number

[Co(NH3)6]3+ Co 6 NH3 III
[NiCl4]2 Ni 4 Cl II
[Co(CN)5F]3 Co 5 CN & 1 F III
[Ni(CN)4]2 Ni 4 CN II
[Ni(CO)4] Ni 4 CO 0
[Ni(H2O)6]2+ Ni 6 H2O II
[Fe(CN)6]4 Fe 6 CN II
[Cu(NH3)4]2+ Cu 4 NH3 II
7. Homoleptic and Hetroleptic Complexes :

Complexes in which central atom is coordinated with only one kind of ligands are called homoleptic
complexes, eg. [Co(NH3)6]3+. Complexes in which central atom is co-ordinated with more than one
kind of ligands are called hetroleptic complexes, eg. [Co(NH3)4 Cl2]+ .
8. Effect atomic Number (EAN rule and Sidgwick Theory) :
In order to explain the stability of co-ordination complexes Sidgwick proposed effective atomic number
(EAN) rule. He suggested that a metal ion will continue accepting electron pairs till the total number of
electrons in the metal ion (after gaining electrons from the donor atoms of the ligands) becomes equal to
that of the next higher noble gas. This total number of electrons is called the effective atomic number
(EAN) of the metal. This will become clear by taking the example of heaxamminecobalt(III) ion,
[Co(NH3)6]3+.
Aomic number of cobalt = 27.

In the present complex, cobalt is present in the oxidation state of +3.

 Total no of electrons in Co3+ = 27 – 3 = 24.
Since each NH3 ligand donates two electrons to the cobalt ion,
Electrons donated by 6 NH3 ligands = 6  2 = 12.
EAN of Co3+ i.e. total no of electron present in Co3+ in complex = 24 + 12 = 36
(36 is the atomic number of Krypton (Kr), the next nearest noble gas)
In general,
EAN = (atomic number – oxidation state) + (C.N.  2)
or EAN = atomic no of the metal – no of electrons lost in ion formation + no of electrons gained from
ligands.
In the above example since the number 36 corresponds to the atomic number of krypton, according to
Sidgwick, the complex will be stable. Though EAN rule (which states that those complexes are stable
whose EAN is the same as the atomic number of the next noble gas) is applicable in many cases, there are
several examples in which EAN rule is not obeyed.
Illustration - 1 Apply the concept of EAN rule, on the complexes [Fe(CN)6]4– and [Fe(CN)6]3–. What
conclusion do you draw about the validity of the EAN rule from these two complexes ? (Atomic number
of Fe = 26)
SOLUTION :
(a) [Fe(CN)6]4– : Let O.S. of Fe in [Fe(CN)6]4– (b) [Fe(CN)6]3– : Let O.S. of Fe in [Fe(CN)6]3–
=x
=x
So, x + 6 (–1) = –4 x = +2
So, x + 6 (–1) = –3
Also, C.N. of Fe in [Fe(CN)6]4– = 6
So, x = +3
( CN– is a unidentate ligand)
Again, C.N. of Fe in [Fe(CN)6]3– = 6
So, EAN of Fe = (Z – O.S.) + 2 (C.N.) ( CN– is a unidentate ligand)
= (26 – 2) + 2 6 = 36 So, EAN of Fe = (26 – 3) + 2 6 = 35 
= Atomic number of Kr (next nearest inert gas). atomic number of Kr (36) (next nearest inert
So, in [Fe(CN)6]4–, EAN rule is valid. gas)
Thus EAN rule is not valid in [Fe(CN)6]3–.

Illustration - 2 Predict the formulae of the carbonyl complexes of Fe (26) and Cr (24).
SOLUTION :
(a) Molecular formula of iron carbonyl [Fe(CO)n] (b) Molecular formula of chromium carbonyl
Calculation of the value of ‘n’ (C.N.) [Cr(CO)m]
Oxidation state of metal in carbonyls = 0 Again, O.S. of Cr in [Cr(CO)m] = 0
Again, according to EAN rule, EAN of Fe = 36 C.N. of Cr = m
(atomic number of Kr, next higher noble gas) Again, according to EAN rule, EAN of Cr = 36
But, EAN = (Z – O.S.) + 2 (C.N.) (atomic number of Kr, next higher noble gas)
 36 = (26 – 0) + 2 n But, EAN = (Z – O.S.) + 2 (C.N.)
So, n = 5 36 = (24 – 0) + 2 m
Thus, formula of iron carbonyl is [Fe(CO)5]. So, m = 6
So, formula of chromium carbonyl = [Cr(CO)6].
Illustration - 3 Calculate the EAN of the underlined atoms in the following complexes
3 2 2
(A)  AuCl2  (B)  Fe  C2O4  
 3
(C) Ca  EDTA  (D)  Ni  NH 3   en  ( Py ) 
 3 
SOLUTION :
(a) [AuCl2]– (Z for Au = 79) (c)  Ca  EDTA  
2
(Z for Ca = 20)
Let O.S. of Au be x.
Let O.S. of Ca be x.
So, x + 2 (–1) = –1 x = +1
So, x + 1 (–4) = –2
Again, C.N. of Au = 2
So, x = +2
( Cl– is a unidentate ligand)
Again, C.N. of Ca = 6
So, EAN = (Z – O.S.) + 2 (C.N.)
A4– is a hexabidentate ligand)
( EDTA
= (79 – 1) + (2 2) = 82.
So, EAN = (20 – 2) + (2 6) = 30.
3
(b)  Fe  C2O 4 3  (Z of Fe = 26) 2
  (d)  Ni  Py   en   NH3 3  (Z for Ni = 28)
 
Let O.S. of Fe be x. Let O.S. of Ni be x
So, x + 3 (–2) = –3 x + 0 + 0 + 3  0 = 2 (all are neutral ligands) ;
So, x = +3 So, x = +2
Again, C.N. of Fe = 6 ( Py and NH3, both are unidentate ligand
( C2O42  is a bidentate ligand) while (en) is a bidentate ligand)
So, EAN = (26 – 3) + (2 6) = 35. So, EAN = (28 – 2) + (2  6) = 26 + 12 = 38.

Illustration - 4 1 mole of CoCl3.4NH3, on reaction with excess of AgNO3 gives one mole of a white
precipitate.
(a) What is the formula of complex ? (b) What is the C.N. of cobalt in this complex ?
SOLUTION :
Since the complex gives one mole of AgCl (a white precipitate) with AgNO3 solution, it indicates that out of
3 Cl– ions, only one is outside the co-ordination sphere, and the remaining Cl– ions, are inside the co-ordination
sphere.
 Two Cl– ions and all the four NH3 molecules are inside the co-ordination sphere.
(a) So, the formula of the complex is
 [CoCl2 (NH3 ) 4 ]  Cl 

[CoCl2 (NH 3 )4 ] Cl 
AgNO3
 AgCl  (white ppt.)
(b) Hence, the complex is [CoCl2(NH3)4]Cl
C.N. of Co in this complex = 6.
NOMENCLATURE OF CO-ORDINATION COMPOUNDS : Section - 3
Co-ordination compounds are formulated and named according to the system set up by Inorganic Nomenclature
Committee of the International Union of Pure and Applied Chemistry (IUPAC). The following rules are
observed while writing formulae and naming co-ordination compounds.
 Rules for Formula writing of Mono-Nuclear Co-ordination Compounds :
(i) Formula of the cation whether simple or complex is written first followed by that of the anion.
(ii) Sequence of symbols within the coordination formula
 The central atom is listed first.
 The ligands are then listed in alphabetical order based on the way the ligand is represented in the
formula.+++
The placement of the ligand in the list does not depend on the charge of the ligand.***
 If an abbreviation is used in a formula to represent a ligand the first letter of the abbreviation is used to
determine the position of the ligand in the alphabetical list.
 Wherever possible, the ligand formula should be written in such a way that the donor atom is closest
to the central atom to which it is attached.
 All the ligands are formuated without any space in between, also there should be no space between
the ligands the the central metal atom within the co-ordination sphere.

Note :
+++ Following things should be kept in mind :
 A single letter symbol always precedes a two-letter symbol with the same initial letter, e.g. B
before Be ; O before OH, the group NH3 is treated as a single symbol and so is listed after Na.
 Where the entities to be arranged in a formula are polyatomic,
 The order of citation is decided by selecting the first symbol in the formula of a polyatomic
group.
For example, C5H5, SCN, NO2 and OH are ordered under C, S, N and O respectively.
 If the first symbols are the same, the symbol with the lesser right index is cited first,
e.g. NO2 precedes N2O2.
 If this still does not discriminate, the subsequent symbols are used alphabetically and numerically
to define the order, e.g. NH2 precedes NO2 which precedes NO3.
 To summarise and exemplify, the order of citation of some nitrogen-containing compounds is :
N3 , NH 2 , NH3 , NO 2 , NO3 , N 2O22  , N3
*** In order to simplify the rules and to resolve ambiguities that may arise when it is not clear whether a
ligand is charged or not, the charge on a ligand is no longer considered in determining ligand order in
the formulae of co-ordination compounds.
(iii) Use of enclosing marks : The formula for the entire co-ordination entity, whether charged or not, is
enclosed in square brackets. When ligands are polyatomic, their formulae are enclosed in parentheses.
Ligand abbreviations are also usually enclosed in parentheses
(iv) Ionic charges and oxidation numbers : If the formula of a charged co-ordination entity is to be written
without that of the counter-ion, the charge is indicated outside the square bracket as a right superscript,
with the number before the sign. The oxidation number of a central atom may be represented by a
Roman numeral, which should be placed as a right superscript on the element symbol.
Examples :
1. [PtCl6]2– 2. [Cr(OH2)6]3+
3. [CrIII(NCS)4(NH3)2]– 4. [CrIIICl3(OH2)3]
5. [Fe–II(CO)4]2–
Other Examples :
1. [Al(OH)(OH2)5]2+
2. [PtBrCl(NH3)(NO2)]–
3. [PtCl2(NH3)(py)]
4. [Co(en)F2(NH3)2]+, but [CoF2(NH2CH2CH2NH2)(NH3)2]+
5. [Co(NH3)5(N3)]2–

 Rules for Naming of Mono-Nuclear Co-ordination Compounds :

(i) Order of naming ions : The positive ion (cation) is named first followed by the negative ion (anion) irrespective
of whether cation is complex or anion is complex. The complex part is written as one word e.g.,
[Co(NH3)6]Cl3, hexaamminecobalt(III) chloride.
(ii) Naming of ligands : Different types of ligands are named differently. (refer to the table)
(a) Negative ligands (organic or inorganic) : These type of ligands end in ‘-o’, e.g., CN (cyano), Cl
(chloro), NO2 (nitro), O2 (oxo). If the name of the anionic ligands ends in ide, ite or ate, the last
‘e’ is replaced by ‘O’ giving ido, ito or ato e.g. SO42 (sulphato), NH2 (amido), ONO (nitrito)
etc.
(b) Neutral ligands : These type of ligands have no special ending and are used as such except for NH3
(ammine), H2O (aqua), CO(carbonyl), CS (Thiocarbonyl) and NO (nitrosyl).
(c) Positive ligands : These type of ligands are used as such. These type of ligands generally end in ium,
e.g., NH2NH3+ (hydrazinium), NO+ (nitrosonium), NO2+ (nitronium) etc.
(d) Organic ligands : Organic free radicals are given their own names, e.g., CH3 (methyl), C2H5 (ethyl). For
organic neutral molecules, their names are used, e.g., P(C6H5)3-triphenylphosphine, C2H5N-pyridine (py)
etc.
Note : Enclosing marks “( )”are required for (a) neutral and cationic ligand names. (however, common ligands
such as aqua, ammine, carbonyl, nitrosyl, methyl, ethyl, etc., do not require enclosing marks, unless there is
ambiguity) ; (b) for inorganic anionic ligands containing numerical prefixes (such as triphosphato); (c) for any
compositional name (such as carbon disulfide) ; (d) for any substituted organic ligand (even if there is no
ambiguity in its use); (e) and wherever necessary to avoid ambiguity.
Denticity Name Ligand Charge Name of ligand in Donor

the complex Atom
Positive Ligands
Nitrosonium ion NO + +1 Nitrosonium N
Monodentate Nitronium ion NO 2 +1 Nitronium N
Hydrazinium ion NH 2 NH 3 +1 Hydrazinium N

Neutral Ligands
Water H2O 0 Aqua/aquo O
Ammonia NH3 0 Ammine N
Carbon monoxide CO 0 Carbonyl C
Nitrgen Oxide NO 0 Nitrosyl N
Thiocarbonyl CS 0 Thiocarbonyl S
Thionitrosyl NS 0 Thionitrosyl N
Monodentate Pyridine (py) C5 H 5 N 0 Pyridine (py) N
Methyl amine CH3NH2 0 Methylamine N
Dinitrogen N2 0 Dinitrogen N
Dioxygen O2 0 Dioxygen O
Phosphine PH3 0 Phosphine P
O
Urea || 0 Urea O
H 2 N  C  NH 2
S
Thio-urea (tu) || 0 Thio-urea S
H 2 N  C  NH 2
Triphenylphosphine Ph3P 0 Triphenylphosphine P

Acetone CH3COCH3 0 Acetone O
Denticity Name Ligand Charge Name of ligand in Donor

the complex Atom
Bidentate Ethylenediamine (en) NH2(CH2)2NH2 0 Ethylenediamine (en) 2 N-atoms
(a bidentate ligand)
  C H
H 2 C  NH 2
| |
Tridentate Diethylene triamine  N
H 2C  N   CH 0 diethylenetriamine (dien) 3 N-atoms
2
H2 H2
  CH  NH
H 2 C  NH 
2 2 3
| triethylene-
Tetradentate Triethylene tetramine   CH  NH
 0 tetramine (trien) 4 N-atoms
H 2C  NH 2 2 3

Negative Ligands
Hydride ion H –1 hydrido H
Monodentate Oxide ion O 2– –2 oxo O
Perioxide ion O 22  –2 peroxo O
Perhydroxide ion O2H –1 perhydroxo O
Hydroxide ion OH –1 hydroxo O
Fluoride ion F –1 fluoro (fluorido) F
Chloride ion Cl –1 chloro (chlorido) Fl
Bromide ion Br –1 bromo (bromido) Br
Iodide ion I –1 iodo (iodido) I
Acetate ion CH3COO – –1 acetato (acetatido) O
Cyanide ion CN  –1 cyano (cyanido) C
Isocyanide ion –1 Isocyano N
Sulphite ion SO 32  –2 sulphito O

Sulphide ion S2 –2 sulphido or thio S
Hydrogen-
sulphide ion HSO3 –1 hydrogensulphito O
Amide ion NH 2 –1 amido N

Imide ion NH2 –2 imido N
Nitrate ion NO 3 –1 nitrato N
Nitro ion NO 2 –1 nitro (nitrito-N) N
Nitrito ion ONO –1 nitrito (nitrito-O) O

Nitrido ion N3 –3 nitrido N
Azide ion N 3 –1 azido N

(iii) Prefixes : Two kinds of numerical prefix are available for indicating the number of each type of ligand
within the name of the co-ordination entity.
(a) Prefixes di, tri, etc. are generally used for simple ligands. Enclosing marks around the ligand are not
required. e.g., if there are four NH3 molecules as ligands, we shall write tetraammine. Here note that
both ‘a’ i.e. last ‘a’ of tetra and first ‘a’ of ammine are to be retained.

(b) Prefixes bis, tris, tetrakis, etc. are used with complex expressions (generally with those ligands which
include a numerical prefix in their names) and wherever required to avoid ambiguity. Enclosing marks
in the nested order must be placed around the multiplicand.
Elaboration : These prefixes are used for ligands containing di,tri etc in their names eg dipyridyl or
ethylenediamine, thus, their numbers are indicated by prefixed, bis-, tris-, tetrakis-, etc., for example
: [PtCl2(NH2CH2CH2NH2)2] (NO3)2 is named as dichlorobis (1, 2-ethanediamine) platinum (IV)
nitrate.
(iv) Preference order : All ligands whether negative, neutral or positive, are named in an alphabetical order.
The prefixes di, tri, etc. are not to be considered while determining this alphabetical order. The names of
the ligands are followed by the name of the central metal atom/ion. e.g. [PtCl(NH3)4(NO2)]SO4 is named
as tetraamminechloronitroplatinum (IV) sulphate.
(v) Naming of complex ion : Ligands are named first, followed by the metal atom. The ending of the name
of the metal depends upon the nature of the complex ion.
(a) If the complex ion is cation or the compound is non-ionic, the name of the central metal ion is written
as such followed by its oxidation state indicated by Roman numeral (such as II, III, IV) in the parenthesis
at the end of the name of the metal without any space in between the two. (0) is used for an oxidation
state of zero and a negative oxidation state is shown by a negative sign before the Roman numeral.
(b) If the complex ion is anion, the name of the central metal atom is made to end in “ate” followed by
the oxidation number in brackets without any space between them.
(c) While naming complex acid of transition metals, ending ‘ic’ is used, e.g. H4[Pt(CN)6] is named as
hexacyanoplatinic(II) acid.
Complex Ions
Example Negative complex Positive/neutral complex
Ni nickelate nickel
Pb plumbate lead
Sn stannate tin
Fe ferrate iron
(vi) Naming of the optical isomers : Dextro and Laevo rotatory optically active compounds are respectively
designated either by (+) and () or by d and  e.g. dextro rotating K3[Cr(C2O4)3] is named as
potassium (+)trioxalatochromate(III) or potassium dtrioxalatochromate(III).

IUPAC Names (Some Examples)

Neutral Complexes :
[Co(NH3)3]Cl3 triamminecobalt(III) chloride
[Ni(CO)4] tetracarbonylnickel(0)
[Fe(CO)5] pentacarbonyliron(0)
[Pt(NH3)2]Cl2 diammineplatinum(II) chloride
[Co(NH3)3(NO2)3] triamminetrinitrocobalt(III)
[Cu(Gly)2] diglycinatocopper(II)
[Ni(DMG)2] bis(dimethylglyoximato)nickel(II)
[CuCl2{O=C(NH2)2}2] dichloridobis(urea)copper(II)
Complex Cations :
[Co(OH2)6]2+ hexaaquacobalt(II) ion
[Zn(NH3)4]2+ tetraamminezinc(II) ion
[Pt(en)2]2+ bis(ethylenediammine)platinum(II) ion
[Ni(en)3]3+ tris(ethylenediammine)nickel(III) ion
[PtCl2(NH3)2]Cl2 diamminedichloroplatinum(IV) chloride
[Cu(NH3)4(OH2)2 ]Cl2 tetraamminediaquacopper(II) chloride
[Co(NH3)5(ONO)]Cl2 pentaamminenitritocobalt(III) chloride
[CoCl(NH3)4(OH2)]Cl tetraammineaquachlorocobalt(II) chloride
[Ag(NH3)2]Cl diamminesilver(I) chloride
Complex anions
K[AgCl2] potassium dichloroargentate(I)
Ba[CuCl4] barium tetrachlorocuprate(II)
K3[Fe(CN)6] potassium hexacyanoferrate(III)
K4[Fe(CN)6] potassium hexacyanoferrate(II)
Cu2[Fe(CN)6] copper hexacyanoferrate(II)
[Au(CN)4]2 tetracyanoaurate(II) ion
[CoBr4]2 tetrabromocobaltate(II) ion
[HgI4]2 tetraiodomercurate(II) ion
[Ni(CN)4]2– tetracyanonickelate(II) ion
[Fe(C2O4)3]3 tri(oxalato)ferrate(III) ion
[Cr Cl2 (en)2]Cl2 dichlorobis(ethylenediammine)chromium(IV) chloride
K3[Cr(C2O4)3] potassium trioxalatochromate(III)

Complexes containing cationic and anioic ions

[Cr(NH3)6][Co(CN)6] hexaamminechromium(III) hexacyanocobaltate(III)
[Pt(NH3)4][CuCl4] tetraammineplatinum(II) tetrachlorocuprate(II)
[Cr(NH3)6][Co(C2O4)3] hexaamminechromium(III) trioxalatocobaltate(III)
[Pt(py)4][PtCl4] tetrapyridineplatinum(II) tetrachloroplatinate(II)
[PtCl2(NH3)4] [PtCl4] tetraamminedichloroplatinum(II) tetrachloroplatinate(IV)
Note :1. The stable oxidation states of some of the transition metals of the three series are given below. These would
be helpful to find the oxidation states of the metal ions while naming complexes having cation and anion both
as complexes.
(i) First Transition Series
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 +2, +3, +2, +3, +2, +3, +2, +3, +2, +3, +2, +3 +2, +3 +1, +2 +2
+4 +4, +5 +6 +4, +7
(ii) Second Transition Series

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
+3 +4 +3, +5 +6 +4, +6, +3 +3 +2, +4 +1 +2
+7
(iii) Third Transition Series

La Hf Ta W Re Os Ir Pt Au Hg
+3 +4 +5 +6 +4, +6, +3, +4, +1, +3 +2, +4 +1, +3 +1, +2
+7 +6 +4
2. Naming of linkage isomers : Read the following eg carefully  [Co(NH3)5(NO2)]2+ has two isomeric
forms having red and yellow colours.
 The red colour isomer [CO(NH3)5(ONO)]2+ is named as :
pentaamminenitrito-O-cobalt(III) [or pentaamminenitritocobalt(III)] while ;
 The yellow isomer [Co(NH3)5(NO2)]2+, is named as
pentaamminenitrito-N-cobalt(III) [or pentaamminenitrocobalt(III)].
3. For some compounds common names are more popular than there IUPAC names eg. ferrocyanide rather
than hexacyanoferrate(II) for [Fe(CN)6]4 and ferricyanide rather than hexacyanoferrate(III) for [Fe(CN)6]3

Isomerism in Co-ordination Compounds

Isomers are compounds having same chemical formula but different arrangment of atoms. Because of different
arrangment of atoms, they differ in one or more physical or chemical property. This phenomenon is called as
isomerism.
The type of isomerism found in co-ordination compound is :
1. Structural isomerism : It is displayed by compounds that have different ligands within their co-ordination
sphere. It may be further sub-divided into different types as follows:
(A) Ionization isomerism : The co-ordination compounds exhibiting this type of isomerism give different
ions in solution. It occurs when the counter ion in a co-ordination compound is itself a potential ligand.
Eg.  PtCl 2  NH 3  4  Br2 , and  PtBr2  NH 3  4  Cl 2 etc.
(B) Solvent isomerism : This is a special type of ionisation isomerism which arises when solvent molecules
can form co-ordination bonds with the central atom/ion. In this, compounds having same composition
differ in the number of solvent molecules present as ligands (in the co-ordination sphere) and as free
solvent molecules of hydration (present outside the co-ordination sphere). This form of isomerism is
known as “hydrate isomerism” in case where water is involved as a solvent. For example, there are
three isomers of hexa-hydrates of chromic chloride with empirical formula CrCl3.6H2O.
[Cr(H2O)6]Cl3 : violet colour
[CrCl(H2O)5]Cl2.H2O : pale or bluish green colour
[CrCl2(H2O)4]Cl.2H2O : dark green colour
Apart from their distinctive colours, the three isomers can be identified by the addition of excess of
aqueous silver nitrate to their aqueous solutions, which precipitates silver chloride in the molar ratio of
3 : 2 : 1 respectively.
(C) Co-ordination isomerism : This type of isomerism is observed in the co-ordination compounds
having both cationic and anionic complex ions. The ligands are interchanged in both the cationic and
anionic ions to form isomers. For example :
(i) [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6] [Co(CN)6]
(ii) [Cu(NH3)4] [PtCl4] and [Pt(NH3)4] [CuCl4]
(iii) [Cr(NH3)6][Cr(SCN)6] and [Cr(NH3)4(SCN)2][Cr(NH3)2(SCN)4]
(D) Linkage isomerism : Co-ordination compounds having ambidentate ligands like NO 2 and SCN,
exhibit this type of isomerism. For example: [Co(NH3)5(NO2)]2+ has two isomeric forms having
red and yellow colours. The red colour isomer is [CO(NH3)5(ONO)]2+, while the yellow isomer is
[Co(NH3)5(NO2)]2+. In the first cation we have Co-(ONO) link, while in the second case, Co-
(NO2) link is there.

2. Stereo-isomerism : This isomerism in coordination compounds is due to differences in arrangement of

ligands in space around a given metal atom or ion. It is of following two types :
(A) Geometrical isomerism
(i) Cis-trans isomerism : This type of isomerism occurs in complexes having square planar and
octahedral arrangement respectively. When similar groups are adjacent to each other, it is called
cis isomer, whereas when similar groups are opposite to each other, it is called trans isomer.
(a) Complexes with general formula, Ma2b2 (where both a and b are monodentate) can have cis-
and trans-isomers.
(b) Complexes with general formula Ma2bc can have cis-and trans-isomers.
(c) Square planar complexes having unsymmetrical bidantate ligands can also show geometrical
isomerism.
For example [Pt(Gly)2] exhibit geometrical isomerism.
(d) Octahedral complexes : of type Ma4b2 and Ma3b3 exhibit geometrical isomerism.

Note :  Complexes with general formula Mabcd can have three isomers isomers.
 Octahedral complexes of general formula, Mabcdef, can have fifteen isomers.

 The complexes of general formulae, Ma3b or Mab3, or Ma4 of square planar geometry do not show
isomerism.
 Geometrical isomerism does not occur in tetrahedral complexes, because the relative positions of the
ligands attached to the central metal atom or ion is same w.r.t. each other.
(ii) Facial and Meridionial isomerism : Another type of geometrical isomerism occurs in octahedral co-ordination
entities of the type [Ma3b3]like [Co(NH3)3(NO2)3]. If each trio of donor atoms occupy adjacent positions
at the corners of an octahedral face, we have the facial (fac) isomer. When the positions are around the
meridian of the octahedron, we get the meridional (mer) isomer shown in figure. Geometric isomer differ in
their physical characterstics, out of which, dipole moments and visible/UV spectra are important.
Note : [Ma 3b3 ] is more popularly classified using Facial & Meridional Isomerism as compared to cis-trans isomerism.
(B) Optical isomerism : The co-ordination compounds having same molecular formula but differing in their
abilities to rotate directions of the plane of polarized light are said to exhibit optical isomerism and such
molecules are called optical isomers (enantiomers or enantiomorphs).
(a) The optical isomers are pair of molecules which are non-super imposable mirror images of each
other.
(b) They possess the property of chirality. The essential requirement for a substance to be optically
active is that the substance should not have a plane of symmetry in its structure.
(c) Optical isomers of a compound have identical physical and chemical properties.
(d) The isomers which rotate the plane of polarized light to left direction are termed Leavo (-form).
While the isomers which rotate the plane of polarized light to right direction are termed Dextro (d-
form) .
 Optical isomers rarely occur in square planar complexes on account of the presence of axis of symmetry.
 Optical isomerism is expected in tetrahedral complexes of the type Mabcd but no optical isomer has been
isolated until now.

 General formulae of optically active complexes :

(i) [M(AA)3]n , [M(AA)2a2]n , [M(AA)2ab]n , [M(AA)a2b2]n (where AA are symmetrical bidentate
ligands)
(ii) [Ma2b2c2]n, [Mabcdef]n , [M(AB)3]n (where AB are unsymmetrical ligands)
For Examples :
(A) [M(AA)3]n : eg. [Co(en)3]3+
(B) [M(AA)2a2]n [Co(en)2Cl2]+
Note : The trans form of [M(AA)2a2]n does not

show optical isomerism.
(C) [M(AA)2 ab]n [Co(en)2(NH3)Cl]2+
(D) [M(AA)a2b2]n eg . [CrCl2(en)(NH3)2]+.
(E) [Ma2b2c2] n eg : [Pt(py)2 (NH3)2 Cl2]2+

(F) [Mabcdef] eg : [Pt(py)NH3NO2ClBrI]
(G) [M(AB)3] eg : [Cr(gly)3]
Illustration - 5 Write hydrate isomers of the following, and also discuss the conductance of the isomers.
(a) [Cr(H2O)6]Cl3 (b) [Cu(H2O)4]Cl2
SOLUTION :
(a) Hydratic isomers of [Cr(H2O)6]Cl3
Greater the number of ions, [Cr(H2O)5Cl]2+ + 2Cl– more is the conductance. Hence, decreasing order of
conductance is I > II > III > IV.
(b) Hydrate isomers of [Cu(H2O)4]Cl2
Hence, decreasing order of conductance is I > II > III.

Illustration - 6 One mole of the complex has two isomers A and B. Each has one Co3+, five NH3, one Br–
and one SO42 stoichiometrically. A gives white precipitate with BaCl2 while B gives yellow precipitate with
AgNO3. What are A and B ? What is the type of isomerism shown by them ?
SOLUTION :
(a) Since A gives white precipitate of BaSO4 with BaCl2 solution, A is
 [Co(NH3 )5 Br]2   SO 42  

[Co(NH3 )5 Br] SO 4 
BaCl 2
 BaSO 4 
(A) (white ppt.)
(b) Since B gives a yellow precipitate of AgBr with AgNO3, B is :

AgNO3
 [Co(NH3 )5SO4 ]  Br  
[Co(NH3 )5SO4 ] Br   AgBr 
(B) (yellow ppt.)
Also, A and B are ionisation isomers.
Illustration - 7 (a)Write structures of all geometric isomers of square planar complexes.

(i) [Pd(NH3)2(Br)(I)] (ii) [Ni(en)Cl2]
(b) For which of the following complexes are optical isomers possible ? Explain your answers and draw
structures of enantiomers. (i) [Cr(NH3)4(C2O4)]+ (ii) [Cr(NH3)2(C2O4)2]–
(c) The compounds(s) that exhibit(s) geometrical isomerism is(are) :
(i) [ Pt (en)Cl2 ] (ii) [ Pt (en)2 ]Cl2 (iii) [ Pt (en) 2 Cl2 ]Cl2 (iv) [ Pt ( NH 3 )2 Cl2 ]
SOLUTION :
(a) (i) Geometrical isomers of [Pd(NH3)2(Br)(I)]
(ii) [Ni(en)Cl2] Only one isomer is possible as ethylene diamine (en) cannot span the trans position.

(b) Optical isomerism is possible in [Cr(NH3)2(C2O4)2]– (because it is of the type[M(AA)2a2]n ) but

[Cr(NH3)4(C2O4)]+ will not exhibit optical isomerism.
Note : General formulae of optically active complexes :
(i) [M(AA)3]n , [M(AA)2a2]n , [M(AA)2ab]n , [M(AA)a2b2]n (where AA are symmetrical
-bidentate ligands)
(ii) [Ma2b2c2]n, [Mabcdef] , [M(AB)3]n (where AB are unsymmetrical ligands)
The geometrical isomeris of [Cr(NH3)2(C2O4)]– are (one trans and three cis isomers) :
Now, only cis-isomers can exhibit optical isomerism because trans-isomers have two superimposable
mirror images.
Thus, [Cr(NH3)2 (C2O4)]– has two geometrical (one trans and one cis) isomers while two optical isomers.
(c) [Pt(en) 2 ]Cl2 can not show geometrical isomerism as all ligands attached to the central atom (Pt) are same
and [Pt(en) Cl2 ] does not show geometrical isomerism as discussed in Q.7(a) part (ii). Rest both
[Pt(en) Cl2 ]Cl2 and [Pt(NH 3 ) Cl2 ] are capable of showing geometrical isomerism as shown below :

WERNER’S CO-ORDINATION THEORY Section - 4
Werner’s Co-ordination Theory

Alfred Werner was the first to formulate a theory to give a correct explaination for the characteristics of the
co-ordination compounds. The fundamental postulates of Werner’s theory are :
(i) Metals possess two types of valencies, namely, primary (principal) and secondary (auxillary) valency.
(ii) Primary valencies are those which a metal normally exhibits in the formation of its simple salts. Thus, in the
formation of PtCl4, CuSO4 and AgCl the primary valencies of Pt, Cu and Ag are 4, 2 and 1 respectively.
Primary valencies may be ionisable. They are non-directional and are only satisfied by negative ions.
(iii) Secondary valencies are those which a metal cation exercises towards a neutral molecule or negative
group in the formation of its co-ordination complexes. Secondary valencies are non-ionisable and are
satisfied by negative ions, neutral molecules (or even somtimes by some positive groups), having atleast
one lone pair of electrons (like H2O, NH3). In every case, the co-ordination number of the metal must be
fulfilled. In modern terminology, the primary valency corresponds to oxidation number and secondary
valency to the co-ordination number of the central metal.
(iv) The secondary valencies are always directed towards a fixed position in space about the central metal ion.
The number and arrangements of ligands in space determines the sterochemistry of a complex. For
example, in case of six secondary valencies the arrangement of secondary valencies is a regular octahedral
while in case of four secondary valencies arrangement might be either in a square planar or a tetrahedral
manner. Thus, this postulate predicates of existence of a variety of isomerisms in co-ordination compounds.
Remember that primary valencies are non-directional.
(v) To distinguish between the two types of valencies, Werner introduced square brakets [ ] to enclose atoms
making up the co-ordination complex and which are therefore not ionised. The portion enclosed in the
brackets is known as co-ordination sphere and the portion present outside the bracket as ionising sphere.
(vi) It is the directional nature of secondary valency due to which co-ordination compounds exhibits the
phenomenon of isomerism.
The important aspect of the structure of five different complexes of PtCl4 with ammonia prepared by
Werner are shown in table.
Co-ordination compounds of PtCl4 with NH3

Complex Modern formula Number of Cl– ions Total number of ions
formed
PtCl4.6 NH3 [Pt(NH3)6]Cl4 4 5
PtCl4.6 NH3 [PtCl(NH3)5]Cl3 3 4
PtCl4.6 NH3 [PtCl2(NH3)4]Cl2 2 3
PtCl4.6 NH3 [PtCl3(NH3)3]Cl 1 2
PtCl4.6 NH3 [PtCl4(NH3)2] 0 0 (non-electrolyte)

In all these compounds, platinum exhibits a primary valency (oxidation number) of four and
secondary valency (co-ordination number) of six.
(vii) Primary valency in the complex, is represented by ‘. . . . . . . .’ and secondary valency by ‘________’.
(viii) In all cases, metal or metal ion should satisfy both primary and secondary valencies. Some negative
ions may satisfy primary as well as secondary valencies (dual nature). In the complexes, they are
____ ’.
represented as ‘ ........
Werner’s Representation of Complexes

Consider the case of CoCl3.xNH3 , where the maximum value of x = C.N. of Co(3+) (which is 6)
and the minimum value of x = C.N. - O.N. = 3
Various structures are summarised in Table.
 From table, it is clear that conductance of the complexes will be in the order D < C < B < A.
 They are represented as shown in the next page.
Note : Compund A & B have colours yellow and purple respectively but compound C (with empirical formula
[CoCl2(NH3)4]Cl ) is found to exist in two colours i.e green and violet showing that there must be two
isomers for empirical formula [CoCl2(NH3)4]Cl.

Werner was the first to describe the bonding features in co-ordination compounds. But his theory could not
answer basic questions like :
(i) Why only certain elements possess the remarkable property of forming co-ordination compounds ?
(ii) Why the bonds in co-ordination compounds have direction optical properties ?
(iii) Why co-ordination compounds have characteristic magnetic aqnd optical properties ?
Many approaches have been put forth to explain the nature of bonding in co-ordination compounds viz.
Valence Bond Theory (VBT). Cristal Field Theory (CFT). Ligand Field Theory (LFT) and Molecular
Orbital Theory (MOT). However we shall be restricting ourselves to VBT and CFT only.
BONDING IN CO-ORDINATION COMPOUNDS : VALENCE BOND THEORY Section - 5
The theory was developed by Pauling in 1931. The basic principles involved in this theory are :
(a) Orbital hybridization : The model utilizes the hybridisation of s, p and d valence orbitals of central
metal atom or ion (in which electron pairs donated by the ligands are accomodated) to account for
observed structures and magnetic properties.
(b) Bonding between ligand and the metal atom or ion : From the valence point of view, formation of
complex involves reaction between lewis bases (ligands) and lewis acids (metal atom/ion) with the
formation of co-ordinate covalent (or dative) bonds between them.
(c) Relation between the observed magnetic behaviour and the bond type : That is, the geometry of co-
ordination entity can be predicted if its magnetic behaviour is known.
The following are the main postulates of this theory :
(i) Metal-ligand bond arises by the donation of pairs of electrons by ligands to the empty hybridised
orbitals of central metal atom or ion. Remember it is basically overlap of atomic orbital of both the
entities
(ii) In order to accommodate these electrons, the metal ion must possess same number of vacant orbitals
of equal energy. These orbitals of metal atom (s,p or d) undergo hybridisation to give a set of hybrid
orbitals of equal energy and with definite directional properties. These vacant hybrid orbitals now
overlap with the ligands to form strong coordinate bonds.
(iii) The non-bonding electrons of the metal occupy the inner orbitals. They are grouped in accordance
with Hund’s rule. However, under the influence of some strong ligands, there may be some
rearrangement of inner electrons in the atomic orbitals (against Hund’s rule). During rearrangement
generally pairing takes place and consequently some orbitals are vacated and made available for
hybridisation.

(iv) (For Octahedral complexes only) The d-orbitals involved in the hybridisation may be either (n  1) d-
orbitals or n d-orbitals***. The complexes formed in two ways are referred to as Inner orbitals
complex (or entity) or Outer orbital complex (entity). On the basis of spin they are also referred as
low spin and high spin complexes respectively.
(*** ‘n’ refers to the outermost principle shell of the central metal atom)
(v) If a complex contains unpaired electrons, it is paramagnetic in nature, whereas if it does not contain
unpaired electrons, it is diamagnetic in nature.
(vi) On the basis of value of magnetic moment, we can predict the number of unpaired electrons present
in the complex. If we know the number of unpaired electrons in the metal complex, then it is possible
to predict the geometry of complex species.
Magnetic Moment, s  n  n  2  B.M.
B.M. = Bohr Magneton, it is the unit of magnetic moment
s = spin only value
n = no. of unpaired electrons in the central metal atom/ion
(vii) Octahedral, square planar and tetrahedral complexes are formed as a result of d2sp3 (or sp3d2), dsp2
and sp3 hybridisation respectively.
For predicting the type of geometry (structure) of a complex species, the following guidelines
would be helpful :
(i) Electronic configuration of first transition series
Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d1 4s2 3d2 4s2 3d3 4s2 3d5 4s1 3d5 4s2 3d6 4s2 3d7 4s2 3d8 4s2 3d10 4s1 3d10 4s2
(ii) For co-ordination number 4, the hybridizations possible are sp3 and dsp2, having tetrahedral and
square planar geometries respectively, while for co-ordination number 6, the hybridizations possible
are d2sp3 and sp3d2, having octahedral geometry in both the cases.
(iii) There are two types of ligands namely strong field and weak field ligands. A strong field ligand is
capable of forcing the electrons of the metal atom ion to pair up (if required). A weak field ligand is
incapable of making the electrons of the metal atom/ion to pair up.
(iv) Some ligands have been arranged below from the weakest to the strongest. This arrangement is called
as spectrochemical series. (As shown in the next page)

I  Br   S2   SCN 2   Cl  F  NO3  OH  , urea  EtOH


weak
 C2O 4  OX   O  H 2O  NCS  EDTA  NH3
2 2
  
Border Line
< NH3 , pyridine < ethylene diammine (en) < dipyridyl (dipy)  phen  NO 2  CN   CO

Strong
Note :  This series has been determined experimentally and is not a postulate of VBT. However, we can use it to
predict the structure, electronic configuration, magnetic properties etc. of a co-ordination complex.
 Ligands given in the borderline criteria act both as strong and weak field ligands. By knowing the value of
magnetic moment, it may be suggested that whether they act as a strong and weak ligand in a particular
case.
 Generally NH3 behaves as a strong field ligand and H2O (or ligands nearby it in the series) as a weak field
ligand. The compound [Co(OX)3]3– , is one of the few rare examples where oxalate (OX) ligand acts as
a strong field ligand.
(vi) The common types of hybridisations are :
(A) Four coordinated complexes :

(A. 1) Tetrahedral Complexes

Illustration - 8 Discuss the formation of [Ni(CO)4]0

SOLUTION : Oxidation state of Nickel in this complex is ‘0’. Its electronic configuration is [Ar] 3d8 4s2.
The CO ligand being a strong ligand will force the pairing of electrons in two half filled orbitalsand then the pair
of electrons from 4s will go to 3d orbital, and thus, the 4s orbital is vacated and can now accept an electron
pair.
Now, the empty 4s and 4p orbitals (i.e 4s, 4px ,4py and 4pz ) hybridize (or mix) to form four equivalent sp3
hybrid orbitals, each of which accepts an electron pair.
Now, each of the four sp3 hybrid orbitals accepts an electron pair from carbon monoxide ligands forming
Ni(CO)4.
Thus, the resulting complex has tetrahedral structure and diamagnetic due to absence of unpaired
electrons(magnetic moment = 0).
Illustration - 9 Discuss the formation of [CoCl4]2–

SOLUTION :
Oxidation state of Co in complex = +2 ; Outer electronic configuration of : Co atom = 3d74s2
 Co2+ = 3d7

(i) Cl being weak ligand is unable to force (iv) Magnetism :

the pairing of electrons.  No. of unpaired electrons = 3
(ii) Hybridisation : sp3  Paramagnetic
(iii) Geometry : Tetrahedral  Magnetic moment
(s) = 3  3  2   15 = 3.87 B.M.
Illustration - 10 Discuss the formation [Zn(NH ) ]2+.

3 4
SOLUTION :
Oxidation state of Zn in complex = +2 ; Outer electronic configuration of : Zn atom = 3d104s2
Zn2+  3d10

(i) Hybridisation  sp3 (iii) Magnetism :

(ii) Geometry  tetrahedral  No. of unpaired e = 0
 Diamagnetic
 Magnetic moment, s = 0 B.M.
(A.2) Square planar complexes :
Illustration - 11 Discuss the formation of [Pt(NH ) Cl ].

3 2 2
SOLUTION :
Oxidation state of Pt in complex = +2 ; Outer electronic configuration of : Pt atom  5d86s2
 Pt2+ ion  5d8
(i) NH3 being a strong ligand forces pairing of (iv) Magnetism

electrons of two half filled 5d-orbitals.
 No. of unpaired e = 0
(ii) Hydrisation : dsp2  Diamagnetic
(iii) Geometry : Square planar  Magnetic moment, s = 0
Illustration - 12 Disscuss the formation of [Cu(NH ) ]2+.

3 4
SOLUTION :
Oxidation state of Cu  +2 ; Outer electronic configuration of : Cu atom  3d104s1
 Cu2+ ion  3d9

(i) Hybridisation  dsp2  No. of unpaired e– = 1

(ii) Geometry  Square planar  Paramagnetic
(iii) Magnetism  Magnetic moment,
s  11  2   3  1.732 B.M
Illustration - 13 Discuss the formation of (A) [Ni(CN)4]2– (B) [NiCl4]2–

SOLUTION :
(A) Formation of [Ni(CN)4]2– ;
Oxidation state of Ni = +2 ; Outer electronic configuration of : Ni atom = 3d84s2
 Ni2+ ion = 3d8

(i) CN– being a strong ligand, forces pairing of (iv) Magnetism

electron of two half filled 3d orbitals.  No. of unpaired e = 0
(ii) Hybrisation  dsp2  Diamagnetic
(iii) Geometry : Square planar
 Magnetic moment = 0 B.M
(B) Formation of [NiCl4]2–

Oxidation state of Ni = +2 ; Outer electronic configuration of : Ni atom = 3d84s2
 Ni2+ ion = 3d8
(i) Cl being weak ligand is unable to force (iv) Magnetism

the pairing of electrons.  No. of unpaired e = 2
(ii) Hybridisation : sp3  Paramagnetic
(iii) Geometry : Tetrahedral  Magnetic moment
 2(2  2)  2.83B.M
Thus the c-oordination entities [Ni(CN)4]2– & [NiCl4]2– illustrate the useful rule originally called” the magnetic
criteria of bond type”, That is, the geometry of a co-ordinated entity can be predicted if its magnetic properties
are known. In above case this theory allows prediction of geometry of a four co-ordinated d8 complex : If the
complex is diamagnetic then its shape will be “Square Planar” and if it is paramagnetic then its shape will be
“Tetrahedral”.
Note : The above generalisation of VB theory is not accurate and is one of its draw backs.
(B) Six Co-ordinated Complexes

In an octahedral complex, two types of complexes occur i.e., inner orbital complex and outer orbital
complex. This distinction between inner and outer orbital complex is based purely on magnetic measurements.
In inner, orbital complex, (n – 1)d orbitals are used for hybridization whereas in outer orbital complex, nd
orbitals are used.

Illustration - 14
Discuss the formation of [Cr(NH3)6]3+ .
SOLUTION :
Oxidation state of Cr = +3 ; Outer electronic configuration of : Cr atom = 3d5 4s1
 Cr3+ ion = 3d3
(i) Hybridisation : d2sp3 (v) Magnetism :

(ii) Geometry = Octahedral  No. of unpaired e = 3
(iii) Inner orbital complex  Paramagnetic
(iv) Spin paired (low spin complex)  Magnetic moment,
s  3  3  2   3.287 B.M

Illustration - 15 Discuss the formation of Ferricyanide ion, [Fe(CN) ]3–.

6
SOLUTION :
Oxidation state of Fe = +3 ; Outer electronic of figuration of : Fe atom = 3d6 4s2
 Fe3+ ion = 3d5
(i) CN being strong ligand forces pairing (vi) Magnetism :No. of unpaired e = 1
of electrons of half field 3d-orbitals  Paramagnetic
(ii) Hybridisation : d2sp3,  Magnetic moment,
Geometry : Octahedral s  1.732 B.M
(iii) Inner orbital complex,
Spin paired (low spin complex)
Illustration - 16 Formation of [CoF ]3 :

6
SOLUTION :
Oxidation state of Co = +3 ; Outer electronic configuration of : Co atom  3d74s2
 Co3+ ion = 3d6

(i) F being weak ligand is not able to force (vi) Magnetism :

pairing of electrons.  No. of unpaired e = 4
(ii) Hybridisation : sp3d2  Paramagnetic
(iii) Geometry = Octahedral  Magnetic moment,
(iv) Outer orbital complex s  4  4  2   4.90 B.M
(v) Spin free (high spin complex)
Illustration - 17 Formation of [Ni(NH ) ]2+

3 6
SOLUTION :
Oxidation state of Ni = +2 ; Outer electronic configuration of : Ni atom  3d84s2
 Ni2+ ion = 3d8
(i) NH3 being weak ligand is not able to (vi) Magnetism :

force pairing of electrons.  No. of unpaired e = 2
(ii) Hybridisation : sp3d2  Paramagnetic
(iii) Geometry : Octahedral  Magnetic moment,
(iv) Outer orbital complex
s  2  2  2   2.83 B.M
(v) Spin free (high spin complex)



Drawbacks of Valence Bond Theory :

(i) It can’t explain why some complexes of metal ion use inner orbitals (d2sp3, low spin complexes)
whereas some other make high spin complexes (sp3d2).
(ii) It can’t predict effectively whether a four co-ordinated complex is tetragonal or square planar e.g.,
[Cu(NH3)4]2+ is suggested to have sp3 configuration by V.B. Theory but X-rays study shows its geometry
as square planar, i.e. dsp2.
(iii) It doesn’t explain the variation of magnetic properties of complex with temperature.
(iv) It doesn’t explain or predict any distortion in symmetrical complexes.
(v) There is no quantitative interpretation of magnetic data.
(vi) It has nothing to say about the spectral properties of co-ordination compounds.
(vii) It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of co-ordination
compounds.
(viii) It does not distinguish between strong and weak ligands.
CRYSTAL FIELD THEORY : Section - 6
Crystal field theory is now much more widely accepted than the valence bond theory. It assumes that the
attraction between the central metal and ligands in a complex is purely electrostatic. The transition metal which
forms the central atom in the complex is regarded as a positive ion of charge equal to the oxidation state. This
is surrounded by negative ligands or neutral molecules which have a lone pair of electrons. If the ligand is a
neutral molecule such as NH3, the negative end of the dipole in the molecule is directed towards the metal ion.
The electrons of the central metal are under repulsive force from those of the ligands. Thus, the outer most
electrons (which are generally present in the d orbitals) of central transition metal atom/ion occupy those d
orbitals which farthest away from the direction of approach of ligands.
In the crystal field theory, the following assumptions are made.
(i) Ligands are treated as point charges.
(ii) There is no interaction between metals orbitals and ligand orbitals.
(iii) The arrangement of the ligands around the central metal ion is such that the repulsion between these negative
points is minimum.
(v) Splitting of d-orbital energies : The five d-orbitals in an isolated gaseous metal atom/ion are degenerate i.e.
they have equal energy. If a spherically symmetric field of negative charges is placed around the metal, the
orbitals will remain degenerate, but all of them will be raised in energy as a result of repulsion between the
negative field and the electrons in the orbitals. If the field results from the influence of real ligands (either anions
or the negative ends of dipolar ligands such as NH3 or H2O), the symmetry of the field will be less than
spherical and the degeneracy of the d-orbitals will be removed. It is this splitting of d orbital energies and its
effects that form the basis of crystal field theory.

Note : There are five d-orbitals namely, d xy , d yz , d zx , d x 2  y 2 , d z 2 which have been shown below :
It is better to divide the set of d orbitals in two groups :

(i) The orbit als in w hich lobes lie on t he axes ( d 2 2 , d 2 ) : referred to as " eg " orbitals in
x y z
Octahedral symmetry and " e " orbitals in Tetrahedral symmetry. (Also called as doubly degenerate
orbitals.)
(ii) The orbitals in which lobes lie in between the axes (d xy , d yz , d zy ) : referred to as " t2 g "
orbitals in Octahedral symmetry and " t2 " orbitals in Tetrahedral symmetry. (Also called triply
degenerate orbitals.)

A. Crystal field splitting of d-orbitals in octahedral

complexes :
In an octahedral complex, the metal is at the centre of
the octahedron and the ligands approach it along the six
corners of the octahedral. The directions x, y, and z
point to three adjacent corners of the octahedron.
The lobes of the eg orbitals (d x 2  y 2 and d z 2 ) point
along the axes x, y and z. The lobes of the t2g orbitals

(d xy,d xz and d yz ) point in between the axes. It
follows that the approach of six ligands along the x, y, z,
 x,  y and  z direction will increase the energy of
the orbitals d and d (which point along the
x2  y 2 z2
axes) more than it increase the energy of the
d xy , d xz and d yz orbitals (which point between the
axes).
Thus, under the influence of an octahedral ligand field the d orbitals split into two groups of different energies
with " eg " orbitals having higher energy than the " eeg " orbitals. To understand this splitting more clearly
we can assume it to be a two step process as shown in fig.
In the first step, the ligands approach the central metal, producing a hypothetical spherical field which re-
pels all of the d-orbitals to the same extent. In the second, the ligands exert an octahedral field, which
splits the orbital degeneracy. In going from the first to the second step, average energy (the barycenter, or
“centre of gravity”) of the orbitals must remains constant and thus, the two eg orbitals to be the further

repelled by 0.6 0 while the three t2g orbitals are stabilized to an extent of 0.4 0 as shown in figure.
This constancy of the barycenter of the d-orbitals holds for all complexes, regardless of geometry.
Significance of o : Consider a d1 co-ordination entity e.g., [Ti(H 2O) 6 ]3 formed in aqueous solutions
of Ti3+ (d1 ) ion, now the single d-electron occupies one of the lower energy t2g orbitals. Similarly in the
d 2 and d 3 co-ordination entities, the d-electrons will occupy the lower energy t2g orbitals in accordance
with the Hund’s rule. For d 4 ions, two possible patterns of electron distribution arise depending upon the
relative values of o and P where P represents the energy required for electron pairing in a single orbital
called the pairing energy.
(i) If o < P (weak field, high spin situation), the fourth electron enters one of the eg orbitals giving the
3
configuration t2g e1g (see fig). If now a fifth electron is added to a weak field co-ordination entity, the
configuration becomes t23g eg2 .
(ii) If o > P (strong field, low spin situation), pairing will occur in the t 2g level with e g level remaining
unoccupied giving configuration t 42g e0g . [Note : the pairing will occur (and consequently the e g level
will remain unoccupied) till the entities of d 6 ions.]
Note : Calculations show that co-ordination entities with four to seven d-electrons are more stable for strong field
as compared to weak field cases.

B. Crystal field splitting of d-orbitals in Tetrahedral Complexes :

Consider eight ligands aligned on the corners of a cube
approaching a metal atom located in the center as shown
in figure.
In this (cubic) arrangement, however, the ligands do
not directly approach any of the metal d-orbitals, but
they come closer to the orbitals directed to the edges of
the cube (the d xy , d xz and d yz ) than to those directed
to the centers of the cube faces
(the d and the d ). Hence the t orbitals are
x2  y 2 z2 2
raised in energy while the e orbitals are stabilized
relative to the bary centre. Furthemore, since the centre-
of- gravity rule holds, the upper levels are raised by
0.4 o and the lower ones stabilized by 0.6 o from
the bary center, giving an energy level scheme that is
exactly the inverse of that for octahedral symmetry.

If four ligands are removed from alternate corners of the cube in figure, the remaining ligands form a
tetrahedron about the metal.
The energy level scheme for tetrahedral symmetry shown in figure is qualitatively the same as that for cubic,
but the splitting (t ) is only half as large because there are half as many ligands. The two sets of degenerate
in this arrangement are labelled as t2 (d xy , d xz ,d yz ) and e (d x 2  y 2 , d z 2 ). The g subscripts which were
used for the octahedral and cubic field are no longer appropriate because the tetrahedron lacks a centre of
inversion.
4
Note : In tetrahedral complexes, mostly t  P ( t   o ) and hence they generally form high complexes
9
C. Crystal field splitting of d-orbitals is square planar complexes :
The square planar geometry may be considered to be derived from octahedral by removing the two ligands
which were approaching the central atom along the Z-axis (called tetragonal distortion). The splitting may
also be explained as : As the lobes of d x 2  y 2 point towards the ligands, this orbital has highest energy..
Though lobes d xy orbitals lie between the ligands but they are coplanar with them, hence this orbital is next
higher in energy. The lobes of d orbital point out of the plane of the complex but the torous around its
z2
centre lies in the plane, therefore d z 2 orbital is next higher in energy. The lobes of d xz and d yz orbitals
point out of the plane of the complex, hence they are least affected by the electrostatic field of the ligands,
and thus have lowest but equal energy. It must be kept in mind that the average energy of the orbitals
remains constant in this redistribution of energy as in previous cases. (the stronger the surrounding field, the
higher the d x 2 -y2 orbital will be raised, however the lower, occupied orbitals will drop in energy by a
corresponding amount)

The square planar geometry is favoured by metal ions having a d8 configuration in the presence of a strong
field. This combination gives low spin complexes with the eight d-electron occupying the low-energy
d xy, d yz , d and d xy orbitals, while the high-energy orbital remains unoccupied.
z2

Number of unpaired electrons in octahedral and tetrahedral complex.

[(W.F.) is the configuration for high spin and weak field complexes) (S.F) is the configuration for low spin
and strong field complexes)

D. Factors affecting the magnitude of orbital splitting energy () :

The important factors are as follows :
(i) Oxidation state of the metal ion : The magnitude of o increases as the charge on the metal
ion increases. For example, for first row of transition metal ions, the values of o for M3+
complexes are roughly 50% larger than the values for M 2+ complexes.
(ii) Nature of the metal ion : In the d-block (transition) elements, within the same group, as we move
from 3d to 4d to 5d elements, the o increases and hence the tendency to form low spin complexes
increases. Thus the elements of the second and third transition series have greater tendency to form
low spin complexes than the first transition series. It is possible to arrange the metals according to a
spectrochemical series as well. The approximate order is
Mn2   Ni 2   Co2   Fe2   V 2   Fe3  Co3 
 Mn3  Mo3  Rh3  Ru 3  Pd 4   Ir 3  Pt 4 

4
(iii) Geometry of the co-ordination entity : As already stated, t   o i.e.  value for
9
tetrahedral complexes is nearly 50% of the  value for octahedral complexes.
(iv) Nature of the ligand : For the same metal ion, different ligands result in different amounts,
pertaining to their position in the spectro-chemical series. Strong field ligands cause higher splitting
compare to the weak field ligands. (Refer to the spectrochemical series)

MISCELLANEOUS CONCEPTS Section - 7
A. Colour in Co-ordination Compounds :

Co-ordination compounds show a wide range of colour. When white light passes through a complex, some
part of it is absorbed and thus, the light which emerges is no longer white. The colour of the compound hence
observed, is complimentary to that of the wavelength which has been absorbed by the complex. Thus, colour
of a complex is not because of the light absorbed but is due to the light reflected (complementary colour). The
complementary colour is the colour generated from the wavelength left over; for example is green light is
absorbed by the complex, it appears red.
Table given the relationship of the different wavelength absorbed and the colour observed.
In co-ordination complexes energy difference () between two sets of d-orbitals is small. Radiations of
appropriate frequency absorbed from visible region can cause excitation of d-electrons from lower energy
orbital to higher energy orbitals. Remeining light is transmitted and the compound appears coloured. Consider
for example, the complex [Ti(H 2O)6 ]3+ , which is violet in colour. This is an octahedral complex where the
single electron ( Ti3+ is a 3d1 system) in the metal d orbital is in the t 2g level in the ground state of the
complex. The next higher state available for the electron is the empty eg level. If light corresponding to the
energy of yellow-green region is absorbed by the complex, it would excite the electron from t 2g level to the
eg level (t2 g 1eg0 

 t2 g 1e0g ) . Consequently, the complex appears violet in colour (Figure). The crystal
field theory thus, attributes the colour of the co-ordination compounds of d-d transition of the electron.

If there are no d-electrons present or completely filled d-orbitals are present then there is no d-d transition
possible and complex appears colourless. For example, removal of water from [Ti( H 2O)6 ]Cl3 on heating
renders it colourless. Similarly, anhydrous CuSO 4 is white, but CuSO 4 .5 H 2O is blue in colour..
The influence of the ligand on the colour of a complex may illustrated by considering the [ Ni( H 2O )6 ]2  com-
plex, which forms when nickel(II) chloride is dissolved in water. If the didentate ligand, enthane-1, 2-
diamine(en) is progressively added in the molar ratios en : Ni, 1 : 1, 2 : 1, 3 : 1, the following series of
reactions and their associated colour changes occur :
[Ni(H 2O)6 ]2+ + en(aq)  [Ni(H 2O) 4 (en)]2+ (aq) + 2 H 2O

green pale blue
[Ni(H 2O)4 (en)]2+ (aq) + en(aq)  [Ni(H 2O) 2 (en) 2 ]2+ (aq) + 2 H 2O
blue/ purple
[Ni(H2O)2 (en)2 ]2+ (eq) + en(aq)  [Ni(en)3 ]2+ (aq) + 2 H 2O

violet
B. Stability of Co-ordination Compounds in Solutions :
A co-ordination compound is formed in solution by the stepwise addition of ligands to a metal ion. Thus,
formation of the complex, ML n may be supposed to take place by the consecutive n steps.

K1, K 2 ............K n are called stepwise stability constants. In general, the values of successive stability
1
constants decrease regularly from K1 to K n .  n is called the overall stability constant (and  is called
n
as instability constant). The higher the overall stability constant value of the complex, the more stable it is.
Alternatively, values called instability constant explain the dissociation of the complex into metal ion and
ligands in the solution. e.g.,  n for [Co( NH 3 ) 6 ]3  is 5  1033.
C. Factors affecting the stability of a complex ion :

The stability of a complex ion depends upon the following factors.
(i) Higher the charge density on the central ion, the greater is the stability of its complexes, i.e., the
Charge
higher value of , the greater is the stability of its complexes. Electronegativity of the
Radius of ion
central ion influences the stability, the higher the electronegativity of the central ion, the greater is the
stability of its complex.
(ii) The stability of the divalent metal ions of the first transition series is in the following order :
Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II)
This order is called Irving Williams order.
(iii) The cyano and ammine complexes are far more stable than those formed by halide ions.This is due
to the fact that NH3 & CN  are strong Lewis bases.
(iv) Greater the basic strength of the ligand, greater is the stability of the complex.
(v) Chelating ligands form more stable complexes as compared to monodentate ligands.
(vi) If the ligand happens to be multidentate and cyclic without any steric effects, the stabilityofthe
complex is further increased. The effect is called macrocyclic effect.
D. Metal Carbonyls & Bonding in Metal Carbonyls

The homoleptic carbonyls (compounds containing carbonyl ligands only) are formed by most of the transition
metals. These carbonyls have simple, well defined structures. Tetracarbonylnickel (0) is tetrahedral,
pentacarbonyliron (0) is trigonalbipyramidal while hexacarbonyl chromium (0) is octahedral.

The metal-carbon bond in metal carbonyls prossess both

s and p character. The M – C  bond is formed by
the donation of lone pair of electron on the carbonyl
carbon into a vacant orbital of the metal. The M – C
 bond is formed by the donation of a pair of electrons
from a filled d orbital of metal into the vacant antibonding
 * orbital of carbon monoxide. The metal to ligand
bonding creates a synergic effect which strengthens the
bond between CO and the metal (and hence decreases,
the bond order between C and O of CO and thereby
the bond length of C – O bond increases). The C – O
bond order will be in the order shown below :
Free CO > Metal carbonyl cation > Neutral metal carbonyl > Metal carbonyl anion.
Illustration - 18 Identify the complexes which are expected to be coloured. Explain :
(A) [Ti(NO3 )4 ] (B)  Cu(NCCH3 )4 + BF4

(C) [Cr ( NH 3 ) 6 ]3 3Cl  (D) K3[VF6 ]
SOLUTION :
(i) [Ti(NO3 )4 ]; Ti 4  : [ Ar ]3d 0 4 s 0 , No. of unpaired electrons = 0,  Colourless
(ii) [Cu ( NCCH 3 ) 4 ] BF4 ; Cu  :[ Ar ]3d 10 4s 0 , No. of unpaired electrons = 0,  Colourless
(iii) [Cr ( NH 3 ) 6 ]3 3Cl  ; Cr 3 : [ Ar ]3d 3 4 s 0 , No. of unpaired electrons = 3,  Colourless

(iv) K 3[VF6 ]; V 3 :[ Ar ]3d 2 4s 0 , No. of unpaired electrons = 2,  Colourless
Due to the presence of unpaired electrons in d-orbitals, two complexes i.e.,
[Cr ( NH 3 )6 ]3 3Cl  and K3[VF6 ] are coloured, others having all paired electrons arecolourless
Illustration - 19 Write down the IUPAC names of the following compounds :

(i) [Co(NH3 )5 ONO]Cl2 (ii) K3[Cr(CN)6 ] (iii) [Cr(NH3 )5 CO3 ]Cl
SOLUTION :
(i) Pentaamminenitritocobalt(III) chloride (ii) Potassium hexacyanochromate(III)
(iii) Pentaamminecarbonatochromium(III) chloride

Illustration - 20 Write the IUPAC name of the compound [Cr(NH3 )5 (NCS)][ZnCl4 ]. Is this compound
coloured?
SOLUTION :
IUPAC name : Pentaammine isothiocyanatochromium (III) tetrachlorozincate (II). This compound is coloured
because Cr 3 has unpaired electrons in d-orbitals ( 3d3 configuration) which show colour through d-d
transition.
Illustration - 21 A, B, and C are three complexes of chromium (III) with the empiricial formula H O Cl Cr.
12 6 3
All the three complexes have water and chloride ion as ligands. Complex A does not react with concentrated
H 2 SO4 , whereas complexes B and C lose 6.75% and 13.5% of their original mass, respectively, on treatment
with concentrated H 2 SO4 . Identify A, B and C.
SOLUTION :
The compound A does not react with concentrated H 2SO 4 implying that all water molecules are co-
ordinated with Cr3+ ion. Hence, its structure would be [Cr(H 2O)6 ]Cl3 .
The compound B loses 6.75% of its original mass when treated with concentrated H 2SO 4 . This loss is
due to the removal of water molecules which is/are not directly co-ordinated to Cr3+ ion.
6.75
The mass of water removed per mole of the complex   molar mass of the complex
100
6.75
  266.5 g  17.98 g
100
This corresponds to one mole of water. Hence, the structure of the compound B will be
[CrCl(OH 2 )5 ]Cl2 .H 2O
The compound C loses 13.5 % of its mass when treated with concentrated H 2SO 4 which is twice of the
mass lost by the compound B. Hence, the structure of the compound C will be
[CrCl2 (OH 2 )4 Cl.2 H 2O.

Illustration - 22 A metal complex having composition Cr ( NH ) Cl Br has been isolated in two forms (A)
3 4 2
and (B). The form (A) reacts with AgNO3 to give a white precipitate readily soluble in dilute aqueous ammo-
nia, whereas (B) gives a pale yellow precipitate solution in concentrated ammonia. Write the formula of (A)
and (B) and state the hybridization of chromium in each. Calculate their magnetic moments (spin only value).
SOLUTION :
Compound (A) on treatment with AgNO3 gives white precipitate of AgCl, which is readily solution in
dil. aq. NH3 . Therefore it has at least one Cl ion in the ionization sphere furthermore chromium has co-
ordination number equal to 6. So its formula is [Cr(NH 3 )4 BrCl]Cl.
Compound (B) on treatment with AgNO3 gives pale yellow precipitate of AgBr soluble in conc NH3 .
Therefore it has Br  in the ionization sphere. So its formula is [Cr(NH 3 )4 Cl2 ]Br .
State of hybridization of chromium in both (A) and (B) is d 2sp3 .
Spin magnetic moment of (A) or (B), spin = n(n+ 2) = 3(3 + 2) = 15 = 3.87 BM
Illustration - 23 Write the IUPAC nomenclature of the given complex along with its hybridization and
structure.
K 2 [Cr ( NO )( NH 3 )(CN )4 ],   1.73 BM
SOLUTION :
The spin magnetic moment,  of the complex is 1.73 BM.   n(n  2)  1.73  n  1
It means that nucleus of the complex, chromium ion has one unpaired electron. Now, if NO is neutral then
Chromium under the influence of strong field ligand CN  would not have any unpaired electron, so the
ligand NO is unit positively charged and the IUPAC name of the compound is Potassium
amminetetracyanonitrosonium chromate(I)

(a) Electronic configuration of Cr + : Cr + ion
(b) Electronic configuration of Cr + under the influence of strong field ligand CN 
So, Hybridization of the complex is d 2sp3 and its shape is Octahedral (as shown).
Illustration - 24 The 0.0001 molal solution of a complex AB10 has the freezing point of 0.0015C in
water. Assuming 100% dissociation of the complex, find the proper representation of the complex.
[ K f H 2O  1.86 Km1 ]
(A) [ AB8 ]B2 (B) [ AB3 ]B7 (C) [ AB7 ]B3 (D) [ AB5 ]B5
SOLUTION :
At 100% dissociation, van’t hoff factor, ‘i’ = n (no. of ions from the complex).
Now T f  i K f m
T f 0.0015
 in  8
Kfm 1.86  0.0001
Thus there should be 8 ions in solution
 The compound should be [AB3 ]B7 .

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Introduction to Organic Chemistry
Introduction to Organic Chemistry

STRUCTURAL FORMULAE Section - 1
We have already discussed that carbon has tetravalency and the formation of covalent bonds by it is explained
in terms of its electronic configuration and the hybridization of s and p orbitals. It may be recalled that
formation and shapes of molecules like Methane (CH4), Ethene (C2H4), and Ethyne (C2H2) were explained
in the terms of sp3, sp2, and sp hybridization of the respective carbon atoms.
Organic chemists use a variety of ways to represent structural formulae for an organic compound. The most
common types of representations are shown below.
Dot Structure (Lewis Structure)

This shows all of the valence electrons, For example, given below is the dot structure of n-propyl alcohol.
Writing dot structure is tedious and time consuming. The other representations are more convenient and are,
therefore, most often used.
Dash Structural Formula

Here, the pair of two electrons forming the covalent bond is represented by a dash. A single dash represents
a single bond, double dash is used for double bond and a triple dash represents a triple bond. The lone pair
of electrons on hetero-atoms like oxygen, nitrogen, sulphur, halogens, etc. may or may not be shown. Given
below is the dash structure of n-propyl alcohol.
Condensed Structural Formula

Condensed structural formulae are easier to write than dash formulae and, when we become familiar with
them, they will impart all the information that is contained in the dash structure. In the condensed formula, all
the atoms bonded to a carbon atom are written after ‘C’ in the same line but their bonds are shown.
Identical group are omitted by indicating their number as a subscript. The atoms or groups other than
hydrogen are written after the hydrogen atom.(in brackets)

Introduction to Organic Chemistry Vidyamandir Classes
Given below is the condensed formulae for n-propyl alcohol and isopropyl alcohol.
CH3(CH2)2OH n-Propyl alcohol
CH3CH(OH)CH3 Isopropyl alcohol
CH3(CH2)4CH3 n-Hexane
Note : The carbon atoms in organic compounds may also be

arranged in rings (Cyclic compounds). For example :
cyclopropane, whose structural formula is given alongside.
Bond-Line Formula
A very simplified formula called Bond-line formula can also be used to represent structures of organic
compounds. In this representation, the C and H atoms are not shown; the chain of carbon atoms is represented
by a zig-zag line. Each intersection of 2 or more lines (junction) and the end of a line represent a carbon
atom. Hetero-atoms (other than carbon and hydrogen) or functional groups are specifically written. Hydrogen
atoms necessary to fulfil the valence of carbon atoms is assumed to be present.
Bond line formulas are very frequently used for cyclic compounds.
Condensed formula Bond line formula
CH3CH 2CH3
CH3CH 2CH 2OH
CH3CH(OH)CH3

Multiple bonds are also included in bond-line formula. For example :
Condensed formula Bond line formula
Three-Dimensional Representation
None of the formulae that we have described so far conveys any information about how the atoms of a
molecule are arranged in space. There are several ways to represent the three dimensional structure of the
organic molecule on paper. For example: by using a solid and dashed wedge formula, the three dimensional
image of a molecule from a two dimensional picture can be perceived. In this representation, bonds that
project upwards out of the plane of the paper are indicated by a solid wedge , those that lie behind
the plane are indicated with a dashed wedge , and those bonds that lie in the plane of the paper are
indicated by a line ( ). Wedges are shown in such a way that the broad end of the wedge is towards the
observer. Generally, we only use three-dimensional formulae when it is necessary to convey information
about the shape of the molecule.
Wedge and Dash Representation

CLASSIFICATION OF ORGANIC COMPOUNDS Section - 2
Based upon the nature of carbon atom skeleton, the organic compounds have been classified into two
categories : Acyclic or Open Chain and Cyclic or Closed chain.

I. Open Chain or Acyclic Compounds : Compounds of carbon having open chain of carbon atoms,
branched or unbranched are called acyclic compounds.
Butane CH3 – CH2 – CH2 – CH3
Isopentane CH3  C H  CH 2  CH3
|
CH3
Open chain compounds are also known as aliphatic compounds since the earlier compounds of this class
were obtained either from animals or vegetable fats. (Greek, aliphatos  fats).
II. Cyclic or Closed Chain or Ring Compounds : Compounds of carbon having closed chain of
carbon as well as of other atoms are called cyclic compounds. Depending upon the constitution of the ring,
these are further divided into the following categories.
1. Homocyclic or carbocyclic compounds 2. Heterocylic compounds
1. Carbocyclic or Hom ocyclic Com pounds : Compounds of carbon having closed chain entirely made up
of carbon atoms are called carbocyclic or homocyclic compounds. These are further divided into two
groups.
(i) Alicyclic Compounds : Closed carbon chains except characteristic benzene ring, resembling in
properties with acyclic compounds. These include cycloalkanes, cycloalkenes and cycloalkadienes.
For e.g.,
(ii) Aromatic Compounds : Closed chain of only carbon atoms with alternate single and double bonds.
Benzene and its derivatives belong to this category. Some important examples of monocyclic, bicyclic
and tricyclic aromatic compounds are as follows.
(a) Monocyclic aromatic compounds :
(b) Bicyclic and Tricyclic aromatic compounds :

2. Heterocyclic compounds : Compounds of carbon having closed chain made up of carbon and other
atoms. The hetero atoms commonly found in these compounds are oxygen, nitrogen and sulphur and occa-
sionally, phosphorus, boron, silicon and some metal atoms like tin, selenium etc, may also be present.
Depending upon the chemical behaviour, these are further classified into the following two categories.
(i) Alicyclic heterocyclic compounds : Alicyclic compounds containing one or more heteroatoms in
their rings are called alicyclic heterocyclic compounds. For example:
(ii) Aromatic heterocyclic compounds : Aromatic cyclic compounds containing one or more het-
eroatoms in their molecules are called aromatic heterocyclic compounds. For example :
Note : An aliphatic compound burns with non-smoky flame (except CHCl3, CCl4). All aromatic compounds burn
with a smoky flame.
NOMENCLATURE OF ORGANIC COMPOUNDS Section - 3

The IUPAC (International Union of Pure and Applied Chemistry) has developed a systematic method of
naming organic compounds. This system gives a unique IUPAC name to every organic compound. However
before the IUPAC system came into existence, the trivial or common names for organic compounds were
used. These were based on their origin or certain properties. Some examples are as follows : (Please note
that the contents of following table are NOT to be memorised).
Compound Trivial Name Source of Compound
CH3OH Wood spirit Obtained by destructive distillation of wood
CH3OH Methyl alcohol Methu-spirit and hule-wood
NH2CONH2 Urea Obtained from urine
CH3COOH Acetic acid Obtained from Acetum-vinegar
(COOH)2 Oxalic acid Obtained from oxalis plant
HCOOH Formic acid Obtained from ants, in Latin Ants  Formicae.
C2H5OH Grain alcohol (Ethanol) Obtained by fermentation of grains.
6 Section
These older names for organic compounds are still widely used by chemists and bio-chemists, and in com-
merce. For this reason it is necessary to learn the common names (Trivial Names) for some of the organic
compounds.
Trivial System Of Nomenclature

Classification of carbon atoms :
In trivial system of naming an organic compound, the carbon atoms of an alkane were classified on the basis
of the number of other carbon atoms attached to them, into four categories, viz., Primary carbon atoms,
Secondary carbon atoms, Tertiary carbon atoms and Quarternary carbon atoms.
Primary carbon atom : When a carbon atom is attached to one carbon atom, then it is primary carbon
atom or 1 carbon atom.
Secondary carbon atom : When a carbon atom is attached to two carbon atoms, then it is secondary
carbon atom or 2 carbon atom.
Tertiary carbon atom : When a carbon atom is attached to three carbon atoms, then it is tertiary carbon
atom or 3 carbon atom.
Quaternary carbon atom : When a carbon atom is attached to four carbon atoms, then it is quaternary
carbon atom or 4 carbon atom.
Consider following structure showing all four types of carbons.
Vinylic Carbon atom : Carbon atom of C = C is called as vinylic carbon atom.

Allylic Carbon atom : sp3 hybridized Carbon atom next to C = C is called as allylic carbon atom.
Benzylic Carbon atom : Carbon atom directly bonded to benzene ring is called as benzylic carbon atom.
Classification of Hydrogen atoms :

The hydrogen atoms of a sp3 carbon are classified on the basis of the carbon atoms to which they are
attached. A hydrogen atom attached to a primary carbon atom is a primary hydrogen atom, hydrogen atom
attached to a secondary carbon atom is secondary hydrogen atom and so forth. But there are no quaternary
hydrogen atoms as no hydrogen atom is attached to a quaternary carbon atom.

Note :
CH3
|
CH 3   CH 2  n  CH3 CH3  CH   CH 2  n  CH3 CH3  C   CH 2  n  CH3
 n  2 | |
CH3  n  0 CH3  n  0
Normal (n) stand for unbranched chain of carbon atoms. Iso indicate one CH3-side chain on second
carbon atom of the chain. Neo indicate two CH3-side chains on second carbon atom of the chain.
Note : Neopentane has only primary hydrogen atoms. Note : Isooctane has different structure.
CH3 CH 3 CH 3
| | |
CH 3  C  CH3 CH3  C  CH 2  CH  CH3
| |
CH3 CH 3
 - Carbon and  - Carbon atoms :

Carbon atom in the structure of compound to which a functional group (–OH, –CHO, Cl,. . . . . . . . . . etc.)
is attached is known as   carbon and the corresponding hydrogen is referred to as   hydrogen. The
carbon atom(s) adjacent to   carbon is known as   carbon(s).
   
C H3  C H 2  Cl C H3  C H 2  COOH
    
C H3  C H 2  CHO CH 3  C H 2  C H(Cl)  C H 3
 
H3 C  C  C H3 HCHO No  - Carbon and no  - Hydrogen
||
O
8 Section
Section 333
Section Self Study Course for IITJEE with Online Support
IUPAC System of Nomenclature

The formal system of nomenclature used today is one proposed by the International Union of Pure and
Applied Chemistry (IUPAC). This system was first developed in 1892 and has been revised at regular
intervals to keep it up to date.The principle of IUPAC system is: Each different compound should have
a different name.
The IUPAC nomenclature involves the use of following terms :
1. Word root 2. Primary suffix 3. Secondary suffix 4. Prefix
1. Word Root : The word root represents the number of carbon atoms in the parent chain. For the
chains up to four carbon atoms special word roots are used whereas words (pent, hex, hept...etc.)
indicating the number of carbons in the chain are used for the compounds containing more than four
carbon atoms.
Some (straight) unbranched chains and their names :
Name Number of Structure Name Number of Structure

C -Atoms C -Atoms
Methane 1 CH4 Octane 8 CH3(CH2)6CH3
Ethane 2 CH3CH3 Nonane 9 CH3(CH2)7CH3
Propane 3 CH3CH2CH3 Decane 10 CH3(CH2)8CH3
Butane 4 CH3(CH2)2CH3 Undecane 11 CH3(CH2)9CH3
Pentane 5 CH3(CH2)3CH3 Dodecane 12 CH3(CH2)10CH3
Hexane 6 CH3(CH2)4CH3 Tridecane 13 CH3(CH2)11CH3
Heptane 7 CH3(CH2)5CH3 Tetradecane 14 CH3(CH2)12CH3

The word root of different carbon chains are obtained by leaving ‘ane’ from the name of the carbon
chain of the respective molecule. Some word roots are given below :
Chain Length Word Root Chain Length Word Root
C1 Meth  C7 Hept (a) 
C2 Eth  C8 Oct (a)
C3 Prop (a)  C9 Non (a) 
C4 But (a)  C 10 Dec (a)
C5 Pent (a)  C 11 Undec (a) 
C6 Hex (a)  C 12 Dodec (a) 
Note : Extra ‘a’ given in parenthesis is used only if the primary suffix (explained later) to be added to the word root
begins with a consonant (execpt y). In general, the word root for any carbon chain is alk.
2. Primary Suffix : Primary suffix is used to indicate saturation or unsaturation in the carbon chain.
While writing the name, primary suffix is added to the word root. Some of the primary suffixes are
given below in the following table.
Nature of Carbon Chain Primary Suffix
Saturated Carbon Chain ane
Unsaturated Carbon Chains
One C=C bond ene
Two C=C bonds diene
Three C=C bonds triene
One CC bond yne
Two CC bonds diyne

3. Secondary Suffix : Secondary suffix is used to indicate the functional group in the organic com-
pound. It is added to the primary suffix by dropping its terminal ‘e’. Secondary suffixes for various
functional groups are given in the following table.
Family of General Functional Secondary IUPAC name of

Compound Formula Group Suffix the family (Saturated)
Alcohols ROH OH ol alkanol
Thioalcohols RSH SH thiol alkanethiol
Amines RNH2 NH2 amine alkanamine
Aldehydes RCHO CHO al alkanal
Ketones RCOR >C=O one alkanone
Sulphonic Acids RSO3H SO3H sulphonic alkane sulphonic acid
Anhydrides CO)2O oic alkanoic anhydride
anhydride
Carboxylic acids RCOOH COOH oic alkanoic acid
Amides RCONH2 CONH2 amide alkanamide
Acid chlorides RCOCl COCl oyl alkanoyl chloride
Esters RCOOR COOR oate alkyl alkanoate
Nitriles RCN CN nitrile alkane nitrile
In addition to these some functional groups are represented as prefixes.They are discussed later
Note : (i) If the name of the secondary suffix begins with a consonant (except y), the terminal ‘e’ of the primary
suffix is retained while adding secondary suffix to it. For example : Thioalcohols have secondary
suffix thiol and thus ’e’ of ane should not be dropped, i.e., IUPAC name is Alkane thiol.
(ii) The terminal ‘e’ of primary suffix is also retained if some numerical prefixes like di, tri etc. are used
before the secondary suffix.

4. Prefix : The part of the name which appears before the word root is called prefix. Different prefixes are
used for different categories of groups present in molecule.
(i) Alkyl Groups : The univalent groups or radicals obtained by the removal of one H atom from a
molecule of paraffin are called alkyl groups. These alkyl groups have names that end in yl. The
symbol ‘R’ is often used to represent an alkyl group. Some alkyl groups with their prefixes are given
in the following table.
Alkane Alkyl Group Abbreviation Prefix
CH4 (Methyl) CH3  Me Methyl
C2H6 (Ethyl) CH3CH2  Et Ethyl
C3H8 (n  Propyl) CH3CH2CH2  nPr nPropyl
C3H8 (Isopropyl) CH3  C H  isoPr Isopropyl or

| (1  Methylethyl)
CH 3
C2H4 (Ethene) CH2= CH- - Vinyl (Ethenyl)
C3H6 (Propene) CH2= CH-CH2- - Allyl
C6H6 (Benzene) C6 H 5 - Ph- Phenyl

(ii) Some functional Groups are always indicated by prefixes instead of secondary suffixes. These with
their prefixes are given in the following table.
Functional Group Prefix Family IUPAC Name
-NO 2 Nitro R-NO2 Nitroalkane
-OR’ Alkoxy R-OR’ Alkoxyalkane
-Cl Chloro R-Cl Chloroalkane
-Br Bromo R-Br Bromoalkane
-I Iodo R-I Iodoalkane
-F Fluoro R-F Fluoroalkane
-N = O Nitroso R-NO Nitrosoalkane
O epoxy epoxyalkane

(iii) In polyfunctional compounds (compounds with more than one functional groups), one of the func-
tional groups is treated as principal functional group and is indicated by the secondary suffix whereas
other functional groups, treated as substituents, are indicated by the prefixes. The order of priority
among various functional groups to be treated as principal functional group has been discussed later in
this chapter. The prefixes for various functional groups are given in the following table.
Prefixes for functional groups in polyfunctional compounds
Functional Prefix Functional Prefix

Group Group
OH Hydroxy COOH Carboxy
CN Cyano COOR Carbalkoxy
NC Isocyano COX Haloformyl
CHO Formyl CONH2 Carbamyl
SH Mercapto NH2 Amino
SR Alkylthio =NH Imino
NHR alkylamino -NR2 dialkylamino
SO3H sulpho >C = O keto / oxo
Writing the IUPAC name of Organic Compounds :

While writing the IUPAC name of a compound word root, prefix, primary suffix, secondary suffix, follow
the order:
Prefix(es) + Word root + Primary suffix + Secondary suffix
The above arrangement is illustrated by the following examples :

Compound Prefix Word root P. suffix Sec. suffix IUPAC Name
CH 3  CH  CH 2  CH 2OH Methyl but an ol 3-Methylbutane-1-ol

|
CH3
CH3  C  CHOH Bromo prop en ol 2-Bromoprop-1-en-1-ol

|
Br
The Rules for naming Organic Compounds :

I. For Saturated Compounds
1. Selection of longest chain :
 The longest possible carbon chain is selected and the compound is named as derivative of hydrocar-
bon using word root.
The chain of 6 carbon atoms is selected.
 If more than one sets of longest possible chains are there, the selected longest chain should have :
(a) Maximum number of side chains or
(b) Minimum number of branched side chains
6 atoms chain with one side chain or one branched side chain is rejected.
6 atoms chain with two side chains or two unbranched side chains is
selected.
2. Numbering of selected chain :

The selected chain is numbered from one end to other. The numbers are called locants.
 Lowest number is assigned to first side chain (alkyl groups) or substituent group.
1 2 3 4 1 2 3 4 1 2 3 4 5
CCCC CCCC C C  C C  C
| |
Cl CH 3

 If two different alkyl groups are at same position from opposite ends, lowest number is given to the
one coming first in alphabetical listing.
7 6 5 4 3 2 1
C C C C C C C
| |
CH3 C2 H 5
Note that ethyl gets ‘3’ as the locant, not methyl.

 If two different substituents are at same position from opposite ends, lowest number is assigned in
order of their alphabets.
1 2 3 4 4 3 2 1
C C  C  C C C  C  C
| | | |
Cl I Cl Br
 If a substituent (such as halogen, or nitro group) and a side chain are at same position from opposite
ends, lowest number is assigned to substituents.
4 3 2 1
C C  C C
| |
CH3 I
 If more than two substituents and side chains are present, then the set of locants are compared term
by term, and that set is preferred which gets the least term at the first point of difference. This is the
lowest set of locants rule.
7 6 5 4 3 2 1
C C C C C  C C 2, 3, 6 is accepted.
| | | 2, 5, 6 is rejected.
CH3 CH3CH3
1 2 3 4 5
C  C C  C C 1, 2, 3, 5 is accepted.
| | | | 1, 3, 4, 5 is rejected.
Cl I CH3 Br
10 9 8 7 6 5 4 3 2 1 2, 7, 8 is accepted.
C  C  C C  C  C C  C  C C
1 2| 3 4 5 6 7 | 8| 9 10 3, 4, 9 is rejected.
C C C

3. Arrangement of prefixes :
 Alkyl nature of side chain or substituent group is identified and reported as prefix with its number
(locant) in hydrocarbon name in alphabetic order.
4 3 2 1
H3 C C H  C H  C H 3
| | 2-Bromo-3-chlorobutane
Cl Br
1 2 3 4
H 3 C H C H C  C H 3 2-Chloro-3-iodobutane
| |
Cl I
1 2 3 4 5
H3 C  H C  H C  C H 2  C H3 3-Chloro-2-methylpentane
| |
H 3C Cl
 If more than one similar alkyl chains or substituents are present, prefix names are modified by putting
di, tri....terms.
4 3 2 1
C H3  C H  C H  C H3 2, 3-Dimethylbutane
| |
CH 3 CH3
 If more than one similar alkyl groups or substituents are present at same position, their locant is also
repeated.
CH3
1 2| 3
H3C  C  CH3 2, 2-Dimethylpropane
|
CH3
 In case side chain is also branched, it is numbered from the carbon atom attached to main chain and
is generally written in brackets.
1 2 3 4 5 6 7 8
C H3  C H  C H 2  C H 2  C H  C H 2  C H 2  C H3 5-(1-Methylethyl)-2-methyl-octane
| 1|
CH 3 C H  CH3
2|
CH3

1 2 3 4 5 6 7 8
C H3  H 2 C C H 2  C H  C H 2  C H 2  C H 2  C H 3 4-(1, 1-Dimethylethyl)octane
|1 2
CH3  C H  C H3
|
CH3
II. For Unsaturated Hydrocarbons

1. Select the longest possible carbon chain having maximum number of unsaturated carbon atoms or maximum
number of double or triple bonds, even if prior rule is violated.
5 carbon atoms chain with two unsaturated carbons or one

double bond is selected.
2. Lowest number (locant) is assigned to first unsaturated carbon even if prior rule is violated.
1 2 3 4 1 2 3 4 1 2 3 4 5 6
C  C C  C C  C C  C C  C C  C  C C
|
CH3
3. In case of unsaturation suffix, name of unsaturation is used with hydrocarbon name, i.e.
C = C bond ane of hydrocarbon is replaced by ene.
C  C bond ane of hydrocarbon is replaced by yne.
4. In case of more than one double bonds we use di, tri etc. For example: diene or triene.
CH3 – CH = C = CH2 Buta-1, 2-diene
CH2 = CH – CH = CH2 Buta-1, 3-diene
5. If a compound contains both the unsaturations then compound is named as Alkenyne with numbering as
low as possible given to multiple bonds, following the lowest set of locant rule.
1 2 3 4 5
H C  C  C H  C H  C H3 Pent-3-en-1-yne
If there is a choice i.e. when the double bond and the triple bond are at the same distance from the two ends
then the double bond gets the preference over the triple bond in the numbering.
6 5 4 3 2 1
H C  C  C H 2  C H2  C H  C H 2 Hex-1-en-5-yne

III. For Functional Groups

1. Select the longest possible carbon chain having maximum number of functional groups even if prior rules are
violated, For example :
5 carbon chain inclusive of two functional groups is selected
2-ethylpentane-1, 4-diol
2. When the functional group itself contains a C atom, then the carbon atom of functional group is to be
included in deciding the longest carbon chain.
C – C – CN 3 carbon chain, i.e., C atom of cyanide is also included.
C – C – C – CHO 4 carbon chain, i.e., C atom of aldehyde is also included.
3. The lowest number (locant) is assigned to the functional group even if prior rules are violated.
5 4 3 2 1 1 2 3 4 5 5 4 3 2 1
C  C C  C C  OH C  C C C  C C  C C  C C
| | |
OH CH3 OH
4. The order for numbering a carbon chain, thus follows the order :
Functional Group then Unsaturation then Substituents and Side chains (or alkyl groups)
7 6 5 4 3 2 1 Lowest number to OH group.

C C C C C CC
|
OH
1 2 3 4 5 6 7
C C C C CCC OH is at equidistant from two ends and thus next low-
| est number to unsaturations.
OH
7 6 5 4 3 2 1 Lowest locant to OH group (not to double bond).
C  CCCCC C
|
OH
IUPAC names of some families of Organic Compounds :

1. Carboxylic Acids : The IUPAC name of acids is derived from the name of the corresponding alkane by
dropping the ending – e and putting the suffix – oic acid.

HCOOH CH3COOH
Methanoic acid Ethanoic acid
The position of the substituent is indicated by the usual numerals
4 3 2 1 5 4 3 2 1
H C  C  C H 2  C OOH H3 C  C  C  C H 2  C OOH
But-3-yn-1-oic acid Pent-3-ynoic acid
The cyclic acids cannot be named in this manner. To name them, the name
of the corresponding cycloalkane precedes the word carboxylic acid.
Cyclobutanecarboxylic acid
2. Aldehydes : Aldehydes have a hydrogen atom attached to the carbonyl group. The common name of an
aldehyde is derived from the corresponding carboxylic acid by dropping the suffix oic acid and adding the
suffix –a. For example :
HCOOH HCHO
Methanoic acid Methanal
4 3 2 1 5 4 3 2 1
H 2 C  C H  C H 2  C HO H C  C  C H  C H 2  C HO
|
CH 3
But-3-en-1-al 3-Methylpent-4-yn-1-al
3. Ketones : The suffix ane is changed to  one i.e. alkanone. The numbering commences from that end of the
chain which gives the lowest number to the carbonyl group. It is always necessary to prefix the name by a
number to specify the position of the carbonyl group.
O O
|| ||
C H3  C  C H3 C H3  C H 2  C  C H3
3 2 1 4 3 2 1
Acetone (Propan-2-one) Butan-2-one
O O
4 || ||
C H3  C H  C H 2  C  C H 3 C H3  C H  C H  C  C H3
5 | 3 2 1 5 4 3 2 1
CH3
4-Methylpentan-2-one Pent-3-en-2-one

4. Ethers : The common name of ethers is derived by naming the alkyl groups and adding the word ether. The
smaller group is written first.
C2H5OCH3 Methyl ethyl ether
C6H5OC(CH3)3 t-Butyl phenyl ether
The IUPAC nomenclature is rarely used. Ethers are named as Alkoxy Alkanes. The larger alkyl group is
chosen as the parent.
4 3 2 1 2
CH3OCH 2CH3 C H3  C H 2  CH  O  CH 3 C H 2  C O  CH 2CH3
1| |
CH3 3 CH3
Methoxy ethane 2  Methoxybutane 2  Ethoxy propene
In cyclic ethers, the oxygen atom is contained in a ring of carbon atoms. While numbering the cyclic group,
oxygen atom is always given number – 1. While naming a prefix Epoxy is added to the name of carbon
atoms in the cyclic chain.
5. Esters : In the IUPAC system the acid chain is used as the stem in naming the ester. The suffix –oate
replaces the –oic acid of carboxylic acids. It is necessary to number the substituent on the chain. The first
part of the name is derived from the alkyl group of the corresponding alcohol.
HCOOCH3 CH3COOCH3
Methylmethanoate Methylethanoate
4 3 2 1
CH3CH2COOC2H5 C H 2  C H  C H 2 C OOC 2 H5
Ethylpropanoate Ethylbut-3-en-1-oate
6. Amines : In the IUPAC system of nomenclature, amines are named similar to alcohols. The longest con-
tinuous carbon chain having max. no of amines determines the root name. The –e ending in the alkane
named is replaced by suffix - amine. A number is needed to specify the position of the substituents.
CH3CH2OH Ethanol
CH3CH2NH2 Ethanamine

4 3 2
C H 2  C H  C H 2  NH 2 But-3-en-2-amine
|
1 CH3
Secondary amines and Tertiary amines :

The name of any alkyl group bonded to nitrogen is preceded by an “N” (in Italic) to indicate that the group
is bonded to a nitrogen rather than to carbon.
H3C  CH 2  N H N-Methylethanamine
|
CH3
1 2
H3 C C H  N H  C H 2  CH 3 N-Ethylbutan-2-amine
|
3 C H2
|
4 CH3
H3C  CH 2  N  CH 2  CH3 N-Ethyl-N-methylethanamine

|
CH3
4 3 2
H3 C C H 2  C H  N  CH 2  CH3 N, N-Diethylbutan-2-amine
| |
1CH3 C H 2
|
CH3
All the substituents (regardless of whether they are attached to the nitrogen or to the parent hydrocarbon)
are listed in alphabetical order. The chain is numbered such that the functional group suffix gets the lowest
possible number.
7. Nitriles : While writing the IUPAC name, the cyano group takes the preference and its carbon atom is
numbered as 1, only suffix -nitrile is added to the name of parent hydrocarbon (including the carbon of
group).
3 2 1 3 2 1 5 4 3 2 1
C H3 C H 2 C N H3 C  C H  C N H 3 C C H  C H  C H  C N
| |
CH 3 CH3
Propanenitrile 2-Methylpropanenitrile 2-Methylpent-3-enitrile

Rules for IUPAC Nomenclature of Polyfunctional Compounds :

Organic compounds having polyfunctional groups are named as follows :
1. Principal functional group : When an organic compound contains two or more different functional
groups, one of the functional groups is selected as the principal functional group while all other groups (also
called the secondary functional groups) are treated as substituents. The choice of the principal functional
group is made on the basis of the following order of preference.
– COOH > – SO3H > – (CO) 2O > – COOR > – COX > – CONH 2 > – CN > – CHO >
> C = O > – OH > – phenol > – SH > – N H 2 > – OR > > –CC–
The secondary suffixes for these functional groups have already been listed before.
All the remaining functional groups such as halo (fluoro, chloro, bromo, iodo), nitroso (NO), nitro
(–NO2), and R (alkyl), C6H5 etc. are always treated as substituent group.
It may be noted that while writing the names of the polyfunctional compounds, the principal functional group
is indicated by adding the secondary suffix to the word root while the secondary functional groups are
indicated by adding suitable prefixes to the word root. The prefixes for secondary functional groups are
listed before.
2. Selecting the principal chain : While selecting the principal chain present in a polyfunctional compound
care should be taken that it must contain the principal functional group and the maximum number of second-
ary functional groups and multiple bonds, if any.
3. Numbering the principal chain : The principal chain present in a polyfunctional compound must be
numbered in such a way that the principal functional group gets the lowest possible number followed by
double bond, triple bond and the substituents, i.e.
Principal functional group > Double bond > Triple bond > Substituents.
4. Alphabetical order : The prefixes for the secondary functional groups and other substituents should be
placed in alphabetical order before the word root as explained earlier. If, however, two groups of the same
family (eg. halogens) occupy identical positions from either end of the parent chain, the lower number must
be given to the group whose prefix comes first in the alphabetical order. For example :
4 3 2 1
Cl C H 2 C H 2 C H 2 C H 2 Br 1–Bromo–4–chlorobutane (Correct)
1 2 3 4
Cl C H 2 C H 2 C H 2 C H 2 Br 4–Bromo–1–chlorobutane (Wrong)
The rest of the rules for numerical prefixes are the same as explained earlier.
If more than one kind of functional groups are present, the functional group placed above( in the order of
preference) decides suffix name.

CH3  C  COOH CH3  C  CH 2OH

|| ||
O O
2-Ketopropanoic acid 1-Hydroxypropan-2-one
O
||
CH3  C  CHO
|| CH3  C CH  CHO
|
O CH3
2-Ketopropanal 2-methyl-3-oxobutan-1-al
Naming of Alicyclic Compounds :

The nomenclature for alicyclic compounds is derived by putting another prefix ‘cyclo’ before the word root
of carbon atoms in ring. The suffixes ane, ene are written depending upon the nature of molecule, i.e.,
saturated (ane) or unsaturated (ene) for double bond.
-1, 1-Dimethylcyclopentane 1-Methylcyclohex-1-ene 1, 2-Dimethylcyclopent-1-ene
3-Methylcyclohex-1-ene 1, 3-Dimethylcyclohex-1-en
3-Bromocyclohex-1-ene Cyclohex-2-en-1-ol 3-Bromocyclohex-2-en-1-ol
Note : From above examples, we can see that substituted cycloalkanes are named as derivatives of parent
cycloalkanes. The substituted alkyl groups or functional groups around the ring from the point of greatest
substitution providing the lowest series of numbers.

Bicyclic Compounds : (This topic is for reference only, not in JEE syllabus).
Bicyclic compounds are compounds that contain two rings.
1. If the two rings share one carbon, the compound is a spirocyclic compound or simply spiro compound.
For example :
2. If the two rings share two adjacent carbons, the compound is a fused bicyclic compound.
3. If the two rings share more than two carbons, the compound is a bridged bicyclic compound.
Nomenclature of Bicyclic Compounds :

1. Bicyclic compounds are named by using the alkane name to designate the total number of carbons and the
prefix bicyclo or spiro to indicate the number of shared carbons.
2. Prefix spiro indicates one shared carbon and bicyclo indicates two or more shared carbons. The following
compound, for example, contains seven carbon atoms and is therefore, a bicycloheptane.

The carbon atoms common to both rings (Number of such carbons is either one in spiro or two in bicyclic)
are called bridgeheads and each carbon chain of atoms, connecting the bridgehead atoms is called a bridge.
3. After the prefix spiro or bicyclic comes brackets that contain numbers indicating the number of carbons in
each bridge. These are listed in order of decreasing bridge length. For example :
4. Numbering in bicyclic compounds starts at any one bridge head carbon and moves along the longest carbon
bridge to the next bridge head carbon. Continue along the next longest carbon bridge to return to the first
bridge head carbon so that the shortest bridge is numbered last.

Note : Number of rings in polycyclic compounds = (S - A+1) where ‘S’ is the number of single bonds in the ring
and A is the number of carbon atoms in the ring.
Some Prominent IUPAC Examples



Nomenclature of Aromatic Compounds :

Aromatic compounds are cyclic compounds which contain one or more benzene type rings. Benzene is the
simplest hydrocarbon of aromatic series which has a planar cyclic ring of six carbon atoms having three
double bonds in alternate positions as shown below :
kekule structures Resonance hybrid

The carbon atoms of benzene are numbered from 1 to 6 as shown above. The benzene ring is called the
nucleus and groups containing at least one carbon atom that too directly attached to benzene nucleus are
called side chains. Benzene forms only one mono substituted derivative. However, it can form three disub-
stituted derivatives; namely 1, 2 ; 1, 3 and 1, 4 derivatives or ortho (o), meta (m) and para (p) deriva-
tives respectively.
Some Important Aromatic Hydrocarbons :
Toluene Ethylbenzene Vinylbenzene(Stryene) Isopropyl benzene(Cumene)
Phenol Anisole Acetophenone Aniline
Benzaldehyde Salicylaldehyde Benzenesulphonic acid Benzoic acid

o-Xylene m-Xylene p-Xylene Mesitylene
o-Cresol m-Cresol p-Cresol Cyano benzene
Catechol Resorcinol Hydroquinol 1, 4-Benzouilone
Salicylic acid m-Toluidiene Methyl benzoate Phthalic acid
Isophthalic acid Terephthalic acid m-Toluic acid Anthranilic acid

Picric acid 2, 4, 6-Trinitrotoluene (TNT) Pyrogallol Aspirin
Cinnamic acid Benzophenone Naphthalene  -Naphthol
 -Naphthol Anthracene Phenanthrene Azzulene
Homologous Series : A homologous series is defined as a family or group of structurally similar organic
compounds all the members of which contain the same functional group, show a gradation in physical and
similarity in chemical properties and any two adjacent (or consecutive) members of which differ by a –CH2
group. For example: alkanes constitute a homologous series.
The first six members of this series are :
CH4 C2H6 C3H8 C4H10 C5H12 C6H14

Methane Ethane Propane Butane Pentane Hexane
These hydrocarbons can be represented by the same general formula, CnH2n+2 where n is the number of
carbon atoms. Further, any two adjacent members of this class differ by a CH2 group.
If a hydrogen atom from the above hydrocarbons is replaced by a hydroxyl group i.e., – OH, we get a new
homologous series. This homologous series is called alcohols. The different members of this series can be
represented by the general formula CnH2n+1 OH. The first four members of this series are :
CH3OH CH3CH2OH CH3CH2CH2OH CH3CH2CH2CH2OH

Methanol Ethanol Propan-1-ol Butan-1-ol
Some other homologous series are alkenes, alkynes, alkyl halides, ethers, aldehydes, ketones, amines,
esters and carboxylic acids etc.

Characteristics of a Homologous Series :

1. Each homologous series can be represented by a general formula. For example, CnH2n+1 COOH is the
general formula of carboxylic acids.
2. All the members of a given homologous series possess the same functional group. For example, the func-
tional group of alcohols is the hydroxyl group i.e., –OH group. Similarly, the functional group of aldehydes
is the aldehydic group i.e., –CHO and that of the ketones is the ketonic group, i.e., > C = O.
3. The successive members of a homologous series differ by a CH2 group or by 12 + 2  1 = 14 mass units.
4. The individual members of a homologous series can be prepared by the general methods of preparation
developed for that series.
5. The physical properties such as density, melting point, boiling point of the members of a homologous series
show a regular gradation with rise in molecular mass.
6. The chemical properties of the members of a homologous series are similar though the first member may
vary considerably from rest of the members.
Degree of Unsaturation (DU)

Degree of Unsaturation also known as “index of Hydrogen deficiency (IHD)” or “rings plus double bonds”
is helpful in Organic Chemistry while drawing Chemical structures.
For a compound with formula : CaHbNcOdXe where X is F, Cl, Br or I,
1
DU   2  2a  b  c  e  or DU  1 [2+ 2  No. of C atoms -No. of H atoms + No. of N atoms -
2 2
No. of Halide atoms]
Rules :
(i) Do not cout group 16 elements e.g. O, S etc. Remove them from the formula but count H-atoms
attached to them.
(ii) Each double bond, adds ‘one’ to DU.
(iii) Each triple bond, adds ‘two’ to DU.
(iv) Each ring adds ‘one’ to DU.
1
(i) C3H6 : DU   2  2  3  6  1  It contains a double bond OR a ring.
2

1
(ii) C5H8 : DU   2  2  5  8  2
2
 Two double bonds OR 1 triple bonds OR 2 rings OR 1 double bond and 1 ring.
(iii) DU = 6: as it contains 3 double bonds, 1 triple bond, and 1 ring.
1 1
(iv) C6 H12O6 : DU   2  2  6  12  1 (v) C6H12 N 2 Br2 : DU   2  2  6  12  2  2   1
2 2
(vi) DU = 1(One ring) (vii) : DU = 2 (Two combined rings)
(viii) : DU = 5 (4 double bonds + 1 ring)
(ix) : DU = 5 (4 double bonds + 1 ring)
Note: DU  4 doesn’t demand but suggest the possibility of an aromatic (benzene) ring.
Illustration - 1 Draw the condensed structures of following compounds. Also write their IUPAC name.
(i) tert-Butyl alcohol (ii) Isopropyl methyl ether (iii) sec-Butyl ethyl ketone
(iv) Phenyl methyl ether (v) Isopropyl isobutyrate (vi) sec-Butyl formate
(vii) Methyl vinyl ether (viii) Isopropyl benzene (ix) Dimethyl n-propyl amine
(x) Methyl n-propyl acetylene
SOLUTION :
OH
1 | 3
(i) C H3  2C  C H3 : 2-Methylpropan-2-ol
|
CH3

1 2
(ii) C H3  C H3  O  CH 3 : 2-Methoxypropane
|
CH3
3
1 2 3 4 5 6
(iii) C H3 C H 2  C C H  C H 2  C H 3 : 4-Methylhexan-3-one
|| |
O CH3
(iv) : Methoxybenzene ; (called as anisole :

trade name as IUPAC name)
O
3 2 ||1 1 2
(v) C H3  C H3  C  O  C H 2  C H3 : (1-Methylethyl) 2-methyl propanoate
| |
CH3 CH3
O
|| 1 2 3
(vi) H  C  O  C H  C H 2 C H3 : (1-Methylpropyl) methanoate
|
CH3
(vii) CH3 – O – CH = CH2 : Methoxyethene
(viii) : (2-propyl) benzene (or cumene)

or (1- Methylethyl) benzene.
(ix) CH3  N  CH3 : N, N-Dimethyl-1-propan - 1 - amine

|
C H3 C H 2 C H3
1 2 3
(x) CH 3  C  C  CH 2  CH 2  CH3 : Hex - 2 - yne

Illustration - 2 Draw the bond line structures for each of above compounds in Illustration - 1
SOLUTION :
(i) (ii) (iii)
(iv) (v) (vi)
(vii) (viii) (ix)
(x)
Illustration - 3
Give the IUPAC names of the following structures.
SOLUTION :
OH
4 | 2 1
1. C H3  3C H  C H 2  C OOC 2 H5 Ethyl 3-hydroxybutanoate
4 3 2 1
2. C H3  C H 2  C H 2  C OCl 2-Bromobutanoyl chloride
|
Br
6 5 4 3 2 1
3. H 2 C  C  C H 2  C H 2  C H 2 C OOH 2- Hydroxy-5-methylhex-5-enoic acid
| |
CH3 OH
4. N-Ethyl-N-methyl-2-methylpropan-1-amine

4 3 2 1
5. C H2  C  C H  C H3 3-Methylbut-3-ene-2-ol
| |
CH3 OH
O
|| 2 3
6. ph  O  C  C H 2  C H3 (phenyl) 2-methylpropanoate
|
CH3
7. 2-Methylbut-3-en-1-al
8. 4, 5-Dimethyloct-4-ene
9. 2-Methyl-3-Oxopentanoic acid
10. 2-Methoxybenzoic acid
11. 2, 2-Dimethylpropan-1-al
12. 2-Methylcyclohexan-1-one
13. 2, 3-Dimethylcyclohex-1-ene

3 2 1
14. ph  C H  C H  C OOH 3-Phenylprop-2-enoic acid
7 6 5 4 3 2 1
15. C H3  C H  C H  C H  C H 2  C H  C HO 6-Hydroxy-2-methoxyhept-4-en-1-al
| |
OH OCH3
1
C H3
|
16. C2 H5  NH  C H  C H 2 C H 3 N-Ethylbutan-2-amine
2 3 4
17. 2(N-Methylamino)propanoic acid
18. N-Ethyl-N-methylaniline
19. 2-Methylpropanamide
20. But-2-en-1-al
2
21. C2 H5  C H  COOCH3 Trival Name : (Dimethyl)--ethylmalonate
| IUPAC Name: (Dimethyl)-2-ethylpropan-1, 3-
COOH3 dioate
3
22. Methylenecyclopentane

IN-CHAPTER EXERCISE-A
1. Give the dash structures of the following :
(i) Isobutyl radical (ii) Neopentyl radical
(iii) tert-Pentyl radical (iv) sec-Butyl radical
(v) tert-butyl radical (vi) Benzyl radical
2. Give IUPAC name of following :
CH3
|
(i)  CH 3 3 C  COOCH 3 (ii)  CH 3 2 CH  CH  CH  CH  CH 2
|
CH3
(iii) CH 3  CH  CH 2COOH (iv)  CH3 2 CH  C  CH3 2

| |
Cl OH
(v) CH 3  CH 2  CH 2  CH  C 2 H5 (vi) CH3  CH 2  C  CH 2CH3

| ||
COOH CH 2
CH3
|
(vii)  CH3 2 CH  CH  C  CH 2 (viii)  CH3 2 CH  CH  CH  CH3 2
| |
CH  CH3 2 N  CH3
|
CH3
C 2 H5
| CH
(ix) CH 3  C  C  C  CH3  2 (x) CH 3  CH 2  CH  CH  O  CH  CH3
| | 3
| |
CH3 CH 3
CH3 C 2 H5
3. Give the structure of following aromatic compounds :

(i) o-Cresol (ii) p-Toludine (iii) m-Toluic acid
(iv) Benzoyl chloride (v) Benzo phenome (vi) Aniline
(vii) Benzoic anhydride (viii) Acetophenone (ix) Phenol
(x) Terephthalic acid

4. Give IUPAC name of following :
(i) CH 3  C  CH3  2 CH 2  CH  CH3 (ii) H3C  CH 2  CH 2  C  CH 2

| |
CH3 C2 H5
(iii) CH 2  C  C  CH 2 (iv) CH3  CH  CH  C  CH3

| | ||
CH3 CH3 O
(v) H  COO  CH  CH3 (vi) CH 2  CHCH 2  C6H 5

|
CH3
NOW ATTEMPT IN-CHAPTER EXERCISE-A FOR REMAINING QUESTIONS

ISOMERISM IN ORGANIC COMPOUNDS Section - 4
Isomerism : The phenomenon of existence of two or more compounds possessing the same molecular
formula but different chemical and physical properties is known as isomerism. Such compounds are indi-
vidually referred to as isomers. For example : CH3CH2OH and CH3OCH3 are isomers of each other.
We have two types of isomerisms:
1. Structural Isomerism : There are also called as Constitutional Isomers.

2. Stereo Isomerism :
Types of isomerism :
Structural Isomerism :
In this type of isomerism, the compounds possessing same molecular formula differ in their properties due
to the difference in the linkages of atoms inside the molecule, i.e., due to the difference in their structure. For
example: CH3CH2OH and CH3OCH3. Both have the molecular formula C2H6O but they differ in their
structures (Ethanol has CCO linkage while Methoxymethane has COC linkage).
H H H H
| | | |
H  C  C O  H H  C O  C  H
| | | |
H H H H
Ethanol Methoxymethane

Structural isomers differ both in their physical as well as chemical properties.

Structural isomerism is classified into following six types.
1. Chain Isomerism : In this type of isomerism, the compounds possessing same molecular formula differ in
their properties due to the difference in the arrangement of carbon chain present in them. In one of them the
chain may be straight while in other the chain may be branched.
 Butane (C4H10) has two chain isomers :
CH3 – CH2 – CH2 – CH3 CH 3  C H  CH 3

|
CH3
n-Butane Isobutane
 Pentane (C5H12) has three chain isomers :

CH3
|
CH3CH2CH2CH2CH3 H3CH 2 C HCH3 CH3  C  CH3
| |
CH3 CH3
n-Pentane Isopentane Neopentane
 Butyl alcohol (Butanol) has a chain isomer :
CH3 – CH2 – CH2 – CH2OH CH 3  C H  CH 2OH

|
CH 3
n-Butyl alcohol Isobutyl alcohol
 1Butene has a chain isomer :
CH3 – CH2 – CH = CH2 CH3  C  CH 2

|
CH3
But-1-ene Isobutene
 Aromatic Compounds may also have chain isomers :
n-Propylbenzene Isopropylbenzene

2. Positional Isomerism : In this type of isomerism, the compounds possessing same molecular formula
differ in their properties due to the difference in the position of either the functional group or the multiple
bond or the branched chain attached to the main carbon chain. For example :
 Pentan-2-ol and Pentan-3-ol are the positional isomers :

CH3 – CH2 – CH2 – CH(OH) – CH3 CH3 – CH2 – CH(OH) – CH2 – CH3
Pentan-2-ol Pentan-3-ol
CH 3  CH 2  CH 2  C H 2
|
CH 2  OH
Pentan-1-ol
 Butene has two position isomers :

CH3 – CH2 – CH = CH2 CH3 – CH = CH – CH3
But-1-ene But-2-ene
 Methylpentane has position isomers :
CH 3  CH 2  CH 2  C H  CH3 CH 3  CH 2  C H  CH 2  CH3
| |
CH3 CH3
2-Methylpentane 3-Methylpentane
Note that the position isomers have same parent chain.
 In aromatic compounds, for example, in benzene ring three different positions are possible for a disubsti-
tuted product. They are 12 (called as ortho), 13 (called as meta), and 14 (called as para). Disubstituted
benzene has three positional isomers. For example :
 Cresol has three positional isomers.
3. Funct ional Isom erism : In this type of isomerism the compounds possessing same molecular formula
differ in their properties due to the difference in their functional group, i.e., the functional isomers differ in the
functional group present in them. For example :

 Alcohols (execept mehanol) have their isomeric ethers.

eg. Ethyl alcohol and Dimethyl ether having molecular formula of C2H6O are functional isomers :
CH3CH2OH H3COCH3
Ethanol Methoxymethane
 Aldehydes have isomeric ketones.

Propionaldehyde (Propanal) and Acetone (Propanone) are functional isomers:
CH3CH2CHO CH3COCH3
Propanal Propanone
Methanal, Ethanal, and Benzaldehyde have no isomeric ketones.

 An acid may be isomeric to an ester.
Propionic acid and Methyl acetate (Methyl ethanoate) are functional isomers:
CH3CH2COOH CH3COOCH3
Propanoic acid Methyl ethanoate
Only Methanoic acid cannot have its isomeric ester.

Note that sometimes an alkadiene may be isomeric with an alkyne. This is also called as functional isomer-
ism.
 Butyne is isomeric to Butadiene :
CH3  CH2 C  CH H2C = CH  CH = CH2
But-1-yne Buta-1, 3-diene
 Unsaturated alcohols are isomeric to Aldehydes :
H2C = CHOH CH3CHO
Vinyl Alcohol Acetaldehyde
 Unsaturated alcohols containing three or more carbon atoms are isomeric to Aldehydes as well as
Ketones :
CH2 = CH  CH2OH CH3CH2CHO CH3COCH3
Allyl alcohol Propionaldehyde Acetone

 Aromatic alcohols may be isomeric to Phenols :
 Primary, Secondary, and Tertiary amines of same molecular formula are functional isomers :
CH3CH2CH2NH2 CH3 NH C2H5 CH3  N  CH3

|
CH3
n-Propyl amine (1°) Ethyl methyl amine (2°) Trimethyl amine (3°)
4. Metamerism : In this type of isomerism the compounds possessing same molecular formula differ in their
properties due to the difference in alkyl groups present in them. Thus, the metamers differ only in the alkyl
groups present and they have same functional group, i.e., they belong to same homologous series. For
example :
 Diethyl ether (Ethoxyethane) and Methyl propyl ether (Methoxy propane) are the metamers :
C2H5  O  C2H5 CH3  O  C3H7
Ethoxy ethane Methoxy propane
 Diethylamine and Methylpropylamine are also the metamers :

C2H5  NH  C2H5 CH3  NH  C3H7
Diethyl amine Methyl propyl amine
 Metamers of 3 amines (C6H15N) :
C2 H 5  N  C 2 H 5 C3H 7  N  CH3 C 4H9  N  CH3

| | |
C 2 H5 C 2H 5 CH3
Triethyl amine Ethyl methyl propyl amine Dimethyl butyl amine
 Esters also show metamerism, n-Propyl formate has Ethyl acetate and Methyl propionate as its metamers.
HCOOC3H7 CH3COOC2H 5 CH3CH2COOCH3
n-Propyl formate Ethyl acetate Methyl propionate

5. Tautomerism : This is a special case of functional isomerism. In this type of isomerism two functional
isomers exist together in equilibrium. The two forms existing in equilibrium are called as tautomers. For
example :
 Consider tautomerism in Acetaldehyde (keto group) and Vinyl alcohol (enol group).
 H C = CHOH
CH3CHO  2
Acetaldehyde Vinyl alcohol
Out of the two tautomeric forms, generally the keto form is more stable and exists in larger proportion. The
equilibrium between the two forms is dynamic, i.e., if one form is somehow removed by a reaction, some of
the amount of the other form changes into the first form so that similar equilibrium exists again.
Due to the presence of keto and enol form this type of tautomerism is known as ketoenol tautomerism. It
is the most commonly observed type of tautomerism.
The keto-enol tautomerism is possible only in those Ketones and Aldehydes in which at least one -
hydrogen atom is present so that it may convert the carbonyl group to enol group.
 Consider the compound Acetone, it has two tautomers, one has a keto group and other has an enol group.
O OH
||  ||
 CH3  C  CH 2
CH3  C  C H3 
keto  form Enol  form
 Another example of ketoenol tautomerism is observed in 2-Butanone. It has two nol forms :
OH O OH
|  ||  |

CH 2  C  CH 2  CH3   H 3C  C  CH 2  CH3
H3 C  C C H 2  CH3 
Hence It is observed that (as above), if the -hydrogen atoms are present on both the carbons attached to
carbonyl group, it can have more than one enol. Thus, larger the number of different -hydrogens in a
ketone, more is the number of enols . In most of the cases, the keto form is more stable than the enol by
some 45-60 kJ/mol (11-14 kcal/mol). The main reason for this difference is that a carbon-oxygen double
bond is stronger than a carbon-carbon double bond.
Stabilized Enols :
Certain structural features can make the keto-enol equilibrium more favourable by stabilizing the enol form
such as extended conjugation, intramolecular H-bonding and aromatic characters etc.

The enol form is phenol, and the stabilization gained by forming an aromatic ring is more than enough to
overcome the normal preference for the keto form.
The 1, 3- arrangement of two carbonyl groups in -diketones leads to a situation in which the keto and the
enol forms are of comparable stability.
6. Ring chain isomerism : Compounds having the same molecular formula but possessing open chain and
cyclic structures are called ring chain isomers and the phenomenon is called ring chain isomerism. For
example:
 Alkenes are isomeric with Cycloalkanes :
CH 3CH = CH2
Propene
CH3CH2CH = CH2
But-1-ene
 Alkynes and Alkadienes are isomeric with Cycloalkenes :

CH3CH2C  CH CH2 = CH  CH = CH2
But-1-yne Buta-1, 3-diene

Stereo-isomerism :
The stereoisomerism is defined as the type of isomerism in which compounds possessing same molecular
formula and same structural formula, differ in their properties due to the difference in the arrangement in
space of their atoms in the molecule. Stereoisomers usually differ in some of their physical properties but
they may not differe much in their chemical properties.
In order to understand stereoisomerism, we need to familiarize ourselves with the following concepts.
Chirality
A molecule or any other object that cannot be superimposed onto its mirror image is said to be chiral, and
the phenomenon is known as chirality. Chirality arises from asymmetry in a molecule.
Objects and molecules that are super-imposable on their mirror images are achiral.
A test for chirality is to look for a plane of symmetry in the molecule. If there exists such a plane of symmetry
that divides the molecule into two identical halves, then such a molecule is achiral.
for e.g. n-butane is achiral while 2-chlorobutane is chiral.
CH3  CH  CH 2  CH3
|
Cl
Plane of symmety No plane of symmetry

n-Butane - ACHIRAL 2-Chlorobutane - CHILAR

Stereocentre-An-Asymmetric Carbon
A sp3 hybridised carbon atom that is bonded to four different substituents or groups (including hydrogen) is
a stereocentre.
;* stereocentre or chiral centre]
For example, consider Lactic acid (2-Hydroxy propanoic acid):
A molecule with only one stereocentre will be chiral, because such a molecule does not posses a plane of
symmetry and hence is non-super imposable on its mirror image.
Note: Molecules containing more than one stererocentre may or may not exhibit chirality depending on whether
they have a plane of symmetry and are superimposable on their mirror images or not.
Plane Polarized Light

Light is an electromagnetic wave, with oscillating electric and magnetic fields.
If we were to view a beam of ordinary light from one end, and if we could actually see the planes in which
the electrical oscillations were occuring, we would find that oscillations of the electric field were occuring in
all possible-planes, perpendicular to the direction of propagation. (The same would be true for magnetic
field)
Oscillations of the electric field of ordinary light occur in all possible planes,
perpendicular to the direction of propagation [Note that the direction of
propagation is perpendicular to the plane of paper].
When ordinary light is passed through a polarizer like Nicole prism, the light
that emerges from the polarizer is oscillating only in one plane. Such light is
called plane-polarized light. In the given figure, the plane of oscillation of the
electric field of plane-polarized light is vertical.

Optical Activity
It is found that some compounds have a tendency to rotate the plane of plane-polarised light i.e., when any
such compound is placed in the path of plane - polarised light, the compound rotates the plane of this light
by a certain angle. Such a rotation is known as optical rotation and the phenomenon is called as Optical
activity.
This optical rotation may be clockwise (+) or anti-clockwise (-). The molecules rotating the plane in clockwise
direction are termed as dextro-rotatory (d) or (+), while the molecules rotating the plane in anti-clockwise
direction are termed as laevo-rotatory (l) or (-). The instrument used to measure optical rotation is called as
Polarimeter.
Optical activity is a characteristic of chiral molecules only. We know that a chiral molecule is one that cannot
be superimposed on its mirror image. Such a molecule and its non-super imposable mirror image form a pair
of enantiomers.
Enantiomers rotate the plane of plane polarized light to the same extent but in opposite direction. i.e., one of
them is dextro-rotatory and the other is laevo-rotatory.
Consider 2-Chlorobutane, CH3-CH(Cl)-CH2CH3.
Whether a compound is dextro-rotatory or laevo-rotatory can only be determined experimently, and not by
merely looking at the 3-D structure of compound.
Another very common example is of Lactic Acid, CH3-CH(OH)-COOH.
Note: Any dissymmetric compound having non-superimposable mirror image is optically active compound.

Racemic mixture
An equimolecular mixture of (+) and () (i.e., d and l) forms of an optically active compound is not able
to rotate the plane of plane - polarised light because of the mutual cancellation. Such a mixture is known as
a racemic mixture or dl mixture or () mixture and is optically inactive. The phenomenon is called as
reacemisation. Thus, lactic acid can be said to be of three types, i.e. (+) lactic acid, () lactic acid, and ()
lactic acid.
Note:  Representation of a molecule in tetrahedral three dimensional shapes is a

little bit difficult. A simplified way to represent such molecules on plane of
paper is by using the Fischer projection formula. In a Fischer projection
formula, (+) lactic acid is represented as:
 Fischer projection formula can’t be rotated by 90o and can’t be lifted from
the plane of the paper.
The chiral carbon atom is represented by a point of intersection of a horizontal and a vertical line. Atoms or
groups attached with horizontal line are supposed to be coming forward above the plane of paper (i.e.,
towards the viewer) while the groups attached with vertical line are going back behind the plane of paper
(away from the viewer). Thus, the two enantiomers of lactic acid are represented as follows :
Compounds Containing Two Stereocentres

A useful rule gives the maximum number of stereoisomers of a compound. Total number of stereoisomers =
2n (only configurational), where n = number of stereocentres in the molecule. So, a molecule with 2
stereocentres can have a maximum of 22 = 4 stereoisomeric forms.
* *
Consider 2, 3-Dibromopentane, CH 3  CH  CH  CH 2CH3 has 4 stereoisomers as shown below..
| |
Br Br

 Enantiomers are non-super imposable mirror images.

 Diastereomers are non-super imposable non-mirror images.
Note that the pairs I & II and III & IV form pairs of Enantiomers (Optical Isomers).
And pairs I and III and I and IV and II and III etc. form pairs of diastereomers.
Meso Compounds and Diastereomers

A structure with two stereocentres does not always have four possible stereoisomers. Sometimes, there are
only three. Thiss happens because some molecules are achiral even though they contain stereocentres. To
understand this, let us consider the example of tartaric acid:
HOOC-CH(OH)-CH(OH)-COOH
Tartaric Acid has only three stereomers.
I and II are non-superimposable mirror images of each other (ENANTIOMERS).

If we look at structure III, it also has 2 stereocentres. But we can also note the presence of a plane of
symmetry in it. As described earlier, such a molecule is achiral, despite the presence of 2 stereocentres, and
it shall be imposable on its mirror image. Such an isomer, which has stereocentres, but the molecule is
overall Achiral is called a meso-isomer.
Note: Observe that in the case of 2, 3-Dibromopentane (above), there is no plane of symmetry in either of
stereomers.
Note: (i) The meso compound and its mirror image both represent a single configuration (i.e., one isomer)
(ii) The meso-isomer is optically inactive (achiral). In the meso-isomer, half part of the molecule gives
clockwise while the other half gives anti-clockwise rotation (due to a plane of symmetry), and thus,
because of internal compensation, the molecule is optically inactive. While the racemic mixture is not
able to show optical rotation because of external compensation, the meso form is not able to show
any rotation because of internal compensation.
(iii) The meso-tartaric acid is not the enantiomer of either I or II forms. The molecules (configurations)
which are not mirror images of one another are called diastereomers. The meso-tartaric acid is a
diastereomer of I and II forms of tartaric acid.

Geometrical Isomerism :
Consider the compound, 2-Buten-1, 4-dioic acid, HOOC CH = CH COOH. This compound can be
expressed in two different forms as follows:
Since free rotation about C = C Pi () bond is not allowed, these two geometries are non-inter convertible
and different. These are geometrical isomers of each other.
In Maleic acid, both  COOH groups are attached in the same direction, while in Fumaric acid, the two
 COOH groups are attached in opposite direction. The geometrical isomer in which the similar groups are
present in same direction (on the same side of double bond) is called as the cis isomer, while the one in
which similar groups are in opposite direction is called as the trans isomer. Geometrical isomerism is also
known as cistrans isomerism. Maleic acid is a cis isomer while Fumaric acid is the trans isomer.
 2Butene also exhibits geometrical isomerism :
 1, 2-Dichloroethene is another example of geometrical isomerism :
 Note that an organic compound having a bond may or may not show geometrical
isomerism.
If two similar groups (or atoms) are attached to same carbon atom(forming a double bond) in a
compound, then it does not show geometrical isomerism.
An organic compound having can have the following different forms :
I. cis-isomer trans-isomer

II. cis-isomer trans-isomer
Such compounds show geometrical isomerism and we can classify them as having cis and trans forms.
III.
Such compounds where 2 similar groups are attached to one carbon atom, do not show geometrical
isomerism.
Important Alkenes which do not show geometrical isomerism include Ethene (CH2= CH2), Propene (CH3CH
= CH2), 1-Butene(C2H5CH = CH2), Isobutene (Me2C = CH2) and Styrene(C6H5CH = CH2).
IV.
Such a pair of compound are geometrical isomers, but cannot be classified as cis-trans.
Note : cis form is comparatively less stable because of the mutual repulsion between the groups. Thus, Maleic acid
is less stable than Fumaric acid. Geometrical isomers differ in their physical properties and also in some of
their chemical properties. The trans form, being symmetrical has a zero dipole moment. Even in the cases
when the trans form is not symmetrical, it has a low dipole moment in comparison to the cis form. Since the
trans form is less polar, it is less soluble in water.
Also, being polar the cis isomer has comparatively higher boiling point. However, melting point of trans
isomer is higher because of better packing in crystal due to symmetry in molecule. Besides, the cis isomer
has higher heat of hydrogenation, heat of combustion, density, and refractive index. Accordingly, Fumaric
acid has higher melting point and is very sparingly soluble in water in comparison to Maleic acid.
Geometrical Isomerism in Cyclic Compounds :

In cyclic compounds the rotation about a C–C single bond is not free because of the rigidity caused by the
presence of other carbons of the ring which keep them tightly held. Thus, a disubstituted cyclic compound
(having the two substitutions at separate carbons) will exist as geometrical isomers. For example, consider
1, 2-Dimethylcyclopentane:

Other examples of Cycloalkanes and their derivatives showing Geometric Isomerism are illustrated below :
Conformational Isomerism :
Conformations are different spatial arrangements of a molecule that are generated by rotation about single
bonds. Conformational analysis is the study of how conformational factors affect the structure of a molecule
and its physical and chemical properties.
I. Conformational analysis of Ethane: Ethane is the simplest hydrocarbon that can have distinct
conformations. These two conformations are the staggered conformation and the eclipsed conformation.
In the staggered conformation, each C H bond of one carbon bisects an H C H angle of the
other carbon.
Some commonly used drawing of the staggered conformation of ethane.
In the eclipsed conformation, each C H bond of one carbon is aligned with a C H bond of the
other carbon. Some commonly used drawings of the eclipsed conformation of ethane.

Note: In a Newman projection (figure C), we sight down the C C bond, and represent the front carbon by a
point and the back carbon by a circle. Each carbon has three other bonds that are placed symmetrically
around it.
The structural feature that above mentioned figure illustrate is the spatial relationship between atoms on
adjacent carbons. Each H-C-C-H unit in ethane is characterized by a torsion angle or dihedral angle, which
is the angle between the H-C-C plane and the C-C-H plane. The dihedral angle is easily seen in a Newman
projection of ethane as the angle between C-H bonds of adjacent carbons.
Note: The staggered conformations have only gauche or anti-relationship between bonds on adjacent atoms. The
staggered and eclipsed conformation inter convert by rotation around the C-C bond, and do so very rapidly.
Note: Different conformations of the same compound are sometimes called conformers or rotamers. Of the two
conformations of ethane, the staggered is 12kJ/mol more stable than the eclipsed. The staggered conformation
is most stable conformations; the eclipsed is the least stable conformation.
Conformations in which the dihedral angle between adjacent bonds are other than 60o are said to have
torsional strain. Eclipsed bonds produce the most torsional strain; staggered bonds none.
Note: In principle ethane has an infinite number of conformations that differ by only tiny increments in their dihedral
angle. Not only is the staggered conformation more stable than the eclipsed, it is the most stable of all of the
conformations; the eclipsed is the least stable.

Figure: Potential energy diagram for rotation about the carbon-carbon bond in ethane
II. Conformational Analysis of Butane :

We consider conformations related by rotation about the bond between the middle two carbon (CH3CH2-
CH2CH3). Butane has four main conformations [two eclipsed type and two staggered type].
Unlike ethane, in which the staggered conformations are equivalent, two different staggared conformations
occur in butane.
The gauche conformation and anti-conformation both are staggered, so are free of torsional strain, but two
of the methyl hydrogens of the gauche conformations lie within 210 pm of each other. This distance is less
than the sum of their van der Waals radii (240 pm), and there is a repulsive force between them. The
destabilization of a molecule that results when two of its atoms are two close to each other is called van der
Waals strain, or steric hinderance and contributes to the total steric strain.

In the case of butane, van der Waals strain

makes t he gauche co nformation
approximately 0.8 kcal/mol less stable than
the anti.
Note: For ethane-1, 2-diol(ethylene glycol HO-CH2-

CH2-OH) gauche conformation is more stable than the
anti-conformation because of H-bonding in gauche
conformation.
III. Conformations of Higher alkanes:

Higher alkanes having unbranched carbon chain are, like butane, most stable in their all-anti conformations.
In depicting the conformations of higher alkanes it is often more helpful to look at them from the side rather
than end-on as in Newman projection. Viewed from this perspective, the most stable conformations of
pentane and hexane have their carbon “backbones” arranged in a zig-zag fashion as shown in the figure. All
the bonds are staggered, and the chain are characterized by anti-arrangement of C-C-C-C units.

Illustration - 4 Of the three conformations of propane shown, which one is the most stable? Which one is
the least stable? Why?
(A) (B) (C)
SOLUTION :
Conformation (A) is the most stable ; all its bonds are staggered. Conformation (C) is the least stable ; all its
bonds are eclipsed.
Illustration - 5 Sight down the C-2-C-3 bond, and draw Newman projection formulas for the :
(a) Most stable conformation of 2, 2-dimethyl butane.
(b) Two most stable conformations of 2-methyl butane.
(c) Two most stable conformations of 2, 3-dimethyl butane.
(d) One of the two staggered conformations of 2-methyl butane is more stable than the other. Which one
is more stable? Why?
SOLUTION :
(a) First write out the structural formula of 2, 2-dimethyl

butane in order to identify the substituent groups attached
to C-2 and C-3.
As shown in above structure C-2 bears three methyl groups, and C-3 bears two hydrogens and a
methyl group. The most stable conformation is the staggered one as shown below. All other staggered
conformations are equivalent to this one.

(b) The constitution of 2-methylbutane and its two most stable conformations are shown.
Both conformations are staggered. In one Newman projection (X), the methyl group at the back is
gauche to the two methyl groups in the front. In the other (Y), it is gauche to one and anti to the other.
(c) The hydrogen at C-2 and C-3 may be gauche to one another (P), or they may be anti (Q).
(d) The 2-methylbutane conformation with one gauche CH3.....CH3 and one anti CH3....CH3 relationship
is more stable than the one with two gauche CH3.....CH3 relationships. The more stable conformation
has less van der Waals strain.

Illustration - 6 Determine whether the two/three structures in each of the following pairs represent
constitutional (structural) isomers or different conformations of the same compound.
(a)
(b)
(c)
SOLUTION:
(a) By rewriting the structures in a form that shows the order of their atomic connections, it is apparent
that the two structures are constitutional (structural) isomers.
(b) Two compounds have the same constitution (structure); both are (CH3)2CHCH(CH3)2. The
Newman projections represent different staggered conformations of the same molecule ; in one the
hydrogens are anti to each other whereas in the other they are gauche. Both are different
conformations of 2, 3-dimethylbutane.

(c) I and II are constitutional isomers.

II and III are two Newman’s projection formula of
the same compound 3-Ethyl-2-methylpentane hence
these are same. II is Newman’s projection formula
about C-3-C-4 bond while III is Newman’s
projection formula about C-2-C-3 bond.
Illustration - 7 Write a structural formula for the most stable conformation of 2, 2, 5, 5-tetramethyl hexane
using Newman’s projection of conformation about C-3- C-4 bond.
SOLUTION :
The structural formula of compound is (CH3)3CCH2CH2C(CH3)3. Both
C-3 and C-4 have two hydrogens and a tert-butyl groups attached. The
most stable conformation has the large tert-butyl groups anti to each
other.
Illustration - 8 (a) Write Newman projections for the gauche and anti conformations of 1, 2-dichloro
ethane (Cl-CH2CH2-Cl).
(b) The measured dipole moment of ClCH2CH2Cl is 1.12 D. Which one of the following statements about
1, 2-dichloroethane is false?
(i) It may exist entirely in the anti-conformation
(ii) It may exist entirely in the gauche conformation.
(ii) It may exist as a mixture of anti and gauche conformations.

SOLUTION:
(a) The dihedral angle between chlorine substituents is 60o in
the gauche conformation and 180o in the anti conformation
of Cl-CH2-CH2-Cl.
(b) All the individual bond dipole moments cancel in the anti conformation of Cl-CH2-CH2-Cl, and this conformation
has no dipole moment. Because ClCH2CH2Cl has a dipole moment of 1.12 D, it can exist entirely in the
gauche conformation or it can be a mixture of anti and gauche conformations, but it cannot exist entirely in the
anti conformation. Statement I is false.
Conformers of Cyclohexane:
The cyclic compounds most commonly found in nature contain six-membered rings because carbon rings of
that size can exist in a conformation-called a chair conformer-that is almost completely free of strain.
Cyclohexane can also exist as a boat conformer, shown in figure like the chair conformer, the boat conformer
is free of strain. However, the boat conformer is not as stable because some of the bonds are eclipsed.
Order of Stability : Chair form > Twisted boat > Boat > Half chair.

1. Write structural formulae for each of the following :

(i) Three primary alcohols and one tertiary alcohol with the formula C4H8O
(ii) A secondary alcohol with the formula C3H6O
(iii) A cyclic ester with the formula C4H4O4
(iv) Two unsaturated dibasic acids with formula C4H4O4
2. Write all the isomers of the formula C5H10O2 and the select pair of one type of isomers.
3. Make tautomer of :
4. Write structure that correspond to the following description :

(i) four esters with the formula C4H8O2 (ii) Two aldehydes with the formula C4H8O
(iii) three ketones with the formula C5H10O (iv) a tertiary amine with the formula C4H11N

RESONANCE & AROMATICITY Section - 5
Resonance
When a molecule or ion can be represented by two or more structures which have the same arrangement of
atomic nuclei but differe in distribution of electrons, the phenomenon is called as Resonance. The various
structures are called contributing or resonating structures. None of these structures truly represents all
the properties fo that molecule or ion. The actual struture is a resonance hybrid of several contributing
structures.
It generally occurs when there is a conjugation of -bonds(alternate double-single-double bond arrangement)
known as conjugated system. It also takes place when there is double bond (C = C or C = O) alongwith
a group (G) present in the carbon chain having a lone pair.
Consider resonance in 1, 3-Butadiene (having a conjugated system):
 -electrons moves from first carbon atom to last carbon atom resulting in different structure.
Note that the relative atomic arrangement of four carbon atoms is same in both the structures (I)
and (II).
Resonance hybrid (actual structure) of butadiene is represented as follows (in square brackets) :
 Consider resonance in Benzene (C6H6) :
 Consider resonance in Vinyl Chloride : Observe that group having a lone pair i.e., Cl is in
conjugation with double (C = C).
The various resonating structures of chlororbenzene, aniline and nitrobenzene are illustrated in
following diagrams.


Rules for Resonance

1. No real existance of Resonance structures: Although the resonating structures have no real existence
of their own, these structures are useful because they allow us to describe molecules and ions for which a
single Lewis structure is inadequate. We write two or more Lewis structures, calling them resonating structures
or contributing structures. We connect these structures by double-headed arrows () , and we say that
the real molecule or ion is a hybrid of all of them.
2. While writing Resonance structures we are only allowed to move electrons: The relative positions
of the nuclie of the atoms must remains the same in all of the structures. Structure III is not a resonance
structure of I or II, in the given example, because in order to form it, we would have to move a hydrogen
atom and this is not permited :

Actually speaking, when we move electrons, we move only those of  bonds(as in the example above) and
those of non-bonding pairs (such as lone pairs).
3. All of the structures must be proper Lewis structures : We should not write structure in which carbon
has five bonds, for example:
This is not a proper resonance structure for methanol because carbon

has five bonds. Elements of the First major row of the periodic table
cannot have more than eight electrons in their valence shell.
4. Resonance Stabilisation: The energy of the actual molecule (Resonance hybrid) is lower than the energy
of any one of all the contributing structures. Hence the resonance hybrid is more stable form.
5. The more stable a structure is, the greater is its contribution to the hybrid.
For example, benzene is highly resonance stabilized because it is hybrid of the two equivalent forms that are
highly stable.
6. The following rules will help us in making decisions about the relative stabilities of resonance structures.
(a) The more covalent bonds a structure has, the more stable it is : This is because a covalent
bond lowers the energy of atoms. This means that out of the following two structures for 1, 3-
Butadiene, I is the most stable and hence imparts greater contribution to the stability of resonance
hybrid.
(b) Structure in which all of the atoms have a complete valence shell of electrons are especially
stable and make large contributions to the hybrid : In the following example, the structure II
makes a larger stabilizing contribution to the cation than the structure I because all of the atoms of
structure II have a complete valence shell.

Also note that structure II has more covalent bonds than structure I.
On the same pattern the structure II of the acyl carbonium ion is more stable than I
(c) Charge separation decreases stability : Separating opposite charges requires energy, hence the
structures in which opposite charges are separated have greater energy (lower stability) than those
that have no charge separation. This means that of the following two structures for vinyl chloride,
structure I makes a larger contribution because it does not have charge separation (This does not
mean that structure II does not contribute to the hybrid ; it just means that the contribution made by II
is smaller).
(d) Resonance contributors with negative charge on highly electronegative atoms are more
stable than ones with negative charge on less or nonelectronegative atoms : Conversly,
resonance contributors with positive charge on highly electronegative atoms are less stable than ones
with positive charge on nonelectronegative atoms.
 Observe the rules (c) and (d) above are illustrated beautifully in the following illustration:
Weakly stabilised by Resonance
Strongly stabilised by Resonance
Carboxylic acids (RCOOH) are less stable than carboxylate ions (RCOO-) because in carboxylic acids,
there is charge separatioin in one of the resonating structure.
Structures where formal charges don’t suit the electronegativity of the atom on which they rest, are less
stable e.g., consider the resonating structure of phenol.

Structure (i) and (ii) are more stable than the others. These are also known as kekule Structures.
Structures (iii), (iv) and (v) are less stable due to:
(a) charge separation (b) +ve charge over Oxygen atom
Illustration - 9 In each of the following pairs showing resonating structures, identify which is more stable
and why?
(A) (B)
(C) (D)
SOLUTION :
(A) I is more stable than II, because in II, the formal charge (-) is on carbon atom which does not suit
its electronegativity.
(B) II is more stable than I. In II, all atoms (except H-atom) have an octet, whereas in I, carbon has
sixet (incomplete octet).
(C) I is more stable than II, since in I all have complete octets.
(D) II is more stable than I because in the former, all the atoms have complete octet.
Aromatic , Anti-aromatic and Not Aromatic

Among planar, monocyclic, fully conjugated polyenes, only those possessing (4n + 2)electrons, where n
is a whole number, will have special stability ; that is, be aromatic.

Condition for a compound to be :

(i) Aromatic : Cyclic, Planar, Complete Conjugation, (4n + 2)e-s (n = 0, 1, 2,...)
(ii) Anti-aromatic : Cyclic, Planar, Complete Conjugation, 4n e-s ( n = 1, 2, ....)
(iii) Not-aromatic : Not cyclic OR Not Planar OR Not Completely Conjugated.
What is Complete Conjugation? Alternate single and double bonds. In other words, every Carbon has to be
sp2 hybridised.
Examples :
(a) : Cyclic, Planar but not completely conjugated. Carbon-(1) is sp3

hybridised.
 Compound is "Not aromatic"
(b) : Cyclic, Planar, Completely Conjugated. Carbon-(1) is sp2

hybridised as it is clear from its resonating structures
Now count the number of e-s in the compound as per the following rules:
(i) Each ‘=’ bond is counted as 2e-s (ii) Count the number of lone pairs.
Singly Bonded: Count as 2e-s
=1 : Check bonding of
atom with lone pair
If the number of lone pairs is: Doubly Bonded: Do not count
>1 : Count them as exactly one lone pair and
go back to the above condition corresponding
to 1 lone pair.
Number of e-s = 4(From 2 doouble bonds) + 2(one lone pair at C-1 and is single bonded)
= 6e-s  Compound is “ Aromatic”

(c) : Cyclic, Planar, Completely Conjugated (See Resonating Structure)

However, in anti-aromatic species delocation of  -electron does not
take place. i.e., they have conjugation but no delocalisation.
Now, count the number of p e-s : 4 (From 2 double bonds)
 Compound is “Anti-aromatic”
(d) : Cyclic, Planar, Completely Conjugated.

Now, count number of e-s : 2 (From I double bond)
 Compound is “Aromatic”
Note : Cyclopropenyl cation is smallest aromatic species.
(e) Pyridine : (C5H5N) :

Cyclic, Planar, Completely Conjugated.
6e-s (From 3 double bonds)
Note : ‘N’ has 1 lone pair and is doubly
bonded.
So, this will not be counted.
(f) Pyrrole : C4H4NH

4e-s (From 2 double bonds) + 2e-
s(From 1 lone pair)
Note : ‘N’ has 1 lone pair and is singly
bonded.
(g) Furan :
Number of e-s
= 4( From 2 double bonds) + 2(From 1
lone pair)

Note : ‘O’ has 2 lone pairs.Count only one lone pair.

(h) Cyclic, Planar, Completely Conjugated

Number of e-s = 2(From 1 double bond) + 2(From 1 lone pair) = 4
 Compound is “Anti-aromatic”
(i) Cyclic, Planar, Not Completely Conjugated.

 Compound is “Not Aromatic”
(j) Cyclic, Completely Conjugated.

Number of e-s = 6 (From 3 double bonds)
(k) Cyclo-Octateraene : Note: It has a tub shape structure

Cyclic, “Not Planar”, Completely Conjugated.
 Compound is “Not Aromatic”
(l) : Cyclic, Planar, Completely Conjugated.

Number of e-s = 4(From 2 double bonds)  Compound is “Anti-Aromatic”
 If a compound is Anti-aromatic, it is less stable than its open chain counter part i.e.,  electrons
conjugation adds de-stability to the compound, if it is anti-aromatic.
 If a compound is aromatic, it adds stability to the compound through  electrons delocalisation.
Note : There are thousands of aromatic compounds that are not monocyclic such as naphthalene, azzulene,
anthracene etc. are polycyclic aromatic hydrocarbons.

ORGANIC REACTIONS [BASICS] Section - 6

Organic compounds are covalent bonded. The carbon atom in these may be sp3, sp2 or sp hybridised.
Hydrocarbons are almost non-polar, but their derivatives containing functional group are polar covalent
compounds. To understand and visualise the mechanisms of organic reactions, first we must go into details
of various types of electrical effects that monitor the properties of various organic compounds. Then we
have to understand various types of Substrates (main organic compound) ; Intermediates formed from these
substrates ; the various types of Reagents and the Medium(solvent) in which organic reactions occur.
All organic reations can be classified into one of the following three categories for the purpose of understanding
reaction mechanisms :
(i) Substitution Reactions (ii) Addition Reactions (iii) Elimination Reactions
Above three categories of reactions may involve : Rearrangement, Cyclissation (Ring opening & Ring closing)
and stereo specific changes (involving optical and geometrical isomers), oxidation and reduction.
1. Substrate : It is the main organic compound acting as reactant and reacts with a reagent to give an new
organic compound as main product. Substrates in general are of two types :
Nucleophilic: The organic compounds which have “electron rich centre or area” are referred to as
nucleophilic in nature. They are acted upon by electron seeking reagents.
Alkenes, alkynes and benzene and its derivatives are some of such important substrates.
Electrophilic : The organic compounds which have “electron definicient centre or area” are referred to as
Electrophilic in nature. They are acted upon by electron rich reagents usually most of organic derivatives
containing functional groups act as electrophilic substrates. Organic Halides, Alcohols, Ethers, Aldehydes &
Ketones and Carboxylic Acids & Derivatives are some of the important electrophilic substrates.
 
Electrophilic centre  C  G
2. Reagents : Based on the attack by the type of attacking reagent, these are further categorised.
The main type of attacking reagents are:

(a) Nucleophile: Electron rich species, looking to attack a +vely charged centre (Electrophilic
substrate).These are classified as follows:
Charged : H  , OH  , RO  , CH 3 , X  , HS .......etc.
Neutral : Covalent compounds in which central atom has complete octet, has atleast one lone pair.

Ambident : Species having two nucleophilic centres, one is neutral (complete octet and has atleast
one lone pair of electrons) and other is charged (negative charge). They basically have
two nucleophilic sites / atoms.
(b) Electrophiles : Electron deficient species, looking to attack an electron rich site (Nucleophilic
substrate). These are classified as follows:
Charged : H+, X+, R+, .......etc, (X : Halogens except flourine)
Neutral : CO2, AlCl3, CS2 . . . . . . .etc.

(c) Free radicals : Atom or group of atoms with their valencies unsatisfied, looking to attack a place so
that they can satisfy their valencies. e.g., (alkyl)
3. Reaction Mechanism :
It gives detailed aspect of as to “How actually an organic reaction proceeds”. It depicts step-by-step
visualisation of an organic reaction.
Organic reactions always involve breaking and reforming of covalent bonds. A covalent bond can break
into two ways; In one of the ways, one of the fragments takes away the bonded electron pair (Heterolytic
cleavage) and in other, each fragment takes away one of the electrons of bond (Homolytic cleavage).
Such fragments are known as Reaction intermediates such as; C+ (carbocations), C-(carbanions) and C
free radicals).
I. Homolytic Fission:
Such type of fission occurs in gas phase or in non-polar solvents (i.e., absence of polarising solvents)
and is catalysed by free radical initiators. In such fission, free radicals are formed. Here the bond pair
is equally shared after the fission.
II. Heterolytic fission :

Such type of fission occurs in polarising solvents (such as H2O, alcohols and acids), catalysed by
acids or bases, greatly influenced by polarity of solvents. Here, the ions are formed. In an organic
compound such as R-G, two types of ions are formed.
(a) (R+ is known as carbocation)
(b) (R- is known as carbanion)

4. Electrical Effects:
For the detailed analysis of Reaction Mechanism, we have to first understand “Electrical Effects” existing in
the Organic Substrate and induced by External Reagents.
There are four kinds of Electrical Effects to be studied for the understanding of Reaction Mechanism.
I. Inductive Effect II. Resonance (Mesomeric ) Effect
III. Electromeric Effect IV. Hyperconjugation Effect
I. Inductive Effect (Polar nature of covalent bonds):

The displacement of an electron (shared) cloud along the carbon atom chain due to the presence of an
electron withdrawing (electron attracting) or electron realeasing (electron repelling) groups in the
carbon chain is known as Inductive Effect (I-effect).
 It is a permanent effect which is transmitted along the carbon-carbon chain.

(G : functional group)
But the effect is insignificant beyond teh third carbon atom.
 Any atom or group which attracts electrons more strongly than hydrogen is said to exert a negative
effect (-I effect) ; an atom or group which attracts electrons less strongly than hydrogen is said to exert
a positive inductive effect (+I effect).
Group producing -I effect : (All functional groups)

-NO2 > - CN  - SO3H > - CHO > - COOH > - F > - Cl > - Br > - I > - OH > - OR > - NH2
> HC  C - > CH2 = CH - > -C6H5 > - H
Note: (i) Alkynyl, vinyl and phenyl groups, because of sp and sp2 hybrid carbon atom exert weak-I effect.
Carbon atoms which are sp and sp2 hybridised are electronegative in character due to dominance of
‘s’ character over ‘p’ character. [50% ‘s’ character in ‘sp’ and 33% ‘s’ character in sp2 hybrid
carbon]
(ii) All such groups are called as Electron Withdrawing Groups (EWG).
Groups producing +I effect : (Only alkyl groups)

H - < D - < CH3 - < CH3CH2 - < CH3CH2CH2 - < (CH3)2CH - < (CH3)3C-
(1o) (1o) (2o) (3o)

Groups producing +I effect : (Only alkyl groups)

H - < D - < CH3 - < CH3CH2 - < CH3CH2CH2 - < (CH3)2CH - < (CH3)3C-
(1o) (1o) (2o) (3o)
Note: (i) All alkyl and cycloalkyl groups because of sp3 hybrid carbon atom exert +I effect. An sp3 hybrid
carbon atom is an electron releasing (donating) due to dominance of ‘p’ character over ‘s’ character.
[75% p character]
(ii) All these alkyl groups are called as: Electron Releasing Groups (ERG) or Electron Donating Group
(EDG).
II. Resonance (or Mesomeric) Effect:

When a molecule or ion can be represented by two or more structures which have the same arrangement
of atomic nuclei but differ in distribution of electrons, the phenomenon is called as Resonance. The
various structures are called contributing or resonating structures. None of these structures truly
represents all the properties of that molecule or ion. The actual structure is a resonance hybrid of
several contributing structures.
When multiple bonding is in conjugation with a functional group (G), then as per the electronic movement,
we can visualise resonance in two ways illustrated below.
+M effect (+R -effect) : When the movement of electrons starts from a particular group (G) towards the
carbon chain (C = C).
It takes place when group (G) has a lone pair or an extra electron (in an anion).

-M effect (-R-effect) : When the movement of electrons takes place towards a particular group (G) from
carbon chain (C = C).
or where G can be : -NO2, -C = O, -CN, -SO3H etc.
Note: In general, in the groups showing (-R/-M) effect, the

“attached atom” of the group is unsaturated with a more
electronegative atom e.g.
III. Electromeric Effect:

It is a temporary polarising effect and operates only in molecules having -electrons (i.e., multiple
bonded compounds) induced by the attacking reagents (nucleophiles & electrophiles) in a chemical
reaction.
 In presence of electrophiles (E+), -electrons shift to other carbon to make adjustment for the incoming
electrophile to be added.
Observe that E+ (electrophile) adds to the atom(group) where electrons are transferred. Such effect
is known as +E effect., when the transfer of electrons takes place towards the attacking reagent.

 In polar bonds, in presence of attacking reagents, a complete transfer of electron (one of e- pair) to
more electronegative atom takes place, e.g., in in presence of nucleophiles like R-, CN-,
HSO3-,  electrons shifts over to O.
Observe that CN- (nucleophile) adds to the atom (group) from where electrons are transferred. Such
effect is known as -E effect i.e., when the transfer of electrons takes place away from the attacking
reagent.
IV. Hyperconjunction Effect:
‘Baker and Nathan’ obeserved that alkyl groups (R) with at least one hydrogen (H) atom on the -
carbon, attached to an unsaturated carbon atom (i.e., having a -C = C - bond), or positive charge (as
in carbocation, C+) or odd electrons (as in free radicals, Co) are able to release electrons by a
mechanism quite similar to that of ‘electrometic effect’ (but it is a permanent effect).
This type of electron released by alkyl group is called as hyperconjugation. It involves delocalisation
of  and  bond orbitals (    conjugation). In structure (II), note that there is no definite bond
between carbon and one hydrogen atom, hence it is also known as No bond resonance,
 Greater the number of C-H bond at   carbon to the unsaturated system, greater will be the elec-
tron release and greater the hyperconjugation effect.
Hence electron release due to presence of three alpha (3 )  C H bonds in methyl groups is greater
than that by an ethyl group, in which there are only two alpha (2 )  C H bonds. Similarly, the effect
decrease in isopropyl group and further in tert-butyl group (no   C H bond ) .
increasing hyperconjugation effect and increasing +I effect
 Stability of Alkenes : Hyperconjugation explains the order of stability of alkenes. Propene is more
stable than ethene because in propene, there are three H-C hyperconjugated bonds and hence
  electrons of C-H bonds can delocalise over three different structures.

Hence greater the number of Methyl (each methyl group has 3  H ) groups, attached to doubly bonded
carbons, the more stable the alkene is
[more H-C bond on same carbon give greater effect]
increasing hyperconjugation and increasing stability
 Illustrating the Concept of Hyperconjugation :
The hyperconjugative stabilities of tert-butyl cation and 2-butene, respectively, are due to :
(A)   p (empty) and    * electron delocalisations
(B)    * and    electron delocalisations

(C)   p (filled) and    electron delocalisations
(D) p (filled)   * and    * electron delocalisations
Note :  * refers to  anti-bonding molecular orbitals.
Correct answer is (A)

Hyperconjugation is tert-butyl carbocation refers to delocalisation of s-electrons over the empty p-orbitals
of carbocation. In 2-butene, it refers to decalisation of   electrons over the  * orbitals of C = C.

5. Reaction Intermediates:
While understanding a reaction in detail (Reaction Mechanism), we have to visualise the overall reaction in
small steps. These steps involve various type of reaction intermediates, whose stability is the key to the
acceptance of a particular reaction mechanism (path). Most typically there are three kinds of intermediate:
Free Radicals Carbocations and Carbanions.
(a) Free Radicals :
An atom (or group of atoms) having an unpaired electron is called as Free Radical. These are formed
via homolytic fission.
(methyl and a halogen free radical is produced)
‘C’ of free radical (alkyl) is sp2 hybridised and hence the shape is planar,
having an unhybridised p-orbital containing an odd electron (Paramag-
netic in nature).
Tertiary alkyl free radicals are more stable than others. The stability of free
radicals follows the order:
The stability of free radicals is explained via hyperconjugation effect. In methyl free radical, there is
no hyperconjugation, as there is no -C-H bond.
Let us draw various hyperconjugation structure of ethyl radical.
Similarly a 2o radical is more stable than a 1o alkyl radical (as number of alpha H-atoms are increas-
ing, the hyperconjugation effect is increasing and hence stability increases).
Apart from alkyl free radicals, other important free radicals are :
Allyl and benzyl free radicals are highly stable due to resonance.

Note : Another kind of free radicals, Carbenes are also formed. Carbenes are neutral, divalent and highly reactive
intermediates.
Free radicals are formed with the help of free radicals generators such as : benzoyl peroxide, tert butyl
peroxide.
There are also some special type of intermediates such as Nitrene; and Benzyne;
(b) Carbocations:
The organic compounds which -carbon is electrophilic due to function attached to it, generally undergo
heterolytic cleavage to form carbocations as follows :
(C+ is known as carbocation)

‘C’ of carbocation (alkyl) is sp2 hybridised with one vacant unhybridised p-orbital. Hence the structure is
 
planar. Important carbocations include : Alkyl, allyl (CH 2  CH CH 2 ) and benzyl C6H 5 CH 2 ) .
The order of stability of carbocations is:
Stabilistions of carbocation is through +I effect and hyperconjugation effect.
 Electron releasing alkyl groups (R--  --- ) disperse +ve charge over carbon.
e.g. is more stable than

More is the number of -H attached to carbon atom having +ve charge, more is the number of
hyperconjugative structures. Hence more stable is carbocation.
Observe that 3o butyl carbocation has 9-H and hence more stable than 2o and 1o alkyl carbocations.

 Electron withdrawing (G--  -- - C  ) pulls electron density away from C+ carbon and hence stability of

carbocation decrease. G : CN -, CL, CHO, NO2 etc. e.g. CH 2  CH 2 CHO is more stable than
+
CH 3 CH  CHO
Stabilisation of carbocation is also takes place through resonance.
Allyl carbocation :
Benzyl carbocation :
Note: More is the number of resonating structures dispersing the +ive charge over carbon, more is the carbocation
  
stability e.g. Stability order follows : C6H 5  C  C6 H5  C6H5  C H  C6 H5  C H 2
|
C6 H 5
Order of stability of carbocation follows:

     
 CH3 3 C  C6 H5 C H2  CH3  CH  C H 2   CH3 2 C H  CH3 C H 2  C H3
 3  1  1  2  1
[tert  butyl  1o Benzyl  1o allyl  3o alkyl  2o alkyl  1o alkyl  methyl]
Also-Note : ;

Properties of carbocations :
(i) H3C H 2C  Nu  

 CH3CH 2 Nu (combination with a nucleophile)

(ii) H3C H 2C 
 CH 2  CH 2  H + (elimination of proton at high temperature or in pres
-ence of strong bases)
 In order to achieve stability (before above two properties), carbocations go through rearrangement
through shift of hydride ion (H-) or methide ion (CH 3 ) from adjacent carbon atom. Hence these shifts
are known as 1, 2-shifts.
(a) (2o is more stable)
(b) (3o is more stable)
(c) (3o is more stable)
(c) Carbanions : (C- is carbanions)

‘C’ of carbanions (alkyl) is sp3 hybridised, hence structure is pyramidal
with one of sp3 hybrid-orbital containing a pair of electrons.
e.g.
Stabilisation of carbanion (through -I effect)

 Electron-withdrawing group enhances stability whereas electron-releasing (R) group decreases sta-
bility.
 The stability of carbanions increases with increase in ‘s’ character (electron withdrawing).
An alkynide ion 50%‘s’(sp) A vinylic ion 33% ‘s’ (sp2) An alkyl ion 25% ‘s’ Character (sp3)

Stabilisation of carbanion (through resonance).

 Allyl carbanions is resonance stabilised.
 Carbanions are negatively charge particles acting as nucleophiles. Other important carbanions are
from carbonyl compounds, esters, nitro compounds.
These are resonance stabilised
 Anions in which negative charge is present on the carbon of aromatic system is known as aromtic
carbanions.
These are most stable carbanions.
cyclopentadienyl carbanion  rule and is aromatic.

It obeys Hukel
 Carbanions participate mainly in condensation reactions (to be studied later).
Note: (i) More is the number of resonating structure for a carbanion, more is its stability. e.g. consider the
stability order:
-CCl is more stable than -CF even though -I effect is more pronounced in the later and this is due to
(ii) 3 3
the formation of p-d back bonding between the unhybridised p-orbital of carbanion and empty d-
orbitals of Cl atom.

Illustration - 10 Arrange the following in increasing order of stability on the basis of resonance:
(A) (i) (ii) (iii) (iv)
(B) (i) (ii)
(iii) (iv)
SOLUTIONS :
(A) (i) < (iv) < (ii) < (iii)
In (iii) there is strong -M effect of -NO2.
In (ii) and (iv) -I effect of Br and -OCH3 are prominent.
In (i) delocalisation due to only phenyl ring is there.
(B) (ii) < (i) < (iii) < (iv)
(i) and (ii) should have greater stability as compared to (iii) and (iv) because of greater number of colvalent
bonds. Also (ii) has got 2o carbocation whereas (i) has 1o carbocation.
(iii) has unlike charges close (less charge separation) to each other but (iv) has no such factor.
Types of Reactions in Organic Chemistry :
Note : The detailed discussion of each of above reactions will be done later in Class XIIth in the chapter of
“Theoretical Organic Concepts”

QUALITATIVE & QUANTITATIVE ANALYSIS OF ORGANIC COMPOUNDS Section - 7
Qualitative Analysis:
Detection of functional groups is an important step in the analysis of organic compounds. It entirely depends
on the correct determination of the constituent elements.
Elemental Detection :
The elements present in organic compounds are carbon and hydrogen. In addition to these, they may also
contain oxygen, nitrogen, sulphur, halogens and phosphorus.
Detection of Carbon and Hydrogen:

Carbon and Hydrogen are detected by heating the compound with copper (II) oxide. Carbon present in the
compound with copper (II) oxide. Carbon present in the compound is oxidised to carbon dioxide (tested
with lime-water, which develops turbidity) and hydrogen to water (tested with anhydrous copper sulphate,
which turns blue).

C+ 2CuO 
 2 Cu+ CO2

2 H  CuO 
 Cu+ H 2O
CO2  Ca(OH) 2 
 CaCO3  + H 2O

5H 2O+ CuSO 4 
 Ca SO 4 .5 H 2O
White Blue
Detection of Other Eelements:

Nitrogen, sulphur, halogens and phosphorus present in an organic compound are detected by “Lassaigne’s
test”. The elements present in the compound are converted from covalent form into the ionic form by
fusing the compound with sodium metal. Following reaction take place :

Na+ C+ N 
 NaCN

2 Na+ S 
 Na 2 S

Na+ X 
 Na X  X = Cl, Br or I 
C, N, S and X come from organic compound.

Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted from the fused masses
by boiling it with distilled water. This extract is known as sodium fusion extract.

(A) Test for Nitrogen :

The sodium fusion extract is boiled with iron (II) sulphate and then acidified with concentrated sulphuric
acid. The formation of Prussian blue color confirms the presence of nitrogen. Sodium cyanide first
reacts with iron(II) sulphate and forms sodium hexacyanoferrate (II). One heating with concentrated
sulphuric acid some iron(II) ions are oxidised to iron (III) ions which react with sodium hexacyanoferrate
(II) to produce iron(III) hexacyanoferrate(II) (ferriferrocyanide) which is Prussian blue in colour.
(B) Test for Sulphur :

(a) The sodium fusion extract is acidified with acetic acid and lead acetate is added to it. A black
precipitate of lead sulphide indicates the presence of sulphur.
S2  + Pb2+ 
 PbS
(Black)
(b) On treating sodium fusion extract with sodium nitroprusside, appearance of a violet colour
further indicates the presence of sulphur.
S2  +[Fe(CN)5 NO]2  
 [Fe(CN)5 NOS]4
(Violet)
In case, nitrogen and sulphur both are present in an organic compound, sodium thiocyanate
is formed. It gives blood red colour and no Prussian blue since there are no free cyanide ions.
Na+ C+ N+ S 
 N aSCN
Fe3  SCN  
 [Fe(SCN)]2
Blood Red
If sodium fusion is carried out with excess of sodium, the thiocyanate decomposes to yield
cyanide and sulphide. These ions give their usual tests.
Na SCN 2 Na 
 NaCN+ Na 2S
(C) Test for Halogens :

The sodium fusion extract is acidified with nitric acid and then treated with silver nitrate. A white
precipitate, soluble in ammonium hydroxide shows the presence of chlorine, a yellowish precipitate,
sparingly soluble in ammonium hydroxide shows the presence of bromine and a yellow precipitate,
insoluble in ammonium hydroxide shows the presence of iodine.
X   Ag + 
 AgX

X represents a halogen -Cl, Br or I.

If nitrogen or sulphur is also present in the compound, the sodium fusion extract is first boiled with
concentrated nitric acid to decompose cyanide or sulphide of sodium formed during Lassaigne’s test.
These ions would otherwise interfere with silver nitrate test for halogens.
(D) Test for phosphorus :

The compound is heated with an oxidising agent (sodium peroxide). The phosphorus present in the
compound is oxidised to phosphate. The solution is boiled with nitric acid and then treated with
ammonium molybdate. A yellow colouration or precipitate indicates the presence of phosphorus.
Na3PO4 +3HNO3 
H3PO4 +3NaNO3
H3PO 4 +12(NH 4 )2 MoO4  21HNO3

Ammonium molybdate
  NH 4 3 PO4 .12 MoO3 + 21NH 4 NO3  12 H 2O


Ammonium phosphmolybdate
Quantitative Elemental Analysis :

After determining the constituent elements of an organic compound, the next step is to determine their
amounts by quantitative methods. The methods usually involve combutions, oxidation etc. of an organic
compound so that they may change into such inorganic compounds as can be estimated either by volumetric
or gravimetric method.
Estimation of Carbon and Hydrogen :

Liebig’s Combustion Method : A weighed amount of the compound is heated in a current of dry air
free from carbon dioxide or pure oxygen till the carbon of the compound changes to CO2 and hydrogen into
water. Carbon dioxide and water thus formed are trapped in a suitable apparatus and weighed.
C+ 2CuO 
CO2  2Cu
2 H+ CuO 
 H 2O+ Cu
The percentage composition is then calculated.

Calculation:
Let the weight of the sample = Wg
Let the weight of water formed = x g (Increase in weight of CaCl2 tube)
and let the weight of CO2 formed = y g (Increase in weight of potash bulb)

Since 44g of CO2 are formed from 12g of carbon.
12
 y g of CO2 are formed from  y g of carbon
14
Since 18 g of water are formed from 2g of hydrogen.
2 1
 x g of water are formed from  x g of hydrogen  x g of hydrogen
18 9
12
Now, Wg of the substance contains  y g of carbon
44
12  100 y
 100 g of the substance contains g carbon
44  W
x
Again W g of the substance contain g of hydrogen
9
100 x
 100 g of the substance contain g of hydrogen
9W
12  100 y
 Percentage of carbon 
44  W
100 x
and Percentage of hydrogen 
9W
Estimation of Nitrogen :
(i) Duma’s Method : In this method the organic compound is heated with copper oxide strongly.
Carbon, hydrogen and sulphur are oxidized to CO2, H2O and SO2 respectively, while nitrogen is set
free. These gases are passed through a nitrometer containing 30% KOH solution. Carbon dioxide
and sulphur dioxide are absorbed, steam condenses and nitrogen collects by the displacement of
KOH solution. From the volume of the collected nitrogen, the percentage of nitrogen is calculated.
y z
C x H y N z  CuO 
 x CO2 + H 2O+ N 2 + Cu
2 2
Calculation :
Let the weight of the sample = W g
Volume of moist N2 = Vcc
Room temperature = toC

Barometric pressure = P mm
Aqueous tension at toC = f mm
PV PV
We know, 1 1  2 2
T1 T2
( P  f )  V 760  V2
Or  V2  Volume of N2 at NTP 
(273  t ) 273
( P  f )  273  V
V2  cc
760  (273  t )
( P  f )  273  V
Volume of N 2 at NTP in cc 
760  (273  t )
Now, 22400 cc of N2 at NTP weigh 28 g.
( P  f )  273  V  28  P  f   273  V 
 at NTP weigh  g
760  (273  t )  760  22400  273  t  
28  P  f   273  V
W g of the substance contain g N2
760  22400  273  t 
28  P  f   273 V 100
 100g of the substance contains g
760  22400 W  273  t 
28 Volume of N 2 at NTP
Percentage of Nitrogen    100
22400 Weight of substance
(ii) Kjeldahl’s Method : The principle of this method is that when an organic compound containing
nitrogen is heated with concentrated sulphuric acid, the nitrogen is converted into ammonium sul-
phate. The resulting solution on treatment with excess of sodium hydroxide solution gives off ammo-
nia. Ammonia is then absorbed in excess of standard sulphuric acid. The amount of ammonia and
hence the amount of nitrogen is determined by finding the amount of acid neutralized by back titration
of the residual acid with a standard alkali solution. From this the percentage of nitrogen is calculated.
This method is not good for those nitrogen compounds which produce nitrogen gas N2 on heating
such as compound containing N in ring, nitro compounds, axo compounds etc.
Calculation :
Let the weight of the substance = Wg and let V cc of N acid is required to neutralize the ammonia
evolved.

 V cc of N acid = V cc of N NH3
1000 cc of N NH3 = 17 g of NH3 = 14 g of nitrogen
14
V cc of N NH3   V N  0.014 N V g
1000
100 0.014  N V 100

 Percentage of nitrogen = Weight of nitrogen  
Weight of subs tan ce W
Estimation of Halogen :
(i) Carius Method : The compound containing halogen is heated with fuming nitric acid in a sealed tube
(Carius tube) in presence of silver nitrate. Carbon and hydrogen present are oxidized to carbon
dioxide and water. The halogens react with silver nitrate to give the precipitate of silver halide. The
precipitate is collected, washed, dried and weighed.
Calculation :
Let the weight of the substance be W g.
Weight of the silver halide be y g.
Atomic weight of halogen

Weight of halogen   yg
Moleclar weight of silver halide
Atomic weight of halogen 100

 Percentage of halogen   y
Moleclar weight of silver halide W
Estimation of Sulphur :
The compound is heated with fuming nitric acid. Sulphur present is oxidized to sulphuric acid. Barium
chloride solution is added. The precipitate of barium sulphate is obtained. It is collected, washed, dried and
weighed.
% of Sulphur  Weight of BaSO4 Atomic weight of Sulphur

  100
Molecular weight of BaSO4 Weight of Organic compound
Silver Salt method for determining molecular weight of Organic acids :

This method on the fact that organic acids form insoluble silver salts which on ignition leave a residue to
metallic silver.
A small quantity of organic acid is treated with water or a suitable solvent and then a slight excess of
ammonia solution added. The solution is boiled to expel excess of ammonia. Excess of silver nitrate solution
is added to this solution when a white precipitated of insoluble silver salt is obtained. The precipitate is
filtered and washed successively with water, alcohol and ether and then dried in an air oven.

A known weight of the silver salt is taken in a weighed crucible and ignited till decomposition is complete.
The curcible is cooled and then weighed. Heating, cooling and weighing is continued till the final weight is
constant.
Calculation :
Weight of crucible + lid = W g
Weight of crucible + lid + silver salt = W 1 g
Weight of crucible + lid + residual silver = W2 g
Weight of silver salt = (W1 - W) g
And Weight of silver = (W2 - W) g
(W2 - W) g of silver is obtained from (W1 - W) g of silver salt.
108 g of silver is obtained from

 W1  W  108 g of silver salt.
 W2  W 
Equivalent weight of silver salt 

 W1  W  108
 W2  W 
But equivalent weight of acid = Equivalent weight of Ag salt - 108 + 1 = Equivalent weight of Ag salt -107
  W  W   108 
 Molecular weight of the acid   1  107   n (where n = basicity of the acid)
  W2  W  
Platinichloride method for determining molecular weight of Organic Bases :

Organic bases (e.g. amines) form insoluble salts known as platinichlorides when treated with
hydrochloroplatinic acid [H2PtCl6]. These salts are represented by the general formula B2H2PtCl6, where
B is one equivalent of the base. These salts on ignition leave a residue of metallic platinum.
The base is dissolved in HCl and a solution of platinic chloride PtCl4 is added. The yellow crystalline salt
that separateds out is filtered, washed and dried. A known weight of the dried salt is ignited in a crucible.
Calculation :
Let X1 g of the platinichloride leave on ignition X2 g of platinum
X2 g of Pt is left by X1 g of the slt on ignition.
 X 195 
195 g (At. weight of Pt) is left by  1  g of the salt on ignition.
 X2 
Molecular weight of the salt  X1  195

X2

Molecular weight of H 2 PtCl6  410
 X1 
 ×195   410
M  M H 2 PtCl6  X 2
Equivalent weight of base B  B2 H 2 PtCl6  
2 2
If the ascidity of the base is n, then
 X   n
Molecular weight of base   1 ×195   410  
 X 2   2
Illustration - 11 0.25 g of an organic compound on combustion gave 0.495 g of CO and 0.2025 g of H O.

2 2
Calculate the percentage of carbon and hydrogen in the compound.
SOLUTION :
Given weight of the substance = 0.25 g
Weight of CO2 formed = 0.495 g
Weight of H2O formed = 0.2025 g
44 g of CO2 are formed from 12g of carbon.
12
 0.495 g are formed from  0.495 of carbon
44
12  0.495
Now 0.25 g of the substance contains g carbon.
44
12  0.495  100
 100g of the substance contains  54.55 g
44  0.25
Since 18 g of H2O are formed from 2g of hydrogen.
2
 0.2025 g H2O are formed from  0.2025 g hydrogen
18
2  0.2025
Now, 0.25 g of the substance contains g hydrogen
18
2  0.2025  100
 100 g of the substance contains  9.09 g hydrogen
0.25  18
% of carbon = 54.55
% of hydrogen = 9.09

Illustration - 12 0.159 g of an organic compound gave 14.01 cc of nitrogen at 19oC and 719.5 mm pressure
by Duma’s method. Calcuate % of nitrogen in the organic compound. Given: Aqueous tension of water =
11.5 mm og Hg at 19oC.
SOLUTION :
Aqueous tension at 19oC = 11.5 mm
We know,
P1V1 P2V2

T1 T2
(719.5  11.5) 14.01 760  VN 2 at NTP

or 
(273  19) 273
708  14.01 273

VN 2 at NTP  cc
760  292
Now, 22400 cc of N2 at NTP weight 28g
28
 1cc of N2 at NTP weigh g
22400
708  14.01 273 28  708  14.01  273

 cc  g
760  292 22400  760  292
28  708 14.01 273

0.159 g of the compound contains g N2
22400  760  292
28  708  14.01 273 100

 100 g of the compound contains  9.60%
22400  760  292  0.159
Percentage of nitrogen = 9.60%
Illustration - 13 0.69 g of an organic compound after heating with concentrated sulphuric acid was dis-
tilled with excess of NaOH. Ammonia liberated was passed into 100 cc of N HCl solution. The excess of the
acid neutralized 80 cc of N NaOH. Calculate the percentage of nitrogen in the compound.
SOLUTION :
80 cc of N NaOH = 80 cc of N HCl = Volume of residual acid
Volume of acid neutralised = (100-80) cc of N HCl = 20 cc of N HCl = 20 cc of N NH3

Now, 1000 cc N NH3 = 14 g of nitrogen
14  20
20 cc N NH3  g of nitrogen
1000
14  20
0.69 g of the substance contains g of nitrogen
1000
14  20  100
 100 g of the substance contains  40
0.69 1000
 Percentage of nitrogen = 40 %
Illustration - 14 0.26 g of an organic compound on heating with fuming nitric acid and silver nitrate give
0.31 g of silver bromide. Calculate the percentage of bromine in the compound.
SOLUTION :
Now, AgBr 
 Br
or (108 + 80)g  80g

 188 g of AgBr give 80 g of bromine.
80
 0.31 g of AgBr give  0.31  0.1319 g bromine
188
Now, 0.26 g of the substance give 0.1319 g bromine.
 100 g of the substance gave
0.1319  100
 50.7
0.26
 Percentage of bromine = 50.7
Illustration - 15 0.40 g of an organic compound gave 0.60 g of barium sulphate after Carius method. Find
out the percentage of sulphur in the compound.
SOLUTION :
Since, BaSO4  S
233 g 32 g

233 g of BaSO4 gives 32 g of sulphur.
32
0.60 g of BaSO4, gives  0.60 g of sulphur = 0.082 g sulphur
233
0.082
 Percentage of sulphur   100  0.205%
40
Illustration - 16 0.167 g of teh silver salt of a monobasic organic acid left on ignition 0.108 g of silver.
Calculate the molecular weight of the acid.
SOLUTION :
Weight of Ag salt = 0.167 g and weight of Ag left = 0.108 g.
The weight of Ag salt that would leave 108 g of silver  0.167 108  167 g
0.108
Equivalent weight of the acid = 167 - 108 + 1 = 167 - 107 = 60

Molecular weight of the acid  60  1 (acidity) = 60
Illustration - 17 Calculate the molecular weight of a monobasic base, 0.298 g of whose platinichloride left
0.0975 g of platinum on ignition.
SOLUTION :
Weight of the platinichloride = 0.298 g (X1) and weight of platinum = 0.0975 g (X2)
0.298
 195  410
Equivalent weight of the base  0.0975 596  410 186
   93
2 2 2
Molecular weight of the base  931(acidity) = 93

Illustration - 18 A mono acid organic base on analysis gave the following results: 0.10 g of the base gave
0.28 g of CO2 and 0.075 g of water and 0.30 g of the base gave 31.32 ml N2 measured at 15oC and 760 mm,
0.30 g of the platinichloride left on ignition 0.093 g of platinum. What is the molecular formula of the base?
SOLUTION :
The molecular formula is derived as follows
(a) Calculation of % of elements
12 0.28
% of carbon    100  76.36%
44 0.10
2 0.075
% of hydrogen    100  8.33%
18 0.10
28 Volume of N 2 at NTP×100
% of nitrogen  
22400 Weight of organic compound
28  31.32  100
% of nitrogen   13.05%
22400  0.3
(b) Calculation of relative number of each atom :
76.36 8.33 13.05

C= = 6.36; H = = 8.33 and N = = 0.90
12 1 14
(c) Calculation os simplest ratio:
6.35 8.33 0.90

C 7;H  9 and N  l
0.90 0.90 0.90
(d) Determination of empirical formula :
It comes to be C7 H9 N , its empirical formula weight = 84 + 9 + 14 = 107
(e) Determination of molecules weight :

The molecular weight of the base is given by,
1 Weight % hexachloroplatinate salt 

B 195   410 
2 Weight % platinum 
1 195  0.3  1
B   410    629  410  109.5
2  0.093  2
B = 109.5

Molecular weight 109.5

n= = 1
Empirical weight 107
Hence, molecular formula = empirical formula = C7H9N
Illustration - 19 A sample of a gaseous hydrocarbon occupying 1.12 litre at NTP was completely burnt in
air and gave 2.2g of CO2 and 1.8 g of H2O. Calculate the weight of compound taken and volume of O2 at
NTP required for its burning. Also calculate the molecular formula of the hydrocarbon.
SOLUTION :
Volume evolved at NTP

Mole of compound 
22400 ml or 22.4 litres
1.12
  0.05 mol
22.4
2.2
Moles of CO2 produced   0.05 mol
44
1.8
Moles of H2O produced   0.10 mol
18
Suppose the hydrocarbon is Cx H y
 y y
Then C x H y   x   O2 
 CO2  H 2O
 4 2
 1 mole of Cx H y gives = 0.05 x mol of CO2
 0.05 x = 0.05
0.05
 x 1
0.05
y
Now, 1 mole of Cx H y gives  mol of H 2O
2
y
 0.05 mol of Cx H y will give = 0.05 mol of H 2O
2
y
0.05  0.10
2
 y=4

Hence, the hydrocarbon is CH4
16  1.12
Weight of 1.12 litre CH4 at STP   0.8 g
22.4
Also, CH 4 + 2 O2 
 CO 2 + 2 H 2O
1 mol of CH4 requires 2  32 g oxygen
 0.05 mol of CH4 requires 2  32  0.05  3.2 g CO2
CH4 requires O2 = 3.2 g
Illustration - 20 An organic compound, A containing C, H, N and O, on analysis gives 49.32 % carbon,

9.59% hydrogen and 19.18% nitrogen. A on boiling with NaOH gives off NH3 and a salt which on acidifica-
tion gives a monobasic nitrogen free acid B. The silver salt of B contains 59.67% silver. Deduce the structures
of A and B.
SOLUTION:
Percentage of oxygen = 100 - (49.32 + 9.59 + 19.18) = 21.91
Elements Percentage Atomic Relative No. of Simplest

composition weight atoms ratio
49.32 4.11
C 49.32 12  4.11 3
12 1.37
9.59 9.59
H 9.59 1  9.59 7
1 1.37
19.18 1.37
N 19.18 14  1.37 1
14 1.37
21.91 1.37
O 21.91 16  1.37 1
16 1.37
Hence empirical formula of A = C3H7NO

Because A, gives NH3 on boiling with NaOH, it can be an amide.

Now, silver salt of B, has 59.67 % silver.
 100  108 
Hence equivalent weight of acid     107  74
 59.67 
Molecular weight of monobasic acid = 74 1  74

Molecular formula of acid = C3H6O2
 Structural formula of acid B is C2H5COOH.
Molecular formula of amide = C3H7NO.
Hence structural formula of amide (A) is C2H5CONH2
CH3 CH3
| |
1. (i) CH3  C H  CH 2  (ii) CH3  C  CH 2  (iii) CH3CH 2  C 
| | |
CH3 CH3 CH3
CH3
|
(iv) CH 3CH 2  CH  (v) (iv) CH3 C
| |
CH3 CH3
CH3
3
| 1
2. (i) C H3  C 2  C OOCH3 (Methyl) 2, 2 - Dimethyl propanoate
|
CH3
CH3
6 5 4 | 2 1
(ii) C H3  C H  C H  C H  C H  C H 2 3, 4, 5 - trimethylhex - 1 - ene
| | 3
CH3 CH3
4 3 2 1
(iii) C H3  C H  C H 2 C OOH 3 - chlorobutanoic acid
|
Cl
CH3
4 3 2| 1
(iv) C H3  C H  C  C H3 2, 3 - Dimethyl butan - 2 - ol
| |
CH3 OH
5 4 3 2
(v) C H3  C H 2  C H 2  C H  CH 2CH3 2 - Ethyl pentanoic acid
|
1COOH
Self Study Course for IITJEE with Online Support Solutions - INE 101
4 3 2
(vi) C H3  C H 2  C  CH 2CH3 2 – Ethyl but - 1 - ene
||
C H2
1
CH3
5 4 3 |
(vii) C H3  C H  C H  C  1CH 2 3 - (1 - Methylethyl) –2, 4 - dimethyl pent - 1 - ene
| | 2
CH3 C H  CH3
|
CH3
(viii) 3 – N, N - Dimethyl –2, 4 - dimethyl pentan - 3 - amine
(ix) 3 - Ethyl - 2, 4, 4 - trimethyl hex - 2 - ene
5 4 3 2
(x) C H3 C H 2  C H  C H  O  CH  CH3 2 - (1 - Methyl ethoxy) - 3 - methyl pentane
| | |
CH3 C H3 CH3
1
3. (i) (ii) (iii)
(iv) (v) (vi)
102 Solutions - INE Self Study Course for IITJEE with Online Support
(vii) (viii) (ix)
(x)
CH3
1 2| 3 4 5
4. (i) C H3  C  C H 2  C H  C H3 2, 2, 4 - Trimethyl pentane
| |
CH3 CH3
5 4 3 2 1
(ii) C H3  C H 2  C H 2  C  C H 2 2 - Ethyl pent - 1 - ene
|
CH 2  CH3
CH 3
4 3 2| 1
(iii) C H2  C  C  C H 2 2, 3 - Dimethyl buta –1, 3 - diene
|
CH3
5 4 3 2 1
(iv) C H3  C H  C H  C – C H3 Pent - 3 - en - 2 - one
||
O
IN - CHAPTER EXERCISE - B
1
1. (A) CH 2  CH  CH 2  CH 2 OH
1
CH 3  CH  CH  CH 2OH
(B) C3H6O : (C) ; C4H4O4
(D) H  C  COOH (cis -) maleic acid and H  C  COOH (Trans -) fumaric acid; C4H4O4
|| ||
H  C  COOH HOOC  C  H
2.
3.
4. (A) CH3CH2COOCH3 ; CH3COOC2H5 ; H – COO – CH2CH2CH3 ; HCOO C H  CH3

|
CH3
(B) CH3CH2CH2CHO ; CH3  C H  CHO
|
CH3
O
||
(C) CH3COCH2CH2CH3 ; CH 3  CO  C H  CH3 ; CH3CH 2  C  CH 2  CH3
|
CH3
(D) CH 3  N  CH 2CH3
|
CH 3
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Organic Concepts
Organic Concepts
BASIC OF REACTION MECHANISM OF ORGANIC COMPOUNDS Section - 1
Reaction of organic compounds can takes place in one step or in many step depending upon nature of
reactants and reaction conditions and also on nature of reactants and their functional group. These chemical
reactions involve breaking and making of the bonds that hold together the atoms of reactant and product
molecules.
In one step reactions, breaking and making of the bonds takes place simultaneous at the same instant. A one
step reaction is represented as : Reactant(s)   Transition State   Product(s)
A many steps reaction involve a time gap between bond breaking and bond making and it results in forma-
tion of an additional species called as reactive intermediate :
Reactant(s)   Transition State   Reactive intermediate [Step 1]
State 1
Reactive intermediate   Transition State   Product(s) [Step 2]
State 2
In two steps reaction one of the step is slow step and other one is fast step. The slowest step of many step
reaction is called as rate determining step (RDS).
Nature of reaction intermediate formed depends upon type of bond breaking. Bond breaking can be
homolytically or heterolytically as illustrated below.
The chemical reactions that involve only homolytic bond cleavage are called as free radical reactions and
those reactions that involve heterolytic bond cleavage are termed as ionic reactions.
The products of bond breaking, shown above are not stable in the usual sense and cannot be isolated for
prolonged study. Such species are reffered to as reactive intermediates, and are believed to be transient
intermediates in many reactions. The general structures and names of four such intermediates are given
below.

Organic Concepts Vidyamandir Classes
The shapes ideally assumed by these intermediates becomes important when considering the stereochem-
istry of reactions in which they play a role. A simple tetravalent compounds like methane, CH4 has a
tetrahedral configuration.
Carbocations have only three bonds to the charge bearing carbon, so it adopts a planar trigonal configura-
tion.
Carbanions are pyramidal in shape but these species invert rapidly at room temperature, passing through
a higher energy planar form in which the electron pair occupies a p-orbital. Radicals are intermediate in
configuration, the energy difference between pyramidal and planar forms being very small. Generally most
of the free radicals adopts a planar trigonal configuration. The shape of carbenes is planar, however, the
valance electron distribution varies.
You have already studied detailed aspect of these intermediates in ‘IOC’ chapter.
Note : CF3 radical is essentially pryamidal in shape. Less % of s-character of orbital help in stabilization
of free radical.
Note : Types of particular intermediate depends upon the type of carbon atom bearing charge. The stability
of charged intermediate is inversely releated to its charge density. The delocalisation of charge decreases
charge density hence increases stability. The presence of electron releasing group increases stability of both
free radical and carbocations. While presence of electron withdrawing group increases stability of carban-
ion.
Alkyl carbocations are stabilized by hyper conjugation.
Note : Hyperconjugation involve formation of 3C-2e bond.
Allylic and benzylic free radical, carbocation and carbanion are stabilized by resonance due to presence of
conjugation.
Note : A carbocation of lower stability can rearrange to a carbocation of higher stability by 1,2-hybride, methide or
phenide shift, if possible.
CH3 CH 3
|  |
1,2-Hydride
CH 3  C  C H 2  CH3  C  CH3
shift 
|
H

CH3 CH3
|  |
1,2-Methide
Ph  C  C H 2  Ph  C  CH 2  CH3
shift 
|
CH3
Alkyl carbocation having cyclo alkyl group (with number of carbon atoms less than six) may undergo ring
expansion because organic compound having five or six membered ring are more stable.
Such type of rearrangement is generally not observed in carbanion and free radicals.
The ionic organic reactions involve the bonding of a nucleophile (electron rich) to an electrophile (electron
deficient). While free radical reactions involve the bonding of a free radical to a radical or neutral molecule.
Electrophile : An electron deficient atom, ion or molecule that has an affinity for an electron pair, and will
bond to a Lewis base or nucleophile.
Nucleophile : An atom, ion or molecule that has an electron pair that may be donated in bonding to an
electrophile (or Lewis acid)

REVIEW EXERCISE
In the Chapter, “Introduction to Organic Chemistry”, you have already learned about details of above basic concepts
(Electrical effects, intermediates formed while visualising reaction mechanisms) and their simple uses in Section – 5 &
6. Before moving forward, please solve the following ‘Review Exercise’ so that you are not only able to review basic
fundamental but also consolidate your understanding.
1. What is the formal charge of oxygen in each of the following Lewis structures?
(A) (B) (C)
2. Consider structural formulas I, II, and III :
(A) Are I, II and III constitutional isomers, or are they resonance forms ?
(B) Which structure have a negatively charged carbon?
(C) Which structure have a positively charged carbon ?
(D) Which structure have a positively charged nitrogen?
(E) Which structures have a negatively charged nitrogen ?
(F) Which is a more stable structure?
(G) Which structure have nucleophilic carbon?
(H) Which structures have electrophilic carbon?
(I) What is the CNN geometry in each structure according to VSEPR?
Species [I], [II] and [III] have same molecular formula, the same atomic positions, and the same number of
electrons. They differ only in the arrangement of their electrons.
NOW ATTEMPT REVIEW EXERCISE BEFORE PROCEEDING AHEAD IN THIS EBOOK

Classification of Organic Chemical Reactions :
1. Classification by Structural Change : On the basis of structural changes reactions of organic com-
pounds are of following types.

2. Classification by Functional Group : Functional groups are atoms or small groups of atoms (usually two
to four) that exhibit a characteristic reactivity when treated with certain reagents.
A particular functional group will almost always display its characteristic chemical behaviour when it is
present in a compound. The following table summarizes the general chemical behaviour of the common
functional groups.
For reference, the alkanes provide a background of behaviour in the absence of more localized functional
groups.

Illustration - 1 Some chemical reactions are shown below classify each as Addition, Elimination, Substi-
tution.
SOLUTION :
Addition : 1, 8, 9, 12 Reaction in which one of the atom or group (H,
Elimination : 2, 5, 11 halogen, OH etc.) is replaced by other substitu-
Substitution : 3, 4, 6, 7, 10 ent is called as substitution reaction.
Organic Compounds having multiple bonds Thus reaction
(C = C, C  C, C = O, C  N) undergoes 3 [Cl is replaced by OH]
addition reactions. Thus reaction 1, 8, 9 and 12 4 [CH3NH is replaced by OH]
are addition reactions.
6 [H is replaced by Br]
Reactions of organic compound that results in
formation of multiple bonds (C = C, C  C) 7 [Li is replaced by H]
are elimination reactions. 10 [Cl is replaced by acyl group] are substitu-
Thus reaction 2, 5 and 11 are elimination tion reactions.
reactions. Reaction 10 : Ring closure
Reaction 11 : Ring expansion
Reaction 12 : Rearrangement

3. Oxidation and Reduction Reactions :

Organic reactions can also be classified by oxidation-reduction terminology.
Carbon atoms may have any oxidation state from – 4(e.g. CH4) to + 4 (e.g. CO2), depending upon their
substituents. Fortunately, we need not determine the absolute oxidation state of each carbon atom in a
molecule, but only the change in oxidation state of those carbons involved in a chemical transformation. To
determine whether a carbon atom has undergone a redox change during a reaction, we simply note any
changes in the number of H bonded to carbon and the number of bonds to more electronegative atoms such
as O, N, F, Cl, Br, I, and S that has occurred. Bonds to other carbon atoms are ignored.
This count should be conducted for each carbon atom undergoing any change during a reaction.
(i) If the number of hydrogen atoms bonded to a carbon increases, and/or if the number of bonds to
more electronegative atoms decreases, the carbon in question has been reduced (i.e. it is in a lower
oxidation state).
NaBH
4  CH  CH  OH
CH3  CH = O  3 2
(ii) If the number of hydrogen atoms bonded to a carbon decreases, and/or of the number of bonds to
more electronegative atoms increases, the carbon in question has been oxidized (i.e. it is in a higher
oxidation state).
K Cr O
2 2 7 CH  COOH
CH3  CH2  OH  3
H+
(iii) If there has been no change in the number of such bond, then the carbon in question has not changed
its oxidation state. In the hydrolysis reaction of a nitrile shown below, the carbon atom of –CN group
has not changed its oxidation state.
O
+ ||
H
 C6 H5  C  OH + NH 4+
C6H 5  C  N + 2 H 2O 


Illustration - 2 Consider the following four addition re-

actions involving the same starting material, cyclohexene.
Identify in which reaction carbon in question has been re-
duced or oxidized or has not changed its oxidation state.
SOLUTION :
In the addition of hydrogen both carbon atoms are reduced, and the overall reaction is termed a reduction
(I). Peracid does epoxidation (III) and addition of Br2 (IV) oxidize both carbon atoms, so this will be
oxidation (IV). The addition of HBr in (II) reduces one of the double bond carbon atoms and oxidizes the
other ; consequently, there is no overall redox change in the substrate molecule (II).
The Variables of Organic Reactions :
The various important properties and characteristics of a reaction that may be observed and/or measured as
the reaction proceeds are listed below.
1. Reactant Structure : Variation in the structure of the reactant may have a marked influence on the
course of a reaction, even though the functional group is unchanged. Thus, reaction of 1-bromopropane
with sodium cyanide proceeds smoothly to yield butanenitrile, whereas 1-bromo-2, 2-dimethylpropane
fails to give any product and is recovered unchanged. In contrast, both alkylbromides form Grignard
reagents (RMgBr) on reaction with magnesium.
alcohol
CH 3CH 2CH 2 Br  CN  
 CH3CH 2CH 2CN  Br 
(fast)
alcohol
 CH 3 3 C CH 2 Br  CN    No Reaction
2. Reagent Characteristics : The minor changes in a reagent may lead to a significant change in the
course of a reaction. For example, 2-bromopropane gives a substitution reaction with sodium
methylthiolate (CH3SNa) but undergoes elimination on treatment with sodium methoxide (CH3ONa).
3. Product Selectivity :
(A) Regioselectivity : It is often the case that addition and elimination reactions may, in prin-
ciple, proceed to more than one product. Thus 1-butene might add HBr to give either 1-
bromobutane or 2-bromobutane, depending on which carbon of the double bond receives
the hydrogen and which the bromine. If one possible product out of two or more is formed
preferentially, the reaction is said to be regioselective.

CH 3CH 2CH  CH 2  HBr  CH3CH 2CHBr CH3 not CH 3CH 2CH 2 CH 2 Br
Regioselective
addition Major
Simple substitution reactions are not normally considered regioselective, since by definition only one consti
-tutional product is possible. However, rearrangements are known to occur during some reactions.
(B) Stereoselectivity : If the reaction’s products are such that stereoisomer may be formed ; a reaction that
yield one stereoisomer preferentially is said to be stereoselective. In the addition of bromine to cyclohexene,
for example, cis and trans-1, 2-dibromocyclohexane are both possible products of the addition. Since the
trans-isomer is the only isolated product, due to anti-addition, this reaction is stereoselective.
In the partial hydrogenation of 2-butyne using Lindlar’s catalyst, cis and trans-2-butene are both possible
products of the addition. Since the cis-isomer is the only product obtained, due to syn-addition, this reac-
tion is also sterco-selective.
(C) Stereospecifically : This term is applied to cases in which stereoisomeric reactants behave differently in a
given reaction. Examples
(i) Formation of different stereoisomeric products, as in the reaction of stereoisomeric 2-butene isomer
with Br2 / CCl4 , shown in the following diagram.

Here, the cis-isomer gives the racemic mixture and trans-isomer produces meso-isomers of 2, 3-dibromo
butane.
(ii) Different rates of reaction, as in the base-induced elimination of cis & trans-4-tert-butylcyclohexylbromide.
(iii) Different reaction paths leading to different products, as in the base-induced elimination of cis &
trans-2-methylcyclohexyl bromide.
Note : A reaction in which a reagent selectively reacts with one of the functional group of a poly functional group
compound is called as Chemoselective reaction.
Illustration - 3 Consider the following reactions and identify their correct classification.

SOLUTION : (B)
I and II are regioselective reaction.
In I and II two structural isomers of the product can be formed but only one isomer is formed as an exclusive
product or in major amount hence these two reactions are regioselective reaction.
III and V are chemoselective. In III MnO2 acts as an oxidising agent and it selectively oxidise only allylic or
benzylic C – OH bond to C = O bond. So this reaction is chemoselective. Similarly NaBH4 is selectively
reduces aldehyde to alcohols not carboxylic acid.
IV is stereoselective because only one stereoisomer of the product is formed.
VI and VII are stereoselective as well as stereospecific because a particular stereoisomeric reactant reacts
to give a particular stereoisomers of the product.
4. Factors that Influence Reactions : Some of the most important factors that influence reactions are
as follows.
(A) Energetics : The potential energy of a reacting system changes as the reaction progresses. The
overall change may be exothermic (energy is released) or endothermic (energy must be added)
and there is usually an activation energy requirement as well. As a rule, compounds constructed of
strong covalent bonds are more stable than compounds incorporating one or more relatively
weak bonds.
 CH3 — CH3 ; H  0 [Addition reaction]

CH 2  CH 2  H 2 
alc.KOH
CH 3 — CH 2 — Cl  CH 2  CH 2 ; H  0 [Elimination reaction]

(B) Electronic Effect : The distribution of electrons at sites of reaction (functional groups) is a par-
ticularly important factor. The charge distribution in a molecule is usually discussed with respect to
two interacting effects such as inductive effect and resonance effect. [As discussed in chapter
IOC]
  addition reaction
CH3  C H  C H 2  HCl   CH 3  CH(Cl)  CH3 [+I effect of CH3 group]

  addition reaction
 Cl3C  CH 2  CH 2  Cl [–I effect of CC3 group]
Cl3C  C H  C H 2  HCl 
(C) Steric Effect : Atoms occupy space, when they are crowded together, vander Waals repulsions
produce an unfavourable steric hinderance. Steric hinderance may influence conformational
equilibria, as well as destabilizing transition states of reactions.
CH 2  CH 2  Cl2  Cl  CH 2  CH 2  Cl
CCl4
CH 2  CH 2  I2  No reaction [Because of large size of I atoms]

CCl 4
H
|
CH3O 
CH 3  CH  CH  CH3   CH 3  CH  CH  CH3  CH3OH  Br 

(Smallsize base) (major)
|
Br
H  Sterically unhindered H atom

|
(CH3 )3 C  O
CH 2  CH  CH 2  CH3   CH 2  CH  CH 2  CH 3  Br   (CH3 )3 COH

(Largesize base) (major)
|
Br
(D) Solvent Effect : Most reactions are conducted in solution, not in a gaseous state. The sol-
vent selected for a given reactions may exert a strong influence on its course. Remember,
solvents are chemicals and most undergo chemical reaction under the right conditions.
For example nitrobenzene can be used as solvent for F.C. acylation reaction of aromatic
compounds although it is also an aromatic compound because -NO2 group deactivates ben-
zene ring for electrophilic substitution reaction. You will study role of solvent in later reac
-tions.
Stability :
Common use of the term stability implies an object, system or situation that is likely to remain unchanged for
a significant period of time. In chemistry, however, we often refer to two kinds of stability.
Thermodynamic Stability : Thermodynamic stability refers to the potential energy of a compound rela-
tive to a reference state. It is related to the bond energies of its constituent atoms. For exothermic reactions
we may say that the products are thermodynamically more stable than the reactants. The opposite would
be true for endothermic reactions.

Chemical Stability : The chemical stability refers to resistance of a compound or mixture of compounds
to chemical change (reaction) with a variety of reagents. It is related to the activation energy barrier it
presents to possible chemical change.
For example, benzene is thermodynamically unstable compared with elemental carbon and hydrogen, but
it is chemically stable under normal laboratory conditions, even when mixed with some reactive compounds
such as bromine.
Note : Compounds or mixtures that are chemically unstable are often called labile.
Kinetic Vs Thermodynamic Control :

In some reactions different products are formed at different temperature depending upon kinetics and
thermodynamics of the reaction. At low temperature, the products are formed irreversibly and reflect rates
of the two competing reaction. This is termed as kinetic control and product formed is called as kinetically
controlled product i.e. product that has higher rate of formation. At higher temperatures, equilibrium is
established between the products, and the thermodynamically favoured product dominates (product stable
at higher temperature). In the case it is called as thermodynamic control and product is called as thermody-
namically controlled product. For illustration refer Chapter hydrocarbon, reactions of conjugated dienes
Illustration - 4 Consider the following reactions of benzene and cyclohexene as given below.
Identify thermodynamically stable and chemically stable reactant.
(A) (B)
SOLUTION :
From heats of hydrogenation we find that cyclohexene has a potential
energy roughly 28.6 kcal/mol higher than cyclohexane, whereas benzene
is 48.9 kcal/mol above cyclohexane. We conclude from these
measurments that both cyclohexene and benzene are thermodynamically
less stable than cyclohexane, and that benzene is thermodynamically less
stable than cyclohexene. We know, however, that the chemical reactivity
of these unsaturated compounds does not reflect this stability order.
cyclohexene reacts rapidly with bromine, whereas benzene is relatively
inert to bromine (in the absence of catalyst and/or heat).The chemical
reactivity of benzene is therefore less than the reactivity of cyclohexene,
and we may say that benzene is chemically more stable than cyclohexene
-at least toward the reagent noted here.

Just as a chain is no stronger than its weakest link, a molecule may be rendered chemically unstable by one
weak bond. We see this in the chemical behaviour of peroxides (R–O–O–R). The O–O bond is less than
half as strong as a C–C bond, and peroxides are notoriously unstable, decomposing via alkoxy radicals
(R–O) on mild heating.
Illustration - 5 Different possible thermal decomposition pathways for peroxyesters are shown below.
Match each pathway from List I with an appropriate structure from List II and select the correct answer using
the code given below the lists.
List - I List - II
(P) Pathway P 1.
(Q) Pathway Q 2.
(R) Pathway R 3.
(S) Pathway S 4.
Codes :
P Q R S P Q R S
(A) 1 3 4 2 (B) 2 4 3 1
(C) 4 1 2 3 (D) 3 2 1 4
SOLUTION : (A)
(P)

(Q)
(R)
(S)
Note : Other radical initiators are given below.

REACTION MECHANISM (A Detailed view) Section - 2
Let us now discuss the mechanisms of Substitution, Addition and Elimination Reactions in detail.
2.A Substitution (Displacement) Reaction :
The replacement of an atom or group from a molecule by a different atom or group is called as substitution
reaction.
RH  X2   RX  HX
RX  NaOH(aq) 
 ROH  NaX
3 AlCl
C6H6  RCl  C6 H5R  HCl
These reactions are further divided into three types depending upon the type of attacking reagent.
(a) Free - radical (b) Nucleophilic (c) Electrophilic
Mechanism of Substitution Reactions :

(a) Free Radical Substitution : It is free radical reaction and involve homolytic cleavage of bonds.
Consider halogenation in alkanes :
It is supposed to proceed via the Free Radical Chain Mechanism involving the following three
steps.
h
(i) Initiation : Cl  Cl  Cl  Cl
hom olysis
Chlorine free radicals
(ii) Propagation : CH 4  Cl 

 CH3   H  Cl
Methyl free radicals
h
CH 3  Cl  Cl  CH3  Cl  Cl
Chlorine free radicals
The chlorine and methyl free radicals generated above, repeat these steps and thereby set up
a chain of reactions. Other propagation steps are also possible and may occur.
 ClCH 2  HCl
CH 3Cl  Cl 
ClCH2  Cl  Cl 
 CH 2Cl2  Cl
(iii) Termination :
The reaction stops after some time due to consumption of reactants and (or) due to the
following side reactions.

The possible chain terminating steps are :

Cl  Cl 
 Cl  Cl ; CH3  CH3 
 CH3  CH3
CH3  Cl 
 CH3  Cl
Halogenated alkane
The above mechanism justifies the formation of ethane, which is actually isolated as a by product
during chlorination of methane.
Note : (i) Rate of reaction of Halogens with alkanes, follows the order : F2 > Cl2 > Br2 > I2
Fluorination is too violent to be controlled, while Iodination is very slow and a reversible reaction.
Iodination can be carried out in the pressure of oxidizing agents such as HIO3 or HNO3.
CH 4  I4 
 CH3I  HI ; HIO3  5HI 
 3I2  3H 2O
(ii) Chlorination of most alkanes whose molecules contain more than two carbon atoms gives a mixture of
isomeric monochloro products (as well as more highly chlorinated compounds). Some examples are
given below. The percentages given are based on the total amount of monochloro products formed in
each reaction. The number of mono-halogenated products formed are equal to the number of different
type of H-atoms.
2 Cl
CH 3CH 2CH 3 
 CH 3CH 2CH 2Cl  CH 3 C HCH 3
light, 25 C |
Cl
Propane n - Propyl chloride Isopropyl chloride
(45%) (55%)
2 Cl
CH3CH 2CH 2CH3   CH3CH 2CH 2CH 2Cl  CH3  C H  CH 2  CH3
light, 25C
|
Cl
n-Butane n - Butyl chloride (28%) sec - Butyl chloride (72%)
CH 3 CH 3 CH 3
| Cl 2
| |
CH 3 C H 2CH 3  
 CH 3 HCH 2 Cl
C  CH 3 C CH 3
light, 25 C |
Cl
Isobutane Isobutyl chloride tert - Butyl chloride
(63%) (37%)
CH 3 CH 3 CH 3
| Cl 2
| |
CH 3 C CH 2CH 3   ClCH 2 C HCH 2CH 3  CH 3 C CH 2CH 3
| 300 C |
H Cl
2 - Methylbutane 1 - Chloro - 2 - methylbutane 2 - Chloro - 2 - methylbutane
(28%) (23%)

CH 3 CH 3
| |
 CH 3 C H C HCH 3  CH 3 C HCH 2CH 2 Cl
|
Cl
2 - Chloro - 3 - methylbutane 1 - Chloro - 3 - methylbutane
(35%) (14%)
 The ratios of products that we obtain in chlorination reactions of higher alkanes are not identical with what
we would except if all the hydrogen atoms of the alkane were equally reactive. We find that there is a
correlation between reactivity of different hydrogen atoms and the type of hydrogen atom (12or 3)
being replaced. The tertiary hydrogen atoms of an alkane are most reactive, secondary hydrogen atoms are
next most reactive, and primary hydrogen atoms are the least reactive.
(iii) Bromine is less reactive toward alkanes in general than chlorine, but bromine is more selective in the site
of attack when it does react. Bromine shows a much greater ability to discriminate among the different
types of hydrogenatoms.
The reaction of isobutane and bromine, for example, gives almost exclusive replacement of the tertiary
hydrogen atom.
CH 3 CH 3 CH 3
| Br2
| |
CH 3  C  CH 3   CH 3  C  CH 3  CH 3 C H 2Br
| light, 25 C | |
H Br H
(~ 99%) (Trace)
Thus bromination is highly selective reaction.

(iv) Relative rate of substitution of H-atoms of alkane in free radical halogenation is :
F2  3° H : 2° H : 1°H ; 1.4 :1.2 :1
Cl2  3° H : 2° H : 1°H ; 5 : 3.8 :1
Br2  3° H : 2° H : 1° H ; 1600 : 82 :1
(v) Fluorine, being much more reactive than chlorine, is even less selective than chlorine. Because the energy
of activation for the abstraction of any type of hydrogen by a fluorine atom is low, there is very little
difference in the rate at which a 1°, 2° or 3° hydrogen reacts with fluorine. Reactions of alkanes with fluorine
give (almost) the distribution of products that we would expect if all of the hydrogens of the alkane were
equally reactive.

Illustration - 6 The relative reactivity of 1 : 2 : 3 hydrogen to chlorination is 1 : 3.8 : 5. Calculate the

percentage of all the monochlorinated products obtained from 2-methylbutane.
SOLUTION :
Relative Amounts
Cl
|
IV. CH 3  C  CH 2CH 3 1  5  5
|
Observe that 2-Methyl butane has 9  1 H- CH3
atoms (6-H atoms are of one type and 3-H
atoms are of other type). Hence percentages of products are :
Hence products are : Relative Amounts 3
(i) 100  13.89
21.6
I. CH 3  CH  CH 2CH 2Cl  3  1 3
| 6
CH3 (ii)  100  27.78
21.6
II. CH 3  CH  CH 2CH3  6  1 6 7.6
| (iii)  100  35.18
21.6
CH 2Cl
5
(iv)  100  23.15
(Reactivity order of 1 : 2 : 3  1: 3.8 : 5 ) 21.6
Observe that there are 2  2 H-atoms ; accor- Note : This is true only for chlorination. Bromination
dingly the product is : is highly selective i.e. 3 bromides are the ab-
solute major product.
Cl
|
III. CH 3  CH  CH  CH3  2  3.8  7.6
|
CH3
Finally there is only 1  3 H-atom.
Allylic substitution :
Alkenes show substitution at allylic position when they react with low concentration of Cl2 at 500°C –
600°C along with addition product.
500C  600C
CH 3CH  CH 2  Cl2   C H 2  CH  CH 2
(gas phase) |
Cl
Allyl chloride

Note that at low temperature and absence of light in liquid phase alkenes show addition reaction. Alkenes
show allylic substitution is presence of NBS in CCl4 (N-bromosuccinimide). NBS is highly selective bromi-
nating reagent at allylic position in alkenes, -carbon to benzene ring (benzylic position) and -carbon to
–C  C and carbonyl group.
Note : (Markovnikov and Anti addition)
Mechanism
NBS reacts usually in presence of non-polar solvent, CCl4. NBS is very slightly soluble in CCl4, which
ensure that low concentration of bromine needed to avoid addition reaction is maintained. The reaction is
catalysed by sunlight or heat.

Br  CH3CH  CH 2 
 C H 2  CH  CH 2  HBr
H–Br is taken up by NBS to avoid addition across double bond.
Note : NBS provides a low concentration of bromide and use up the HBr formed (avoiding addition reaction)
 In case of unsymmetric allylic intermediates, allylic rearrangement takes place to give mixture of two
products.

(b) Nucleophillic Substitution Reactions :

1. Aliphatic Nucleophilic Substitution Reactions :
It proceeds by ionic mechanism. On the basis of time of bond cleavage and bond formation, a
nucleophilic substitution reaction can takes place by two different mechanisms.
They are divided into two categories :
(i) SN2 mechanism :
These are Bimolecular reactions. When rate of reaction depends upon concentration of both
substrate (organic compound) and the nucleophile, the reaction is said to follow bimolecular
mechanism (path) and is represented as SN2.
Consider the alkaline hydrolysis of CH3Cl 
H3C+  Cl + OH 
 H3C  OH + Cl
The nucleophile OH  attacks from the opposite side of Cl atom, and a transition state results
where both OH  and Cl- are partially bonded to carbon atom, to form a pentavalent activa-
ted complex known as transition state (T.S) in the slow step.The transition state then gives
the product and the halide ion. SN2 reaction mechanism is one step reaction mechanim.
(ii) SN1 mechanism :

These are Unimolecular reactions. When the rate of nucleophillic substitution depends only
on the concentration of the substrate, the reaction is said to follow unimolecular path and is
represented by SN1.
Consider hydrolysis of tertiary butyl bromide :
It follows two steps process :
 Heterolytic fission forming carbonium ion.
slow step
 CH3 3  C  X   CH3 3  C  X 
 Attack of nucleophilic on planar carbonium ion.
fast step
 CH 3 3  C   OH    CH3 3  C  OH

(Nu )

Note 1 :  Stronger is the nucleophile, more is the chance of SN2 mechanism.

(large and easily polarised groups are stronger nucleophiles : HS, I, CH3COO–)
 Higher is the concentration of nucleophile, higher is the rate of SN2 mechanism.
 1Alkyl Halides (RX) will always follow SN2 path (absence of steric hindrance).
 2Alkyl Halides will follow SN2 in presence of stronger nucleophile and non-ionising aprotic polar
solvents (such as acetone, DMSO).
Note 2 :  3Alkyl Halides (RX) will always follow SN1 path (greater stability of 3Alkyl carbocations).
 2Alkyl Halides will follow SN1 path when ionising solvents such as H2O or EtOH are used.
If H 2O acts as reagent :
fast step H
(CH3 )3  C+ + HOH  (CH3 )3  C OH 2 
(CH3 )3  C OH

(Nu ) Protonated alcohol
 Polarising medium such as water, alcohols favour heterolytic fission and hence favour SN1. These
solvents after ionising the substrate act as nucleophiles in fast step. This is referred to as solvolysis
(SN1). In solvolysis, we have to visualise rearrangement to get the most stable carbocations (Also
refer to addition & elimination reactions involving carbocations).
 Adjacent C = C or C = 0  system increase the rate of SN 2 reaction by stabilizing the transition
state.
 Adjacent C = C  system increase the rate SN 1 reactions by stabilizing the carbocation.
 Among the fastest of all SN 2 reactions are those where the leaving group is adjacent to a carbonyl
group.
i.e.
 Bicyclo bridge head 3 alkyl halide does not react with nucleophiles either by
SN 1 or by SN 2.
It does not react by SN 1 because the carbocation cannot become planar, nor
by SN 2 because the nucleophile cannot approach the carbon atom from the
opposite side.
Note 3 :  Ease of SN1 mechanism : benzyl > allyl > 3° > 2° > 1° > methyl
(It depends upon stability of carbonium ion).
 Ease of SN2 mechanism :   halocarbonyl > benzyl  methyl > allyl > 1 > 2 > 3
(It depends upon ease of attack of nucleophile ; steric factors).

 There are three outcomes for a reaction at an asymmetric carbon atom and these are inversion, retention
and racemisation. Consider the replacement of a group X by Y in the following reaction :
If (A) is the only compound obtained, the process is called retention of configuration.
If (B) is the only compound obtained, the process is called inversion of configuration.
If a 50 : 50 mixture of the above two is obtained then the process is called racemisation and the product is
optically inactive, as one isomer will rotate light in the direction opposite to another.
 Retention : Retention of configuration is the preservation of integrity of
the spatial arrangement of bonds to an asymmetric centre during a chemi-
cal reaction or transformation. It is also the configurational correlation
when a chemical species X Cabc is converted into the chemical species
Y Cabc having the same relative configuration.
In general, if during a reaction, no bond to the stereocentre is broken, the product will have the same general
configuration of groups around the stereocentre as that of reactant. Such a reaction is said to proceed with
retention of the configuration.
Note 4 : In SN2 mechanism, Nu attacks from back side i.e., side opposite to halide atom.
This means in SN 2 mechanism, the inversion of configuration takes place i.e., spatial arrangements of four
different substituents around chiral carbon atom get changed. In SN 2 path, the nucleophile attacks the
substrate from back side and forms an intermediary transition state giving a molecule with opposite configu-
ration. This means that there is complete inversion which is also referred to as Walden Inversion. Since

Nu  attacks   carbon from back, the steric hindrance around   carbon is the key to an effective SN2
attack. Note that hindrance is almost negligible around 1  C  atom. Therefore SN2 reaction is
stereoselective as well as stereospecific. Note that only one stereoisomer is formed.
Note 5 : In SN1 mechanism, first carbonium ion is formed which is sp2 hybridised and planar.
Hence in SN1 path, a racemic mixture (product) is expected. However on analysing the products, one
observes that only 90 – 95% racemization occurs. The above discussion (Note 4 & 5) provides a strong
evidence for SN1 and SN2 mechanisms.
Note 6 : The nature of solvent also affects the mechanism of the reaction.
 A polarising (ionising) solvent (water, alcohols, acids) favours SN1 path because of :
(i) the formation of carbonium ions is easy as the ions formed are easily solvated.
(ii) Nu– are also solvated (stabilised) in polaring solvents.
The ionising power of solvent depends upon its dielectric constant. e.g., the order of ionising
power of some solvents is : H2O > HCOOH > CH3OH > C2H5OH > CH3COOH (Such
solvents are also called as Protic Solvents).
 A Non-ionising solvent such as DMSO (Dimethyl Sulphoxide) : (CH3 )2 SO
or DMF : Dimethyl Formamide : H – CON(CH3)2 or Acetone favour SN2 path because :
(i) the formation of carbonium ions is not possible as such solvents does not stabilise anions
effectively.
(ii) the strength of nucleophile is increased as it being an anion is not solvated.
(Such solvents are also called as Aprotic Solvents)
Note 7 :Nature of leaving group (i.e. halide ion) :
A good leaving group is one, which is able to stabilise itself. It is observed that a weak base is a good
leaving group. Among halide ions, I  weakest base and hence a good leaving group. A good leaving group,
however cannot decide whether a given reaction will be SN 1 or SN 2. A good leaving group will enhance
the rate of both SN 1 or SN 2 reactions. Among halide ions, I  (weak base : conjugated base of strong
acid, HI) is best leaving group. [Nature of living group : I  > Br  > Cl >> F ] Other good leaving group
are : sulphonates such as tosylates or mesylates.

Note 8 :For a given alkyl group, the reactivity of the halide, R  X, follow the same order in both SN1 and SN2
mechanism.
R  I > R  Br > R  Cl >> R  F
Ambident Nucleophiles
A nucleophile which can attack a substrate through two possible sites.
e.g. Cyanide ion (CN  ) : can attack through ‘C’ or ‘N’ atom
Nitrite (NO 2 ) : can attrack through ‘N’ or ‘O’ atom
It is important to note that the atom of the ambident nucleophile, which attacks the electrophilec site
depends upon the nature of the attacking reagent.
 It KCN (Ionic) is there, then the attack takes place from the carbon side. This can be understood by
observing the structure of  CN which suggests the greater electron density over carbon making
it better nucleophilic site.
 It AgCN (covalent) is there then the attack takes place from nitrogen side (having lone pair). Since
AgCN is covalent therefore we do not expect free  CN ion, so the attack takes place from the lone
pair of nitrogen only.

 If KNO2 (Ionic) is there, then the attack takes place from oxygen side. In NO2 ion, negative charge
of oxygen makes it a better donor as compared with the lone pair of nitrogen.
 If AgNO2 (Covalent) is there, then the attack takes place from nitrogen side. This time there is a
competition between the lone pair of nitrogen and oxygen. Nitrogen being less electronegative comes
out as a better nucleophilic site.
RX + CN  
 RCN + RNC
Haloalkane Nitrile Isonitrile
RX + NO 2 
 RNO2 + R  ONO
Haloalkane Nitro Nitrite
Consider the following reactions :
CH 3 CH3
| |
3 CH OH
(i) CH 3  C  Br + AgCN  CH 3 C NC (Major)
| |
CH3 CH3

3 CH OH
(ii) CH3CH2 Br + KCN  CH3CH 2CN (Major)
CH3 CH3
| |
3 CH OH
(iii) CH3  C Br + AgNO2  CH3  C NO2 (Major)
| |
CH3 CH3
3 CH OH
(iv) CH3  CH2 Br + KNO2  CH3CH 2  ONO (Major)
Summary of structural variations and nucleophilic substitution.
Neighbouring group participation Reaction Mechanism :

Some compounds having a substituent with lone pair or   electron at the carbon next to the reaction
centre [at  carbon atom of leaving group] undergoes nucleophilic substitution reaction by a mechanism
known as neighbouring group participation (NGP). These substituents are called as neighbouring groups.

First Step : It is intramolecular nucleophilic attrack of neighbouring group through its lone pair electron or
  bond electron.
Second Step : It is intermolecular nucleophilic attack of attacking nucleophile on three membered ring inter-
mediate.
It is understood from reaction mechanism that NGP is two successive SN 2 reactions on reaction centre. The
involvement of neighbouring group increase the rate of the substitution reaction.
As you know, SN 2 reactions go with inversion but nucleophilic substitution by NGP on stereogenic centre
proceed with retention of configuration of stereogenic centre [Because of two successive SN 2 reactions on
same chiral carbon atom]
Note :  Retention of configuration in nucleophilic substitution reaction, is an indication of neighbouring group

participation.
 Sulphides, esters, carboxylate, ethers and amines, phenyl groups can assist substitution reactions
through NGP
 Intramolecular reactions (including participation of a neighbouring group) that give three, five, or six
membered rings are usually faster than intermolecular reactions.
 In some cases there may be rearrangement during nucleophilic substitution reaction by NGP mecha-
nism.

Illustration - 7 Find the major product of the reaction given :
SOLUTION :
It is neighbouring group participation (NGP) reaction in which a three membered cyclic intermediate is
formed in first step of reaction (intramolecular SN 2 attack).
In second step there is further SN 2 attack on least hindered carbon atom of three membered cyclic
intermediate.
Illustration - 8 Identify the product(s) formed in each of the following reactions, Identify the paths as
SN 1 or SN 2?
SOLUTION :
(a) OH  (aq) is a strong Nu  , will initiate an SN 2 attack in cyclo alkyl bromide (in 2 cycloalkyl halides,
the steric hindrance is not very high unlike in 2 alkyl halides). OH  will attack   carbon from
the side opposite to Br -atom resulting in the formation of trans product (equivalent to Walden inver--
sion in optically active compounds). This illustrates stereo-selective and stereo – specific aspect.
(b) H 2O (a weak Nu  ) being highly polarising will favour SN 1path (solvolysis).
Note that the Carbocation is planar, hence Nu  an attack it from two sides giving a mixture of two products.

Illustration - 9 Answer the following questions with proper explanation :

(i) KI in acetone, undergoes S N 2 reaction with each of P, Q, R and S. Compare their relative rates.
(ii)
SOLUTION :
(i) In SN 2 reactions, apart from strength of Nucleophile the steric factors are very important for the rate of
reaction.
But in special cases, where   carbon having a strongly electron withdrawing group (EWG), rate of
SN 2 is very fast as in option [S]. The relative rates of SN 2 are as follows :
(ii) It is NGP reaction so there is retention in configuration of chiral carbon atom.

In this reaction I can attack as nucleophile on benzylic C atom having
Br atom. But lone pair electron of oxygen of methoxy group will attack
intramolecularly so reaction proceed by NGP reaction mechanism.The
configuration of chiral carbon atom remain unchanged
Illustration - 10 What are the minor and major products, when the following compound undergoes hy-
drolysis in aqueous acetone?

SOLUTION :
Hydrolysis in aqueous acetone will involve solvolysis (SN 1).
II. Aromatic Nucleophilic Substitution Reaction : Activated SN 2

In general, nucleophilic substitution is not possible on unsaturated carbon
atom under normal reaction conditions. This is because of an increase in
bond dissociation energy of C – X bond due to resonance. Visualise the
case of Aromatic Halides and Vinyl Halides.
However, if a deactivating group (EWG) is present in the ring, it can

“activate” the ring for nucleophilic substitution reaction by the withdrawal
of benzene ring  e  s towards itself.
Aryl halide also undergoes nucleophilic substitution reaction under vigorous reaction conditions i.e. at high
  
temperature and high pressure by using stronger nucleophiles such as RO , NH 2 , R etc., or in presence
of KNH 2 .
On the basis of relative reactivity towards nucleophile, aryl halides are classified as follows.

Activated aryl halide :

Aryl halide having EWG on ortho and/or para positions.
Deactivated aryl halide:

Aryl halide having ERG on any positions.
Unactivated aryl halide :

Unsubstituted aryl halide or aryl halide having EWG on meta position.
Note :  Activated aryl halides means aryl halides activated for nucleophilic substitution reactions and
de-activated aryl halides means less reactive (de-activated) for nucleophilic substitution reaction.
 EWG-Electron withdrawing group ; ERG – Electron releasing group.
 The EWG must be present at ‘o’ or ‘p’ position w.r.t. the substituent (to be undergone nucleophilic
substitution).
 Any substituent that deactivates the benzene ring towards electrophilic substitution, activates the
same ring towards nucleophilic substitution.
 “To be replaced” substituent must be a weaker base as compared to the attacking nucleophile.
Activated aryl halide undergoes nucleophilic substitution reaction by two step reaction mechanism called as
addition-elimination reaction mechanism under proper reaction condition.
Consider the following reaction :

The generally accepted mechanism for the reaction is as shown below :

 Attack of the strong nucleophile on the halogen substituted aromatic carbon forming an anionic
intermediate (Cyclohexadienyl anion).
 Loss of the leaving group, the halide ion restores the aromaticity.
 Kinetics of the reaction are observed to be second order.

 The addition step (step – 1) is the rate determining step (Loss of aromaticity).
 Nucleophilic substitution, and therefore reaction rate, is facilitated by the presence of a strong elec-
tron withdrawing group ortho or para to the site of substitution, which stabilize the cyclohexadienyl
anion through resonance.
 Aryl halide reactivity order : Ar – F > Ar – Cl > Ar – Br > Ar – I (Note the contrast to simple
nucleophilic substitution).
 The more electronegative the group the greater the ability to attract electrons which increase the rate
of formation of cyclohexadienyl anion.
This addition-elimination reaction mechanism is a bimolecular nucleophilic substitution reaction mechanism
represented as SN 2 Ar. [Aromatic bimolecular nucleophilic substitution]
Note : Presence of EWG on ortho and/or para position increase rate of reaction because intermediate car-
banion is stabilized by EWGs
Order of reactivity :
Note : Deactivated and unactivated aryl halides undergoes nucleophilic substitution under proper reaction condi-
tions by elimination-addition reaction mechanism [Benzyne reaction mechanisms].

Illustration - 11 Explain the formation of products in the reaction given below.
SOLUTION :
Under normal reaction conditions chlorobenzene is inert towards nuleophilic substitution reaction. But in
presence of drastic reaction conditions (high temperature and high pressure) it under goes nucleophilic
substitution reaction by elimination-addition reaction mechanism or benzyne reaction mechanism. Benzyne
reaction mechanism is two steps reaction mechanism.
First step : Elimination of HCl (1, 2-elimination)
Second step : Addition of OH 
For the reaction given in question
Note : Benzyne is symmetrical intermediate hence nucleophile can attack on any carbon atom of C  C of benzyne
(c) Electrophillic Substitution (SE)

Substitution in benzene and its derivatives follows electrophillic substitution mechanism. Important SE reactions
include halogenation, nitration, sulphonation, Friedal Craft alkylation and acylation. The mechanisms proceeds
via the following three steps :

1. Formation of Electrophile (E+)

(a) Chlorination (Bromination), Alkylation and Acylation of benzene
In each of these reactions, in anhydrous AlCl3, being a Lewis acid, helps in the generation of the
electrophile.
 Cl  AlCl4
Cl  Cl  AlCl3 
Chlorinium ion
 CH3  AlCl4
CH3  Cl  AlCl3 
Alkyl carbocation

 CH 3 C O  AlCl 4
CH 3COCl  AlCl3 
Acyl carbocation

(b) In the case of Nitration, NO2 (Nitronium ion) is produced by the acid-base reaction of H2SO4
and HNO3, as shown below. H2SO4 acts as Bronsted acid (Proton donor) and HNO3 acts as
Bronsted base (Proton acceptor).
Step - 1
Step - 2
Note : In sulphonation SO3 acts as an electrophile.
2. Formation of Intermediate (Arenium ion) :

E+ attacks benzene due to nucleophillic character of ring and via Electromeric effect. This results in the
formation of a complex (an intermediate) known as arenium ion, in which one of the carbons is sp3 hybridised.
The arenium ion is resonance stabilized.

The complex does not have an Aromatic character because delocalisation of electrons stops at sp3
hybridised carbon.
3. Elimination of proton
In order to restore the Aromatic character, the complex release a proton.
AlCl4 (in case of halogenation, alkylation, and acylation) and HSO 4 (in case of nitration) abstracts a
proton from the sp3 hybridised carbon atom to give monosubstituted benzene derivative.
Note 1 :The number of products formed on monosubstitution is equal to the number of different types of H atoms in
the substrate.
Note 2 :In benzene derivatives (C6 H5  G), the functional group G can also be classified on basis of their polar
nature as : Activating or Deactivating.
The various groups are classified as electron donating and electron withdrawing. Those that withdraw
electrons inductively (polar effect) are said to exert a I effect and those that withdraw electron conjugatively
are said to exert a M effect. Similarly +I and +M effect terms are used for electron donating.
 An activating group (an electron donating group via mesomeric effect) is one which makes benzene
more reactive (nucleophillic) than benzene itself. Such groups are : NH2, OH, OR etc. Note
that these group exert –I effect over the ring, but in these cases +M effect > –I effect.
 A de-activating group (an electron withdrawing group via mesomeric effect) is one which makes
benzene less reactive (nucleophillic) than benzene itself. Such groups are COOH, C = O,CHO,
NO2, CN etc. Note that these group exert –I effect over the ring, which makes these even
more strongly deactivating.

 The halogens exert a very strong –I effect over the ring which outweighs their +M effect, hence these are
weakly deactivating groups. Note that these are weakly ortho & para directing due to +M effect.
 The alkyl group are weakly activating due to only +I effect. They are ortho & para directing because of
hyperconjugation effect (explained below).
In toluene,  CH3 has weak + I effect and considered to be a weaker activating group ; still it is an o/p
directing group for incoming electrophiles. It is due to hyperconjugation. Let us visualize hyperconjugation in
toluene.
More is the number of H – C bonds (  H ) attached to the unsaturated system, more is the probability of
electron release by this effect.
In the given reaction, which is the major product (A) or (B)?
Answer is obviously (A) since  CH3 is more activating than  CH(CH3 )2 as the former has ‘3’   H
whereas latter has only ‘1’   H .
Orientation of Electrophilic Substitution in Benzene :

A typical electrophilic substitution reaction in benzene can be represented as :
If there is already a substituent attached to the benzene ring (as a substrate), the incoming electrophile may
be directed to ‘o’, ‘m’ or ‘p’ positions (w.r.t. the substituent) based on the stability of   complex (arenium
ion) formed as an intermediate.

Consider the following reaction :
Out of the above shown products, which will form to what extent depends on the “behavior” of the substitu-
ent already attached to benzene ring. We can draw the intermediate arenium ion formed during the above
electrophilic substitution reaction based on the position of the electrophilic attack and then look at the
stability of the intermediate formed.
The product formed will depend on the stability of the resonance hybrid as per the “behavior” of substituent
‘X’.
(i) If ‘X’ has +I effect or electron donating effect (+R) e.g.  CH3 group, it will stabilize the carbocation
 CH3 can also stabilise the carbocation through hyperconjugation).
Thus, (1) and (5) will be the most stable resonating structures.
 ‘o’/ ‘p’ isomer will be formed in greater amount.


(ii) If ‘X’ has a –I effect (e.g.  NR 3 ) or electron withdrawing effect (e.g.  NO2 ), it will destabilise the
carbocation. Clearly, the destabilizing effect will be much lesser in case of (7), (8) and (9) as compared to
the ‘o’ and ‘p’ resonating structures.
 ‘m’ isomer will be formed
Note : Electrophilic substitution is quite interesting in case of halo benzenes. ( I) effect of halogens exceed their
(+M) effect, the overall effect of the substituent is deactivating but still it is o, p-directing.
[Remember : All groups that donate electrons by resonance are otho-para director]
As a special case consider hyperconjugation in benzotrichloride.
It means,  CCl3 is a strong m-directing group. Such type of hyperconjugation is known as Reverse
Hyperconjugation.
Note 1 : The presence of activating groups in benzene ring increases the ease of electrophillic substitution, whereas
the deactivating groups do just the opposite. Observe the ease of SE reaction in various substituted benzenes.
C6H 5 NO 2  C6 H5CN  C6 H5CCl3  C6 H5CHO  C6 H5COOH  C6 H5Cl
 C6 H 6  C6 H 5 CH 3  C6 H 5 OCH 3 ~ C 6 H 5 NHCOCH 3  C 6 H 5OH  C 6 H 5 NH 2
Note 2 : (i) In Friedal Craft (F.C.)alkylation, rearrangement in carbocation takes place to give most stable
carbocation via hydride (H–) or methide (CH3–) shift.
(ii) In F.C. alkylation, poly alkylation may occur as alkyl groups are ‘o’ & ‘p’ directing.

(iii) Mono substituted benzene having strongly deactivating groups such as –NO2,– SO3H and –CN do not
give F.C. alkylation.
(iv) There is no rearrangement in acyl carbocation (RCO) as it is resonance stabilised due to oxygen atom.
(v) In F.C. acylation, there is no change of poly acylated product formation as  COR group deativates the
ring.

(vi) In F.C. acylation, if alkyl group (R) in R C O is 3°, alkylation occurs as follows :
[3° Carbocation is highly stable]
(vi) Mono substituted benzene having strongly activating groups such as  NH 2 and  OH do not prefer F.C.
alkylation as AlCl3 being acidic coordinate with these groups.
Now this +ve charge over nitrogen atom deactivates the benzene ring.
In Friedel-Craft acylation reaction, phenolic ether reacts rapidly with the AlX3 catalyst to form complex.
Ph  OCH3 + AlX3 
 Ph(CH3 ) O  AlX3 
 Ph(CH3 ) O AlX3
Illustration - 12 For the reaction given in below, explain why different products are obtained when
different amounts of AlBr3 catalyst are used.
SOLUTION :
In Friedal-Craft acylation reaction, phenolic ether reacts rapidly with the AlX3 catalyst to form complex.
Ph  OCH3 + AlX3 
 Ph(CH3 ) O  AlX3 
 Ph(CH3 ) O AlX3

The adduct of phenolic ether and AlX3 is much less reactive than benzene or phenolic ether in electro-
philic aromatic substitution reactions because, as show in above equation, the oxygen electrons are delo-
calized onto the electron-deficient aluminium. Because of their delocalization away from the benzene ring,
these electrons are less available for resonance stabilization of the carbocation. Intermediate formed within
the ring during Friedal-Crafts acylation.
Note 3 : Orientation in Disubstituted Benzene :

1. When the two substituents are so situated that their influence reinforces at a point, further substitution
can be predicted without any difficulty.
2. When both groups are activating, further substitution is controlled by the stronger activating group.
3. When one substituent is meta-directing and the other is o, p-directing, but they are situated meta to
each other the third substituent goes otho to the meta directing group. This is known as ortho effect.

Note 4 : During intramolecular SE reaction electrophile attack on ortho-position of existing substituents. It is a

cyclization reaction. Five membered or six membered cyclic product is formed. Observe the following in
tramolecular F.C. alkylation.
Directive influence of substituents on Benzene

The following table illustrates the directive influence of various functional groups over benzene for second
substitution.

Note :  NH3 is strongly deactivating and both ‘p’ and ‘m’ directing. Think it in terms of –I effort NOT –M .
Remember it as a fact.
  NO group shows both  M as well as  M effect and it is weakly deactivating but o, p-directing.

Illustration - 13 Give the products in each of the following reactions.

3 AlCl
(a) C6 H 6  (CH 3 )3  C  CH 2Cl 
3 AlCl
3 1. BH /THF HF
(b) C6 H 6  CH 2  CHCH 2Cl  A 
 B 
C
 0C
2. H 2O2 / OH
SOLUTION :
(a) This reaction is an illustration of Friedel – Craft alkylation ( SE reaction).
Now it is simply F.C. alkylation. Here we have visualized the formation of 1C  as there is no
other pathway.
Note : In SE reaction involving carbocation (Friedal Craft alkylation), a stable carbocation is to be

taken as an attacking Electrophile (i.e. visualise rearrangement).
(b)
Note : Observe that Friedel –Craft Alkylation can also be achieved with ROH/HF or RCH = CH 2 / HF at
very low temperature.

Illustration - 14 Identify the product and propose the mechanism :
SOLUTION :
Try yourself : Propose the mechanism for the following reaction :

NOW ATTEMPT PRACTICE EXERCISE-I BEFORE PROCEEDING AHEAD IN THIS EBOOK
2.B Addition Reactions
Reactions in which atoms or groups of atoms are added to a molecule are called addition reactions. Usually
such reactions take place in unsaturated compounds containing double and triple covalent bonds.
These are also classified into three types depending upon type of attacking reagent.
(a) Electrophillic
(b) Free radical
(c) Nucleophillic

Mechanism of Addition Reactions :

(a) Electrophillic Addition Reactions :
Alkenes are  e  rich so are prone to be attacked by an electrophile, so predominantly undergo

electrophile addition reaction i.e. it gets converted to a saturated compound by undergoing addition
reaction, initiated by attack of electrophile. Electrophilic addition on alkenes proceed through follow
ing mechanisms :
Mechanism I :
Specific Features :
Electrophile causes shifting of   bond (i.e. electromeric effect) in a manner so as to form a stable
carbocation.
Carbocation intermediate may rearrange if possible. Racemisation is possible as carbocation is in-
volved and it is planar intermediate.
It’s a Markovnikov’s addition i.e. nucleophile gets attached to the carbon, where most stable carbocation is
favoured, after rearrangement (if possible). Addition of HX, H + / H 2O follows above mechanism.
Mechanism II :
Specific features :
(i) Electrophile causes polarization of  and e  density to form a cyclic ion.
(ii) No rearrangement, as carbocation is not involved.
(iii) Nucleophile attacks cyclic ion in an anti manner i.e. it attacks cyclic ion from theopposite side of at-
tached E in order to avoid steric and electrostatic repulsion.
(iv) It’s a Markovnikov’s addition i.e. the nucleophile attacks cyclic ion on the carbon where a stable
carbocation is possible, i.e. a carbon attached to stabilising alkyl groups (+I, +H)

Following reactions proceeds through above mechanism :
Oxymercuration-demercuration  Hg(CH3COO)2 / THF H2O, NaBH 4 / HO 

Addition of Halogen [X 2 / CCl4 , X 2 / H 2O]
Addition of HA :
Consider addition of HBr to ethylene :
Step 1 : Electrophile (H+) attacks the C = C bond via electromeric effect, (+E effect). Seeing the
incoming electrophile (H+), electromeric shift (effect) occurs, and  electron cloud is dis-
placed towards one of the carbon atoms.
Step 2 : Nucleophile (Br) adds to the carbonium ion :


CH3  CH 2  Br    CH3CH 2 Br
Fast
In case of CH3CH = CH2 (i.e., unsymmetrical alkenes), electromeric shift can occur in either direction to
give two carbocations.
+ +
H+ H+
CH3CH 2  CH 2 
 CH3CH = CH 2 
 CH3  H C CH 3
1° carbocation ; lessstable 2°carbocation ; more stable
Hence the major product formed is CH3  HC(Br)  CH3. This is in accordance with Markonikov’s
addition. In addition reactions of alkenes with HX and H 2 O/ H + , the same mechanism is followed.
 Reactivity of Halogen acids for addition reaction : HI > HBr > HCl
Such addition reactions are referred to as regioselective reactions.
Note : If an electron withdrawing group is present at one end of the alkene, then the addition is reversed. For
example consider addition of HCl to 3, 3-Dichloro propene.
 Cl 2CHCH 2CH 2Cl  Cl 2  CHCH  Cl  CH 3

Cl 2  CHCH  CH 2  HCl 
(m a jo r ) (mi n o r)
The reason for this is the stability of intermediate carbonium ion. I effect of the Cl atoms decreases stability
of carbonium. Try to compare the two possible carbonium ions formed.
 
Cl 2CHCH 2  C H 2 Cl 2CH C H 2  CH 3
(i) (ii)
(More stable) (Less stable)
In (i), two Cl atoms are at a greater distance from C+ site, whereas in (ii), two Cl atoms are nearer to C+
site. Hence I effect de-stabilises the carboction. (ii) to a much greater extent than it does in (i), and hence
the major product is with respect to intermediate (carbocation) (i).

Observe the following addition of HBr in 2-Methyl-2-butene.
CH3
|
Now the major product eventually will be : CH 3  C  C H  CH3
| |
Br H (tert. pentyl chloride)
So let us red line Markonikov’s rule as : “Electrophillic addition to a carbon - carbon double bond involves the
intermediate formation of the most stable carbocation”.
Rearrangement in addition reaction
Observe the following example of hydration of alkene in acidic medium carefully.
H
CH 3  C H  CH  CH 2  ?
| H2O
CH3
First visualise formation of initial carbocation via electromeric effect.
Now H– (hydride) from the adjacent 3° carbon occurs to give more stable 3° carbocation.
So, you have observed a rearrangement in addition reaction to give the most stable carbocation.

Illustration - 15 Predict the major products in the following reactions :
(i) HBr (ii)

CH3  CH  CH  CH 2  CH 3 

SOLUTION :
In all the given reactions, visualise the addition across the  bond (starting with addition of an electrophile)
through more stable carbocation.
(i)
or
Note : (II) is more stable than (I) due to more number of   H available for hyperconjugation.
 For major product :
(ii)

 Addition of X2 in CCl4 :
Addition of Halogens (X2) in CCl4 follows the mechanism involving cyclic intermedimate.
(i)
The bromine molecule is polarised when it approaches alkene. It then transfers a +ve Br atom (an
electrophile) to form a cyclic bromonium ion.
(ii)
The bromide ion (Br) attacks one of the carbon like an attack in SN2 reaction, which results in
opening of ring to give viccinal dibromide.
 Addition of X2 in H2O : ( HO  X  )
The first step is same as for halogens (Br2) shown above.
In next step, instead of bromide ion, H2O acts as a nucleophile and attacks a carbon of the ring
forming protonated halohydrin.

In the given example, the structure of the product tells us that what attacks the more highly substituted
carbon.
Br
2 (CH ) C  CH Br
(CH 3 ) 2 C = CH 2  3 2 2
H2O |
OH
2 - Methylpropene 1- Bromo- 2 - methyl- 2 - propanol (Major)
This suggests that, as water attacks the bromonium ion, positive charge develops on the carbon from which
the bromine departs. The transition state has some of the character of a carbocation. We know that more
substituted carbocation are more stable than less substituted ones ; therefore, when the bromonium ion ring
opens, it does so by breaking the bond between bromine and the more substituted carbon.
 The above additions are region-selective as one of the product dominates over the other.
 Whereas, the addition of Br2 in CCl4 and hydroxylation are sterco-specific and sterco-selective reac-
tions as illustrated by following examples.

Note : Both-cis-2-pentene and trans-2-pentene on reaction will Br2 form racemic mixture, as there will not be any
plane of symmetry in both cases.
Illustration - 16 When 3-Buten-2-ol reacts with HBr, two isomeric products are obtained. Explain with
proper mechanism.
SOLUTION :
Usually alcohols do not give nucleophilic substitution, as OH  , the leaving group is poor being strong base.
However, in presence of H + ions, 2 and 3 alcohols give SN 1 type of nucleophilic substitution as H 2O
(weak base) is now the good leaving group.
Allylic carbocations are resonance stabilised.

 Note that in the above question H  attacks on the lone pair in preference to   bond. If H + attacks

  bond, the intermediate formed is : CH 3CH (OH )  C HCH 3 , which is less stable as compared to
+
CH3  CH  CH = CH3
Carbocation (allylic)
 If both lone pair and   bond are in conjugation with each other, then H + attacks on   bond to give a
stable carbocation.
(b) Free radical addition

In the presence of peroxide, addition of HBr follows Anti-Markonikov’s addition (Peroxide or Kharash
effect).
Consider addition of HBr in propene in presence of Benzoyl peroxide. The following free radical chain
mechanism has been proposed :
Chain initiation :
O O O
|| || ||
Homolysis
(i) C6H 5  C  O  O  C  C6 H5    
 2C6 H5  C  O  2 C6 H5   2 CO 2
Benzoyl peroxide

Homolysis
(ii) C6H5   H  Br   C6 H6  Br
Chain Propagation Step :
(i)
Recall stability of free radicals via Hyperconjugation effect.

Homolysis
(ii) CH 3  CH  CH 2  Br  H  Br 
 CH 3  CH 2  CH 2  Br  Br
(Major product)
and CH3  C H 2  CH 2  H  Br 
 CH3  C H  CH3  Br
| |
Br Br
(Minor product)

Note : HCl and HI do not add similarly in the presence of peroxides because one of the step of chain propagation
steps becomes endothermic. The reaction with H  Cl fails because of higher H  Cl bond energy, which
prevents its cleavage by the free radical [step (ii)]. The H  I bond is weaker, but iodine free radicals com
-bine to form iodine molecules instead of adding to the double bond.
(c) Nucleophilic Addition Reaction
Consider the addition of CNtoaldehydes and ketones.
 In presence of CN (nucleophile),  e’s of bond are shifted towards more electrone-
gative oxygen atom via –E effect).
Presence of EWG increase reactivity while presence of ERG decrease reactivity towards nucleo-
philic addition reactions.
Reactivity Order in Carbonyl Compounds : H  C H > R  C H > R  C R
|| || ||
O O O
Addition of Grignard Reagent with carbonyl compounds follows the above mechanism. The conden-
sation reactions (to be studied later) usually follow nucleophilic addition reaction pathway.
2.C Elimination Reactions :
These reactions involve loss of atoms or group of atom from a molecule to form multiple bonds.
Mechanism of elimination reactions :

(a) Dehydrohalogenation of alkyl halides : It can be achieved by E1 (unimolecular)
or E2 (bimolecular) path.

E2 Elimination : It is one step reaction mechanism.

Consider elimination in tertiary butyl bromide by ethoxide ion.
 Base (B)is this case is ethoxide, C2H5O or (ethanolic KOH : OH– as base or NH2–) which forms a
transition state with alkyl halides as shown below (just like an SN2 path). Ethoxide EtO  attacks -
proton (H), and abstracts it.
Observe that the reaction is bimolecular i.e., it follows E2 path, just like SN2 path.
Note 1 :  Since all nucleophiles are good bases, SN2 products also follow along with E2 products.
 3 and 2 alkyl halides give alkene (E2) as major product.
 1 alkyl halides give SN2 as major product. (Williamson’s synthesis of ethers)
 1 alkyl halides, however give alkenes with strong and sterically (bulky) hindered bases such as tert.
butoxide.
Note 2 :  The reaction rate of elimination increases with increasing strength of the base :
CH3COO < HO < C2H5O < (CH3)3CO < NH2
 The ease of elimination follows : 3 > 2 > 1 (alkyl halides)
 The elimination occurs more easily when the halides are already unsaturated. e.g., elimination occurs
readily in
CH2 = CH  CH2CH2Br than in CH3CH2CH2CH2Br.
Visualise the product on elimination. (a conjugated diene is formed)
Note 3 : (Orientation of products)
 Two different alkenes may be formed when there are two -hydrogen atoms. The major is one having
more alkylation about the double bond (in accordance with Zaitsev Rule or Saytzeff Rule). It is also a
regio-selective reaction.

This is referred to as Saytzeff Rule. The exception to Saytzeff rule comes when a large (bulky) and strong
bases such as teritary butoxide are used, then due to steric hindrance (in base) less substituted alkene (Anti-
saytzeff product) is formed. It is also known as Hoffmann’s product.
 Note that Saytzeff’s (Zaitsev) rule is not used in cases, where alkyl halide has double bond or benzene ring.
In such cases, conjugated double bonds have a greater stability (including conjugation with benzene ring).
 In case of alkyl fluorides, the product of E2 reaction is also Anti-Zaitsev. F is a poor leaving group, so
remember it as a fact that Zaitsev product is minor.
3 CH O
CH 3  CH  CH 2CH3 H 2C = CH CH 2  CH3 + CH3  CH = CH  CH3
| CH3OH Major Minor
F
E2 An anti Elimination :
2
In the following substrate, observe that there are two  H -atoms. H1 atom is anti to Br atom and H atom
is in the same plane as that of Br atom. Note that E2 is an anti-elimination, which means  hydrogen and
the leaving halogen atom (Br) must leave from opposite planes. In the following Illustration, observed that
product formed is not a Saytzeff product. Which justifies the concept of anti-elimination.

E1 Elimination : Its is a two steps reaction mechanism.

Elimination may take a different path (E1 path is just like SN1 path). Consider the elimination of
(CH3 )3  C  Br via E1 as :
(i)  CH 3 3  C  Br   CH 3  3  C   Br 

(ii)  CH3 3  C  OEt 

  CH3  3  C  OEt

as Nu SN 1 product
(iii)  CH3 3  C  OEt 

 CH 3  C  CH 2
as Base |
CH 3
E1 product
 This means E1 path will always accompany SN1 and usually SN1 product dominate over E1 product. Note
that usually a good base is always a good Nucleophile and vice-versa except among halide ions. (I is a
good nucleophile, but weaker base and F is a poor nucleophile, but stronger base). Hence we should
visualize above elimination via E2 path, using strong bases and slightly polarised (weak) nucleophiles.
(RO  , OH abc , NH 2 )
 In such unimolecular reactions (i.e., in E1 and SN1), wherever structure permits, rearrangement occurs,
since reactivity depends upon stability of carbocations.
E1 is observed when using weak bases which are usually polarizing. (H 2O, EtOH)
CH3 CH3
| EtOH |
CH3  C H  C H  CH3   CH3  C H  C H  CH3 
| or H 2 O 
Br
The product I, II and III are formed. Product (II) is most stable and major product. In the above path,
we also expect SN1 product, as H 2O and EtOH are also weak nucleophiles. At low temperature, SN1
product usually dominate and at high temperature, E1 product dominate.

Note : E1 elimination also occurs in cases where there is no -hydrogen. Visualise rearrangement via CH3– (methide)
shift.
CH3 CH3 CH3

| alcoholic
| |
CH3  C CH 2 Br  CH3  C  CHCH3  CH 2  C CH 2CH3
| KOH
(Major) (Minor)
CH3
Neopentyl bromide
(E2 is not possible & SN2 is also not possible)
A double bond in a six-membered ring is usually more stable in an endocylic position than in an exocyclic
position.
Illustration - 17 Visualise both E1 and E 2 paths for dehydrohalogenation

of 1-Bromo-1-methyl cyclohexane.
SOLUTION : E1 path : First step is similar to that of SN 1 path.
It can give two E1 products losing a proton to base being used for dehydrobromination.
E2 path :
Base (such as RO or alcoholic KOH  OH  as base) abstracts a   H atom which simultaneously results
in loss of Br  ion in a bimolecular (E2) path. Note that in given case orientation of product is important as
there are two   H atoms.
If we take (CH3 )3 CO  as a base, the products ratio will get reversed.

Note : Just by change E1 and E2 both give same products. It is not necessary that two paths give the same
products. Usually dehydrohalogenation occurs via E2 pathways as SN 1 always competes with E1
at normal temperature.

Illustration - 18 Predict the product (X) of the following reaction :
SOLUTION :
Clearly the given reaction involves dehydrohalogenation of alkyl halides and under the given condition,
3 cycloalkyl halide will follow E2 path. Now E2 mechanism involves   elimination of hydrogen, so we
need to keep one thing in mind that the   H to be removed should be present in an anti-position (or
exactly opposite position) w.r.t the bromine atom. In other words, E2 mechanism involves “anti-elimina-
tion”.
Hence in this question, product (X) will be the less stable

anti-Saytzeff (Hoffmann’s product). The more stable
Saytzeff’s product (Y) would have formed if the substrate
was as shown in reaction :
E1 versus E2
 With respect to the substrate, the reacitivity of both E1 ad E2 increases from 1°, 2° and to 3° alkyl
halides. Note that reactivity of E2 increases due to greater stability of more highly branched alkenes
formation (Saytzeff Rule) ; whereas the reactivity of E1 increases because of the greater stability of
carbocations in rate determing step.
 The rate of E2 is proportional to concentration and strength of the base, whereas rate of E1 is inde-
pendent of nature of base.
 For a given substrate, E2 is the path for dehydrohalogenation in presence of more concentrated base
or a strong and slightly polarised base (RO–, NH2–, OH– ions).
 E1 path is followed by 2° and 3° alkyl halides in presence of weak bases such as alcohols i.e.
basically when base is the solvent.

ElcB is a rare mechanism of   elimination reaction of organic compound having poor leaving group and
more acidic   Hydrogen atom.
OH 
CH3  CH(OH)  CH2  CH = O  CH3  CH = CH CH = O ;

alc. KOH
Ph 2CH  CF3 
Ph 2C = CF2


Conditions for SN 2 reaction :

Steric hinderance should be minimum, so usually 1 and 2 substrate show SN 2 reactions. Hence it is not
possible for 3 substrate to show SN 2 reactions.
Nucleophilic should act as a pure nucleophile i.e. the basic nature of nucleophile should not dominate over
its nucleophilic character.
If any (or both) of the above two conditions are violated, it results in E2 reaction.
CH3
|
alc. KCN
CH3  CH 2  C CH3 
 E 2 (3°substrate)
|
Br
3 alkyl halide
alc.
CH3  CH 2  CH 2  Br 
SN 2 (Both conditions satisfied)
KCN
1 alkyl halide
NaNH
2  E 2 (strong base)
CH3  CH 2  CH 2  Br 
or
alcoholic KOH
1 alkyl halide
alc. KCN
CH 3  CH 2 CH 2  CH3 
 SN 2 (strong nucleophile)
|
Br
2 alkyl halide
Illustration - 19 Give major and minor products when each of the given compounds (bromides) reacts with
aqueous KOH. Also identify the path (SN1 or SN2).
CH 3 Br
| |
(A) CH 3  C H  CH 2 Br (B) CH 3  C  C H  CH 3
| |
CH 3 CH 3
(C) (D)

SOLUTION :
(A) Note that aq. KOH OH– as Nu– and alc. KOH OH– as base.
aq.
CH3 C H  CH 2 Br 
| KOH
CH 3
Observe that substrate is 1° halide and OH– is a strong Nu–. Hence product will be via SN2 path (1° halides
have no hindrance to Nucleophilic attack).

OH
CH 3 C HCH 2 Br  CH3 C HCH 2  OH  CH3  C  CH 2
SN 2 |
| |
(Minor)
CH3 CH3 CH3
(E2)
Note : SN1 path is not favoured as 1° carbocation is weakly stable.

(B) Observe that substrate is 2° halide, and reagent is aq. KOH. Aqueous solution i.e. H2O is a strong polarising
solvents, hence SN1 path will be followed.
Note that due to strong hindrance, SN 2 will not be possible.
(C)
Observe that substrate is 1° [as in (A)], so SN2 path is followed.
Note that SN1 Path will not occur as 1° carbocation is weakly stable.

(D)
Observe that substrate is 3°, so SN1 path will be favoured as intermediate will be highly stable 3° carbocation.
Note that in 3° halides, SN2 is not possible due to steric hindrance.
Illustration - 20 Give the major and minor products in the following reaction.
SOLUTION :
Note that H2O is a strong ionising solvent (protic) and a weaker nucleophile. Substrate is 2° halide and
aqueous medium serves as polarising (protic polar) solvent favouring SN1 path. This is an illustration of
solvolysis.

Illustration - 21 Identify various products obtained when 1 - Bromomethyl cyclohexene undergoes solvolysis
in the presence of C2H5OH. Propose a proper mechanism and identify the type of paths (mechanism).
SOLUTION :
1-Bromomethylcyclohexene
(i) C2H5OH is a weakly polarising (protic polar) solvent which favours SN1 type of path giving carbocations as
intermediate. in slow (RDS) step.
..
(ii) C2H5 OH serves as a weak nucleophile in the fast step to give ethers as SN1 products.
Note that the carbocation formed is resonance stabilised (Allylic type).
Note : SN1 path (products) is usually competed by E1 path (products), since carbocations can loose a proton to
give alkene (E1) as product.
II :

Observe that :
1. Intermediate : I cannot loose proton.
2. Usually SN1 products are formed at normal room temperature. Here as a special case, E1 is very important
as a conjugated diene is formed which is highly stable (due to resonance).
3. If instead of C2H5OH, we use aqueous solution of KOH, the reaction will be faster and instead of ethers,
alcohols are formed as SN1 products. However E1 product will remain same.
Illustration - 22 Give the products (s) that can be formed in each of the following reactions. Also identify
the path (SN1, SN2, E1, or E2) in each case.
MeOH Me C  OH
(a) CH 3CH 2CH 2 Br  MeO   (b) CH 3CH 2CH 2 Br  Me3CO  
3

50 C 50 C
CH OH CH OH
(c)
3 
2  brom obutane  NaHS  (d) Et3C  Br  OH  
3 
50 C 50C
CH 3 OH Me C  OH
(e) Et3C  Br   (f) CH 3CH 2CH ( Br )CH 3  Me3CO  
3 
25 C 50C
SOLUTION :
(a) The substrate is a 1° halide. The attacking species is CH3O–, a strong base (but not a hindered one) and
a good nucleophile. So we should visualise an SN2 reaction mainly, and the major product should be
CH3CH2CH2 OCH3 .
A minor product might be CH3CH = CH2 by an E2 pathway.
(b) Again the substrate is a 1° halide, but the reagent is (CH3)3CO–, is a strong and hindered base. We should
expect, therefore, the major product to be CH3CH = CH2 by an E2 path, and a minor product to be
CH3CH2CH2OC(CH3)3 by an SN2 path. Note that here a -H is abstract which is not sterically hindered.
(c) The reactant is 2-bromobutane, a 2° halide, and one in which the leaving group is attached to a chiral centre.
The reagent is HS–, a strong nucleophile, but a weak base. We should expect mainly an SN2 reaction,
causing an inversion of configuration at the chiral centre and giving an inverted stereoisomer.
(d) The base/nucleophile is OH–, a strong base and a strong nucleophile. However, the substrate is a 3°halide;
therefore, we should not expect an SN2 reaction. The major product should be CH3CH = C(CH2CH3)2
via E2 reaction. At this higher temperature, and in the presence of a strong base, we should not expect an
appreciable amount of the SN1 product, CH3OC(CH2CH3)3, however we can expect the product :
CH 3CH = C(CH 2CH3 )2 via E1 also.

(e) This is solvolysis; the reagent is simply the solvent, CH3OH, which is a weak base (therefore, no E2
reaction) and a poor nucleophile. The substrate is tertiary (Therefore, no SN2 reaction). At this lower
temperature we should expect mainly an SN1 pathway leading to CH3OC(CH2CH3)3. A minor product, by
an E1 path would be : CH3CH = C(CH2CH3)2.
(f) Refer (b), (CH3 )3 CO  will abstract less hindered   H to give 1-Butene as major product (Anti-Saytzeiffs
product).
Illustration - 23 Find the product (A) and (B) :
SOLUTION :
At 0C , product will be controlled kinetically i.e. according to stability of intermediate,  1, 2-addition.
At 65C , product will be controlled thermodynamically i.e. according to the stability of products,  1, 4-
addition.

Illustration - 24 What are the major/minor products obtained in each of the following reactions. Also iden-
tify paths.
OTs
| CH 3 COOH OH
(a) CH 3CH 2  C H  CH 3  CH 3  COO    (b) Tert. pentyl bromide  
EtOH
HCl
(c) CH3CH  CH  CH  CHCH 3 
 (d)
SOLUTION :
(a) Note that substrate is 2° and CH3COO– is a weak base, so elimination is not possible. However CH3COO–
acts a good Nu– to give SN2 product as major. Also observe that TsO– , tosylate is a very good learing
group.
OTs O  CO  CH3
| SN 2 |
CH 3  CH 2  C H  CH3  CH3COO    CH3CH 2  C H  CH3  TsO
SN 2(Ester)
There may be minor, E2 product.

(b) Note that alc. KOH  OH as a base. Here, substrate is 3° and OH a good Nu and a good base, will give
E2 products (SN2 will not be possible due to steric factors at 3° –  – carbon)
CH3 CH3 CH3
| OH
 | |
CH 3  C  CH 2CH3   CH3  C  CHCH3  CH 2  C  CH 2CH3
| EtOH Major : Saytzeff Minor (Anti-Saytzeff)
E2
Br

H
(c) CH 3CH  CH  CH  CHCH 3 Visualise electrophilic addition in alkenes.

Cl

This is referred to as conjugate (E+) addition in dienes.

Note : If electromeric effect in diene occurs as follow, another (minor) addition product can be formed.
(d) Clearly it will follow SN1 path as C2H5OH is a polarising solvent and weak nucleophile.
CH3 CH3
| SN 1
|  CH3
 
CH 3  C  CH 2 Br   CH3  C  C H 2  CH 3  C  CH 2CH3
| | shift |
CH3 CH3 CH3
+ +
1°C : Less stable 3C : More stable
Accordingly 3° carbocation can give both SN1 (Major) and E1 (Minor) products.
(b) Dehydration of Alcohols

It can also be achieved via E1 or E2 paths.
E1 path :
Consider Dehydration in tertiary butyl alcohol
Step 1 : Formation of Oxonium ion :
In this reaction, first conc. H2SO4 gives a proton (H+). The electrophile (H+) attacks oxygen atom
(OH) containing lone pairs of electrons to form an unstable intermediate called as oxonium ion
(protonated alcohol).

Step 2 : Formation of Carbocation :

The oxonium ion (being unstable) loses a water molecule to give a carbocation.
Step 3 : Elimination of Proton :

This carbocation loses a proton to give an alkene at 170C.
An alkene is formed and water accepts a proton (H+) to give H3O+.

Note 1 :
 The important intermediate in this reaction is carbocation ion. So you have to check its stability, while
proposing the mechanism. In the above case, the carbocation ion formed is tertiary butyl carbocation,
which being a tertiary ion is highly stable (Recall the stability of carbonium ions). In other case, you have
to make proper rearrangements for the stability of carbonium ion.
For example consider Dehydration of the following alcohol :

In Dehydration of alcohols, Saytzeff rule is always obeyed, unlike in dehydrohalogenation.

Note 2 :
In alcohols having cycloalkyl radicals, ring expansion occurs and cycloalkenes are formed. For example
consider following dehydration.
What is major/minor product(s) ?
E2 path :
The E1 mechansim is clearly followed by secondary (2°) and tertiary (3°) alcohols as the corresponding
carbocations are stable and hence are formed. Primary alcohols do not prefer E1 path as the corresponding
(1°) carbocations are not formed, being poorly stable. These alcohols follow E2 dehydration as follows :
After protonation of –OH group (similar to E1 path) in step-1, a primary protonated alcohol reacts with the
conjugate base of mineral acid (HSO4–) by -elimination (similar to E2 elimination in halides by RO–).
H SO 
2 4  RCH CH O H  HSO 
RCH 2CH 2OH  2 2 2 4
[ Not neccessarily a saytzeff product]

Note :(i) E2 products always accomany SN2 products (just like in case of alkyl halides) since steric hinderance
is absent at 1° -carbon. HSO4– can attack ‘ – C’ to give alkyl sulphate ester.
(ii) In this reaction, we can also expect an ether to be formed if a second alcohol molecule makes an SN2
attack at 1° -carbon.
Hence acid-catalysed dehydration involving 1° alcohols is not a good method to prepare alkenes.
(iii) Alcohols cannot show E2 reactions with bases, as –OH will be a poor leaving group. So we use acid
catalysed dehydration (as above i.e., E1). But to prepare alkenes from 1° alcohols, E1 is not a good
method. So an alternative method is first convert alcohol to alkyl sulphonate and then carryout E2 with
sterically hindered base such as tert. butoxide
3 6 4p  CH  C H SO Cl
2  RCH CH O  Ts  HCl
RCH 2CH 2OH  2 2
Pyridine
Ts : tosyl  CH3 – C6H4 – SO2 –


RO /R OH
RCH 2CH 2OTs   RCH  CH 2  OTs
E2
(TsO– : Tosylate : a very good leaving group)
(R’ 3 alkyl group)
Note : Although dehydration of Primary Alcohols is an E2 reaction, the product in most of the cases is identical to
the product that could be obtained if a carbocation has been formed in an E1 reaction and then had rearranged.
This can be explained as per the following reaction mechanism :

Illustration - 25 What are the major and minor products obtained when the given
compound is dehydrated is presence of heated conc.H2SO4 ?
SOLUTION :
The six different Alkenes (A, B, C, D, E and F) are the possible products. The order of stability of these
alkenes is in order :
D > E > F> C > B >A Hence major is D and minor is E (second important product).
Note : (i) In such reaction i.e., involving carbocations, always visualise the most stable carbocation (visualise
rearrangement or ring expansion) and then proceed.
(ii) Usually endocyclic cycloalkenes are more stable, but watch for special case (as above) considering
stability via Hyperconjugation.
(iii) In 1 alcohols with   carbon being 3 or 4, E1 elimination occurs as follows. In such cases E2
can not occur due to steric factor or absence of   H .

IN - CHAPTER EXERCISE - E
1. Give the mechanistic symbols (SN 1,SN 2, E1, E 2) that are most consistent with each of the following
statements :
(A) Methyl halides react with sodium ethoxide in ethanol only by this mechanism.
(B) Unhindered primary halides react with sodium ethoxide in ethanol mainly by this mechanism.
(C) When cyclohexyl bromide is treated with sodium ethoxide in ethanol, the major product is formed by
this mechanism.
(D) The substitution product obtained by solvolysis of tert-butyl bromide in ethanol arises by this mecha
-nism.
(E) In ethanol that contains sodium ethoxide, tert-butyl bromide reacts mainly by this mechanism.
(F) These reaction mechanisms represent concerted processes.
(G) Reactions proceeding by these mechanisms are stereospecific.
(H) These reaction mechanisms involve carbocation intermediates.
(I) These reaction mechanisms are the ones most likely to have been involved when the products are
found to have a different carbon skeleton from the substrate.
(J) Alkyl iodides reacts faster than alkyl bromides in reactions that proceed by these mechanism.
NOW ATTEMPT PRACTICE EXERCISE-II BEFORE PROCEEDING AHEAD IN THIS EBOOK

Example - 1 Arrange the following in increasing order of stability on the basis of resonance :
(A) (i) (ii)
(iii) (iv)
 
(B) (i) C H 2  CH = CH  CH = O CH3 (ii) CH 2 = CH  C H  CH = O CH 2
 
(iii) C H 2  CH  CH = CH  O CH3 (iv) CH 2 = CH  C H  CH  O CH3
 
(C) (i) CH 2 = CH  CH = CH  CH 2 (ii) CH 2 = CH  CH  CH = CH 2
   
(iii) CH 2 = CH  CH  C H  CH 2 (iv) CH 2  CH = CH  C H  CH 2

(D) (i) CH 2 = CH  CH = CH  CH = CH 2 (ii) CH 2 = CH  CH  CH = CH  C H 2

(iii) CH 2  CH = CH  CH = CH  C H 2
SOLUTION :
(A) (i) < (iv) < (ii) < (iii)
In (iii) there is strong  M effect of NO 2 .
In (ii) and (iv)  I effect of Br and OCH3 are prominent.
In (i) delocalization due to only phenyl ring is there.
(B) (iii) < (iv) < (ii) < (i)
(i) and (ii) should have more stability as compared to (iii) and (iv) because of more number of covalent
bonds.
Also (i) has got 1 carbanion whereas (ii) has got 2 carbanion. Hence (ii) < (i)
In (iv), carbocation is close to oxygen hence it is more stable due to the lone pairs on oxygen.  (iv) > (iii).
(C) (ii) > (i) > (iii) > (iv)
(i) and (ii) should have greater stability as compared to (iii) and (iv) because of greater number of covalent
bonds.
Also (ii) has got 2 carbocation whereas (i) has 1 carbocation.
(iii) has unlike charges close to each other but (iv) has no such factor.
(D) (iii) < (ii) < (i)
(i) is most stable due to maximum number of covalent bonds.
(ii) has got 2 carbocation whereas (iii) has got 1 carbocation. Hence (ii) > (iii).
Example - 2 7-bromo-1, 3, 5-cycloheptatriene exists as ionic species in aqueous solution while 5-bromo-
1, 3-cyclopentadiene doesn’t ionise even in presence of Ag  (aq). Explain.
SOLUTION :
Example - 3 MATCH THE FOLLOWING :

Column 1 [Reactions] Column 2 [Type of reaction]
(A) (P) Electrophilic Substitution
(B) (Q) Free radical substitution
(C) (R) Electrophilic addition
(D) (S) Free radical addition
SOLUTION : [A-P] [B-Q] [C-R] [D-S]

Benzene is an aromatic compound and aromatic compounds undergoes electrophilic substitution reactions.
Cyclohexane is a saturated aliphatic hydrocarbon and it undergoes free radical substitution reaction in
presence of light.
1-Methyl cyclohexene is unsaturated hydrocarbon and it undergoes electrophilic addition reactions. But
addition of HBr in presence of peroxide takes place by free radical addition reaction mechanism.
Example - 4 MATCH THE FOLLOWING :

Column 1 [Reactions] Column 2 [Type of reaction]
(A) (P) Substitution reaction
(B) (Q) Elimination reaction
(C) (R) Addition reaction
(D) (S) Intramolecular reaction

(T) Rearrangement
SOLUTION : [A-P] [B-Q, T] [C-R] [D-P, S]
Derivative of benzene undergoes electrophilic substitution reactions. Alcohols on heating with conc. H2SO4
undergoes dehydration (elimination reaction). In this case alcohol is primary alcohol without -hydrogen
atom hence it dehydrated by E1 reaction through formation of carbocation. Primary carbocation formed
will rearrange to more stable 3carbocation.
Reduction of ketone is an addition reaction.
When attacking nucleophile and leaving group are part of same substrate then reaction is intramolecular
reaction.
Example - 5 Consider reactions 1 through 6. Those carbon atoms undergoing change, as part of a
functional group, are coloured. In the cases shown, each carbon atom has either been reduced or oxidized.
Your job is to identify the change in oxidation state that has occured for each of the colored carbons.
Br
2  CH CHBrCH Br
1. CH3CH  CH 2  3 2
2 6 1. B H
2. CH 3CH  CH 2 
 CH 3CH 2CH 2OH
2. H 2O2 , NaOH
NaBH
4  CH CH CH OH
3. CH3CH 2CH  O  3 2 2
Ag 
4. CH3CH 2CH  O 
 CH 3CH 2CO2 H
H 2O, pH  8
5. Heat
CH3COCH 2CO2 H  CH 3COCH 3  CO2
6. tautomerization
H 2C  C (OH )C2 H 5 
 H 3CCOC2 H 5
SOLUTION :
Addition of electronegative atom to carbon is oxidation. Removal of hydrogen atom from carbon is also
oxidation. While addition of hydrogen atom or removal of electronegative atom result in reduction of car-
bon. So in reaction :
(1) Both carbon atoms are oxidized (2) One is reduced, other is oxidized
(3) Carbon is reduced (4) Carbon is oxidized
(5) One is reduced, other is oxidized (6) One is reduced, other is oxidized
Example - 6 Explain why the doubly allylic alkyl halide (A) undergoes much more rapid solvolysis in
aqueous acetone than compound (B). Also then explain why compound (C). Which is also a doubly allylic
alkyl halide, is solvolytically inert.
(A) (B) (C)
SOLUTION :
Solvolysis reaction is nucleophilic substitution reaction in which both nucleophile and solvent are same
chemical species e.g. hydrolysis reaction. Generally solvolysis reactions of alkyl halides are proceed by
SN 1 reaction mechanism. The doubly allylic halide (A) easily undergoes solvolysis reaction because
allylic carbocation is resonance stabilized.
The compound (C) is also doubly allylic alkyl halide but it is solvolytically inert because on ionization it form
least stable anti-aromatic carbocation intermediate.
Example - 7
MATCH THE COLUMN :
Column 1 [Reactions] Column 2 [Reaction mechanism]
(A) (P) NGP
(B) (Q) SN 2
(C) (R) SN 1
(D) (S) Intramolecular nucleophilic

substitution
SOLUTION : [A-r][B-q, s][C-q][D-p,s]
Lone pair of electron on adjacent carbon atom of reaction centre stabilize carbocation so reaction proceed
by SN 1.
S N 2 reactions adjacent to groups are usually fast due to neighbouring group participation.
Observe the rearrangement in NGP.
SOLUTIONS TO REVIEW EXERCISE
1. If bonds formed by an atom are more or less than its valency, it has some charge called as formal charge.
Formal charge = Valence electrons in isolated atom – No. of bonds formed – No. of unshared electron
2. A, B and C are resonance forms of diazomethylene (CH 2 N 2 )
The structure (C) is least stable due to incomplete octet. But structure (B) is most stable because negative
charge is on more electronegative atom.
The structure (A) contains nucleophilic carbon atom while structuere (C) contains electrophilic carbon atom.
Both (A) and (B) have linear geometry while (C) has bent geometry. This is an example of how VSEPR can
fail when comparing resonance structures.
Self Study Course for IITJEE with Online Support Solutions 78

IN - CHAPTER EXERCISE - E
1. (A) Methyl halides are unhindred and react rapidly by the SN 2 mechanism.
(B) Sodium ethoxide is a good nucleophile and will react with unhindered primary alkyl halides by the
SN 2 mechanism.
(C) Cyclohexyl bromide is a secondary halide and will reacts with a strong base (sodium ethoxide)
predominatly by the E2 mechanism.
(D) The tertiary halide tert-butyl bromide will undergo solvolysis by the SN 1 mechanism.
(E) The presence of the strong base sodium ethoxide will cause the E2 mechanism to predominate.
(F) Concerted reactions are those that occur in a single step. The bimolecular mechanisms SN 2 and E2
represent concerted processes.
(G) In a stereospecific reaction, stereoisomeric reactants yield products that are stereoisomers of each
other. Reactions that occur by the SN 2 and E2 mechanisms are stereospecific.
(H) The unimolecular mechanisms SN 1 and E1, involve the formation of carbocation intermediates.
(I) Rearrangements are possbile when carbocations are intermediates in a reaction. Thus reactions occuring
by the SN 1 and E1 mechanisms are most likely to have a rearranged carbon skeleton.
(J) Iodide is a better leaving group than bromide, and alkyl iodides react faster than alkyl bromides by
any of the four mechanisms SN 1, SN 2, E1 and E2 .

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Hydrocarbons
Hydrocarbons
Hydrocarbons
ALKANES Section - 1
Hydrocarbons are the binary compounds of carbon and hydrogen only. Hydrocarbons occur in nature in
the form of coal, natural gas and petroleum. All the organic compounds (other than hydrocarbons) are
derived from hydrocarbons, by substituting hydrogen with a functional group or by adding a functional
group. Hydrocarbons are classified into two categories: Aliphatic hydrocarbons (open chains) and Cyclic
hydrocarbons (closed chains). Here, we will first study aliphatic type, which are further divided into Saturated
hydrocarbons (Alkanes) and Unsaturated hydrocarbons (Alkenes, Alkynes), and then cyclic hydrocarbons,
which are further divided into Cycloalkanes, Cycloalkenes and Aromatic Hydrocarbons.
ALKANES : [CnH2n + 2]
Alkanes form a homologous series, represented by a general formula : CnH2n+2. These have a tetrahedral
structure around carbon atom or one can say that all the carbon atoms in alkanes show sp3 type of
hybridisation. The important members of alkanes are: Methane (CH4), Ethane (CH3CH3), Propane
 CH3  C H  CH3 
(CH3CH2CH3), n-Butane (CH3CH2CH2CH3) and its isomer, Iso-butane  | .
 CH3 
 
Generally, alkanes are also represented as : RH, RCH3, R-R, R-R (where R and R are alkyl radical)
Preparation of Alkanes :
1. Reduction of Alkenes and Alkynes :
H
2 C H
Cn H 2n  n 2n  2
Ni/573 K
Alkane
2 2H
Cn H 2n  2  Cn H 2n  2
Pt or Ni/573 K
Alkane
This is known as Sabatatier-Sandern’s reaction.
Note : For the reduction of alkenes, and alkynes Pd – carbon/Ethanol at 25°C (50 atm) is generally used.
Pd  C/C H OH
2 5  CH
 CH3 2  C  CH 2 
  3 2 CHCH3
25 C, 50 atm
Isobutane

Hydrocarbons Vidyamandir Classes
2. From Alkyl Halides :

(a) By reducing Alkyl Halides :
Reducing agents : Zn + CH3COOH ; Zn + HCl ; Zn + NaOH ; ZnCu Couple ; Al  Hg amalgam.
RX + H2 
 RH + HX
Alkyl iodides are reduced by HI in red P under high temperature and pressure.
Re d P
RI + HI 

 RH + I2 (I2 is removed by P as : 2P + 3I2  
 2Pl3)
150 C, high pressure
(b) Wurtz Reaction :

It involves the condensation of two molecules of alkyl halide with Na and dry ether, to give sym-
metric alkanes
dry
2RI + Na   R – R + NaI
ether
If we start with RI and RI, we get mixture of alkanes. Hence it is not good method for unsymmetric
alkanes.
Note : Methane cannot be formed by this method.
Order of reactivity of alkyl halides RI > RBr > RCl > RF.
(c) Frankland Reaction :

RI + Zn + RI 
 R – R+ ZnI2
3. Reduction of Alcohols :
Re d P
ROH  2HI  RH  I2  H 2O
150C, high Pressure
4. Reduction of Aldehyde and Ketones :

Zn  Hg NH 2 NH 2
RCHO  2H 2   RCH3  H 2O RCH RCH3 + H 2O
HCl alc. KOH
Zn  Hg NH 2 NH 2
RCOR  2H 2   RCH 2 R  H 2O RCOR RCH 2 R + H 2O
HCl alc. KOH
This is known as Clemmensen’s Reduction. This know as Woff-Kishner’s Reduction.
5. From Carboxylic Acids :

(a) Reduction :
Re d P
RCOOH  6HI RCH3  2H 2O  3I2

(b) Decarboxylation :
It is obtained by heating sodium salts of carboxylic acids with sodalime (NaOH - CaO).
CaO
RCOONa  NaOH  RH  Na 2CO3

Note : In the product there is one carbon less than parent compound. So this reaction is an important method to
reduce a carbon atom in organic synthesis (known as Step-down method).
(c) Kolbe’s Electrolysis :

electrolysis
2CH3COONa  2H 2O 
 CH3  CH3  2CO 2  2NaOH  H2
 
(At Anode) (At Cathode)
6. From Grignard Reagent ( Alkyl magnesium halides, RMgX) :
Note : Any copound having acidic H atom(s), decomposes Grignard reagent.
7. By action of water on Aluminium and Beryllium Carbide :
 3CH 4  4Al  OH 3
Al4C3  12 H 2O 
 CH 4  2 Be  OH 2
Be 2C  4 H 2O 
Note : Only Methane is formed by this reaction.
8. Through formation of Lithium Dialkycuprates :

diethyl
RX  2Li  RLi  LiX
ether
2RLi  CuI 
 R 2CuLi  LiI
Lithium diakyl
cuprate
 Gilman 's Reagent 
Self Study Course for IITJEE with Online Support Section

Section 11 3
R 2CuLi  R 'X 
 R  R '  RCu  LiX
This is known as Corey House Synthesis
Note : (i) R can be 1°, 2°, 3° alkyl or aromatic group.

(ii) R should be 1° alkyl or 2° cycloalkyl group or even aromatic group.
Physical Properties of Alkanes :

The physical properties of alkanes such as boiling point, density and solubility depend upon the intermolecular
forces of attraction. The magnitude of these forces of attraction depend upon the surface area of contact
between adjacent molecules. Greater the surfae area, stronger are the forces of attraction.
1. Physical State : The normal alkanes C1 to C4 are colourless gases, C5 to C17 are colourless liquids and
from C18 onwards are colourless waxy solids.
2. Boiling Point : The boiling points of the unbranched alkanes show a regular increase with increasing
molecular weight. The increase is by 20 – 30°C for each –CH2 unit added to the chain. Branching of the
alkane chain, however, lowers the boiling point.
CH3
CH3 |
CH3CH2CH2CH2 -CH3 | CH 3  C  CH3
CH3  C H  CH 2CH3 |
CH3
n-Pentane Isopentane Neopentane
B.P. = 309 K B.P. = 301 K B.P. = 282.5 K
The explanation for these effects lies in the vander waals forces. With unbranched alkanes, as molecular
weight increases, so does molecular surface areas. With increasing surface area, the van der Waals forces
between molecules increase, therefore more energy is required to separate molecule from one another.
Branching in the chain, on the other hand, makes a molecule more compact, reducing its surface area. As a
result, the strength of the van der waals forces operating between the molecules decreases. This results in
the lowering the boiling point.(Observe the boiling points of isomericpentanes above)
3. Melting point : The melting points of alkanes do not follow a very smooth gradation with the increase of
molecular size. Alkanes with even number of carbon atoms have higher melting point than the next lower and
next higher alkanes having odd number of carbon atoms.

It is explained by the fact that alkanes with an odd number of carbon atoms have their end-carbon atoms on
the same side of the molecule and the even numbered carbon atoms alkanes have their end-carbon atoms
on the opposite sides of the molecules. Thus, alkanes with even number of carbon atoms pack closely in
such a manner as to permit greater inter molecular attraction and therefore have slightly higher melting point.
The more compact molecule, the more is the packing efficiency of a molecular solid. This results in higher
melting point. For example, neopentane when packed (in solid form) has a higher melting point as com-
pared to n-pentane (less effective packing due to open chain structure).
Name Formula B.P. (K) M.P. (K) Density
(as liquids)
Methane CH4 111.0 90.5 0.4240
Ethane CH3CH4 184.4 101.0 0.5462
Propane CH3CH2CH3 230.9 85.3 0.5824
n-Butane CH3(CH3)2CH3 272.4 134.6 0.5788
Isobutane  CH3 2 CH  CH3 261.0 114.7 -
n-Pentane CH3(CH2)3CH3 309.1 143.3 0.6264
Isopentane  CH3 2 CH  CH 2  CH 3 300.9 113.1 -
Neopentane  CH 3 3 C  CH3 282.5 256.4 -

3. Solubility : ‘Like dissolves like’ is the general rule of solubility. In the light of this rule, alkanes which are
predominantly non-polar are insoluble in polar solvents such as water, alcohol, etc. but are highly soluble in
non-polar solvents such as Petroleum either, Benzene, Carbon tetrachloride, etc.
4. Density : The density of alkanes increases with the increase in the molecular masses till the limiting value
of about 0.8 g cm3 is reached. This means that all alkanes are lighter than water.
Reaction of Alkanes :
Alkanes being saturated compounds undergo only substitution reactions, at C  H bond. The hydrogen atom is
replaced by other atom(s) such as : X-(halogens), NO2 (nitro), etc.
1. Halogenation :
Replacement of H-atom by X-atom (X = Cl, Br, I) in presence of UV light. The substitution reaction is
explained by free radical mechanism.
2 Cl /h 2 Cl / h
2  CHCl 
2 Cl / h Cl / h
CH 4  CH3Cl  CH 2Cl2  3  CCl4
The bromination is same as chlorination but it is relatively slow and high temperature favours it.
The iodination is reversible reaction :  CH3I + HI
CH4 + I2 
Note : HI is a reducing agent, so oxidising agents, such as HIO3, HNO3, HgO are used to oxidise HI.
5HI + HIO3 
 3H2O + 3 I2
Fluorination of alkanes is too vigorous to be controlled under ordinary conditions. Further-more, fluorina-
tion brings about extensive rupture of C  C and C  H bonds leading to a mixture of product. Alkyl
fluorides are more conveniently prepared indirectly by heating suitable chloroalkanes with inorganic fluo-
rides such as AsF3, SbF3, AgF, HgF2 etc. For example,
2 CH3CH 2 – Cl + Hg2F2 
 2 CH3CH2 – F + HgCl2
The above reaction is known as Swarts reaction.
Ease of halogenation : 3 H > 2H > 1H > CH4

Reactivity of X2 : F2 > Cl2 > Br2 > I2
The reactivity decreases with the electronegativity of the halogens.

Consider halogenation in Isobutane.

Cl
Cl2 , h
|
CH3  C H  CH3   CH3  C H  CH 2Cl  CH3  C  CH3
| 25 C | |
CH3 CH 3 CH3
(63%) (37%)
Br
Br2
|
CH3  C H  CH3   CH3  C CH 3
127C
| |
CH3 CH3
(99%)
The above reactions show that Bromine is less reactive toward alkanes (in general) than chlorine. But
bromine shows greater ability to identify among different types of hydrogen atom (i.e., primary, secondary
and tertiary). It gives exclusive replacement of tertiary hydrogen atom. Chlorine, on the other hand is less
selective than Bromine. Fluorine is even less selective than Chlorine and gives equal percentage of substituted
products. (We will discuss mechanism of this reaction later)
Note :  Laboratory chlorination of alkanes is often done with SO2Cl2 (sulphuryl chloride), instead of Cl2 and an
organic perioxide, ROOR is used as an indicator.
 During monchlorination, number of monochlorinated products formed are equal to number of different
types of hydrogen atoms in the alkane.
2. Nitration :
Lower members do not react with conc. HNO3 at ordinary temperatures but long chain members on
heating with HNO3 yield nitro-alkanes.
400C
C6H13  H  HONO2  C6H13 NO 2  H 2O
(vapour)
However, when a mixture of vapour of an alkane and nitric acid is heated at 400 - 450°C, nitroalkane is
formed readily. By this process lower as well as higher alkanes can be converted into nitroalkanes.
450C
CH 3  H  HONO 2  CH3 NO2  H 2O

(vapour)
In alkanes having two or more carbon atoms, there is always a possibility that the C - C bonds may break
at high temperature and a mixture of nitro alkanes is formed.
HNO
3  CH CH CH NO  CH  C H  CH  CH CH NO  CH NO
CH 3CH 2CH3  3 2 2 2 3 3 3 2 2 3 2
400 C |
NO2

3. Sulphonation :
Lower alkanes do not undergo sulphonation but higher member (from hexane onwards) are sulphonated
slowly when treated with fuming sulphuric acid at about 400°C.
SO
3
C6H13  H  HOSO3H  C6H13SO3H  H 2O
Hexane sulphonic acid
However lower members such as Propane, Butane, Pentane, etc., react with SO3 in vapour phase to form
Sulphonic acids.
4. Cracking : (Pyrolysis)
The decomposition of a compound by heat is called pyrolysis. The alkanes, on heating under high tempera-
ture in absence of air, are broken down into lower alkanes, alkenes and hydrogen during cracking of
alkanes,either rupture of carbon-hydrogen bonds or rupture of carbon-carbon bonds take place resulting in
the formation of mixture of lower alkanes, alkenes and hydrogen. The rupture of C – H bonds is catalysed
by oxide of Chromium, Vandium, Molybednum, etc., and the rupture of C – C bonds is catalysed by Silica,
Alumina, Zinc oxide, etc.
500C
C2 H 6   CH 2  CH 2  H 2
Cr O2 3
500C
C3H8   CH3CH  CH 2  H 2
Cr O 2 3
500C
C3H8   CH 2  CH 2  CH 4
Al2 O3
5. Reaction with Steam :

Ni
CH 4  H 2O   CO  3H 2
1273 K
6. Combustion :
(a) Complete Combustion :
CH4 + 2O2 
 CO2 + 2H2O
3n  1 
CnH2n + 2 +   nCO2 + (n + 1) H2O + heat
 O 2 
 2 
Note : Enthalpy of combustion increases with increase in number of carbon atoms in alkane. For isomeric alkane,
enthalpy of combustion decreases with increase in branching

(b) Incomplete Combustion : If the combustion of alkanes is carried out in limited supply of air or
oxygen, CO is produced along with unburnt carbon in the form of carbon black or soot.
2CH4  3O2 
 2CO  4 H2O
(limited)
CH 4  O 2 
 C  H 2O
(limited) Carbonblack
Carbon black is used in the preparation of black inks, paints, polishes etc.
(c) Catalyst Oxidation : Different prodcuts are formed under different conditions.
(i) When a mixture of methane and oxygen (9 : 1 by volume) at a pressure of 100 atm. is passed
through a copper tube at 573 K, methanol is formed.
100 atm. 573 K
2 CH 4  O2 
 2 CH3OH
Cu tube
Methane Methanol
(ii) When a mixture of methane and oxygen under pressure is passed over heated molybdenum
oxide, it is oxidised to methanal.
Mo O
2 3  HCHO  H O
CH 4  O2  2
 , pressure
Methane Methanal
(iii) Higher alkanes on oxidation in presence of silver oxide give carboxylic acids.
2 Ag O
2 R  CH3  3O 2  2 RCOOH  2 H 2O

Alkane Carboxylic acid
(iv) In presence of oxidising agents such as KMnO4, K2Cr2O7 etc.
CH3 CH3
| |
alk .
CH 3  C  H  (O)  CH3  C  OH
KMnO4
| |
CH3 CH3
Isobutane tert-Butyl alcohol
7. Aromatisation :
Cr O  Al O
2 3 2 3  C H (Benzene)  4 H
CH3   CH 2  4  CH3 
 6 6 2
600 C /15atm

8. Isomerization :
When n-alkanes are heated with anhydrous aluminium chloride and hydrogen chloride at 573 K under a
pressure of about 35 atm, they are converted into branched chain alkanes. For example,
CH 3
AlCl3 / HCl
|
(i) CH3CH 2CH 2CH3   CH3  C H  CH3
573K
Isobutane
CH3 CH3
AlCl3 / HCl
| |
(ii) CH 3  (CH 2 )4  CH3   CH 3  C H  CH 2CH 2CH3  CH3CH 2  C H  CH 2CH3

n - Hexane 2 - Methylpentane 3 - Methylpentane
Illustration - 1 Identify A, B, C, D.
SOLUTION :

ALKENES : [CnH2n] Section - 2
Alkenes form a homologous series, represented by a general formula : CnH2n. These have one C=C bond
or one can say that two carbon atoms (adjacent) in alkenes show sp2 type of hybridisation. The important
members of alkenes are: Ethene (CH2 = CH2), Propene (CH3 CH = CH2), 1-Butene (CH3CH2CH = CH3)
and its isomers, 2-Butene (CH3CH = CHCH3) and Iso-butene  CH3  C  CH 2  .
 | 
 CH 
 3 
Generally, alkenes are also represented as :
1. Terminal alkenes RCH = CH2, R2C = CH2
2. Non-terminal alkenes RCH = CHR, R2C = CHR, R2C = CR2 (where R : alkyl radical)
Preparation of Alkenes :
1. Dehydration of Alcohols :
The dehydration of alcohols is generally carried out in either of two ways :
(a) Heating the alcohol with conc. H2SO4 or H3PO3 to temperature as high as 170°C.
(b) Passing the vapours of alcohol over alumina (Al2O3) at 350 – 400°C.
RCH2CH2OH 
 RCH = CH2 (alkene) + H2O
Ease of dehydration is 3° alcohol > 2° alcohol > 1° alcohol.

Dehydration is governed by Saytzeff or Zaitsev rule i.e., the greater is number of alkyl groups attached to
doubly bonded ‘C’ atoms, the more stable is the alkene.
conc. H SO
2 4  CH CH  CHCH  CH CH CH  CH
CH 3CH 2  C H  CH3  3 3 3 2 2
| T 170C (80%) (20%)
OH
Order of Stability : R2C = CR2 > R2C = CHR > R2C = CH2 > RCH = CHR > RCH
= CH2 > CH2 = CH2
Note : If there are two geometric isomers, i.e., cis and trans isomers, then it is the trans isomer which is more
stable than the cis one.

2. Dehydrohalogenation of Alkyl Halides :

alc. KOH, 
CH3CH2CH 2 Br  CH3CH  CH 2
alc. KOH, 
CH 3CH 2  C H  CH3 
 CH3  CH  CH  CH3  CH 3  CH 2  CH  CH 2
| 2-Butene 1-Butene
Br (major) (minor)
Saytezeff prodcut Hoffmann product
The formation of less substituted alkene in an elimination reaction is called as a Hoffmann Elimination and
that of more substituted alkene as a Zaitsev Elimination or Saytzeff’s elimination.
Ease of dehydrohalogenation is in the order : 3° alkyl halide > 2° alkyl halide > 1° alkyl halide.
Ease of dehydrohalogenation for different halogens is in the order : Iodine > Bromine > Chlorine.
We can also used alkoxide ion, RO  , which acts as a strong base. The alkoxide ion abstracts a proton from
  carbon . Then dehydrohalogenation is known as   elimination or 1, 2  elimination.
CH3 CH3
| |
EtO
 CH3  C  EtOH  Br 
CH3  C  Br 
| Ethoxide ||
CH3 CH 2
Note : (i) In case of 1 RX, alkoxide (R’ O  ) does nucleophilic substitution of form ethers [R' O R].
(ii) By using alc. KOH [ KOH / ROH ], 1, 2,3 alkyl halides give elimination products.
3. By dehalogenation of Viccinal Halides :
CH 2BrCH 2Br  Zn 
 CH2  CH2  ZnBr2
4. Electrolysis of aqueous solution of sodium salts of dicarboxylic acids : (only for Ethene)
5. Cracking of Alkanes :
500C
C2 H 6  C2 H 4  H 2
Cr2 O3

500C
CH3CH 2CH3  CH3CH  CH 2  H 2
Cr2O3
6. Partial Hydrogenation of Alkynes :

The hydrogenation of alkynes to an alkene is brought about by the use of special catalysts. This is an
example of “Stereospecific reaction’’.
Note : Reaction that produce a particular stereoismers of the product is called as steroselective reaction.
(a) Using Lindlar catalyst (Pd/CaCO3 or Pd/BaSO4) in quinoline to give a cis alkene.
This is also called as syn addition, as two H-atoms are added to the same side.
This reaction can also be achieved by using Ni2B (called as P - 2 catalyst)
(b) Using Lithium (or Sodium) in NH3 (or in ethyl amine) at low temperature, gives trans alkene.
This is also called as anti addition, as two H-atoms are added to the opposite side of the bond.
Stability of Alkenes :
The reactivity of different types of alkenes in decreasing order is as follows : (As per heat of hydorgenation)
CH 2  CH 2  R  CH  CH 2  R  CH  CH  R  R 2 C  CH 2  R 2 C  CHR  R 2 C  CR 2
The heat of hydrogenation is always exothermic and experimentally it has been found that :

1
Stability of alkene  (i.e., higher is the heat of hydrogenation, higher is
Heat of hydrogenation reactivity and lower is the stability of an alkene)
Thus stability of alkenes in decreasing order is as follows :
R 2 C  CR 2  R 2 C  CHR  R 2 C  CH 2  RCH  CHR  RCH  CH 2  CH 2  CH 2

trans > cis
Physical Properties of Alkenes :

1. Physical state and smell : The first three members of the family, i.e., Ethene, Propene and Butene
are colourless gases. The next eleven members (C5  C15) are liquids while the higher ones are solids.
Except Ethene which has a pleasant smell, all other alkenes are odourless.
2. Melting points : The melting points of alkenes do not show regular gradation. However, the melting
points of alkenes are higher than those of the corresponding alkenes.
Amongst isomer of alkenes, trans-alkenes have higher melting points than their corresponding cis-
isomers.
3. Boiling points : The boiling points of alkenes, like alkanes, show a regular gradation with the increase
in the number of carbon atoms. Amongst the alkenes which show geometrical isomerism, cis-alkenes
have higher boiling points than the corresponding trans-isomers. This is due to the reason that cis-
alkenes being polar have stronger dipole-dipole interactions while trans-alkenes being non-polar (or
weakly polar) have weak induced dipole interactions.
4. Solubility : Alkenes like alkanes being either non-polar or weakly polar molecules are practically
insoluble in water and other polar solvents but are quite soluble in non-polar solvents such as benzene,
CCl4, petroleum ether, etc. and weakly polar solvents such as ether.
5. Density : The densities of alkenes, like those of alkanes, increase with the increase in molecular mass
till they have a limiting value of 0.89 g cm3. Thus, all alkenes are lighter than water.
Compound M.P. (°C) B.P. (°C) Density (g/mL)

Ethene –169 –104 0.384
Propene –185 –47 0.514
1-Butene - –6.3 0.595
cis-2-Butene –139 3.7 0.621
trans-2-Butene –106 0.9 0.604
1-Pentene –165 30 0.641
2-Methyl-1-butene –138 31 0.650

Reaction of Alkenes :
Alkenes undergo mainly addition reactions.
An addition that puts the part of AB on the same face of the reactant is called as syn addition.
The opposite of syn-addition is an anti-addition. An anti-addition puts the parts of AB on opposite faces
of reactants.
The addition reaction of alkenes are usually electrophilic addition.
Electrophile (E+) : An electron loving species looking for electron rich regions such as localised
pi   electron in alkenes and lakynees. Important Electrophiles :
H  , CI  , Br  , CH 3 etc.
Nucleophile (Nu) : A nucleus loving (electron rich) species looking to attack the electrophilic sites.
Important Nucleophiles : X  , OH  , OR  , CH 3 etc.

1. Addition of hydrogen halides (HX) :
The addition of HX to alkene is an electrophilic addition reaction. The reactivity order follows : HI > HBr
> HCl. The addition follows Markonikov’s rule. It states that in the addition of HX to an alkene, the
hydrogen atom adds to the carbon atom of the double bond that has the greater number of hydrogen atoms,
or the negative part of reagent adds to carbon having less number of hydrogen. The following examples
illustrate Markonikov’s addition.
(a) CH 2  CH  CH3  HI 
 CH3  C H  CH3  CH 3  CH 2  CH 2 I
|
I
2 - Iodopropane  Major  1 - Iodopropane  Minor 
(b) When 2-Methylpropene reacts with HI, the major product is tert. butyl iodide.
CH3 CH3
| |
CH3  C  C   HI 
 CH3  C  C   CH3  C H  C  I
| |
CH3 I
Major Minor
Anti Markonikov’s addition : When addition of HBr takes place in presence of perioxides (ROO
R or benzoyl peroxide), addition occurs in an anti-markonikov’s manner, i.e., Br is added to the carbon
having large number of H-atom.
ROOR
CH 3CH  CH 2  HBr 
 CH3CH 2CH 2Br
In presence of peroxides, free radical addition occurs in an anti-Markonikov’s fashion unlike the electrophillic
addition in above case (i.e., Markonikov’s addition).
Note : (i) Addition of HX in cycloalkenes also follows Markonikov’s addition.
(ii) Addition of HCl and HI in presence of perioxide follows Markonikov’s rule.

2. Addition of H2O :
The acid catalysed addition of H2O produces alcohols and follows Markonikov’s addition. The acids used
to catalyse the reaction are H2SO4 or H3PO4 (phosphoric acid).
CH3 CH 3
|  |
H
CH 3  C  CH 2  H 2O   CH 3  C  CH3
25C
|
OH
Isobutene tert. butyl alcohol
3. Addition of H2SO4 (cold and concentrated) :

Alkene react with cold concentrated H2SO4 to give alkyl hydrogen sulphates following Markonikov’s addi-
tion.
CH3  CH  CH 2  H  OSO3H 
 CH3  C H  OSO3H
cold |
CH3
Note : Alkyl hydrogen sulphates when boiled with water give alcohols. It is an irreversible reaction.
H O
2 
CH3  C H  OSO3H  CH3  C H  OH
boil
| |
CH3 CH3
Isopropyl hydrogen sulphate Isopropyl alcohol
4. Addition of Halogens (Cl2, Br2, I2) :

Alkenes decolourises Bromine water (Br2 in CCl4) following addition of Br2 across double bond. This
serves as a test of unsaturation. It follows anti-addition.
Cl
|
Low temp
CH3  CH  CH 2  Cl2  H3C  C H  C H 2  anti addition 
 anti addition  |
Cl
Viccinal dichloride

Note : (i) The addition of Br2 to cycloalkenes also follows anti-addition.
(ii) The addition of halogens to alkene is an anti-addition and provides an illustration for a stereoselective
and stereospecific reaction. For example, cyclohexene gives trans-1, 2-Dibromocyclohexane
(geometric isomer) is an example of stereoselective reaction. Consider addition of Br2 to cis and
trans-2- Butenes, which is an example of stereospecific reaction as the reactant (2-Butene) also
shows stereochemistry).
Note : The details of reaction mechanisms of all the addition reactions will be discuss later in the Chapter “Organic
Concepts”.
The above reaction, it is visulised as follows and remember the nature of product(s) : (Refer to the next
page)

5. Addition of halogen in aqueous solution :

When halogens are added in presence of H2O / THF (tetrahydrofuran) or NBS (N-bromo succinimide),
halohydrins are formed.
OH
| | | |
THF
 C  C   X 2  H 2O    C C
Alkene |
X
Halohydrins
The above reaction follows Markovnikov’s rule. It is an anti-addition reaction.
Note : (i) The cycloalkenes also reacts with aqueous Br2 to give anti-addition products.
(ii) In case of unsymmetrical alkene, halogen is added to the carbon atom with greater number of H-
atom, (i.e., Markonikov’s addition).
OH
|
H 2O or THF
CH 3  C  CH 2  Br2  CH3  C C H 2
| | |
CH3 H 3C Br

6. Oxymercuration - Demercuration :
An important method of formation of alcohols from alkenes. It occurs in two steps.
(i) Alkenes react with mercuric acetate Hg (CH3COO)2 or represented as, Hg (OAc)2 in a mixture of
THF and water to give a mercury compound.
O O
| | || | | ||
THF/ H2 O
 C  C   H 2O  Hg(O  C  CH3 ) 2    C  C   CH3  C  OH
| |
OH Hg  OAc
This step is known as Oxymercuration.
(ii) The mercury compound is reduced to alcohol with sodium borohydride.
| | NaBH 4 , OH
 | |
C  C     C  C   Hg  CH3  COO
| | | |
HO Hg  OAc HO H
Alcohol
The above reaction occurs in accordance with Markonikov’s addition. The ‘H’ becomes attached
to the carbon atom of the double bond with greater number of hydrogen atom.
H H H H
| | 1. Hg  OAc  /THF, H 2O | |
R  C  C  H  2 R  C  C H

2. NaBH 4 , OH | |
OH H
2 alcohol
Note : Observe that in the final product, OH comes from H 2O and H comes from NaBH 4 / OH  .
7. Hydroboration - Oxidation :
Hydrocration-oxidation serves as an important method for synthesis of alcohol 1 & 2  . It can be repre-
sented as :

H
| | | | |
 C  C  H  B  H 
  C  C
| | | |
H B H
|
H
Alkene Boron hydride Organoborane
Note : (i) The addition of boron hydride is syn-addition.

It is generally carried out by BH3 (boron hydride) B2H6 (diborane) in THF.
3 BH / THF
3CH 2  CH 2 
 (C2 H5 )3 B
Triethyl borane
3 BH /THF 3 CH CH  CH
2  (n  Pr) BH 
3 2  (n  Pr) B CH CH  CH
CH 3CH  CH 2 
 (n  Pr) BH 2  2 3
(ii) In each addition, the boron atom becomes attached to the less substituted carbon atom of double
bond and H is transferred from boron atom to the other carbon atom of double bond. Thus it
follows Anti-Markonikoff’s addition.
The organoboranes formed are oxidised and hydrolysed to alcohols by the addition of hydrogen
peroxides in an aqueous base.
H O
2 2  3ROH + Na BO H O2 2  3PrOH + Na BO
R 3B  3 3 (n  Pr)3 B  3 3
NaOH,25° C NaOH, 25°C
Note that alcohol formed is a primary alcohol (unlike that in Markonikov’s addition)
Consisder hydrobration and oxidation in 1-Methyl cyclopentene. It show syn-addition and anti-Markonikov’s
addition of H2O to alkene.
Note : Observe that in the final product, OH comes from H 2O 2 / OH  and H comes from BH 3 .
Note : Compare the alcohols formed above with those formed by Oxymercuration-Demercuration.

8. Hydroxylation of alkenes (Oxidation by cold alkaline KMnO4) :

The hydroxylation of alkene is brought about by alkaline KMnO4 or osmium tetraoxide (OsO4) to give 1, 2-
diols (or glycols).
| | KMnO 4
| |
 C  C     C  C (Vicinal alcohols or glycols)
OH  , cold | |
OH OH
| | 1. OsO 4 , pyridine
| |
 C  C     C  C (Vicinal alcohols or glycols)
2. NaHSO3 / H 2O
| |
OH OH
It represents syn-addition.
1. OsO , pyridine
4
CH 3  CH  CH 2   CH3  C H  C H 2
2. NaHSO3 / H 2 O
| |
OH OH
1, 2 - Propanediol
Note : Osmium tetra oxide, OsO4 gives a better yield than KMnO4. The hydroxylation like addition of Br2 is also
stereospecific. Consider hydroxylation in cis and trans isomeric alkenes.

9. Hydrogenation :
The hydrogenation of alkenes is a syn-addition, carried out by many reagents such as :
Na in liquid NH3 and alcohol ; H2, PtO2/CH3COOH ; H2/Ni at 573 K ; H2/Pd-Carbon in ethanol.
| | H2
| |
 C  C    C  C 
Ni (573K) | |
H H
This reaction also follows syn-addition rule.sheel

Consider hydrogenation in 1, 2-Dimethyl cyclohexene.
10. Oxidation of Alkenes :

(a) Oxidation by hot. conc. KMnO4 :
It gives acids or ketones depending upon structure of alkenes. The terminal alkenes gives acids
(ketones) and CO2, whereas non-terminal alkenes gives mixture of acids and ketones.
(O)
CH2  CH2 
 2CO2  2 H2O (HCOOH formed is oxidised further)
O
CH3CH  CH 2 
 CH3COOH  CO 2  H 2O
O
R  CH  CH  R 
 RCOOH  R 'COOH

O
CH 3  C  CHCH 3 
 CH3  C  O  CH3COOH
| |
CH 3 CH3
Note : Observe that the dialkylated side of double bond gives corresponding ketone.
Oxidation of cycloalkenes leads to the ring opening and gives dicarboxylic acids or keto acids.
(b) By Ozone (ozonolysis) :
Consider the ozonolysis of cycloalkenes :

Note : In ozonolysis, observe that we are using Zn/H2O or Pb/H2O or (CH3)2S which reduces the nascent oxygen
(O) given by ozonide.This is referred to as Reductive Ozonolysis. If Zn/H2O is not used, the product
aldehyde is oxidised to acid.
11. Alkylation :
CH3 CH3 CH3 CH3
| H2 SO4
| | |
CH3  C  CH 2  H  C  CH3   CH3  C H  CH 2  C  CH3  CH3  C  C  CH3
| | 0 10 C | | | |
CH3 CH3 CH3 CH3 CH3 CH3
 mixture of higher alkanes is formed 
12. Addition of oxygen :
13. Subst it ut ion in alkenes : (Partial Oxidation)

High temp.
CH 2  CH  CH3  X 2   CH 2  CH  CH 2 X  HX
or Low conc. X 2
Here, halogen replaces one of the hydrogen atoms of the methyl group. These hydrogen are allylic hydrogen
atom and hence the substitution is called as allylic substitution.
400 C  500 C
CH 2  CH  CH3  Cl2   CH 2  CH  CH 2Cl  HCl
gas phase
Allyl Chloride
Propene undergoes allylic bromination when it is treated with N-bromo succinimide (NBS) in CCl4 in
presence of perioxides or light.
NBS/CCl
4  CH  CH  CH Br
CH 2  CH  CH3  2 2
in ROOR or light
Allyl bromide
The mechanism is free radical substitution initiated by Br° (bromide free radical) to give intermediate allyl
radical which is stable. Consider allylic substitution in cyclohexene using NBS in CCl4.

Another intersting aspect of this reaction is that it also occurs in alkyl benzens.
14. Polymerisation :
High Temp
(i) n(CH 2  CH 2 )   (CH 2  CH 2  )n (Polyethene)
High pressure
(ii) Polymerization of substituted ethenes : A number of polymers can be obtained by using

substituted ethenes as monomers in place of ethene. For example,
 CH 2  C H  Polymerisation  CH 2  C H  
n |    | 
 Cl   Cl 
   n
Chloroethene 
Polyvinyl chloride PVC 
 Vinyl chloride 
n |    | 
 C H   C H 
 6 5  6 5 n
Styrene Polystrene
n |    | 
 CN   CN n
 
Acrylontrile or Polyacrylontrile(PAN)
vinyl cyanide
Polymerisation
n  CF2  CF2  
  CF2  CF2  n
Tetrafluoroethene Polytetrafluoroethene
 PTFE, Teflon 
Polyvinyl chloride (PVC) is used for making plastic bottles, syringes, etc. Polyacrylontrile is used for making
Orlon and Acrilan fibres used for making clothes, carpets and blankets.

Illustration - 2 Compound A (C6H13Cl)on treatment with hot alcoholic potassium hydroxide gave a
mixture of two isomeric alkense B and C, having formula C6H12. The mixture of (B) and (C), on ozonolysis,
furnished four compounds :
(i) CH3CHO (ii) C2H5CHO (iii) CH3COCH3 (iv) (CH3)2CHCHO
What are the structures of A, B and C ?
SOLUTION :
3 O
Alkenes C6H12 (B and C)  mixture of products
Zn  H 2 O
Try to draw the structures of alkenes (working backwards in ozonolysis reaction). Note that while joining
the products, keep in mind that on combining two products the sum of carbon atom must be six.
On carefully examining the products, alkenes B and C are :
3O
CH 3  C  CH  CH 2CH3  CH3COCH3  CH3CH 2CHO
|
CH3
O
3
and CH3  C H  CH  CH  CH3  (CH3 )2 CH  CHO  CH 3CHO
|
CH3
The structure of A must be :
alc.
CH3  C H  C H  CH2  CH3   CH3  C  CH  CH 2  CH3  CH3  C H  CH  CH  CH3
| | KOH,  | |
CH3 Cl CH3 CH3
(Major) (B) (Minor) (C)

Illustration - 3 Give the stucture of the major organic products form 3-Ethy-l-2-pentene form under
each of the following reaction conditions :
(A) HBr in the presence of peroxide (B) Br2/H2O (C) Hg(OAc)2/THF/H2O, NaBH4/OH–
SOLUTION :
Illustration - 4 A hydrocarbon X, C6H12 decolorizes bromine water and is oxidized to an acid Y by hot
acidic potassium permanganate solution. The acid Y can be resolved into two forms. Identify X and Y.
SOLUTION :
X is terminal alkene as it gives only Y.

Visualise the structure of Y (having a chiral centre) :
 O
 X is C2H5  C H  CH  CH 2 
 C2H5  CH  COOH Y
| |
CH3 CH3
Illustration - 5 Identify A, B, C, D. . . . .
SOLUTION :
Illustration - 6 Identify the products
SOLUTION :
Note that the dialkylated site in alkene give the same producer (Ketone) on oxidation and ozonolysis.

ALKYNES : [CnH2n – 2] Section - 3
Alkynes form a homologous series, represented by a general formula : CnH2n – 2. These have one C  C
bond or one can say that two carbon atoms (adjacent) in alkynes show sp type of hybridisation. The
important members of alkynes are: Ethyne (CH  CH), Propyne (CH3C  CH), 1-Butyne (CH3CH2C 
CH) and its isomer, 2-Butyne (CH3C  CCH3).
Generally, alkynes are also represented as :
1. Terminal alkynes RC  CH
2. Non-terminal alkynes RC  CR, RC  CR (where R : alkyl radical)
Preparation of Alkynes :
1. Dehydrohalogenation of Dihalides : (Gem and Vicinal)
Br
2  CH BrCH Br  alc 2  CH  CH NaNH
CH 2  CH 2  2 2  CH 2  CHBr 
KOH, 
Viccinal dihalide
alc.
CH3 CH Br2 
 CH  CH
KOH, 
Gem dihalides
If alcoholic KOH to be used, vinylic halides are formed, as it is unable to remove vinylic hydrogen. So
NaNH 2 Sodamide) is used to produce alkynes.
2. Dehalogenation of Tetrahalides :
Br Br Br Br
| | | |
Zn
H  C  C  H  Zn 
 H  C  C  H  CH  CH
| |
Br Br
3. By dehalogenation of haloform :
Trihaloderivative of methane is knwon as haloform  CHX3  .
Chloroform and Iodoform on heating with silver powder undergo dehalogenation to form ethyne.
Trihaloalkane  R  CX3 on heating with silver powder also undergo dehalogentation to form symmetrical
internal alkyne.

4. Kolbe’s electrolytic reaction :

Acetylene can be prepared by electrolysis of a concentrated solution of sodium or potassium salt of Maleic
acid or Fumaric acid. Thus,
This reaction is called Kolbe’s electrolytic reaction.
Note : On electrolysis of aqueous solution of Potassium succinate, we get Ethylene (C2H4) as a product at anode.
5. From Graphite :
Electric arc
2C  s   H 2  g  

 CH  CH (Only acetylene can be formed)
1000 C
6. From calcium carbide :

CaC2 + 2H2O 
 C2H2 + Ca (OH)2 (Only acetylene can be formed)

Note : (i) Calcium carbide is formed as follows :

2000C
CaCO3 
 CaO  CO2

2500C
CaO  C 
 CaC2  CO 
(ii) Carbides of Na, K, Ca, Mg, Ba are considered to be ionic and give acetylene with H2O.
(iii) However, carbides of Cu and Ag are covalent and hence do not give acetylene with H2O.
7. Higher alkynes from Lower alkynes :
2 NaNH , liq. NH
3  CH  CNa  R 'X
CH  CH   CH  C  R ' (Terminal alkynes)
excess 1.0 eq.
NaNH 2 , liq. NH3 R 'X

CH  CH   Na  C  C  Na   R ' C  C  R ' (Non-terminal Alkynes)
2.0 eq. excess
2 NaNH , liq. NH RX
3  R  C  C  Na  
R  C  CH   R  C  C  R  (Non-terminal alkynes)
1.0 eq
Note : R’ can only be 1o and 2o alkyl or cycloalkyl groups only.
Physical Properties of Alkynes:
1. Physical state : The first three members of this family (Ethyne, Propyne and Butyne) are colourless
gases, the next eight are liquids while the higher ones are solids.
2. Smell : All the alkynes are odourless. However acetylene has garlic smell due to the presence of
phosphine as impurity.
3. Melting and boiling points : The boiling points and melting points of alkynes are slightly higher
than those of the corresponding alkenes and alkanes. This is probably due to the reason that
because of the presence of a triple bond, alkynes have linear structures and hence their molecules
can be more closely packed in the crystal lattice as compared to those of corresponding alkenes
and alkanes.
Hydrocarbon Ethane Ethene Ethyne

M.P. (K) 101 104 191
B.P. (K) 184.5 171 198

4. Solubility : Alkynes like alkanes and alkenes being non-polar are insoluble in water but readily
dissolve in organic solvents such as petroleum ether, benzene, carbon tetrachloride etc.
5. Density : Densities of alkynes increase as the molecular size increases. However, they are all
lighter than water since their densities lie in the range 0.69  0.77 g/cm3.
Reactions of Alkynes :
1. Electrophillic Addition Reactions :
YX X Y
|| | |
XY XY
C  C     C  C     C C
| |
X Y
(a) Addition of Hydrogen :
H
2  CH  CH 
2  CH  CH H
CH  CH  2 2 3 3
Pt /573K Pt /573K
Read hydrogenation of alkynes in the preparation of alkenes.
(b) Addition of Halogens : (X = Cl, Br, I)
Cl Cl
2Cl2
| | BaCl2 , 
CH  CH   H C CH   CCl 2  CHCl
solvent
| | Westrosol
Cl Cl
Westron
(c) Addition of Halogen acids : (HX)

HBr
CH  CH  HBr 
 CH 2  CHBr   CH3  CHBr2 (Markonikov’s rule )
(d) Addition of Hypohalous acids(HOX) :

Similarly,
(e) Addition of water (H2O) is presence of acid :
Note : The addition of water to alkynes also follows Markonikow’s rule. The hydrogen atom become attached to
the carbon atom with the greater number of hydrogen atoms. Therefore, when higher terminal alkynes are
hydrated, ketones, rather than aldehydes are formed.
However, if the unsymmetrical alkyne is nonterminal, a mixture of two isomeric ketones is obtained
in which the methyl ketone predominates. In case of benzene ring, phenyl ketones is major product .
O O
HgSO4 / H2 SO4
|| ||
 CH3CH 2  C  C  CH3   CH3CH 2CH 2  C  CH3  CH3CH 2  C  CH3CH3
333 K
2 - Pentanone (Major) 2 - Pentanone (Minor)
(f) Addition of HCN :

CH CHHCN 
 CH2 = CHCN (Vinyl cyanide also known as acrylonitrile)
Note : Acrylonitrile is used in manufacture of BuNa-S rubber and Orlon fibre.
(g) Addition of Acetic acid (CH3COOH) :

(h) Addition of Arsenic trichoride (AsCl3) :

CH CClAsCl2 
 ClHC = CHAsCl2
(Lewisite, a poisonous gas)
2. Nucleophillic Addition reactions :
CH  CH  Nu  
 H C  C H
|
Nu
(Vinylic carbanion)
Vinylic Carbanion is formed which is more stable than vinylic carbonium ion.
Addition of Methanol :
3 CH O  K 
HC  CH  CH3OH 
 CH 2  CH  OCH3
Acetylene 433  473 K Methyl vinyl ether
Methyl vinyl ether is used for making polyvinyl ether plastics.
3. Oxidative - Hydroboration
3 BH ,THF 2 2 H O ,OH 
  CH3  CH  CH  3 B 
CH 3  C  CH 
 CH3 
BH3 ,THF H 2 O 2 , OH 
CH3  C  C  CH3 
  |  B 
 CH  CH  C  
 3 3
4. Acetylide Formation :
AgNO
3  Ag  C  C  Ag
CH  CH 
ammonical
silver Acetylide, (white ppt.)

Note : This reaction shows the acidity of terminal alkynes and serves as a test for terminal alkynes.
CuCl
2 Cu  C  C  Cu
CH  CH 
amm.
Copper Acetylide (Red ppt.)
5. Oxidation of Alkynes :
(a) Oxidation in Neutral KMnO4 :
KMnO , H O
4 2  CH  C  C  CH
CH 3  C  C  CH3  2 (O)  3 3
298  303 K
But-2-yne || ||
O O
 Butan-2, 3-dione 
(b) Oxidation with cold dilute alkaline KMnO4 :
Alkynes are readily oxidised by cold dilute alkaline KMnO4 solution to give dicarbonyl compounds.
In case of terminal alkynes,  CH part is oxidised to – COOH group while in case of non-terminal
alkynes, CR part is oxidised to R  C  O group, For example :
|
O
1. NaOH, KMnO 4
||
CH 3  C  CH  3(O)   CH3  C  COOH
298  303 K
Propyne 2-Oxopropanoic acid
2. H

O O
NaOH, KMnO 4
|| ||
CH 3  C  C  CH 3   CH3  C  C  CH3
298 303 K
Acetylene, however, under these conditions gives oxalic acid probably due to further oxidation of
the initially formed glyoxal.
4 KMnO , NaOH  2(O)

HC  CH  2(O)  OHC  CHO 
 HOOC  COOH

Acetylene 298  303 K Glyoxal H Oxalic acid
During this reaction, the pink colour of the KMnO4 solution is discharged and a brown precipitate
of manganese dioxide is obtained. This reaction is, therefore, used as a test for unsaturation under
the name Baeyer’s test.
(c) Oxidation by acidic KMnO4 (hot) :

KMnO
4  R  COOH  R 'COOH
R  C  C  R ' 

H , heat
Not that it is similar to the oxidation of alkenes.

6. Ozonolysis :
(a) For non-terminal alkynes :
O O
1. O3
|| ||
R  C  C  R '   R  C  C R '
2. Zn, H2O
Note : If, Zn or Pb is not used, then the product is mixture of acids.

O O
O3
|| ||
R  C  C  R   R  C  OH  R   C  OH
mixture of acids
(b) For terminal alkynes :

3 O
H  C  CH  OHC  CHO
Zn / H 2 O
 Glyoxal 
O
O3
||
R  C  CH  R  C  CHO
Zn /H 2 O
   alkyl glyoxal 
7. Polymerization Reactions of Alkynes :

Like alkenes, alkynes also undergo polymerization reactions. For example,
(a) When acetylene is passed through red hot iron tube, it rimerises to give benzene.
(b) In presence of nickel cyanide as catalyst and under high pressure, four moelcules of acetyrene
combine to form a tetramer called cycloocta-1, 3, 5, 7-tetraene.
(c) However, in presence of CuCl/NH4Cl, acetylene first gives vinylacetylene and then divinylacetylene.
Thus,

CuCl/ NH Cl
4  H C  C  CH  CH  HC  CH
2 HC  CH  2  H 2C  CH  C  C  CH  CH 2
CuCl/ NH 4 Cl
Acetylene Vinylacetylene Divinylacetylene
Vinylacetylene is widely used in the manufacture of chloroprene which is the starting material for the
synthetic rubber neoprene.
Cl
|
Markonikov 's
CH 2  CH  C  CH  HCl   CH 2  CH  C  CH 2
addition
Vinylacetylene  one mole  across C  C Chloroprene
(d) Under suitable conditions, polymerization of acetylene produces the linear polymer polyacetylene.
It is a high molecular weight conjuated polyene containing the repeating unit (CH = CH  CH =
CH)n. Under proper conditions, this material conducts electricity. Since polyacetylenes have much
higher conductance than metal conductors, these can be used to prepare lighter and cheapter batteries.
Acidic character of Alkynes :

(a) Formation of alkali metal acetylides :
475C
 2HC  C Na   H2
2 HC  CH  2Na 
Ethylne Sodium acetylide
(Acetylene)
Liq. NH
R  C  CH 3
 NaNH 2  R  C  C  Na   NH3
196 K
(A terminalalkyne) (An acetylide)
During these reactions, the acetylenic hydrogen is removed as a proton to form stable carbanions (acetylide
ions). Sodium acetylide is decomposed by water regenerating acetylene. This shows that water is a stronger
acid than acetylene and thus displaces acetylene from sodium acetylide.
HC  C Na   H 2O 
 HC  CH  NaOH
Acetylene
(b) Formation of heavy metal acetylides :

CH  CH  2  Ag  NH3 2  OH  
 AgC  CAg  2 H 2O  4NH3
Ethylne Tollen's reagent Silver acetylide
(White ppt.)


R  C  CH   Ag  NH3  2  OH  
 R  C  C  Ag  H 2O  2NH3
Tollen's reagent Silver acetylide
(White ppt.)

HC  CH  2 Cu  NH3 2  OH  
 CuC  C  Cu  H 2O  4NH3
Ethyne Copper acetylide
(Red ppt.)
Unlike alkali metal acetylides, silver and copper acetylides are not decomposed by water. They
can, however, be decomposed with dilute mineral acids to regenerate the original alkynes.
AgC  CAg  2 HNO3 

 HC  CH  AgNO3
Silver acetylide Acetylene
CuC  CCu  2 HCl 

 HC  CH  2CuCl
Cooper acetylide Acetylene
(c) Formation of alkynyl Grignard reagents :

Dry
HC  CH  RMgX 
 HC  CMgX  RH
Acetylene Grignard reagent ether Acetylenic Alkane
Grignard reagent
Dry
R '  C  CH  RMgX 
 R '  C  CMgX  RH
Terminal alkyne ether Alkynyl
Grignard reagent
Illustration - 7 How would convert acetylene to acetone ?
SOLUTION :
HC  CH  CH3COCH3
In such question, try to visulaise formation of CH3COCH3 . It is formed by hydration of CH3C  CH.
So now convert HC  CH to CH3C  CH.
NaNH  CH Br
3  HC  C  CH 
2  HC  C  N a  2 H O/ H  / Hg 2
HC  CH  3  CH3COCH3
1.0 eq
 via Tautomerism 

Illustration - 8
Identify A, B, C . . . . . . . . .
1.NaNH
2 A 
2  B  H
3 C  D O
(a) Me  C  CH 
2.EtBr Pd  BaSO 4 Zn / H 2 O
quinoline
(b)
1. NaNH (2.0eqv.)
2 2, 2 4C H Liq.Li Br /CCl
(c) HC  CH  A 
 B 
2. EtBr (2.0eqv.) NH3
SOLUTION :
(a)
(b)
(c)

CYCLOALKANES AND CYCLOALKENES Section - 4
These are closed chain hydrocarbons having CnH2n as general formula. These are isomeric to alkenes.
Cyclo propane or C3H6 or
Cyclo butane or C4H8 or
Cyclo pentane or C5H10 or
Cyclo hexane or C6H12 or
The bond angles in lower members, i.e., in cyclopropane and cyclobutane are quite different from normal
tetrahedral bond angle of 109.5°. Hence these are unstable as compared to higher member such as
cyclopentane and cyclohexane which have bond angles nearer to tetrahedral bond angles. The two small
cycloalkanes are said to have a ring strain due to bond deformation. This is referred to as Baeyer strain
theory. Due to this strain, cyclopropane and cyclobutane are highly reactive and tend to open their rings.
Cycloalkenes : These are isomeric to alkynes and alkadienes. Some important cycloalkenes are :
Cyclo propene or C3H4 or

Cyclo butene or C4H6 or
Cyclo pentene or C5H8 or
Cyclo hexene or C6H10 or
1-Methyl cyclopentene
1, 2-Dimethyl cyclohexene
Preparation of cycloalkanes and cycloalkenes :

1. Dehalogenation of iolated dibromides :
It is not a good method because of poor yield.
2. From diazomethane (CH2N2) :

Diazomethane or simple heating gives Carbene, : CH2, which adds to the double bond of alkenes to give
cyclopropane.

CH2 N2 
 : CH2  N 2

Note that the addition of : CH 2 (carbene) is sterospecific as 2-butene exist in cis and trans forms.
3. Simmon - Smith Reaction :

It is another method to form cyclopropane and its derivatives. Instead of diazomethane, di-iodomethane,
CH2I2 with Zn-Cu alloy in diethyl ether is used. The rest of the reaction is same as above.
4. Heating calcium/barium salts of dicarboxylic acids :

By heating barium salts of discarboxylic acids, cyclic ketones are formed, which on Clemmensen’s reduc-
tion (Zn-Hg/HCl) give cyclopentane, cyclohexanes and other higher derivatives.

5. Hydrogenation of benzene :
6. Diel - Alder Reaction :

It is an important reaction of conjugated dienes with double bonded compounds to form unsaturated cyclic
compounds. Let us take 1, 3Butadiene as conjugated diene and consider its reaction with some unsaturated
compounds such as Ethene and Vinyl alcohol. The unsaturated compounds are called as dienophiles. This
reaction proceed beacuse of formation of six membered cyclic transition state.
Note : (i)
‘G’ is preferably an electron withdrawing group (electronegative in nature) such as OH, NH2, 
CN, NO2, etc.
(ii) Each of the product can be hydrogenated to give a saturated compound.

Reaction of cycloalkanes :
1. Ring opening :
The ring of 5 carbons being stable does not open after reaction with hydrogen.
2. Chlorination :
3. Oxidation :
Note : Cyclobutane is opened in the presence of hydrogen and Ni. At ordinary temperatures, cyclobutanes resists
the action of halogens and hydrogen halides.
Reaction of Cycloalkenes :
The cycloalkenes show the reaction of alkenes. (Refer to the reaction of Alkenes). For a quick review of
the reactions, please go through the following page carefully. It shows all the typical reaction of alkenes
taking 1 - Methylcyclopentene as the substrate.


ALKADIENES Section - 5
Alkadienes are isomers of alkynes and cycloalkenes. These are classified in three categories.
(a) Hydrocarbons containing cumulated double bonds are called allenes or cumulated dienes.
CH2 = C = CH2 Propadiene C3H4
CH2 = C = CHCH3 Butadiene C4H6
(b) Those dienes which have an alternate system of double and single bonds are called conjugated
dienes.
CH2 = CH–CH = CH2 1, 3 Butadiene
CH 2  C CH  CH 2
| 2-Methyl-1, 3-Butadiene
CH3
1, 3-Cyclohexadiene
(c) In case, when two or more sp3 hybridised carbon atoms come in between the double bonds in
dienes, then they are called isolated dienes.
CH2 = CH2– CH2 – CH2 = CH2 1, 4-Pentadiene
Note : Conjugated dienes are most stable among dienes. They are stabilised due to resonance.
Preparation of Conjugate dienes :

1. From isolated dihalides
NaNH
2  CH  CH  CH  CH
C H 2  CH 2  CH 2  C H 2  2 2
| |
Cl Cl 1, 3 - Butadiene
NaNH
2  CH  CH  CH  CH  CH  CH  CH  CH  CH  CH
CH 3  C H  CH 2  CH 2  C H 2  3 2 2 2 2
| |
Cl Cl 1, 3 - Pentadiene (Major) 1, 4 - Pentadiene (Minor)

2. From isolated diols :
H SO
2 4  CH  CH  CH  CH  CH  CH  C  CH
CH3  C H  CH 2  C H 2  2 2 3 2
| | T 170C
OH OH 1, 3 - Butadiene (Major) 1, 2 - Butadiene (Minor)
H SO
2 4  CH  CH  CH  CH  CH  CH  CH  CH  CH  CH
CH3  C H  CH 2  CH 2  C H 2  3 2 2 2 2
| | T 170C
OH OH 1, 3 - Pentadiene (Major) 1, 4 - Pentadiene (Minor)
Reactions of Conjugate Dienes :

For the discussion of reactions of conjugated dienes we shall take 1, 3-Butadiene as an example.
1. Electrophillic Addition :
1, 3-Butadiene when reacts with HCl show unusual behaviour to give mixture of two products :
3-Chloro-1-butene (1, 2-addition product) and 1-Chloro-2-butene (1, 4-addition product)
(a) The formation of 1, 4-addition product is interesting.
HCl
CH 2  CH  CH  CH 2 
 CH3  C H  CH  CH 2  CH3  CH  CH  CH 2Cl
25 C |
Cl
(1, 2 - addition) (1, 4 - addition)
Note : Usually 1, 4-addition product is major.
(b) Addition of HBr to 1, 3-Butadiene takes place differently at different temperatures to give 1, 2-
addition and 1, 4-addition products as follows :
CH2 = CH – CH = CH2 + HBr 

(i) At – 80°C (Low temperature) :
CH3  C H  CH  CH 2  CH3  CH  CH  CH 2 Br
|
Br
(1, 2 - addition)(80%) (1, 4 - addition) (20%)

(ii) A 40°C (Near room temperature and above) :
CH3  C H  CH  CH 2  CH3  CH  CH  CH 2 Br
|
Br
(1, 2 - addition)(20%) (1, 4 - addition) (80%)
Note : At high temperatures, in case of HBr, 1, 2-addition product rearranges to give 1, 4-addition product.
(c) Addition of Br2 to 1, 3Butadiene also gives a mixture of 1, 2-addition and 1, 4-addition products.
Br2
(i) CH 2  CH  CH  CH 2   C H 2  C H  CH  CH 2  C H 2  CH  CH  CH 2 Br
15C
| | |
Br Br Br
 1, 3 - Butadiene  (1, 2 -addition) (54%) (1,4 - addition) (46%)
2 Br
(ii) CH 2  CH  CH  CH 2  1, 4  addition is major
T  27 C
2. Free radical addition :

In presence of perioxides, both 1, 2-addition product and 1, 4-addition products are formed. Consider
addition of BrCCl3 in presence of perioxide.
 Cl3C  CH 2  C H  CH  CH 2  Cl3C  CH 2  CH  CH  CH 2 Br
CH2 = CH – CH = CH2 + BrCCl3 
|
Br
(1, 2 -addition) (1, 4 - addition)
Note : Temperature dependency of products is similar to that HBr addition. Also refer to Diel - Alder reactions
(diense with alkenes) in cycloalkenes.
3. Reduction :
Catalytic hydrogenation of conjugated dienes in presence of H2/ Li gives a mixture of 1, 2-addition and 1, 4-
addition product with the 1, 4-addition products being major.
H H H H
H 2 / Li
| | | |
CH 2  CH  CH  CH 2   CH 2  C H  CH  CH 2  CH 2  CH  CH  CH 2
Buta - 1,3 - diene But - 1 - ene (Minor) But - 2 - ene (Major)
However, the chemical reduction of 1, 3-Butadiene with sodium in alcohol gives mainly the 1, 4-addition
product, i.e., But-2-ene.

Na /alcohol
CH 2  CH  CH  CH 2 
 CH3  CH  CH  CH3
1, 3-Butadiene But-2-ene
Under these conditions the isolated double bonds are not reduced. This suggests that dienes are much more
reactive than simple alkenes.
4. Polymerization :
Peroxides
n  CH 2  CH  CH  CH 2    CH 2  CH  CH  CH 2   n
Buta-1, 3-diene Polybutadiene
Since each repeating unit in polybutadiene contains a double bond, it may have either cis or trans-configu-
ration. Actually the polybutadiene polymer obtained by free-radical polymerisation has trans-configura-
tion.
 CH3 
Peroxides
n |  
 CH  C CH  CH 
 2 2
2-Methylbuta-1, 3-diene
(Isoprene)
 Cl   Cl 
Peroxides
n  |    | 
 CH  C CH  CH   CH  C  CH  CH  
 2 2  2 2 n
2-Chlorobuta-1, 3-diene Polychloroprene
(Chloroprene) (Neoprene)
Neoprene is an important substitute for natural rubber and is superior to natural rubber in being
more resistant to oil, gasoline and other organic solvents.
50 Section
Illustration - 9 Isomers A, B, C, and E have a common molecular formula C4H6. Identify A, B, C……as
per given instructions.
(a) A reacts with RMgBr to give a hydrocarbon.
(b) B reacts with Br2 to give a mixture of two products.
(c) C, an alicyclic compound, when oxidised by hot acidic KMnO4, gives a dicarboxylic acid whose
sodium salt on electrolysis gives an alkene, D. Also identify D.
(d) E is an alicyclic compound which is oxidized by hot KMnO4 to give 3-Oxo-1-butanoic acid.
SOLUTION :
C4H6 : can be alkyne, or alkadiene, or cycloalkene
(a) A should be terminal alkyne as it react with Grignard reagent.

 R MgBr
(A) CH3CH2C  CH  RH  CH3CH2C  C  MgBr
(b) B should be a conjugated diene as it gives a mixture of products.

Br
2  C H  C H  CH  CH  C H  CH  CH  C H
CH 2  CH  CH  CH 2  2 2 2 2
(B) | | | |
Br Br Br Br
(1, 2 - addition) (1, 4 - addition)
(c) D is clearly ethene as it is the only lakene

formed by Kolbe’s electrolysis.
(d)

Illustration - 10 Give the products.
(a) (b)
SOLUTION :
(a)
Note that aldehyde group is oxidised to acidic group
(b)

AROMATIC HYDROCARBONS Section - 6
Benzene : [C6H6]
Structure :
Its molecular formula is C6H6. This implies unsaturation in benzene. It shows addition reactions : addition of
3 molecules of Hydrogen, 3 moles of Cl2 and 3 moles of Ozone (like alkenes).
This leads to idea of three double bonds. However, benzene fails to give unsaturation test (i.e., Baeyer’s test
or decolouration of bromine water). Benzene also gives substitution reactions like halogenation, nitration
etc. (like alkanes). On addition of H2, benzene forms cyclohexane (a cyclic hydrocarbon) C6H12. Kekule
(1865) proposed following structure the basis of the structure of cyclohexane. But this structure fails to
explain ozonolysis of Xylene [C6H4  (CH3)2], a derivative of benzene. So benzene is found to be a
resonance hybrid of two Kekule structures :
This is supported by ozonolysis of o-Xylene, which gives a mixture of Glyoxal, Methyl glyoxal, Dimethyl
glyoxal which can not be explained by either of Kekule structures.
Now benzene is considered as resonance hybrid of two Kekule structures. Resonance imparts stability to
the benzene due to delocalisation of  electrons over entire benzene ring . Since  electrons are not concen-
trated in any specific region, addtion reaction (electrophillic) are not common is benzene. However, in
benzene electrophillic substitution reactions are common as they are stabilized by resonance stabilisation of
intermediate Carbonium ion. When a group is introduced in benzene nucleus (ring), only one product
(monosubstitued) is obtained. On the other hand, when a group of electrophillic nature is introduced in a
mono-substituted benzene, three different isomers are possible.
In the above sequence, nature of X (group over mono-substituted benzene) is responsible for the formation
of either ‘m’ or ‘o’ & ‘p’ derivatives.

Directive (orienting) influence of groups :

(a) o and p directing groups : These groups direct the incoming group predominantly to the ‘o’ &
‘p’ position. Some important groups are :
 NH 2 ;  NHR ;  ;
 OH  ;
 OR  ;  R
X
All of these groups exerts +M effect over benzene and tends to increase electron-density over
benzene and make benzene strongly nucleophillic towards electrophiles. These groups are called
activating groups. -I effect (elctronegative or electron withdrawing nature) of these groups is weaker
as compared to +M effect. Halogens exerts +M effect over benzene but their -I effect is very
powerful. Though they are o and p directing (+ M effect) but are de-activating in nature and hence
it is difficult to carry out electrophillic substitution in halo benzenes. Alkyl group (R) are o and p
directing due to hyperconjugation (to be discussed later).
(b) m-directing groups : These groups direct the incoming groups predomintly to m-positions. Some
of the important groups are :
O OH R H
|| || | |
 C  OH ;  S  O ; C  O ;  C  O ;  NO 2 ;  CCl3
||
O
All m-directing groups, (except CCl3) either possess a positive charge or the key atom of substituents
has an electronegative atom linked by a multiple bond. The benzene nucleus containing these groups
undergo strong –M, –I, effect such that the displacement of electron takes place away from the
benzene ring. These groups tends to deactivate the benzene ring and hence makes it less nucleophillic
towards electrophiles.These are called as de-activating groups. Benzene having these groups will
have greater difficulty in electrophillic substitution reactions.
Preparation of Benzene :
1. Decarboxylation of Sodium Benzoate :
2. From Chlorobenzene :

3. From Phenol :
4. From Sulphonic Acid :
5. Synthesis :
Red hot Fe tube
3C2 H 2  C6 H 6
6. From Benzene Diazonium Chloride :
7. Manufacture :
(a) n-hexane :
2 3 Al O  Cr O
2 3
CH3  CH 2 4 CH3 
600C, pressure
This is known as Hydroforming or catalytic Reforming or aromatisation
(b) Coal Tar :
fraction
Dry distillation 
 COAL  TAR  Ligt  oil  fraction 

of wood Distillation 80  170C
Physical properties of Arenes :

1. Benzene and its homologues containing upto eight carbon atoms are colourless liquids with charac-
teristic smell.
2. Due to large hydrophobic hydrocarbon part, arenes are not soluble in water but are soluble in
organic solvents.
3. The melting points and boiling points of arenes increase with increase in the molecular size due to
a corresponding increase in the magnitude of van der Waal’s forces of attraction. Amongst isomeric
arenes, i.e., o-, m- and p-Xylenes, the p-isomer is most symmetrical, has the highest melting point.

Reaction of Benzene :
When benzene is treated with bromine in carbon tetrachloride in the dark or with aqueous potassium in the
dark or with aqueous potassium permanganate or with dilute acids, none of the expected reactions (addition
reactions) occurs. Benzene does add hydrogen in the presence of finely divided nickel, but only at high
temperature and under high pressures.
Benzene does react with bromine except in the presence of catalyst such as ferric bromide. The interesting
aspect of this reaction is that benzene show substitution not addition (like alkenes).
Substitution :
FeBr
3  C H Br  HBr
C6H 6  Br2  6 5
Addition : Benzene does not show addition reaction of Br2 or H2 at all under normal conditions.
When benzene reacts with bromine, only one monobromobenzene is formed. That is, only one compound
with the formula C6H6Br is found among the products. Similarly, when benzene is chlorinated, only one
monochlorobenzene results.
Two possible explanations can be given for these observations. The first is that only one of the six hydrogen
atoms in benzene is reactive toward these reagents. The second is that all six hydrogen atoms in benzene are
equivalent, and replacing any one of them with a substituent results in the same product. From the concept
of Resonance we know all six carbon atom form equivalent C – C and C – H bonds. Hence this is the
correct explanation.
Structure of Benzene
The fact that the bond angles of the carbon atoms in the benzene ring are all 120strongly suggests that the
carbon atoms are sp2 hybridized. If we accept this suggestion and construct a planar six-membered ring
from sp2 carbon atoms, a representation like and shown in figure emerges. In this model, each carbon is sp2
hybridized and has a p-orbital available for overlap with p-orbitals of its neighbouring carbons. If we con-
sider favaourble overlap of these p-orbitals all around the ring, the result is the model shown in figure.
(a) Six sp2-hybridized carbon atoms are joined in a ring (each carbon also bears a hydrogen atom).
Each carbon has a p-orbital with lobes above and below the plane of the ring. Fig.(1)
Fig. (1)
(b) Overlap of the p-orbitals forming pi() bonds around the ring results in the delocalisation of pi()
electrons on the ring. [Refer to Fig.(2), (3), (4)]

Fig. (2)
Fig. (3)
Fig. (4)
The six  electrons are thus delocalised and can move freely about the six carbon nuclei, instead of any two
as shown in figure (4). The delocalised  electron cloud is attracted more strongly by the nuclei of the
carbon atoms than the electron cloud localised between two carbon atoms. Therefore, presence of delocalised
 electrons in benzene makes it more stable than the hypothetical cyclohexatriene. X-Ray diffraction data
reveals that benzene is a planar molecule. It also indicates that all the six C – C bond lengths are of the same
order (139 pm) which is intermediate between C – C single bond (154 pm) and C – C double bond (133
pm). This absence of pure double bond in benzene accounts for the reluctance of benzene to show addition
reactions under normal conditions, thus explaining the unusual behaviour of benzene.
1. Addition of Hydrogen (H2) :

2. Ozonolysis :
3. Oxidation :
Benzene is unreactive towards even strong oxidising agents such as : KMnO4/K2Cr2O7. However
in drastic conditions, it can be oxidised slowly to CO2 and H2O. It can be burned (i.e., combustion)
to give luminous and smoky flame.
(a) Controlled oxidation with air :
Benzene on oxidation with air at 773 K in presence of V2O5 as catalyst gives Maleic anhy-
dride.
(b) Oxidation of alkyl benzene :
Note : If R is a 3alkyl group, then it resists oxidation the benzene ring is destroyed.
3. Substitution Reactions :
Most important reactions of benzene are electrophillic substitution reactions. These are also denoted as SE
reactions.

Elecrophiles :
  +
Cl+ (Chloronium ion), N O 2 (Nitronium ion), SO3 (Sulphur trioxide), R (Carbonium ion), R  C  O
(Acylium ion).
(a) Halogenation :
 FeCl4  Cl
FeCl3  Cl2 
Note : (i) In iodination, oxidising agents like HNO3 or HIO3 are used to oxidise HI, a reducing agent.
(ii) In presence of sunlight and absence of halogen carriers (i.e., AlCl3, FeBr3, etc), benzene adds three
molecules of chlorine to form Benzene hexachloride (BHC) or Gammexane.
h
C6 H 6  3Cl2 
 C6 H6 Cl6
It may be noted that this is an addition reaction, not a substitution reaction.
(b) Nitration :

 HSO 4  H O NO 2 
HNO3  H 2SO 4   NO2  H 2O
Base Acid |
(Nitrating mixture) H
(c) Sulphonation :
H 2S2O7 
 SO3 + H 2SO4
electrophile
(d) Introduction of alkyl and acyl groups in presence of Catalysts : AlCl3, FeCl3, SbCl3 (acting
as Lewis acids) or protonating agents like HF, H2SO4, H3PO4 etc. These are known as Friedal
Craft reactions.

(i) Alkylation :
 AlCl4 
RCl  AlCl3  R (alkyl carbonium)
Electrophile
Note : The above reaction can be achieved with :
(a) An alcohol in HF or dil H2SO4 (b) An alkenne in HF or dil. H 2SO 4 (at low temperature)
(a)
(b)
Obseve that 3 carbon is attached to the ring.

While during alkylation, we expect formation of polyalkylated products as alkyl groups are o- and p-directing and
activating
(ii) Acylation :
O
||
RCOCl  AlCl3 
 R C  AlCl4

Acylium ion is Electrophile

The above two reaction are called as Acctylation and Benzoylation respectively.
Some Friedal Craft acylation are shown below :
The above reaction is also known as Gatterman - Koch reaction.
Note : (i) Aryl and vinylic halides cannot be used in Friedal craft reactions as they do not form carbocations
easily.
(ii) In substituted benzenes, Friedal Craft reactions gives poor yield when electron withdrawing (de-
activating) groups are present on the ring. These include :
O
||
 NO 2 , CN  ,  COOH,  C  R,  CCl3 ,  SO3H
(iii) In Friedal craft alkylation. most stable carbocation (from alkyl halide or alkene) determines the final
substitution product.

It does not give npropyl benzene since CH3 – C HCH3 , being a 2° carbocation is more stable

than CH3CH 2CH 2 1  .
* The detailed mechanism of SE reaction will be discussed later in the chapter “Organic Concepts”.
(iv) Intramolecular Friedal Craft reactions of - & - alkyl alkanoic acid or alkanoyl chlorides give
cyclic products.
4. Dehydrogenation :
Toluene :
Preparation of Toluene :
1. Friedal craft alkylation :

2. From dialkyl cuprates :

 CH3 2 CuLi  C6 H 5I 
 C6H 5  CH 3  LiI  CH 3Cu
Reactions :
1. Oxidation :
(a)
(b)
This is also known as Etard reaction.
2. Substitution :
(a) Side chain substitution :

(b) CH3 group being o and p directing directs incoming electrophile to o and p position :
3. Addition Reactions :

Illustration - 11 One of the benzene ring of [4] phenylene undergoes catalytic hydrongation readily under
conditions usually used for ordinary alkenes, but the other benzene ring do not. Identify which of these two
reaction correctely represent product of hydrogenation of [4] phenylen ?
I.
II.
(A) Only I (B) Only II (C) Both I and II (D) None
SOLUTION
Reaction I correctly represent product of hydrogenation of [4]-phenylen beacuse of loss in anti-aromatic

characters of all four memebered rings.

Illustration - 12 Which is the major product of the following

intramolecular F.C. acylation reaction ?
SOLUTION
Enolic form is more stable than keto form due to more aromatic characters in enolic form.
NOW ATTEMPT IN-CHAPTER EXERCISE-F BEFORE PROCEEDING AHEAD IN THIS EBOOK

Example - 1
Give the structure of A, B and C (explanation are not required) :
(i) A (C4H8) which adds on HBr in the presence and in the absence of peroxide to give same product,
C4H9Br
(ii) B (C4H8) which when treated with H2O/H2SO4 gives C4H10O which cannot be resolved into optical
isomers.
(iii) C (C6H12), an optically active hydrocarbon which on catalytic hydrogenation gives an optically
inactive compound C6H14.
SOLUTION :
(i) A: CH3CH = CHCH3 symmetric alkenes give same product.
OH
H 2O
|
(ii) B: CH3  C  CH 2 
 CH 3  C  CH3 ; optically inactive (No chiral centre)
| H |
CH3 CH3
H H
| H 2 / Pt
|
(iii) C: CH3  C*  CH  CH 2 (active)   CH3  C  C2 H5
|  |
C 2H 5 C 2 H5
(* : Chiral centre)
optically inactive (No chiral centre)
Example - 2
An organic compound E (C5H8) on hydrogenation gives compound F (C5H12). Compound
E on ozonolysis gives formaldehyde and 2-ketopropanal. Deduce the structure of compound E.
SOLUTION : In such questions, by working backwards we join :
Note : Since 2-ketopropanal has two keto groups, hence there must be 2 moles of HCHO.
O
O3
||
(E)  2HCHO  CH3  C  CHO  E is :
Zn  H2 O
Self Study Course for IITJEE with Online Support Subjective Solved Example 67
Example - 3 The hydrocarbon, A adds one mole of hydrogen in the presence of a platium catalyst to
form neo-hexane. When A is oxidised vigorously with KMnO4, a single carboxylic acid, B is isolated. Give the
structures of A and B.
SOLUTION :
CH3
|
Hence A is : CH3  C  CH  CH 2
|
CH3
CH3
|
Clearly B is : CH3  C  COOH
|
CH3
Example - 4 What are product A, B and C in the following rection ?
2 H (O)

 A 
 B  C
Lindlarcatalyst
SOLUTION : Visualise the structure of given compound as follows :
Example - 5 Identify the products A, B and C and the reagent R in the following reactions :
alc. KOH 2 H O
(i) (CH 3 )2 C  CH 2CH 3  A (ii) HC  CH 
 2
B
| H / Hg
Cl
(iii) R
A 
BC
SOLUTION :
CH3 CH3
| RO |
(i) CH3  C  C HCH 3  CH3  C  CHCH3 (Saytzeff’s product)
| | (A)
Cl H
H O Tautomerises
2 

(ii) HC  CH   CH 2  CHOH 
 CH3CHO
 2
H / Hg
(B)
CH3
| R
(iii) CH 3  C  CHCH3  CH3CHO  (C)
R is clearly O3/Zn-H2O and (C) is acetone (CH3COCH3)

CH3
| O3
CH 3  C  CHCH 3   CH3CHO  (CH 3 )2 C  O
Zn /H 2 O
(A) (B) (C)
Example - 6 De-hydro-bromination of two compounds A and B gives the same compound C. C

regenerates A and B when reacts with HBr in the presence and absence of peroxide respectively. The hydrolysis
of A and B gives isomeric products D and E respectively. C when reacts with benzene in presence of H+ ions
gives 1, 1-Diphenylethane. Identify the compounds A to E.
SOLUTION : Visualizing the flow chart of the question as follows.
Recall Friedal Craft alkylation
 C is an alkene containing a – C = C – bond, hence C is vinyl benzene. C :
As per given reactions in question :
A: B: D: E:
Example - 7 An organic compound A, C5H9Br de-colourises bromine water and alk. KMnO4. It gives
B, C5H11Br when treated with H2, Pd-carbon in methanol. The reaction of A with NaNH2 gives C with the
evolution of NH3. C does not react with sodium but reacts with Lindlar catalyst to give D. It also reacts with
Na/liquid NH3 to give E. Both D and E are isomers. Identify the compounds A to E with proper reasoning.
SOLUTION :
Visualizing the flow chart of the question as follows :
Hydrocarbons
Since D and E are isomers obtained by partial hydrogenation of ‘C’ (C : an alkyne) from two different
reagents, D and E must be geometric isomers with molecular formula C5H10. “Check this as follows”
NaNH 2
(A) C5H9 Br  C5H8  NH3  Br 
(Dehydrobro min ation)
2H
C(C5H8 )   C5H10 (D and E)
The alkene with molecular formula, C5H10 showing geometric isomerism is only 2-Pentene
[CH3CH = CHC2H5]
Hence the compound (C) is 2-Pentyne (Non-terminal alkynes do not react with Na).
A can be :
CH 3 C  CH  C 2 H5 or CH3CH  C  C 2H5
| |
Br Br
Both will give 2-Pentyne with NaNH2.

Accordingly B can be :
CH 3 C H  CH  C2 H5 or CH3CH 2  C HC 2 H5
| |
Br Br
72 Subjective Solved Example Self Study Course for IITJEE with Online Support
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Organic Halides
Halogen containing Organic Compounds
ALKYL HALIDES : [RX] Section - 1
In ‘Hydrocarbons’ last chapter, you have observed that hydrocarbons react with halogens to form Organic
Halides. These compounds are called halogen derivatives of hydrocarbons. Here, the halogen atom (X)
acts as a functional group and is attached to the carbon atom by a covalent bond. These organic halides are
of two types: Alkyl Halides (aliphatic) and Aryl Halides (aromatic).
The alkyl halides are classified into three categories based on type of carbon atom to which the halogen
atom is attached.
Primary (1°) Halide : RCH2X Secondary (2°) Halides : R2CHX Tertiary (3) Halide : R3CX
(R : alkyl radical, X : F, Cl, Br, I)
The Organic Halides are further classified as monohalides, dihalides and trihalides depending upon number
of halogen atoms.
Tri-haloderivative of CH 4 are known as HALOFORM. Fully halogenated hydrocarbons are also called
perhalohydrocarbons. (C n X 2 n+2 ). For Example : Perfluorethane C2 F6
Preparation of Alkyl Halides :

1. Halogenation :
(a) From Alkanes : Halogenation of alkanes is carried out in the presence of heat or light. Chlorination is
fast, bromination is slow while direct iodination is not possible as the reaction is reversible.
Direct halogenation does not form pure mono-halogen derivatives since a mixture of polyhalogen
derivatives is always obtained. For example, in chlorination of Methane we get a mixture of products.
2 Cl
CH 4  CH3Cl  CH 2 Cl2  CHCl3  CCl4
Methane h or 520  670 K Chloromethane Dichloromethane Trichloromethane Tetrachloromethane
In case of higher alkanes, even mono-halogenation gives a mixture of all the possible isomeric
haloalkanes.
2 Cl , h
CH 3CH 2 CH3  CH3  CH 2  CH 2  Cl  CH 3  CH(Cl)  CH 3
Propane 298K 1-Chloropropane(40%) 2-Chloropropane(55%)
2 Cl , h
CH3 CH 2 CH 2 CH3  CH3CH 2 CH 2 CH 2 Cl  CH3CH 2  CH(Cl)  CH 3
298K 1-Chlorobutane(28%) 2-Chlorobutane(72%)
In general, the ease of substitution of various hydrogens follows the sequence :

Allylic > 3° > 2° > 1° > CH4.

Organic Halides Vidyamandir Classes
Iodination is reversible, but it may be carried out in the presence of an oxidising agent, such as, HIO3,
HNO3, HgO, etc., which oxidises the HI as it is formed.
hv

CH4 + I2  
 CH3I + HI ; 5HI + HIO3 
 3I2 + 3H2O
Flourination : The best way to prepare alkyl fluorides is by halogen exchange. An alkyl chloride or bromide
is heated in the presence of a metallic fluoride, such as AgF, Hg2F2, CoF3 or SbF3 to give alkyl fluorides.
CH 3 Br  AgF 
 CH 3 F  AgBr
Bromomethane Fluoromethane
2CH3CH 2  Cl  Hg 2 F2 
 2 CH3CH 2  F  Hg 2 Cl2
Chloroethane Fluoroethane
This reaction is called Swarts reaction.

When the organic halide contains two or three halogen atoms at the same carbon, CoF3 or the more easily
available SbF3 is used. For example,
3CH3  CCl2  CH3  2SbF3 

 3CH3  CF2  CH 3  2SbCl3
2,2 - Dichloropropane 2,2 - Difluoropropane
(b) From Alkenes : Alkenes react with halogen acids to form haloalkanes.
The order of reactivity is : HI > HBr > HCl > HF.
RCH  CH 2  HX   R C H  CH3
|
X
The unsymmetrical alkenes follows Markovnikov’s rule during addition forming secondary or tertiary
alkyl halides predominantly.
Note : In presence of peroxides, the addition of HBr only (not HCl or HI) to unsymmetrical alkenes takes place via
Anti Markovnikov’s rule forming primary alkyl bromides. This is known as Peroxide effect or Kharasch
effect.
(c) Allylic halogenation : When alkenes (except Ethylene) are heated with Cl2 or Br2 at a high temperature of
about 773 K, the hydrogen atom at the allylic carbon (i.e., carbon next to the double bond) is substituted
by a halogen atom. For example,

773K
CH 3  CH  CH 2  Cl2  Cl  CH 2  CH  CH 2
3-Chloroprop-1-ene (Allyl chloride)
However, a more specific reagent for allylic bromination is Nbromosuccinimide (NBS).
Allylic chlorination can also be carried out with sulphuryl chloride.

475, h
CH 3  CH  CH 2  SO2 Cl2 
 Cl  CH 2  CH  CH 2  HCl  SO 2
Traces of peroxide
2. From Alcohols : Generally alkyl halides are prepared from alcohols by replacement of OH group by an
halogen ion. This is usually by using HX or PCl5 .
R – OH + X– 
 R – X + OH
–
(a) By the action of Halogen acids :

Catalyst
R – OH + HX  R – X + H2O
Note :(i) The order of reactivity for halogen acids is : HI > HBr > HCl and for alcohol is : 3 alcohol > 2 alcohol
> 1 alcohol.
(ii) The catalyst used is generally a dehydrating agent such as ZnCl2 or conc. H2SO4.
(i) Using HCl :

anhyd.
CH3CH2OH + HCl(g) 
ZnCl
 CH3CH2Cl + H2O
2
anhyd.
CH3  C H  CH 3  HCl  g   CH3  C H  CH3  H 2 O
ZnCl2
| |
OH Cl
Anhydrous ZnCl2 helps in the cleavage of C – O bond. Being a Lewis acid, it co-ordinates with the
oxygen atom of the alcohol. As a result, C – O bond weakens and ultimately breaks to form carbocations
(C+), which form chlorides.
Room
 CH3 3  C  OH  HCl 
temp
  CH3 3  C  Cl  H 2 O
 conc.
The yield can be improved when the vapours of alcohol and HCl are passed over alumina at 350C.

(ii) Using HBr :

Alkyl bromides are obtained by refluxing the alcohol with constant boiling in HBr (40%) in presence
of a little conc. H2SO4.
H 2SO4
CH3CH2 – OH + HBr 
Reflux
 CH3CH2 – Br + H2O
C2H5OH + KBr + H2SO4 

 C2H5Br + KHSO4 + H2O
Note : The mixture of KBr and H2SO4 is not used in case of secondary and tertiary alcohols as their dehydration
may occur, to give alkenes.
(iii) Using HI :
Re flux
CH3 – CH2 – OH + HI   CH3CH – I + H2O

CH3OH + KI + H3PO4   CH3I + KH2PO4 + H2O
(b) By the action of Phosphorus Halides :

Phosphorus halides react with alcohols to form haloalkanes in excellent yield (80% or above).
ROH + PX5 
 R – X + POX3 + HX
Here X can be either chlorine or bromine or iodine.

3ROH + PCl3 
 3R – Cl + H3PO3
Since PBr3 and PI3 are not very stable compounds, these are generally prepared in situ by the action
of red phosphorus on bromine and iodine respectively.
P  Br
2  R  Br 2 PI
P4  6X 2 
 4 PX 3 ; R  OH  ; R  OH  R I
This method gives good yield of primary alkyl halides but poor yields of secondary and tertiary
alkyl halides.
The method is useful for preparing lower alkyl bromides and iodides in the laboratory.
(c) By the action of Thionyl chloride : (Darzen’s method)

Chloroalkanes are conveniently prepared by refluxing alcohol with thionyl chloride (SOCl2) in
presence of pyridine (C5H5N).
Pyridine
R  OH  SOCl2 
 R  Cl  SO 2   HCl 
Reflux
Thionyl chloride method is preferred over hydrogen chloride or phosphorus chloride method for the
preparation of chloroalkanes since both the by-products (SO2 and HCl) in this reaction being gases
escape, leaving behind chloroalkanes in almost pure state.

Note : Bromides and iodides are not prepared by this method, because thionyl bromide is unstable and thionyl
iodide does not exist.
3. From Silver salt of fatty acids :

4 CCl , Reflux
CH3CH2COOAg + Br2  CH3CH2 – Br + CO2 + AgBr

This reaction is called as Borodine Hundsdiecker reaction and is a free radical reaction. This reaction
gives the product with one carbon atom less than the fatty acid. The yield of the alkyl halide formation with
this reactions is :
primary > secondary > tertiary.
Chloroalkanes can also be prepared by this method by using Cl2 instead of Br2 but the yields are poor.
With I2, silver salts give esters instead of iodoalkanes.
2RCO2Ag + I2 
 RCOOR + CO2 + 2AgI
Note : This method is very popular in the formation of aromatic bromides as they yield is very high.
4. Halogen exchange reaction :

Iodoalkanes can be easily prepared from the corresponding chloroalkanes or bromoalkanes by heating
with sodium iodide in acetone or methanal.
Acetone
RCl + NaI  RI + NaCl X = Cl or Br

This reaction is called Frinkelstein Reaction.

Its a halide exchange reaction which involves a substitution of Cl/Br by I. The reaction was specially de
signed to prepare iodo-alkanes which were not easily prepared using simple halogenation method. (Due to
the reversibility of Iodination)
Acetone X = Cl or Br
R  X+ NaI  R  I+ NaX 
Reaction is believed to be based on the principle of greater solubility of NaI in acetone as compared to
NaCl or NaBr because of greater covalent character in NaI. That is why despite of being a weaker reagent
than Cl / Br  , I  still substitues them and the NaCl/NaBr formed precipitates out driving the equilibrium in
forward direction.
Note : Fluoro alkanes are difficult to prepare as all the hydrogen atoms are replaced by fluorine. The monofluoro
alkanes are prepared by heating alkyl halides with KF in diethyl glycol.
KF
RX  RF  KX
(CH 2 OH) 2

Physical Properties :
1. Physical state, colour, odour, etc : Alkyl halides are colourless when pure, but bromides and particularly
iodides develop colour when exposed to light. Methyl chloride, Methyl bromide, Ethyl chloride and some
Chlorofluoromethanes and Chlorofuloroethanes are gases at ambient temperatures. Other chloro, bromo,
iodo compounds are either liquids or solids. Many volatile halogen compounds have sweet smell.
2. Melting points and boiling points : The melting points and boiling points of haloalkanes are several
degrees higher than those of parent alkanes mainly due to greater magnitude of van der Waals forces of
attraction.
For the same alkyl group, the boiling points of haloalkanes decrease in the order : RI > RBr > RCl > RF. This
is because with the increase in the size and mass of the halogen, the magnitude of the van der Waal’s forces of
attraction increases.
For isomeric alkyl halides, the boiling points decrease with branching, because with branching the surface area
of the alkyl halide decreases and hence the magnitude of the van der Waal’s forces of attraction decreases.
The boiling points of chloro, bromo and iodo compounds increase as the number of halogen atoms increases.
3. Solubility : Even though haloalkanes (dipole moment, 2.05 – 2.15 D) are polar molecules still they are
insoluble in water. This is due to the reason that haloalkanes can neither form hydrogen bonds with water nor
can they break the hydrogen bonds already existing between water molecules. However, they are quite
soluble in organic solvents of low polarity such as petroleum ether, benzene, ether chloroform, carbon tetra-
chloride etc.
4. Density : Alkyl fluorides and chlorides are generally lighter than water whereas alkyl bromides and iodides
are heavier. Their relative densities follow the order : RI > RBr > RCl.
5. Stability : Since the strength of the C – X bond decreases in the order : C – F > C – Cl > C – Br > C  I,
therefore stability of the haloalkanes having same alkyl group is in the order :
R – F > R – Cl > R – Br > R  I.
That is why alkyl iodides, on standing become violet or brown because of their decomposition in presence of
light to give iodine.
Light
2R – I  R – R + I2
6. Dipole moment : CH3  Cl > CH3  F > CH3  Br > CH3  I
Reactions of Alkyl halides :

The alkyl halides are highly reactive compounds due to the polarity of C – X. The order of reactivity is :
With respect to halogen atom : RI > RBr >R Cl ; With respect to alkyl groups : 3° > 2° > 1°

1. Nucleophillic Substitution Reactions :

 
In alkyl halides, C  X bond is highly polar, so nucleophile (Nu–) attacks electrophillic carbon atom easily..
Hence alkyl halides give Nucleophillic Substitution Reactions readily. The halogen atom is replaced by a wide
range of nucleophiles to give almost all important organic families.
RX  Nu  
 R  Nu  X
Nucleophile Leaving group
Note : Nucleophile is a species which is seeking to attack electrophilic region i.e., carbon with a +ve charge or
  charge. It is able to share its rich electron cloud with electrophilic species. Some important electron
rich nucleophiles are OH  , CN  , RO  , RCOO  and RS ions.
The mechanism of nucleophile substitution reaction will be discussed in next chapter ‘Organic
Conepts’.
(i) Substitution by aq. KOH :
H O
2  RCH RCH OH + KX
RCH2X + KOH  2 2

(ii) Substitution by moist Silver oxide (AgOH) :
2  AgOH H O
Ag2O 
RCH2X + AgOH 
 RCH2OH + AgX
(iii) Substitution by Sodium alkoxides (RONa) :

Na
RCH2OH  RCH2O–Na+
RCH2O– acts as strong nucleophile and attacks on alkyl halides to produce ethers..
– 
CH3Br + RCH2O Na+ 
 CH3 – O – CH2R + NaBr
The above reaction is called as Williamson’s synthesis of ethers.
Note : (i) 2° and 3° alkyl halides, however prefer to give alkenes as elimination products.
(ii) The ethers are also prepared by use of Ag2O.

2RI  Ag 2 O 
 ROR  2AgI
(dry)
(iv) Substitution by Hydro sulphide group : (Formation of Thioalcohols).

2 5 2 C H OH / H O
RX  NaSH  R  SH  NaX
 Thioalcohol

(v) Substitution by Mercaptide group : (Formation of Thioethers).

(a) By heating an alkyl halide with Sodium or Potassium mercaptide : (Na–S–R)
2 5 C H OH / H O
2 R  S  R   Na  X 
RX  NaSR  
 Thioether
(b) By heating an alkyl halide with Sodium or Potassium sulphide :
2 R  X+ Na 2S 
 R  S R + 2 NaX
Thioether
(vi) Substitution by Amino group : (Formation of Amines)

Haloalkanes when heated with an ethanolic solution of ammonia in a sealed tube at 373 K, form a
mixture of 1, 2 and 3 amines along with quaternary ammonium salts.
2 5 C H OH
RX+ NH 3  RNH 2 + HX
 1° Amine
Note : If alkyl halide is in excess, then 2 and 3 amines and even quaternary salts are also formed.
NH RX RX RX

RX  3  RNH 
2  R 2 NH 
 R 3 N 
 R 4 N X
alcohol
1°Amine 2°Amine 3°Amine (Quaternay salt)
This reaction is called Hoffmann ammonolysis of alkyl halides.
(vii) Substitution by Cyanides :
2 5 C H OH / H O
2  R CN  KX
(a) RX  KCN 

(KCN is an ionic compound giving – CN as nucleophile)
Note : In this reaction, if alkyl halide, RX is tertiary (3), instead of substitution, elimination occurs to give an alkene.
(CN– acting as a base against 3° halides).
H O
2  RCOOH  NH 
Note : R  C   4
H
2 5 C H OH / H O
2  RNC
(b) RX  AgCN   AgX

Isocyanides

(AgCN is covalent compound giving  N  C , an amident nucleophile)

(viii) Substitution by salts of Carboxylic acids :

O
||
Ethanol
RCH 2 Br  R COOAg  RCH 2 O  C  R   AgBr
 Esters
(ix) Substitution by Acetylides : (Formation of higher alkynes)
RX  R   C  C  Na 
 R C  C  R  NaX
Sodium Alkynide Higher alkynes
Note : In this reaction also, if alkyl halide, RX is tertiary (3), instead of substitution, elimination occurs to give an
alkene.
Sodium alkynides are themselves prepared by the action of sodamide (or Na in liq. NH3 at 196 K) on
terminal alkynes.
Liq. NH  
R  C  CH  NaNH 2  3 R  C  C  N a  NH3
196 K
(x) Substitution by AgNO2 and KNO2 :

 C H OH /H O
RX  K   O  N  O 
2 5 2  R  O  N  O  KX

 Alkyl nitrite
O
C2 H5 OH /H 2 O
||
RX  Ag  O  N  O   R  N  O  AgX

Nitroalkane
–
(xi) Substitution by N3 (Azide ion) :
RX+ N 3 
 RN3 + X
Alkyl azides
2. Elimination reaction with alc. KOH/NaOH : (Dehydrohalogenation)

alc.
RCH 2CH 2 X 
 RCH = CH 2 + KX+ H 2O
KOH,  Alkenes
If the structure of the alkyl halide is such that it can undergo elimination in two different ways, due to availability
of different types of -hydrogen, then the more highly substituted alkene is the major product of
dehydrohalogenation. This is known as Saytzeff ’s rule.
  
alc.
R C H 2  C H 2  C H 3  RCH  CHCH3  RCH 2 CH  CH 2  KX  H 2 O
| KOH Major Minor
X

The reaction is also referred to as -elimination (1, 2-elimination), as -H is lost.

In general the ease of dehydrohalogenation for a given alkyl group decreases in the order : 3 > 2 > 1 and
for a given halogen, the order decreases as : R – I > R – Br > R – Cl.
Note : The above elimination is also achieved using alkoxide ( RO  / ROH ), as discussed in “Organic Concepts”.
3. Action of Heat :
Alkyl halides when heated above 300C, tend to lose a molecule of hydrogen halide forming alkenes.
300C
RCH2CH2X   RCH = CH + HX
2
The decomposition follows the order :

With respect to alkyl group : 3 > 2 > 1 and With respect to halogens : R – I > R – Br > R – Cl
4. Wurtz Reaction :
dry
2 RI + 2 Na 
 R  R+ 2 NaI
ether
Reaction usually gives
mixture of products.
This is referred to as “intramolecular wurtz reaction”.
5. Formation of Grignard Reagent :
ether
RX  Mg 
 R  Mg  X
Alkyl magnesium halides
The alkyl magnesium halides are known as Grignard Reagent. The chemistry Grignard Reagent is dis-
cussed is section 5.
6. Reaction with other active metals :
Dry
CH3 CH 2 Br  2 Li   CH 3CH 2 Li  LiBr
ether
Ethyl bromide Ethyllithium
Alkyl lithiums are similar in properties with Grignard reagents. These are highly reactive reagents.
Dry
4CH3CH 2 Br  4 Pb / Na 

ether
 CH3CH 2 4 Pb  4 NaBr  3Pb
Ethyl bromide Sod. lead alloy Tetraethyllead  TEL 

Tetraethyl lead (TEL) is used as an anti-knocking agent in gasoline used for running automobiles.
2 C 2 H5 Br  Na  Hg 
  C2 H5 2 Hg  NaBr
Sodium amalgam Diethylmercury
Ether
2C 2 H5 Br  2 Zn   C2 H5  2 Zn  ZnBr2

Dialkyl zinc compounds are called Frankland reagents.
7. Reduction : (Formation of alkanes).

(i) Hydrogen in the presence of a metal catalyst such as Ni or Pd or Pt :
Ni
RX  H 2  RH  HX

(ii) Hydro-iodic acid in the presence of red phosphorus :
Re d P
CH 3CH 2  I  HI  CH3  CH3  I2
420 K
(iii) Nascent hydrogen produced by the action of zinc or tin or hydrochloric acid or by the action of zinc-
copper couple on alcohol.
Zn  HCl
CH 3CH 2 Cl  CH3  CH3  HCl
or Zn  Cu  alcohol
(iv) Substitution by hydride ion : H  from LIAlH 4 as a Nucleophile.
dry ether
LiAlH 4  4 RX  4R  H  AlX3  LiX
(R  3 alkyl group as 3 RX prefer elimination)
Tertiary alkyl halides, however, undergo dehydrohalogenation to give alkenes. On the other hand sodium
borohydride (NaBH4) reduces secondary and tertiary alkyl halides but not primary whereas tri-phenyl tin
hydride (Ph3SnH) reduces all the three types of alkyl halides.
8. Isomerisation : When a haloalkane is heated to 573 K or at a lower temperature in presence of anhy

drous AlCl3 (Lewis acid) it undergoes isomerisation.
Cl
|
573K
CH 3  CH 2  CH 2  Cl 
 CH3  C H  CH3
Anhyd. AlCl3

Illustration - 1 Identify the compounds A, B, . . . . . . . in the following reaction setup.
NBS HBr / Peroxide Na / ether

C3 H 6 
 A 
 B  C
1. H O
+
KCN 3
A  D 
E
2. [ O ]
SOLUTION :
NBS
C3H 6  A (Visualize allylic substitution in alkenes)
CCl 4
Hence C3H6 is an alkene (Note that C3H6 also represents cyclopropane).
Note : Heating effect on Di-carboxylic acids and   Keto acid,
Oxalic Acid : 
(COOH) 2 
 H2O+ CO+ CO2

Malonic Acid : CH 2 (COOH)2   CO2 + CH3COOH
Succinic Acid :
  Keto acid:

Illustration - 2 Identify (A) to (G) in the following series of reactions. Also identify the major product
among F and G.
SOLUTION :
Note : (i) Diene (i.e., elimination product) will be major here, since conjugated diene is highly stable.
(ii) Usually cycloalky bromide (2) prefer elimination over substitution will RO .
(iii) OH  (aq) acts as a nucleophile whereas OH  (alcoholic) acts as a base.
Illustration - 3 Identify P, Q, R, .... in the following reaction set up.
SOLUTION :

IN-CHAPTER EXERCISE - A
1. Identify A, B, C, . . . . .
1. HBr / Peroxide 1. A
(a) C2 H 4 
 C2 H5 I (b) C6 H 5CH 2 Br  C6 H 5CH 2COOH
2. A 2. B
2. Identify (A), (B), (C), . . . . . in each of the following.

PBr
3  A  B  Alc.KOH HBr AgCN
(a) CH 3CH 2CH 2OH        C    D 
+
Alc .KOH H /H O
2   B   SOCl
2   C    D  H
(b)  CH 3 2 CHCl   A  
LiAlH 4
NBS Alc .KOH HBr

(c) CH 3CH 2CH = CH 2   A    B  
 C 
CCl4
CH OH
3  A  2 Br EtONa
(d) CH 3  CH 2 3 MgBr      B  
 C  +  D 
127C EtOH / NaOH
NOW ATTEMPT IN-CHAPTER EXERCISE-A REMAINING QUESTIONS IN THIS EBOOK

ARYL HALIDES : [Ar - X ; Ar - Aryl group) Section - 2

The halogen derivatives in which the halogen atom is directly attached to the carbon atom of benzene ring
are known as aryl halides. Chloro, Bromo and Iodo benzenes, Chlorotoluenes, Chlorophenols are some of
important aryl halides.
Preparation of Aryl halides :
1. Direct halogenation :
Note : (i) Here FeCl3 is acting as a halogen carrier.

(ii) Iodides are not formed this way, as HI is strong reducing agent. By using ICl, one can get iodo
benzene.
C6H6 + ICl   C6H5  I + HCl
2. From Benzene Diazonium Chloride :
The formation of benzene diazonium chloride is known as Diazotisation.

(a) Sandemeyer Reaction :
Note that Iodides are not formed in the given manner.
(b) For iodides :
Note that it is not Sandemeyer reaction.

(c) For fluorides :
Note : Haloarenes particularly chloro and bromo arenes can also be prepared by Gattermann reaction. It is a
modification of the Sandmeyer reaction. In this reaction, a mixture of freshly prepared copper powder in
the presence of corresponding halogen acid (HCl or HBr) is used instead of cuprous halide as used in
Sandmeyer reaction. The yield of this reaction is around 40%.
3. From Silver salt of carboxylic acids : (For bromides only).

CCl
4  C H  Br  CO  AgBr
C6 H5 COOAg  Br2  6 5 2
70 C
The above reaction is known as “Hundsdicker Reaction”. By this method mainly aromatic bromides are
formed as the yield in case of aliphatic bromides is poor.
4 CCl
RCOOAg + Br2 

RBr + CO2 + AgBr
70 C
4. Commercial preparation of chlorobenzene :

CuCl
2  2 C H Cl  2 H O
2 C6 H 6  2 HCl  O2  6 5 2

Physical Properties : Physical properties of aryl halide is similar to alkyl halide.

The boiling points of isomeric dihalobenzenes are very nearly the same but the melting points of the para
isomers are higher than the ortho and meta isomers. Being more symmetrical, the para isomer fits better in
the crystal lattice of the soid form than the ortho or meta isomers.
Boiling point o > p > m Melting point p > o > m
Reactions of Aryl Halides :

Aryl halides are relatively un-reactive towards nucleophillic substitution under conditions which are used for
alkyl halides since the lone pair of electrons over halogen atom is involved in resonance with benzene ring.

As a result of resonance, -C of ring loses its electrophillic character, so Nu fails to attack -C in aryl
halides. C - Cl bond acquires a partial double bond character (C - Cl), which is difficulat to break by Nu  .
For example, Chlorobenzene does not react with aq. NaOH. It does not give a precipitate of AgCl with
alcoholic AgNO3.
However, Aryl halides show nucleophilic substitution reaction under drastic conditions of high temperature
and pressure along with use of copper salts.
1. Nucleophillic substitution reactions :

350 , 200 atm
C6 H5  Cl  NaOH 
 C6 H5  OH  NaCl
Cu salt
This reaction is referred to as Dow’s process for the manufacture of phenol.

200 C, 50 atm
C6 H5  Cl  2 NH3 
 C6 H5  NH 2  NH 4 Cl
Cu salt
This reaction is known as Dow’s reaction.
250 C
C6 H5  Cl  CuCN 
 C6 H5  CN
pyridine
Note : (i) The presence of a deactivating group (strong electron withdrawing group) such as nitro, cyano in ‘o’ or ‘p’
position makes nucleophillic substitution possible. This results in an increase in electrophillic character of -
Carbon atom (which otherwise to lost due to resonance).
(ii) With strong bases like NaNH2 or KNH2, aryl halides reacts easily to form aniline.

(iii) Chlorobenzene reacts with methyl cyanide in presence of NaNH2 at room temperature to
give benzyl cyanide.
2 NaNH
C6H5Cl + CH3CN  C6H5CH2CN + HCl
base
2. (a) Wurtz - Fittig reaction :

ether
C6H5 – Br + 2Na + CH3Br   C6H5 – CH3 + 2NaBr
heat
Toluene
(b) Fittig reaction :
3. Ullmann reaction :
4. Reduction :
5. Reaction with Metals :

ether
C6 H5  I  Mg 
 C6 H5  MgI (Grignard Reagent)
ether
C6 H5  I  2 Li 
 C6 H5 Li  LiI (Aryl Lithium)

6. Formation of DDT :
Two moles of Chlorobenzene reacts with chloral in H2SO4 to give 1,1,1-Trichloro-2,2-(p-chlorophenyl)
ethane, an insecticide commonly known as DDT.
7. Electrophillic substitution reaction (involving benzene ring) :

Halogen are weakly deactivating group because of their strong electron withdrawing tendency, but due to
+M effect, they are weakly ‘o’ and ‘p’ directing.

Illustration - 4 How will you convert.

(a) Bromobenzene to styrene (in 4 steps) (b) Bromobenzene to Benzyl alcohol (in 3 steps)
SOLUTION :
Illustration - 5 Anisole can be prepared by either of following methods. Which of the two methods is the
correct ?
Method : I Method : II
SOLUTION :
Aryl halides do not give nucleophilic substitution reaction under normal conditions (whereas alkyl halides give
this reaction). It is due to resonance in these compounds. C – X bond is not polar as in alkyl halides and due
to partial double bond character (Resonance), it is not easily broken.
Hence Method - II is not correct.
 Clearly Method - I is the correct choice for the formation of anisole as it is a simple nucleophillic substitu
-tion of CH3Cl by Phenoxide, as nucleophile. Hence for preparing aromatic ethers, we should always
prefer Method - I in general.

Illustration - 6 Identify A, B, C ...... in the following reaction set up.
SOLUTION :
1. Identify A, B, C, . . . . .
1. A 1. A
(i) C6 H 5 NH 2  C6 H 5 I (ii) C6 H 5Cl  C6 H 5COOH
2. B 2. B
A aq.
(iii) C6 H 5Cl 
 B ( DDT ) (iv) o-Bromobenzyl bromide  A
KOH
1. Mg / ether ( excess )
(v) o-Bromobenzyl bromide  B
2. H 2 O
3 HNO ( conc.) 3 CH ONa

(vi) C6 H 5 Br 
 ( A  B )  (C  D )
H 2 SO4 ( conc.)

POLYHALOGEN DERIVATIVES Section - 3
Di-Halides
These compounds are divided into two categories : Geminal dihalides and Vicinal-(1, 2)-dihalides.
Geminal dihalides (or Gem-dihalides) Vicinal - (1, 2) - dihalides
[or, alkylidene dihalides] [or alkylene dihalides]
RCHX2 (Terminal) ;
Preparation of Di-halogen derivatives :

1. From Alkenes and Alkynes :
 CH2X  CH2X
CH2 = CH2 + X2  Viccinal dihalide
CH  CH + 2 HX 
 CH3 CHX2 Geminal dihalide
CH3 – C  CH + 2 HX 
 CH3 – C(X)2 – CH3 Geminal dihalide
2. By the action of Phosphorus pentachloride (PCl5) :
CH3CHO + PCl5 
 CH3CHCl2 + POCl3
Aldehyde Gem dihalide
CH 3COCH3 + PCl5 
 CH3  CCl2  CH 3 + POCl3
Gem dihalide
Reactions of Di-halogen derivatives :

1. Action of alcoholic KOH : (Dehydrohalogenation)
alc.
XCH 2 CH 2 X  CH  CH
Viccinal KOH
alc.
CH3 CH X 2  CH  CH
Gem KOH

2. Action Zinc dust : (Dehalogenation)

Zn
XCH2CH2X  CH2 = CH2 (alc. alcoholic medium)
alc.
3. Action of aq. KOH : (Alkaline hydrolysis)
XCH 2CH 2X + 2 KOH(aq) 

 CH 2  CH 2
(vicinal) | |
OH OH Ethylene glycol
CH 3CHXCH 2X + 2 KOH(aq) 
 CH3  CH 2  CH 2
(vicinal) | |
(Propan-1, 2-diol)
OH OH
CH 3CHX 2 + 2 KOH(aq) 
 CH3CH(OH)2   CH3CHO
H O 2
(gem) Acetaldehyde
CH3CX 2CH3 + 2 KOH(aq) 

 CH3  C(OH)2  CH3 
 CH3  CO CH3
 H2O
(gem) (Unstable) Acetone
Note : The above reaction is used to distinguish between gem and viccinal dihalides.
Gen diols are unstable and loses H 2O to form carbonyl compounds.
4. Reactions of alc. KCN :

alc. 2  ( CH COOH ) H O
X  CH 2  CH 2  X  2KCN  NC  CH 2  CH 2  CN  2 2
 H
(succinicacid)
alc. H O  
CH3 CHX 2  2KCN  2  CH C H  COOH   CH CH COOH
 CH3CH (CN) 2  3 2 3 2
H H O 2
(  -methylmalonicacid)
Note : Malonic acid and its  - alkyl derivatives loses CO2 on heating to give corresponding monocarboxylic
acid.
Tri-Halogen Derivatives :
Trihaloderivative of methane is called as haloform.
CHCl3 CHBr3 CHI3

Chloroform Bromoform Iodoform
(Liquid) (Liquid) (Yellow solid)

Haloforms are prepared by haloform reaction. Any organic compound having

CH3  CH  R or CH3  CH R type of
| ||
OH O
structure undergoes haloform reaction on treatment with halogen and alkali or with hypohalite salt (NaOX).
X2
CH 3  CH  R or CH3  C R   CHX3  RCOO
| || 
OH
OH O
R = H, alkyl phenyl
CH3  CH(OH)  R+ 4 X 2 + 6 NaOH 

 CHX3 + RCOONa + 5 NaX + 5H2O
CH3COR + 3X 2 + 4 NaOH 
 CHX3 + RCOONa + 3 NaX + 3H 2O
Mechanism of Haloform Reaction :

X2
(i) Oxidation : CH 3  C H  R   CH 3  C  R  2 HX
| Oxidation ||
OH O
(ii)   Halogenation :
Similarly remaining   H atomos undergoes halogenation to form tri-haloketone.
(iii)
Chloroform : [ CHCl3 ]
It is a sickly sweet smelling liquid with b.p. as 61C. It is sparingly soluble in H2O but readily soluble in
ethanol and ether. It is used in surgery as an anaesthetic. It is non-inflammable but its vapours may burn with
green flame.

Preparation of Chloroform :
1. By distilling ethanol with a suspension of bleaching powder in water : (Laboratory method)
CaOCl2 + H2O 
 Cl2 + Ca(OH)2
(Bleaching powder)
Here chlorine acts both as an oxidising as well as a chlorinating agent.
Oxidation : CH3CH2OH + Cl2 
 CH3CHO + 2HCl
Chlorination : CH 3CHO  3Cl2 

 CCl3CHO
Trichloro acetaldehyde
 Chloral 
H2 O
Ca(OH)2 + 2CCl3CHO   2CHCl
3
+ (HCOO)2Ca
Chloroform cal. formate
Note : (i) In place or CaOCl2, we can use NaOH/Cl2.

NaOH + Cl2 
 NaOCl + HCl
NaOCl 
 [O] + NaCl
(ii) Pure Chloroform can be prepared by the action of sodium hydroxide solution on chloral hydrate.
CCl3CH(OH)2 or CCl3CHO.H 2 O  NaOH 

 CHCl3  HCOONa  H2 O
Chloralhydrate Chloroform Sod.formate
CCl3CH(OH)2 is stable due to H-bonding as :
2. From Acetone :
CH3 COCH3  3Cl2 

 CCl3 COCH3
Trichloroacetone
2CCl3COCH3 + Ca(OH)2 
 CHCl3 + (CH3COO)2Ca
Note : Acetone is preferred to Ethyl alcohol, as the yield is better.
3. From Carbon tetrachloride :

Fe + H O
2 CHCl + HCl
CCl4 + 2[H]  3
HCl

4. From chlorination of Methane at 370°C :

370°C
CH 4 + 3Cl2 
 CHCl3 +3HCl
diffuse sunlight
Reactions of Chloroform :
1. Oxidation : Chloroform in presence of sun light and air (O2) undergoes slow oxidation to form a highly
poisonous gas, Phosgene, COCl2.
light
2CHCl3 + O2 
 2COCl3 + 2 HCl
Phosgene
Note : Chloroform is stored in brown bottles to cut off light and filled upto brim to stop the above decomposition.
1% ethanol is also added which destroys the trace of phosgene that may be formed on storage.
2 C 2 H5 OH  COCl2 
 (C 2 H5 ) 2 CO3  2 HCl
Diethyl carbonate
(Non - toxic)
2. Reduction :
Zn  HCl
CHCl3  2  H   CH 2 Cl2  HCl
Zn + H O
2  CH + 3HCl
CHCl3 + 6[H]  4
3. Heating with Silver powder : (Dehalogenation)

High temp.
2 CHCl3  6 Ag 
 CH  CH  6 AgCl
4. Nitration : CHCl3  HNO3 

 CCl3 NO 2  H 2 O
Chloropicrin
Chloropicrin is a poisonous liquid and used as insecticide and in chemical warfare.

5. Condensation with Ketones :
OH
|
KOH
 CH3 2  C  O  H  CCl3   CH3 2  C  CCl3
Acetone Chloretone
Chloretone is a colourless crystalline solid and is used as a hypnotic (sleep inducing drug).

6. Carbylamine reaction :
alc.
RNH2 + CHCl3 + 3KOH 
 RNC + 3 H2O + 3 KCl
(aliphatic 1° amine) Alkyl Isocyanide
alc.
C6H5NH2 + CHCl3 + 3KOH 
 C6H5NC + 3 H2O + 3 KCl
(aromatic 1° amine) Phenyl Isocyanide
Isocyanides (carbylamines) have a very disagreeable smell, so the above reaction is used as a test (under the
name Carbylamine Test) of chloroform and test of both aliphatic and aromatic primary amines.
7. Reimer - Tiemann reaction :
Note : You will study the details of Reimer-Tiemann reaction later in Chapter on Phenols.
8. Hydrolysis :
Iodoform : [CHI3 ]
Iodoform resembles chloroform in the methods of preparation.
Preparation of Iodoform :
1. With Ethyl alcohol :
C2 H5 OH  4I2  6 NaOH 
 CHI3   HCOONa  5 NaI  5H 2 O
Iodoform
(Yellow solid)
 CHI3 + 5NaI + HCOONa + 3CO2 + 2H2O

C2H5OH + 4I2 + 3Na2CO3 

2. With Acetone :
 CHI3 + 3NaI + CH3COONa + 3H2O
CH3COCH3 + 3I2 + 4NaOH 
Note : This reaction is known as Iodoform reaction or Iodoform test. Since the iodoform is a yellow coloured
solid, so the iodoform reaction is used to test ethyl alcohol, acetaldehyde, secondary alcohols of type
R(CH3)CHOH (methyl alkyl carbinol) and methyl ketones (RCOCH3), because all these form iodoform.
The side product of the iodoform reaction, sodium carboxylate is acidified to produce carboxylic acid
(RCOOH).
Iodoform is a pale yellow solid, with m.p. 392 K, having characteristic odour. It is insoluble in water but
dissolves readily in ethyl alcohol and ether.
It is used as an antiseptic for dressing wounds.
Reactions of Iodoform :
Tetra - Halogen Derivatives :

Carbon Tetrachloride : CCl4
Preparation of Carbon tetrachloride :
1. From Methane :
hv
CH 4 + 4 Cl2  CCl4 + 4 HCl
CuCl 2 (Impure)
Methane used here is obtained from natural gas.

2. From Carbon disulphide :
AlCl
3 CCl + S Cl
CS2 + 3Cl2  4 2 2
Fe/Cl2
S2Cl2 is separated by fractional distillation. It is then treated with more CS2 to give CCl4. CCl4 is washed with
NaOH and distilled to obtain pure CCl4.
2S2 Cl2  CS2 

 CCl4  6S
(Pure)

3. From Propane :
400°C
CH3CH 2CH3 + 9 Cl2 
 CCl4 + C2Cl6 + 8HCl
70-100 atm (Liquid) (Solid)
Note : CCl4 is a colourless and poisonous liquid which is insoluble in H2O. It is a good solvent for grease and oils.
CCl4 is used in fire extinguisher (esp. electric fires) as Pyrene. It is also an insecticide for hookworms.
Organic halogen compounds are less inflammable than the hydrocarbons. The inflammability decreases with
increasing halogen content. Because they are good solvents for fats and oils and do not catch fire easily,
polychloro compounds (tri and tetrachloro ethylenes) are widely used as solvents for dry cleaning, carbon
tetra-chloride is used in fire extinguishers and called as pyrene. 1, 1, 2-Trichloroethylene called westrosol.
Reactions of Carbon tetrachloride :

500°C
1. Oxidation : CCl4 + H 2O   COCl2 + 2 HCl
(steam) Phosgene
Fe/H 2 O
2. Reduction : CCl4 + 2[H]   CHCl3 + HCl
 2 KOH
3. Hydrolysis : CCl4 + 4 KOH(aq)   C(OH)4   CO2   K 2CO3 + H 2O
2 H O
4 KCl (Unstable) 2
SbF
6  CCl F + 2 HCl
4. Action of HF : CCl4 + 4 HF  2 2
Freon-12
5 SbCl
5. Action of SbF3 : 2CCl4  2SbF3  3CCl2 F2  SbCl3
Note : Freon is widely used as a refrigerant cooling agent in refrigerators and air conditioners. It is also used as a
propellant in aerosols and foams. Recently, it is discovered that Freon depletes ozone layer. So, its uses
have been banned in many countries.
6. Reimer – Tiemann reaction :
Some other Important Halides :

Vinyl Chloride : [CH2 = CHCl ; vinyl group CH2 = CH– ]

Preparation of Vinyl chloride :

HgCl2
1. From Acetylene : CH  CH  HCl   CH 2  CHCl
70 C
2. From Ethylene Chloride : (Viccinal dihalides)

NaNH
2  CH  CHCl
C H 2  C H 2  2
| | 1.0 eqv.
Cl Cl

ClCH2 – CH2Cl   CH2 = CHCl + HCl
600  650 C
600 C
3. From Ethylene : CH 2  CH 2  Cl2  CH 2  CHCl  HCl
Properties of Vinyl chloride :

Vinyl chloride is a colourless gas at room temperature, with b.p. as –13C. The halogen atom in vinyl chloride is
not reactive as in other alkyl halides. However, –C = C– bond of vinyl chloride gives the usual addition reactions.
The non-reactivity of of vinyl chloride innucleophillic substitution reactions is due to resonance in it.
Reactions of Vinyl chloride :

It gives same reactions as given by alkenes.

Allyl Chloride : [CH2 = CHCH2Cl]

Preparation of Allyl chloride :
1. From Propene :
500-600°C
CH 2 = CHCH 3 + Cl2  CH 2 = CHCH 2Cl + HCl
Propene Allyl chloride
2. By the action of Phosphorus halide on allyl alcohol :


CH 2 = CHCH 2OH + PCl5 
 CH 2 = CHCH 2Cl + POCl3 + HCl
Allyl alcohol

3CH 2 = CH  CH 2OH + PCl3 
 3CH 2 = CH  CH 2Cl + H3PO3
3. Allyl bromide is prepared using NBS :
NBS
CH3CH = CH 2  CH 2 - CH = CH 2 (NBS : N - Bromosuccinimide)
CCl4 |
Br
Reactions of Allyl chloride :

1. Addition Reactions :
CH2 = CH  CH2Cl + Br2 
 Br – CH2 – CH(Br)  CH2Cl
CH2 = CH  CH2Cl + HBr 

 CH3CH(Br) – CH2Cl
2-Bromo-1-Chloropropane
Note : The addition follows Markonikov’s rule. However in presence of peroxides, 1,3-Dibromopropane is formed.
HBr
CH 2  CH  CH 2Br  C H 2  CH  CH 2Br
Peroxide |
Br

Since in allyl chloride, there is no resonance (unlike in vinyl chloride), nucleophillic substitution reactions take
place with ease. For example :
CH2 = CH – CH2Cl + KOH(aq) 
 CH2 = CHCH2OH + KCl
CH2 = CH – CH2Cl + NH3 
 CH2 = CH-CH2NH2 + HCl
CH2 = CHCH2Cl + KCN 
 CH2 = CH-CH2CN + KCl
dry ether
CH2 = CHCH2Cl + Mg   CH2 = CHCH2 MgCl
(Allylic Grignard Reagent)
CH2 = CH – CH2Cl + CH3ONa 
 CH2 = CH – CH2 – O – CH3 (Allyl methyl ether)

Benzyl Chloride : [ C6H5CH2Cl ]

Preparation of Benzyl chloride :
1. From Toluene :
2. By heating benzene with formaldehyde :
3. By the action of PCl5 on benzene alcohol :
Note : Benzyl bromide is prepared by action of NBS/CCl4 on toluene (Allylic bromination).
Reactions and Properties of Benzyl Chloride :

It is a colourless bad smelling liquid, with b.p. at 179C. Its vapours bring tears from eyes and are irritating.
It is insoluble in water but soluble in organic solvent.
The main reactions of benzyl chloride and bromide are like those of Alkyl halides. Nucleophillic substitution
reactions occur with ease unlike in case of aryl halides (due to resonance in aryl halides).

2. Wurtz Reaction :
3. Wurtz - Fitting reaction :
4. Oxidation :
5. Reduction :
Zn  Cu
C6H 5CH 2Cl + 2[H] 
 C6H 5CH 3 + HCl
couple Toluene
Illustration - 7 Identify A, B, C, . . . . .
PCl
5  A  aq.KOH NaOH
(a) CH 3CHO   C     D  aq.
 B 
Cl2
aq.KOH NaOH / I
2 C   D aq.
(b) C3 H 6Cl2 ( A) 
 B   
SOLUTION :
(a)
aq.KOH NaOH
(b) C3H6Cl2 
 B  C (s)  D (aq)
(A) I2
Since (B) gives iodoform test, so (B) is either a 2º alcohol of type CH3 — C H — R or a methyl ketone
|
OH

of type CH3 — C — R .
||
O
Now (B) is obtained by hydrolysis of a dihalide (A). A must be gem-dihalide, as viccinal dihalide gives glycols
on hydrolysis. Now (A) can be terminal gem-dihalide or a non-terminal one. (A) cannot be terminal gem-
dihalide as it will give CH3CH2CHO on hydrolysis which will not respond to iodoform test. Hence (A) is
Cl
|
CH3 — C— CH3 .
|
Cl
Cl
|
aq.KOH NaOH
CH3 — C — Cl   CH3COCH3  CHI3 (s)  CH3COONa (aq)
| I2
Cl Yellow solid
Iodoform
Illustration - 8 An organic compound (A) ; C4H8Cl2 on hydrolysis forms another compound (B) ; C4H8O.
(a) If the compound (B) responds positively to iodo form test, then identify (A) and (B).
(b) If (B) does not responds to iodo form test, then identify possible structures of (A) and (B).
(c) If all possible structures of (B) visualised above in (a) and (b) are treated with Zn–Hg/HCl, what are the
products ?
SOLUTION :
(a) KOH(aq) NaOH

A 
 B 
 CHI3
I2
C4 H8Cl2 C 4 H8 O
 (B) is a methyl ketone since it responds positively to iodoform test.

O
||
Hence (B) is CH3 — C — CH 2 CH3
Cl
|
Clearly (A) will be CH3 — C— CH 2 — CH3
|
Cl

(b) If (B) does not give iodoform test, it can be an aldehyde.

Hence (B) may be : CH3CH2CH2CHO or CH3 — C H — CHO
|
CH3
aq.
Accordingly (A) will be : CH3CH 2CH 2 C H  Cl   CH3CH 2CH 2CHO
| KOH
Cl
aq.
or  CH3 2 CH  C H  Cl 
KOH
 CH3 2 CH  CHO
|
Cl
(c) The possible structures of B and their reduction products with Zn – Hg/HCl (Clemmenson’s reduction) are:
Illustration - 9 An organic compound (A), C H Br reacts with aq.KOH solution to give another com-
8 9
pound (B), C8H10O. The compound (B) upon treatment of alkaline solution of iodine gives a yellow precipi-
tate. The filtrate on acidification gives a white solid (C), C7H6O2. Give structures of A, B, C and explain the
reactions involved.
aq.KOH NaOH
SOLUTION : C8 H9Br 
 C8H10O  CHI3 
I 2
(A) (B) Yellow ppt
Since (A) is hydrolysed, Br is not attached to ring i.e., it is attached to the side chain. (A) could be :
Since (B) responds positively to iodoform test, (A) is certainly

The filtrate contains sodium benzoate : which is acidified to give a white solid benzoic
acid (C7H6O2).
Illustration - 10 An alkene (A) C16H16 on ozonolysis gives only one product (B) C8H8O. Compound (B) on
reaction with NaOH/I2 yields sodium benzoate. Compound (B) reacts with Zn-Hg/HCl yielding a hydrocarbon
(C) C8H10. Write the structures of compounds (B) and (C). Based on this information two isometric structures
can be proposed for alkene (A). Write their structures and identify the isomer which on catalytic hydrogena-
tion (H2/Pd – C) gives a racemic mixture.
SOLUTION :
(s) Clearly the compound (C) is iodoform ; CHI3
O
—
—
Hence the structure of B is : C — CH3 (C8H8O) Acetophenone

(A) must be a symmetric alkene as it gives only one compound, C8H8O.
(A) is : C = C
—
Me Me
A shows Geometrical isomers : A1 and A2
Me
C=C C=C
Me Me Me
cis - form trans - form
2 H ,Pd /C
A1 or A2  Racemic mixture
Recall that hydrogenation is a ‘syn’ addition.

1. What is the final product in each reaction ?

HNO CHCl
3 ?
(a) 3 ?
CHCl3  (b) C6 H 5 NH 2 
KOH
2. What happens when ? Give equations only :

(a) Chlorine reacts with CS2 in presence of anhydrous aluminium chloride
(b) Chlorine is passed through ethyl alcohol
(c) Chloral is treated with aqueous sodium hydroxide
(d) Chloroform is boiled with aqueous potassium hydroxide
3. Identify the products (A), (B) and (C).

HBr Hydrolysis2 3 C Na CO
  A  
C2 H 4    B    
I2
4. Explain the following :

(a) Carbon tetrachloride is used as fire extinguisher
(b) Iodoform gives precipitate with AgNO3 on heating while chloroform does not.
(c) Alkyl iodides become darken on standing in presence of light.
(d) While preparing alkyl halides form alkanes, dry gaseous halogen acids are used instead of their
aqueous solutions.
5. Match the following :

(A) Carbon tetrachloride I. Antiseptic
(B) Chloretone II. Refrigerant
(C) Westrosol III. Chloroform
(D) Freon IV. Polymer
(E) Iodoform V. Hypnotic
(F) Teflon VI. Pyrene
(G) Carbylamine reaction VII. Solvent
NOW ATTEMPT IN-CHAPTER EXERCISE-C REMAINING QUESTIONS IN THIS EBOOK

THE CHEMISTRY OF GRIGNARD REAGENT Section - 4
Introduction :
Organo-magnesium halides popularly known as Grignard reagents were discovered by French chemist
Victor Grignard. The organic part may be derived from various types of hydrocarbons. The most important
type is alkyl magnesium halide. It is represented as RMgX (X : Cl, Br or I).
Generally Grignard Reagent is prepared by treating an organic halide with magnesium metal in ether as
solvent.
reflux in
RX + Mg RMgX Alkyl magnesium halide
ether
Reflux is a technique, allowing one to boil the contents of a vessel over an extended period.
‘R’ may be primary (1), secondary (2) or tertiary (3) alkyl, may be replaced by cycloalkyl, alkenyl, aryl
or alkynyl group.
The halide ions are Cl, Br or I. Fluorides are least reactive, so they are not considered. The reactivity of
halides follows the order : I > Br > Cl > F. Alkyl halides are more reactive than aryl and vinyl halides.
Aryl and vinyl halides are best prepared by using THF (Tetrahydrofuran) instead of ether as solvent.
THF
CH 2 = CHCl + Mg 
 CH 2 = CHMgCl
60° C
Note : In the preparation of Grignard reagents, ether as a solvent is must. The Grignard reagent are unstable in
aqueous medium so avoid aqueous medium.
( O  H), 1° and 2°alcohols (  O H), primary amines
Properties :
 
Grignard Reagent, RMgX is a very strong base because of polarisation of RMg bond  R  MgX. It
abstracts a proton from species containing acidic hydrogen such as water (– O  H), 12 and 3
alcohols (– OH), 1 and 2 amines (– N  H), terminal alkynes (– C  C – H). In the reactions with these
species, a proton is transferred to the negatively polarised carbon atom of the Grignard Reagent to give a
hydrocarbon.
Grignard Reagent, RMgX is not only a strong base, but also a strong nucleophile i.e., it shows a strong
tendency to donate the electron cloud to the species seeking electrons (Electrophiles).
Reactions As Base :
Grignard reagent as a base reacts with compounds such as acids, water, primary alcohols, primary amines
and terminal alkynes, all containing active Hydrogen atom (H) to give alkanes. “This reaction is also used to
determine active hydrogen atoms in the organic compoud”.


  
R  M gI  HO  H 
 RH  Mg(OH)I
δ  δ+
R  MgI + R   O  H  RH + Mg  OR   I
 
 RH  Mg  NHR   I
R  MgI  R  NH  H 
 
R  MgI  R   C  C  H 
 RH  R   C  C  MgI
Reactions As Nucleophile :
Grignard reagent acts as a strong nucleophile and shows nucleophillic addition reactions to give various
products. Alkyl group being electron rich (carbanian) acts as a nucleophile in Grignard reagent and reacts
with carbonyl compounds, esters, acid halides, cyanides etc.
   
R  Mg X  R  Mg X
1. With carbonyl group :
(a) With aldehydes :
(i)
(ii)

(b) With ketones :
2. With acid chloride :
Note : Ketones (e.g., acetone) formed above further reacts with Grignard reagent to form 3 alcohols if one uses
excess of Grignard reagent. However with 1 : 1 mole ratio of acid halides and Grignard reagent, one can
prepare only ketones.
3. With Esters :
(a) With formates :
Note : The aldehydes react further with CH3MgBr to give 2 alcohol, if it is present in excess. But with 1 : 1 mole
ratio of reactants will certainly give aldehydes only.

(b) With carboxylates
Note : The ketones react further with CH3MgI to give 3 alcohol, if it is present in excess. But 1 : 1 mole ratio of
reactants will certainly give ketones only.
(c) With Lactones (cyclic esters)
Note : If an organic compound has both ester and keto group, the Grignard regent prefers to attack keto group
(keto group has higher electrophillic character than ester group).
4. With cyanides :
5. With CO2 :
O O O
|| || H2O
||
R MgI  C  O 
 R  C  OMgI 

 R  C  OH  Mg (OH)I
dryice H
Carboxylic acid

6. With Oxygen :
1 H 2O
RMgI  O 2  ROMgI   ROH  MgI(OH)
2 H
7. With ethylene oxide (oxiranes) :
Note : All the above reactions can also be visualised by taking phenyl group (ph : C6H5 –) instead of R (Alkyl) to
get corresponding aromatic compounds.
8. With inorganic halides :

(Formation of Organometallics)
4C2 H5MgBr  2PbCl2 

 (C2 H5 ) 4 Pb  Pb  4MgBr(Cl)
Tetraethyl lead
 
TEL
2RMgBr  CdCl2 
 (R)2 Cd  2MgBr(Cl)
Dialkylcadmium
Illustration - 11 Identify compounds A, B, C ............ in the following reaction setup.
SOLUTION :

The formation major and minor products during the dehydration of alcohols will be discussed more exten-
sively in upcoming modules.
Illustration - 12 Identify componds A, B, C, .............. in the following reaction setup.
SOLUTION :

Illustration - 13 Identify the final product in the given sequence of reactions.
SOLUTION :
Formation of (C) from (B) is referred to as “intramolecular nucleophilic addition”.
Illustration - 14 Identify all the possible products in the given reaction. One or more options may be cor-
rect.
2 ? NaNH
CH 3  C  CH  Me3C  Br 
(A) Me3 – C – C  C – Me (B) Me2C = CH2
(C) Me3C – CH2 – C  CH (D) CH3C  CH
SOLUTION :

NaNH
CH3  C  CH  
2  CH  C  C  Na 
3
Terminal alkyne Propynide anion
Acidic Hydrogen
 Propynide anion can act as nucleophile and also as a base.
 Me3 – C – Br (tert. butyl bromide) is a tertiary (3) halide, which prefers elimination over substitution.
Hence the correct options are (A), (B) and (D).

IN-CHAPTER EXERCISE - D
1. Identity A, B, C, - - - - - - - - - in the following.
PCl
5  A  Mg 1. cylohexamone
(a) EtOH  B 
C
Et 2O 2 H 3O +
(b)
(c) MeMgBr 1. cyclopentanone

HC  CH  A   B ; B C
2.H3O+
(d)
NH
3  A 
2  B  Br Na
(e) CH 3CH 2CH 2 MgBr  C
127°C ether
NOW ATTEMPT IN-CHAPTER EXERCISE-D REMAINING QUESTIONS IN THIS EBOOK

SOLUTIONS - IN-CHAPTER EXERCISE-A

HBr NaI
1. (a) CH 2  CH 2  CH3CH 2 Br  C2 H5I
Peroxide Acetone
NaI in acetone : I– becomes a strong Nu– and substitutes Br– ion.
(b)
 KCN H3 O
 
A : KCN  RBr   RCN   RCOOH 

 
B : H3O+ * alkyl, allyl and benzyl halides give above substitution.
2. (a)
(b)
(c)

(d)
SOLUTIONS - IN-CHAPTER EXERCISE-B
1. (i)
(ii)
(iii)
(iv)
(v)

(vi)
Note : No reaction (No substitution for aryl bromide)

* If NO2 (a deactivating group) is at ‘o’ or ‘p’ position, then substitution is possible.
SOLUTIONS - IN-CHAPTER EXERCISE-C

HNO3
1. (a) CHCl3   CCl3  NO2
3 CHCl
(b) C6H5 NH 2  C6 H5 NC
KOH
AlCl3
2. (a) CS2  3Cl2   CCl4  S2Cl2
[O] Cl2
(b) C2 H5OH  Cl2  CH3CHO   CCl3CHO (Chloral)
(c) CCl3CHO  NaOH 

 CHCl3  HCOONa
(d) CHCl3  4KOH (aq.) 

 HCOOK  3KCl  2 H2 O
HBr Hydrolysis
2 3 CHI Na CO
3. C2 H4  C2 H5 Br 
 C2 H5OH  3
I 2
4. (a) Dense vapours of CCl4 form a protective layer on the burning objects and present the oxygen or air to come
in contact with the burning objects.
(b) C – I bond being less stable than C – Cl bond and thus undergoes fission on heating giving I– ions which
combines with Ag+ ions to form a yellow ppt.

(c) Alkyl iodides are less stable and lose free iodine. This iodine makes the remaining iodides darken.
(d) Dry hydrohalogen acids are stronger acids and better electrophiles than H3O+ formed in aqueous solutions.
Furthermore, H2O is a nucleophile and can easily react with R – X to form alcohol.
5. [A-VI], [B-V], [C-VII], [D-II], [E-I], [F-IV], [G-III]
SOLUTIONS - IN-CHAPTER EXERCISE-D
1. (a)
(b)
(c)
(d)
(e)

Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Oxygen Containing Organic Compounds - I
Oxygen Containing Organic Compounds - I

(Alcohols, Phenols, Ethers, Glycols & Glycerol)
Alcohols Section - 1
The compounds in which hydroxyl group (OH) is attached to a saturated carbon atom are called as
Alcohols. The compounds in which a hydroxyl group is attached to an unsaturated carbon atom of a double
bond are called as Enols. The saturated carbon may be that of an alkyl, alkenyl, alkynyl, cycloalkyl or
benzyl group. However if a hydroxyl group is attached to a benzene ring, the compounds are called as
Phenols.
The alcohols are further classified as : Monohydric (containing one OH group), Dihydric (containing two
OH groups) and Trihydric (containing three OH groups).
Some important Monohydric alcohols are :

CH3OH (Methanol), CH3CH2OH (Ethanol), (CH3)2CHOH (Propan-2-ol / Isopropyl alcohol), (CH3)3C
OH (2-Methylpropan-2-ol / Tert. butyl alcohol), CH2 = CHCH2OH (Prop-2-en-1-ol / Allyl alcohol),
HC  CCH2OH (Prop-2-yn-1-ol), C6H11OH (Phenol),
Monohydric alcohols are further classified as: Primary (1) RCH2OH, Secondary (2) R2CHOH, Tertiary
(3) R3COH.
Preparations of Alcohols
1. Hydrolysis of alkyl halides : Alkyl halides undergo hydrolysis when heated with aqueous alkalies or
moist silver oxide. The hydrolysis occurs by a nucleophillic substitution reaction.
H O
2  R  OH  NaX
R  X  NaOH 
C2 H5  Br  KOH  aq  
 C2 H5  OH  KBr
Sometimes this method is not satisfactory as Olefins (alkenes) are also formed as side products
specially if halide is tertiary. If R is 3, then alkyl halides mainly give alkenes, when NaOH is concen
-trated (–OH as base).
 CH3 3 C  Br  NaOH  conc. 

  CH 3  2 C  CH 2   CH 3 3 C  OH
Major product Minor product

Oxygen Containing Organic Compounds - I Vidyamandir Classes
However satisfactory results are obtained by using moist Silver oxide (AgOH) or aqueous K2CO3.
RI  AgOH 
 R  OH  Ag  I
2. From alkenes :
(a) By acid-catalysed hydration of alkenes : Alkenes react with cold concentrated H2SO4
to give alkyl hydrogen sulphates following Markonikov’s addition.
2  CH  C H  CH H O
CH 3  CH  CH 2  H  OSO3H 
 CH 3  C H  CH 3  3 3
Propene Cold |  |
OSO3H OH
Isopropylhydrogensulphate
Note : Alkyl hydrogen sulphate when boiled with water give alcohols.
(b) Hydroboration - Oxidation of alkenes : Alkenes react with diborane in presence of THF as sol
vent to form alkyl boranes (Hydroboration). Alkyl boranes are then oxidised and hydrolysed by the
addition of hydrogen peroxide in aqueous base.
2 6 1.B H /THF
CH 3CH  CH 2  CH 3 C H C H 2
| |
2.H 2 O 2 /OH  ,H  OH
H OH
Here the net addition (syn) of H – OH to alkenes is in accordance with Anti-Markonikov’s rule and
free from any rearrangement. It is an important method for preparing 1 alcohols.
Note : In the above reaction, ‘H’ comes from B2 H6 and ‘OH’ comes from H 2O molecule.
(c) Oxymercuration and demercuration : Mercuric acetate (Hg(OAc)2 ) in presence of water -

tetrahy drofuran solution reacts with alkene to form alkyl mercury compound. The mercury com
pound is reduced with NaBH4 when alcohol is formed.
H
1. Hg  OAc  2 / THF, H  OH
|
R  CH  CH 2  
 R  C H  C H2
2. NaBH 4 , OH |
OH
(2 Alcohol)
The above reaction (anti) occurs in accordance with Markonikov’s addition (unlike Hydroboration
reaction). The ‘H’ becomes attached to the carbon atom of the double bond with greater number of
hydrogen atoms. It too does not involve rearrangement.
Note : In the above reaction, ‘OH’ comes from H 2O and ‘H’ comes from NaBH 4 .

3. Reduction of Aldehydes and Ketones : Aldehydes and Ketones on reduction yield alcohols. A
number of reducing agents like H2/Ni, Pt, Pd or Na/C2H5OH or Zn/HCl or LiAlH4 in ether or
NaBH4 in alkali can be used for this purpose.
(a) Bouveault - Blanc reduction : The reducing agent used is sodium and ethanol. The aldehyde
and ketones are reduced by nascent hydrogen into corresponding alcohols.
Na
RCHO  2  H   RCH 2OH (1° alcohol)
EtOH
(b) Reduction with LiAlH4 : It is better reducing agent for the conversion of carbonyl com-
pounds into alcohols. LiAlH4 is soluble in ether, the common solvent and it does not reduce
the carbon - carbon double bond.
LiAlH
4  CH CH  CHCH OH
CH 3  CH  CH  CHO  2  H   3 2
ether
Note : (i) NaBH4 also does not reduce carbon - carbon double bond. Also, NaBH 4 is a mild reducing agent.
(ii) Catalytic hydrogenation reduces carbon – carbon double bond as well as carbonyl group.
Ni
CH 2  CHCHO  4  H  
 CH 3CH 2CH 2OH
Catalyst
(iii) Ketones are reduced to secondary alcohols by Aluminium isopoxide in Isopropyl alcohol. The reduc
-tion by this method is known as Meerwin-Pondorrf-Verley (MPV) reduction and is considered as
an important method for the formation of secondary alcohols.
 CH3  CH  O  Al
 2 3
R 2C  O  R 2CH  OH
in Isopropyl alcohol
(iv) As a special case, LiAlH 4 also reduces double bond if conjugated with a phenyl group, in  ,  
unsatured carbonyl compound along with carbonyl group.
4 LiAlH
Ph  CH = CH  CHO  Ph  CH 2  CH 2  CH 2OH
ether
(v) NaBH 4 can reduce aldehydes, ketones and acyl chlorides to alcohols.
LiAlH 4 can reduce carboxylic acids, esters (to alcohols) and amides (to amines) also.

4. Hydrolysis of Ester : (Base or Acid catalysed)

Esters on hydrolysis by mineral acids or alkalies form alcohols and carboxylic acids. Hydrolysis of
ester takes place by acyl-o-cleavage reaction mechanism.
* H
 or OH  *
R  CO  O R '  H  OH  R 'O H  RCOOH

Alcohols being more volatile than acids can be easily separated by distillation.
5. From Ethers :
(a) Hydrolysis : Ethers when heated with dil. sulphuric acid under pressure are hydrolysed to the
corresponding alcohols.
H SO
2 4  ROH  R 'OH
R  OR '  H 2O  (Separated by fractional distillations)
dil.
(b) With concentrated HI :

HI
(i) If symmetric : R  O  R   ROH  RI
HI
(ii) If mixed : R  O  R '  (Iodide contains smaller alkyl group
 ROH  R ' I
except when R is 3)
HI
C2 H5  O  CH3  C 2 H5OH  CH 3I
Note : (i) The details of this reaction are given in Section - 3 (Ethers)
(ii) In this reaction, refluxing the products with KI(aq) gives only alcohols.
HI KI/ H 
C 2 H 5OCH 3  C 2 H 5OH  CH 3I 
 C 2 H 5OH  CH 3OH
HI (aq)/ H 
6. Action of Nitrous acid on primary amines : Primary alcohols are formed when primary amines
(only) are treated with nitrous acid (HNO2).
RNH 2  HONO 
 ROH  N 2  H 2O
C2 H5 NH 2  HNO2 
 C2 H5OH  N 2  H 2O
Note : Under similarly conditions, Methylamine does not yield Methanol. The product formed is Methylnitrite or
Dimethyl ether.
CH3 NH 2  2 HNO 2 
 CH3  O  N  O  2H 2O  N 2
or 2CH3 NH 2  2HNO 2 
 CH 3  O  CH 3  3H 2O  2 N 2

7. Reduction of Carboxylic acid and its derivatives :

(a) Catalytic Hydrogenation : It follows the order : RCOCl > RCOOR > RCOOH.
However, catalytic hydrogenation is used in industries because extremely high pressures and
temperatures are required.
(b) Bouveault – Blanc reduction :
Na
RCOOC 2H 5  RCH 2OH  C 2 H 5OH
EtOH
(c) Reduction by LiAlH4 : The acids can be reduced to primary alcohols by LiAlH4
(not by NaBH4).
1. LiAlH in ether
4
RCOOH   RCH 2OH
2. H O 2
Esters are more easily reduced than carboxylic acids by LiAlH4. Two alcohols are formed
from each ester molecule; one is derived form the acyl part and other from the alcoholic part.
O
|| 1. LiAlH 4
R  C  OR '   R  CH 2OH  R 'OH
2. H O 2
8. From Grignard Reagent : All the three types of monohydric alcohols can be prepared by the use
of Grignard reagents.
(a) Primary alcohols : Primary alcohols are obtained when Grignard reagent is reacted with
oxygen or Formaldehyde or Ethylene oxide.
(i)
The alcohol has same number of carbon atoms as present in the alkyl group of the
Grignard reagent.
(ii)
The alcohol has one carbon atom more than the alkyl group of the Grignard reagent.
(iii)
The alcohol has two carbon atoms more than the alkyl group of the Grignard reagent.

(b) Secondary alcohols : Secondary alcohols are obtained when Grignard reagent is reacted
with an aldehyde other than formaldehyde.
(i) 2 alcohols are obtained when Grignard reagent is reacted with an aldehyde other
than formaldehyde.
(ii) Formate esters on treatment with Grignard reagent first forms aldehyde which then
reacts with second molecule of Grignard reagent and forms secondary alcohols.
(c) Tertiary alcohols :

(i) Tertiary alcohols are obtained when Grignard reagent is reacted with ketones.
(ii) Esters on treatment with Grignard reagent first forms ketone which then reacts with
second molecule of Grignard reagent and forms tertiary alcohols.
9. Industrial Methods :
(a) Methanol : [CH3OH : Also known Carbinol or wood spirit]
(i) Destructive distillation of wood 
 Methanol (Natural method)
(ii) From Water gas (Synthetic method) :


C  H 2O  CO  H 2
Red hot coke Steam Water gas
300 C
CO  2H 2   CH 3OH
200 atm
A mixture of CuO, ZnO, Cr2O3 is used as catalyst for this reaction.

(iii) Oxidation of Methane :

Cu tube
CH 4  O 2 

 CH 3OH
100 C /200 atm
(b) Ethanol : [C2H5OH]

(i) Fermentation of Molasses (C12H22O11) :
Invertase Zymase
C12 H 22O11  C 6 H12O 6  C 6 H12O 6 
 2 C 2 H 5OH  2 CO 
H O 2
Molasses Glucose Fructose
From molasses, both glucose and fructose are formed, which are converted to ethyl alcohol
by zymase.
(ii) From Starch (C6H10O5)n :
2 nH O Maltase
2  C6 H10O5  n  n  C12 H 22O11   n  C6 H12O 6   n  C6H12O 6 
Diastase H 2O
Starch Maltose Glucose Fructose
From starch, both glucose and fructose are formed, which are converted to ethyl alcohol by
zymase.
(c) For 1° alcohols (OXO - Process) :

high temp. pressure
2 H / Ni
CH 2  CH 2  CO  H 2  CH 3CH 2CHO  CH 3CH 2CH 2OH
 CoH (CO)   4
high temp. pressure

CH 3CH  CH 2  CO  H 2  CH 3CH 2CH 2CHO  CH 3  C H  CHO
 Co (CO) 4  2 |
CH 3
 These can be reduced to give corresponding 1 and 2 alcohols.
Note : Absolute alcohol (100% pure ethyl alcohol). Rectified spirit (containing 95.87 % C2H5OH + 4.13 % H2O)
cannot be converted into absolute alcohol simply by distillation because the mixture of ethanol and water in
the ratio of 95.87 : 4.13 (a ratio present in rectified spirit) is a constant boiling mixture (azeotropic mixture)
having b.p. 78.13C.
Methylated spirit (Denaturated alcohol) It is rectified spirit (industrial alcohol) mixed with poisonous sub-
stances like CH3OH, pyridine, acetone, etc. to make it unfit for drinking purposes. The usual composition
of denatured alcohol is 8590% rectified spirit + 1015% methanol.
Power alcohol. Alcohol used for the generation of power is called power alcohol. It is a mixture of petrol
and alcohol in the ratio of 4 : 1 in presence of benzene or ether.

Physical Properties
1. The lower alcohols are readily soluble in water and the solubility decreases with the increase in molecu-
lar weight. The solubility of alcohols in water can be explained due to the formation of hydrogen bond
between the highly polarised –OH groups present both in alcohol and water.
     
H  O.........H  O.........H  O
| | |
H H H
Relative solubility of isomeric alcohols in water is 1 > 2 > 3.
2. Boiling points of alcohols are much higher than those of the corresponding alkanes and ethers. It is due to
the formation of hydrogen bonding between the hydroxyl groups of the two molecules of an alcohol with
the result several molecules are associated to form a large molecules.
     
H  O ............ H  O ............ H  O
| | |
 
H H H 
Among the isomeric alcohols, b.p. show the following trend.

Primary > Secondary > Tertiary (e.g. visualise of C4 H9OH.)
3. Lower alcohols form solid addition compounds with anhydrous metallic salts like CaCl2 and MgCl2, viz.,
CaCl2.4C2H5OH and MgCl2.6C2H5OH.
By analogy to water of crystallisation, these alcohol molecules are referred to as alcohol of crystallisation.
For this reason, alcohols cannot be dried over anhydrous calcium chloride.
4. Methanol is highly toxic. Ingestion of even small quantities of methanol can cause blindness ; large quantities
can cause death. Methanol poisoning can also occur by inhalation of the vapours or by prolonged exposure
to the skin. Ethanol is a hypnotic (sleep producer). Ethanol is much less toxic than methanol.
Reactions of Alcohols
Let us examine the electron distribution in the alcoholic functional group,
and its impact on the reactivity :
(i) Oxygen atom of an alcohol polarizes both CO bonds and the OH bond of an alcohol. Polarization
of the OH bond makes the hydrogen partially positive and explains why alcohols are weak acids.
In such reactions alcohols act as acids and cleavage of the OH bond takes place. The order of
reactivity of different alcohols for such reactions is :
CH3OH > 1 > 2 > 3 alcohols.

(ii) Polarisation of the CO bond makes the carbon atom partially positive, and hence it would have
been susceptible to nucleophilic attack if OH– were not a strong base, i.e., if OH– were not a poor
leaving group.
Protonated alcohols easily undergo nucleophilic substitution which may be SN2 or SN1 depending
upon the class of alcohol.
Mechanism of Nucleophilic substitution reactions of Alcohols (SN 1 and SN 2 paths) :
Note that alcohols do not give typical nueleophilic substitution reaction since OH  ion being a strong base
is a poor leaving group.
But alcohols do give nucleophilic substitution in presence of halogen acids. In presence of acids, leaving
group is H 2O instead of  OH group. Primary alcohols having   carbon as 1 or 2 always give
S N 2 reaction. Secondary alcohols having   carbon as 1 also give S N 2 reaction. All tertiary alcohols
give S N 1 reaction.
S N 1 path :
+
1st step : HX
(CH3 )3 C OH 
(CH3 )3 C OH 2
fast
2nd step :
3rd step : (CH3 )3  C+ + X  

(CH3 )3  C X
Note that it is almost similar to S N 1 in alkyl halides. Allyl and benzyl alcohols also follow the same path
(S N 1).

HX +
S N 2 path : RCH 2OH 
 RCH 2 O H 2
Note : (i) In SN 2 reactions, X  being weak base do not bring elimination by removing   hydrogen. How
ever in SN 1 reaction, carbocations formed may lose proton to give alkenes (EI).
(ii) Another method to bring out substitution in alcohols especially by SN 2 path is to convert them into
halides with PX3 or into sulphonates with TsCl.
(iii) At a high temperature, and in the absence of a good nucleophile, protonated alcohols are capable of undergo-
ing elimination reactions.
1. With active metals:

Alcohols are acidic in nature and hence react with alkali metals to form metal alkoxides with the evolution of
hydrogen gas.
 2 R  O  M   H2
2 ROH  2 M  (where M  Na, K, Mg, Al, etc.)
2CH 3OH  2Na 

 2CH 3  O  Na  H 2
Note : (i) Alcohols behave like acids when O – H bond cleaves.

(ii) Reactivity of alcohols with metals is in order : CH3OH > 1 > 2 > 3
(iii) R – O Na+ can be decomposed by H2O to give back alcohol. However alcohols do not react with
NaOH.
RO Na   H 2O 
 ROH  NaOH
(iv) Since most alcohols are weaker acids than water, most alkoxide ions are stronger bases than the
hydroxide ions. (CH3)3 CO > C2H5O > OH > CH3O (Relative basic character).

Alcohols as acids
Alcohols have acidities similar to that of water. Methanol is a slightly stronger acid than water but most
alcohols are somewhat weaker acids. In general, the order of acidity of alcohols is as follows :
H 2O > CH3CH 2OH > (CH3 )2  CH  OH > (CH3 )3  C  OH.
The reason sterically hindered alcohols such as tert-butyl alcohol are less acidic arises from solvation effects.
With unhindered alcohols, water molecules are able to surround and solvate the negative oxygen of the alkoxide
ion formed when an alcohol loses a proton. Solvation stabilizes the alkoxide ion and increases the acidity of
the alcohol. Any factor that stabilizes the conjugate base of an acid increases its acidity.
If the R– group of the alcohol is bulky, solvation of the alkoxie ion is hindered, and the alkoxide ion is not as
effectively stabilized. The alcohol, consequently, is a weaker acid.
All alcohols, however, are much stronger acids than terminal alkynes, and are very much stronger acids than
hydrogen, ammonia, and alkanes.
Relative Acidity H2O > ROH > RC  CH > NH3 > RH > H2
The conjugate base of an alcohol is an alkoxide ion. Sodium and potassium alkoxide can be prepared by
treating alcohols with sodium or potassium metal or with the metal hydride. Because most alcohols are weaker
acids than water, most alkoxide ions are stronger bases than the hydroxide ion.
Relative basicity H– > R– > NH2– > RC  C– > RO– > OH–
Alcohols reacts with diazomethylene in presence of BF3 , Grignard reagent due to acidic nature.
+ BF
3  ROCH + N
ROH+ C H 2  N  N  3 2
Ether
ROH + CH3  MgBr  CH 4 + ROMgBr
2. Action of acids (Esterification):

* H * 


(a) Ester of Carboxylic acids : RCOOH  H  O R  
 RCO O R   H 2O [*  O18 ]
Reactivity in esterification :
 For alcohols : CH3OH > 1 > 2 > 3
 For acids : HCOOH > CH3COOH > RCH2COOH > R2CHCOOH > R3CCOOH.
Note : (i) Esterification reaction proceed by acylo-o-cleavage reaction mechanism.

(ii) Tert. alcohols react so slowly in acid-catalysed esterification that they usually undergo elimination to
form alkenes.
(iii) Esters are also formed by the reaction of alcohols with acyl chlorides or acid anhydrides.
CH 3  CO O  CO CH3 + H  OR 

 CH 3  CO OR + CH3  COOH

Unlike the reaction with carboxylic acids, these reactions are irreversible, hence yields of esters via
this route are always high.
(iv) Reaction with acyl chlorides or acid anhydrides is used to determine number of hydroxyl groups in
polyhydric alcohols.
Molar mass of product  Molar mass of polyhydric alcohol
Number of OH groups =
42
(v) Suitable hydroxycarboxylic acid undergoes intramolecular esterification to form cyclic ester. (Called
as Lactone)
The mechanism of the reaction will be discussed in Carboxylc Acids.
(b) Esters of Sulphonic acids :

base
CH3  SO 2  Cl + H  OC2 H5 
 CH3  SO2  OC2 H5 + HCl
Methyl Sulphonyl chloride Ethyl methyl sulphonate
(c) Esters of Inorganic acids : Alcohols react with inorganic acids, viz. HNO3, H2SO4, H3PO3
and H3PO 4 to form esters of inorganic acids.
H

ROH  HONO 2   RONO 2  H 2O
2CH3OH + H 2CO3 (CH3 )2 CO3 Dimethyl carbonate
 H 2O
CH OH
3  CH OSO OCH
CH 3OH  HO  SO 3H 
 CH 3OSO3H  3 2 3
Methyl hydrogen sulphate Dimethyl sulphate

3. Conversion of alcohols into alkyl halides :

2 ZnCl
(a) Reaction with halogen acids : R  OH  HX   R  X  H 2O
anhyd.
The order of reactivity of the hydrogen halides is HI > HBr > HCl (HF is generally unreac
tive), and the order of reactivity of alcohols is 3° > benzyl  allyl > 2° > 1° > CH 3 . This
reaction follows nucleophillic substitution mechanism.
Note : The mixture of HCl and anhydrous ZnCl2 at room temperature is called Lucas reagent and the reaction is
referred to as LUCAS TEST. (appearance of a white turbid solution). 3 alcohols give Lucas Test instantly
; 2 alcohols give it after sometime and 1 alcohols do not give this test.
Note : Mechanism : Secondary, tertiary, allylic, and benzylic alcohols appear to react by SN1 mechanism.
Step 1 :
Step 2 :
Step 3 :
Most of the primary alcohols and methyl alcohol react by SN2 mechanism.
Why CH3OH reacts faster than other primary alcohols ?

Actually, methyl substrate is least capable of heterolysis and thus reacts only by SN2 reaction. Although
most of the primary substrates also react by SN2 mechanism, but because of increased steric hinderance
they react less rapidly than the methyl.
(b) Reaction with Phosphorus halides :
 
3ROH  PCl3   3RCl  H 3PO 3 ; ROH  PCl5   RCl  POCl3  HCl
Generally, in place of PBr3, red P and Br2 can be used. Similarly for PI3, red P and I2 is used.
(c) Reaction with Thionyl chloride :
Pyridine
ROH  SOCl 2 
 R  Cl  SO 2   HCl 
SN 2
R  OH  SOCl 2 
 R  Cl  SO 2   HCl 
SNi

If reaction takes place on chiral carbon atom then product is formed with retention in configuration because
reaction proceed by intramolecular nucleophilic substitution (SN i) reaction mechanism.
Note : The reaction of alcohols with phosphorus and Sulphur halides involves no rearrangement unlike with HX.
4. Dehydration to Alkenes : Alcohols on reaction with conc. H2SO4/, H3PO4 or catalysts such as anhy-
drous zinc chloride or alumina, loose the water molecule and form alkenes.
conc. H SO  excess 
2 4
C 2 H 5OH 

 CH 2  CH 2
170 C
2 4 conc. H SO  excess 
CH 3CH 2 C H  CH 3  CH 3CH  CHCH 3  CH 3CH 2CH  CH 2
|  Major Minor
OH
 The ease of dehydration is 3 > 2 > 1 alcohols.
 The Dehydration always follow Saytzeff rule.
Al O
2 3  CH  CH
 In gas phase, alcohols are heated with alumina to give alkene. C 2 H 5OH 
 2 2
350 C
Note : (i) If alcohols are in excess, then ethers are formed.


140 C
C2 H 5OH  H 2SO 4  C 2 H 5  O  C 2 H 5  H 2O
(Excess) (conc.) Diethyl ether
200 C
C2 H5OH  Al 2O3  C 2H5  O  C2 H5
(Excess)
(ii) Note that , at 170C or above dehydration occurs and at around 140C, ethers are formed when
conc. H2SO4 is used.
(iii) When conc. H2SO4 is in excess, alkenes are formed and when alcohols are in excess, then ethers are
formed.
5. Reaction with Ammonia : When a mixture of the vapours of an alcohol and ammonia are passed over
heated alumina or thoria catalyst at 360C, a mixture of primary, secondary and tertiary amines is pro-
duced.
Al O
2 3  RNH  ROH ROH
ROH  NH 3  2  R 2 NH   R 3N
360 C Al 2 O3 Al 2 O3
1amine 2°amine 3°amine
6. Reaction with Grignard Reagent :

Re d P
7. Reduction : ROH  2HI  RH  I 2  H 2O

8. Oxidation : The oxidation of alcohols is used to distinguish between 1, 2, 3 alcohols.
O
1 alcohols : RCH 2OH 
 O  
 RCHO  RCOOH
25C
aldehyde acids
2 alcohols :
Secondary alcohols are oxidised to ketones by chromic anhydride (CrO3).

CrO
3  R  C R'
R  CH  R' 
| ||
OH O
O
3 alcohols : R 3C  OH   do not oxidise
Tertiary alcohols do not undergo oxidation reaction. Under strong reaction conditions such as strong oxidising
agents (KMnO4) and elevated temperatures, cleavage of various C–C bonds takes place and a mixture of
carboxylic acids containing lesser number of carbon atoms is formed.
The important oxidising agents are : KMnO4/H+, Na2Cr2O7/H+, Chromic acid (H2CrO4). Some examples
are :
2 H CrO
4  CH CHO 
2 4  CH COOH H CrO
CH 3CH 2OH  3 3 ;
Note : (i) H2CrO4 does not oxidises double or triple bond in alcohols unlike KMnO4 and K2Cr2O7.
OH O
| H 2 CrO 4
||
H 2C  CH  C H  CH 3   H 2C  CH  C  CH 3
(ii) Cycloalkanols in presence of 50% HNO3 at 55C undergo cleavage forming dioic acids.

(iii) It is difficult to stop oxidation at aldehydic stage in aqueous solution. Hence a special oxidising agent,
Pyridinium chlorochromate (PCC) in CH2Cl2, is used to convert alcohols to aldehydes.
PCC
CH 2  CH  CH 2CH 2OH 
 CH 2  CH  CH 2CHO
CH 2Cl 2
PCC only oxidises 1 and 2 alcohols, not unsaturated bonds. PCC does not oxidise 3 alcohols. It
is however mainly used for 1 alcohoos.
(iv) Manganese dioxide selectively oxidises the alcoholic group of allylic and benzylic 1 and 2 alcohols
to give aldehydes and ketones respectively.
MnO
2  CH  CH  CH  CHO
CH 3  CH  CH  CH 2  OH  3
MnO
2  C H  CHO
C 6H 5  CH 2  OH  6 5
(v) Jones Reagent : H2CrO4 in acetone at 35C oxidises 1 and 2 alcohols to aldehydes and ketones
respectively. It, however does not oxidise double bond. It is mainly used for 2 alcohols.
9. Dehydrogenation : (With hot Copper)

This reaction also serves as a test for 1, 2, 3 alcohols.
Cu
1 alcohols : CH 3CH 2OH  CH 3CHO  H 2
300C
Aldehyde
Cu
2 alcohols : CH 3  C H  OH   CH 3  C  O  H 2
573 K 2
|
CH 3
Cu
3 alcohols :  CH3 3 C  OH   CH3  2  C  CH 2  H 2O (Alkenes are formed)
573 K
10.Lucas Test : Lucas reagent (a mixture of conc. HCl and ZnCl2) reacts with alcohols to form correspond-
ing alkyl chlorides which are soluble.
2 ZnCl
1 alcohols : RCH 2OH  No reaction at room temperature.
HCl
ZnCl
2  R C  Cl
2 alcohols : R 2CH  OH  3 White turbidity after 5 – 10 minutes.
HCl
ZnCl
2  R C  Cl
3 alcohols : R 3C  OH  3 White turbidity instantaneously.
HCl
Note : Allyl and Benzyl alcohol reacts as rapidly as 3alcohol to form soluble chloride with Lucas reagent.

Function of ZnCl2 in Lucas reagent : Since chloride ion is a weaker nucleophilie than bromide or iodide
ions, HCl does not react with less reactive 1 and 2 alcohols unless some good Lewis acid like ZnCl2 is
added to the reaction mixture. Zinc chloride, a good Lewis acid, forms a complex withthe alcohol. The
complex provides a better leaving group for the reaction than H2O.
(i) In case of 2 and 3 alcohols, the function of acid is to help in the formation of carbocations.
(ii) In case of methyl and 1 alcohols, the function of acid is to produce a substrate in which the leaving
group is a weakly basic species ; H2O or [Zn(OH)Cl2]– rather than a strongly basic hydroxide ion.
(ii) 3and Benzyl alcohols are more reactive due to formation of more stable corresponding carbocations.
11. Victor Meyer Test : This test is based upon the fact that three types (1, 2 and 3) of nitroalkanes
(formed by alcohols) react differently with nitrous acids followed by the action of Sodium hydroxide(alkali).
P/I
2  RCH I  AgNO
2  RCH NO 
2  R – C – NO HNO
1° Alcohol : RCH 2OH  2 2 2 2
or HI ||
NOH
Nitrolic acid
 Nitrolic acid on treatment with alkali dissolve in it to give a red colouration.

 Pseudonitrol on treatment with alkali does not dissolve but gives blue colour.
P /I 2
2  R C  I  AgNO 2  No reaction. HNO
3° Alcohol : R 3C  OH  3  R 3C  NO 2 
PHENOLS Section - 2
Phenols are compounds containing an hydroxyl group : OH group, attached directly to an aromatic ring.
These generally are derivative of main member phenol, C6H5OH (ph – OH). The compounds in which OH
group is not attached directly to the ring such as benzyl alcohol, C6H5CH2OH are not phenols. These are
called as side chain aromatic alcohols having properties similar to aliphatic alcohols.
Some important phenols are :
Preparation of Phenols
1. From Chlorobenzene :
2. From Benzene sulphonic acid :

3. From Cumene :
Reactions involved in above synthesis are as follows :
I. SE reaction II. Free radical III. Acid catalysed hydrolytic rearrangement
II.
III.
4. From Benzene Diazonium chloride :
5. From Benzene :

6. From Grignard Reagent :
Reactions of Phenol
(A) Reactions of –OH group :
1. Salt Formation : Phenol is a weak acid and turns FeCl3 solution violet, but fails to give litmus
test. It reacts with sodium and NaOH to give phenoxides. Phenol however does not react with
Na2CO3 and NaHCO3.
The reaction of phenol with aqueous sodium hydroxide indicates that phenols are stronger acids
than alcohols and water.
Due to the higher electronegativity of sp 2 hybridised carbon to which  OH is attached, electron

density decreases on oxygen. This increases the polarity of O – H bond and results in an increase
in ionisation of phenols than that of alcohols. Also phenoxide, the conjugate base of phenol is
more stabilised than alkoxide, the conjugate base of alcohols. The delocalization of negative
charge (structures I-V) makes phenoxide ion more stable and favours ionisation of phenol.

2. Formation of Ester : The acetylation and benzoylation of phenols are called as Shautan-Bauman
reactions.
3. Formation of Ethers :
4. With PCl5 : (Formation of Aryl halides)
5. With Zn-dust : (Reduction)
6. Oxidation :

7. Condensation with Pthalic anhydride : Phenol undergoes a special Friedal Craft acylation with
pthalicanhydride in presence of H2SO4 to form phenolphthalein (an acid-base neutralisation indica-
tor).
8. With NH3 :
(B) Reactions of Benzene group :

Phenol undergoes electrophillic substitution reactions much more readily as compared to benzene due to
electron releasing ability of OH group (activating agent). Also OH group over benzene is strongly ‘o’ and
‘p’ directing due to +M effect of OH group.
1. Halogenation :

Note : Halogenation of phenol takes place even in absence of Lewis acid (AlBr3 , FeBr3 ) due to the highly activat
-ing effect of  OH group.
Note : OH group is strongly activating, hence a tri-substituted product is formed. However, in CS2 at 0C, only
Ortho (o) and Para (p) derivatives are formed.
2. Nitration :
(Poor yield, because NO2 group is deactivating)
Note : With concentrated nitric acid, phenol forms 2, 4, 6 - Trinitrophenol, commonly known as Picric acid.With
dilute acid, however, a mixture of o- and p- nitrophenol is formed. This mixture can be separated by
steam distillation.

3. Sulphonation :
At 25C, phenol gives only o-hydroxy benzene sulphonic acid, whereas at 100C, it gives p-hydroxy
benzene sulphonic acid.
Picric acid is prepared in good yield by treating phenol first with concentrated H 2SO 4 which con-
verts it to phenol-2, 4-disulphonic acid, then with concentrated HNO3 to get 2, 4, 6-trinitrophenol.
4. Nitrosation :
5. Alkylation :
Phenols undergo Friedal Craft alkylation to give the product according to the most stable intermedi-
ate carbonium ion.
6. Reimer - Tiemann Reaction :

Ortho product is formed as major because :

(i) Ortho position is more activated
(ii) Stabilization by chelation
Mechanism of Reimer – Tiemann Reaction: The reaction involves electrophillic substitution on the
highlyreactive phenoxide ring. Here the electrophile is dichlorocarbene : CCl2 , generated from CHCl3 by
the action of a base.
7. Kolbe’s Reaction :
Mechanism of Kolbe’s Reaction : CO2 acts as an electrophile in this reaction.

Note : (i) Transition state is stabilized by small size of (ii) If the reaction is carried out on potassium phenox-
Na + ion. ide the salt of the p-acid becomes the major prod
uct.
Because transition state formed by attack at ortho

positions is not stabilize due to bigger size of K +
The salicyclic acid formed above in Kolbe’s reaction is used to produce a number of important derivatives
used as medicines.

ETHERS Section - 3
In ethers, the oxygen atom is bonded to two carbon atoms. The hydrocarbon group may be alkyl (1, 2
and 3), allylic, vinyl, alkynyl or aryl. Consider some examples :
CH3 – O – CH3 C2H5 – O – CH3 CH2 = CH – O – CH3
Dimethyl ether Ethyl methyl ether (Phenetole) Methyl vinyl ether
CH2 = CH – O – CH = CH2 CH2 = CHCH2 – O – CH3 CH3 – O – C6H5

Divinyl ether Allyl methyl ether Methyl phenyl ether (Anisole)
There are various types of cyclic ethers. Cyclic ethers consisting of two carbons in a three member ether are
called oxirane or epoxides. Cyclic ethers consisting of three carbons in a four member ether are called
oxetanes. Cyclic ethers consisting of four carbons in a five member ether are called tetrahydrofurans.
Preparations of Ethers
1. From alcohols : Dehydration of alcohols by H2SO4 at 170C gives alkenes, whereas at 140C
gives ethers. The dehydration of alcohols to ether is helped by distilling the ether as it is formed.
H SO
2 4  CH  CH
CH 3CH 2OH  2 2 (Alkene)
170 C
H SO
2 4  CH CH  O  CH CH
CH 3CH 2OH  3 2 2 3 (Ether)
140C
The formation of ethers occurs by SN2 mechanism with one molecule of alcohols acting as the nucleo
phile and another protonated molecules of the alcohols acting as the substrate. The mechanism of the
reaction is given below.
Step : 1 The alcohol accepts a proton from the acid to give a protonated alcohol.
Step : 2 The other molecule of alcohol acts a nucleophile and attacks the protonated alcohol in an
SN2 reaction to give a protonated ether.

Step : 3 The protonated ether transfers the proton to water molecule to give ether.
Note : (i) In case, when alkyl groups are 3, SN1 type path is followed. 3 alkyl alcohol forms a carbocation
(stable) and second alcohol acting as a nucleophile adds to it (solvolysis). An elimination product is
also formed as a minor product.
CH 3 CH 3 CH 3 CH 3
| | H 2SO 4
| |
CH 3  C  OH  CH 3  C OH 
140C
 CH 3  C O  C H  CH 3   CH 3 2 C  CH 2
| | | (Minor product)
CH 3 H CH 3
(ii) This method is generally limited to the preparation of symmetrical ethers, because a combination of
two alcohols usually yields a mixture of three ethers.
2. Williamson’s Synthesis : This is the most important method of formation of ethers (nucleophillic substitu
tion reaction), also known as Williamson’s synthesis. It consists of SN2 attack by alkoxide ion on an alkyl
halide, alkyl sulphate or alkyl sulphonate.
The alkoxide ion reacts with substrate in an SN2 reaction to give an ether. The substrate must have a good
leaving group. Important leaving groups are : halides (X), sulphates (OSO2OR) and sulphonates
(OSO2R). The substrate must have a primary alkyl group for good yield. In case of tertiary substrate,
elimination occurs. The other factor which contributes to substitution is low temperature.
Note : The aromatic ethers are formed when phenoxides reacts with alkyl sulphates in an SN2 reaction.
C 6 H 5 O Na  CH 3  OSO 2O  CH 3 
 C 6 H 5OCH 3  NaOSO 2OCH 3
Sodium phenoxide Dimethyl sulphate Methyl phenyl ether
3. Gas phase reaction :
2 3 Al O
2ROH  g  
 
R  O  R  H 2O
260  280 C
vapours

4. Oxymercuration - Demercuration :
Note : If water is used instead of alcohols and acid, an alkene is formed as per Markonikov’s addition.
5. By the action of Diazomethane : Methyl ethers can also be prepared by the action of diazomethane
(CH2N2) on alcohols in presence of HBF4 as catalyst.
4 HBF
CH 3CH 2OH  CH 2 N 2  CH 3CH 2  O  CH 3  N 2
6. From Grignard Reagents : Higher ethers can be prepared by treating -halo ethers with suitable Grignard
reagents. For example,
Dry
 CH 3  O  CH 2CH 3  Mg  I  Cl
CH 3  O  CH 2Cl  CH 3MgI 
ether
7. By treating Alkyl halide with dry Silver oxide :
2(CH 3 ) 2 CHCl  Ag 2O 
 (CH 3 ) 2 CH  O  CH(CH 3 ) 2  2 AgCl
Physical properties of Ethers :

(i) Dimethyl ether and ethyl methyl ether are gases. All others are colourless liquids with pleasant odours.
(ii) They are lighter than water. Lower ethers are highly volatile and very inflammable.
(iii) They are sparingly soluble in water but readily soluble in organic solvents. Solubility of ethers in water
in presence of small amount of alcohols perthaps due to hydrogen bonding between ether and water
 
molecules (R 2 O  H  OH). Ethers themselves are very good solvents.
(iv) Boiling points of ethers show a gradual increase with increase in molecular mass. Ethers have low
boiling points than isomeric alcohols as there is no association between the molecules as in alcohols
due to hydrogen bonding. The boiling points of ethers are close to the boiling points of alkanes.
(v) On account of R – O – Rbond angle being 100°, two dipoles do not cancel each other and mol-
ecules have small net dipole moment making the ethers somewhat polar.

Reactions of Ethers
Ethers are in general are less reactive and react only with acids. The reactive sites in ethers are : C – H
bonds (as in alkanes) and – O – group of ether bond. Ethers resist the attack of nucleophiles and bases.
However ethers are very good solvents in many organic reactions due to their ability to solvate cations by
donating the electron pair from oxygen atom.
1. Halogenation of ethers : Ethers like alkanes undergo halogenation in dark to give halogenated
ethers. The hydrogen atom attached to the carbon atom directly linked to oxygen atom is replaced
by halogens.
Cl
2  CH CH  O  C HCH 
2  CH C H  O  C HCH Cl
CH 3CH 2  O  CH 2CH 3  3 2 3 3 3
| | |
Cl Cl Cl
2. Ethers as Base : The oxygen atom of ethers makes them basic. They react with a proton donor to
give oxonium salts.
H
|
 CH 3CH 2  O  CH 2CH 3 Br 
CH 3CH 2  O  CH 2CH 3  H  Br 

3. Reaction with acids :
Ethers undergo cleavage under quite vigorous conditions, such as concentrated acids (usually HI and
HBr) and high temperatures.

R  O  R '  HX   RX  R 'OH
If the acid is present in excess, then the alcohol formed, further reacts with HX to give a halide
(Nucleophillic substitution).
 A di-alkyl ether (symmetric ether) yields two alkyl halide molecules, if HX is present is excess,
under hot conc. conditions.
R  O  R  HX 
 ROH  RX ; ROH  HX 
 RX  H 2O
HX
R  O  R 
 2 RX
excess
( hot conc.)
 For Mixed Ethers

(i) In case when both alkyl groups are 1 or 2 (i.e. R or R '  3 ), then SN2 path occurs.
I– as a nucleophile attacks the smaller of the two alkyl groups to give an alkyl iodide.
As I– makes an SN2 attack, consider steric factors. So, the smaller of the alkyl groups
goes with the iodide ion and the larger group forms alcohols.
(ii) If any one of R or R is 3, then we have different products via different mechanism. Here SN1
type of path is followed. Let R be 3.
 
H slow
R '  O  R 
 R '  O  R   R 'OH  R  (3 carbocation, highly stable)
step
|
H
R   I  
RI (Hence 3R forms iodide)
Note :  Excess of HX gives a mixture of alkyl halides.

 Reactivity of halogen acids : HI > HBr > HCl
 Alkyl aryl ethers are cleaved at the alkyl – oxygen bond due to the more stable aryl-oxygen bond. The
reaction yields phenol and alkyl halide.
Phenols do not react further to give halide (Nucleophillic substitution does not take place in aromatic
compounds).
Important :
Since it is SN2 path, X– should be a strong nucleophile. Hence in cleavage of aromatic ether, only HI (I
being strong nucleophile) can be used.
 With hot concentrated H2SO4 : Secondary and tertiary ethers react with hot conc. H2SO4 to give
a mixture of alcohols and alkenes.
H SO
2 4  CH
 CH3 3  C  O  CH 3 
hot conc.
 3 2  C  CH 2  CH 3OH
Note : Ease of formation of alkene follows : 3 > 2 > 1 (with respect to alkyl group).

4. With Phosphorus pentachloride : Phosphorus pentachloride also brings about the cleavage of C – O
bond of ethers leading to the formation of alkyl halides.
CH3CH 2  O  CH 2CH 3  PCl5 

 2 CH 3CH 2  Cl  POCl3
5. Reaction with Acid chloride and Anhydrides : Acid chlorides and anhydrides react with ethers when
heated in the presence of anhydrous. ZnCl2 or AlCl3 to form alkyl halides and esters.
2  C H Clanhyd. ZnCl
Et  O  Et  CH 3COCl  2 5  CH 3COOEt

Diethyl ether Acetyl chloride Ethyl chloride Ethyl acetate
However with anhydrides only esters are formed.

3 anhyd. AlCl
 C2 H 5 2 O   CH 3CO  2 O 

2 CH 3COOC 2H 5
Diethyl ether Acetic anhydride Ethyl acetate
6. Action of Air and Light : (Formation of Peroxides) : When exposed to air and light for a long time,
ethers are oxidised to form hydro-peroxides or simply peroxides.
light
Et  O  Et  O 2 
 CH 3  C H  O  Et
Diethyl ether |
O O  H
1 - Ethoxyethyl hydroperoxide
Therefore, serious explosions may occur during distillation of old samples of ethers if peroxides are not
removed. Presence of peroxides in old samples of ethers may be detected by shaking them with a freshly
prepared solution of FeSO4 followed by addition of KCNS. Appearance of a red colour indicates the
presence of peroxides. A simple method to remove peroxides is to shake an old sample of ether with
aqueous solution of KI or ferrous salt.
7. Hydrolysis of Ethers : Ethers when treated with dilute aqueous acids give alcohols.
3 H O
2  2 ROH H O
R  O  R 
Oxirane (Epoxide)
Epoxides are cyclic ethers with three membered rings. In IUPAC system, epoxides are called as Oxiranes.
The most common epoxide is ethylene oxide.

Preparation of Oxiranes
1. Oxidation of Ethylene : Epoxide or ethylene oxide is prepared by partial oxidation of ethylene in
presence of Ag2O.
2. Epoxidation : The most important method of formation of epoxides is the reaction of an alkene with
an organic peroxy acid or peracid, such as perbenzoic acid (C6H5COOOH) or peracetic acid
(CH3COOOH) or mCPBA (m-chloroperoxobenzoic acid). This process is known as epoxidation.
Note : The above reaction is a stereo specific reaction i.e., it involves cis-addition of an electrophillic oxygen atom.
It means cis-alkene will give only cis-epoxide and a trans-alkene will give only trans-epoxide.
Reactions of Oxiranes
Due to the strain in the ring, epoxides are highly reactive towards nucleophillic substitution reaction
(unlike ethers). They undergo ring opening reactions so as to release the strain. Epoxides undergo acid
catalysed and base catalysed opening of the ring.
1. Acid Catalysed Opening : The acid reacts with epoxides to produce a protonated epoxide. The
protonated epoxide undergoes ring opening by attack of nucleophile (A–) on sterically hindered car-
bon atom, because acid catalysed ring opening is SN 1type reaction
2. Base Catalysed Opening : Epoxides can also undergo base-catalysed ring opening provided the
attacking nucleophile is also a strong base such as an alkoxide or hydroxide ion. A strong nucleophile
(alkoxide, RO) is able to open the ring by a backside attack (as observed in a SN2 reaction)

Note :  Under acidic conditions, ring opening in protonated epoxide occurs to give a more stable (3)
carbonium ion.
 Under basic conditions, the alkoxide simply attacks the less hindered carbon atom in an SN2 type
displacement.
 Symmetrically substituted epoxides give the same product in both the acid-catalysed and base-catalysed
ring openings. An unsymmetrical epoxide gives different products under acid-catalysed and base-
catalysed conditions,
3. Cleavage of Oxiranes by Grignard Reagent and LiAlH4: In case of Grignard reagent, the Nu end, i.e.,
R attacks on the carbon atom of the epoxide. Here nucleophile attacks at less substituted ring carbon in the
base catalysed ring opening (As explained above).
Epoxides are reduced to alcohols an treatment with LiAlH4 ; hydride ion (as Nu–) is transferred to the less
crowded carbon.
Electrophillic substitution reaction in Aromatic Ethers

The alkoxy group is an Activating and ortho and para directing, just like – OH group in phenol. The following
SE reactions are observed.
(i)
Anisol undergoes bromination with Br2 in ethanoic acid, even in the absence of Iron (III) bromide
catalyst.

(ii) Friedel - Crafts Reactions :
(iii) Nitration :
Claisen Rearrangement of Allyl phenyl ether :

Allyl phenyl ether can be prepared by following reaction.

DIHYDRIC ALCOHOLS Section - 4
Dihydric alcohols are called as diols. There are two types of diols :
(i) Geminal diol (ii) Vicinal diol
Geminal diols are unstable because of steric reason. There are hydrates of carbonyl compounds.
Some geminal diols are stable due to intramolecular H-bonding.
The viccinal type of dihydric alcohols are called as Glycols (Di-ols). Some Important Glycols are given
below :
Pinnacol(s) : Completely substituted vicinal diol is called as pinacol.

Preparations of Glycols
1. Hydroxylation of Alkenes
Note :  The reaction involves ‘syn’ addition.
2. Hydrolysis of Halohydrins
HOCl aq
CH 3CH  CH 2  CH 3  C H – C H 2  CH 3 – C H – C H 2
KOH
| | | |
OH Cl OH OH
(Halohydrins)
3. Acidic Hydrolysis of Oxiranes
aq
4. Hydrolysis of Viccinal Dihalides C H 2 – C H 2  C H 2 – C H 2
KOH
| | | |
Br Br OH OH
Viccinal dihalides
5. Reductive hydrolysis of carbonyl compounds (An important method for Pinncols)

 CH 3 – CO 
 1. Mg
 
|   CH 3  2  C  C   CH 3 2 (Pinnacol)
 CH 3  2. H 2O
| |
 
OH OH
H H
| |
1.Mg
2 CH 3CHO   CH 3 – C – C – CH 3
2.H 2 O
| |
OH OH
6. Reduction of Glyoxal(s)
Reactions of Glycol
1.
2. Reactions with Organic and Inorganic Acids

3. Polymerisation
4. Acetal (ketal) formation (cyclic acetals : dioxolan)
Note : (i) Acetals are stable in alkaline medium and are not reduced. Hence keto groups are protected in acetal
forms. Acetals are very easily hydrolysed in acidic medium to give back aldehyde and ketones.
(ii) Aldehydes are more reactive than ketones in this reaction.
5. (a) Oxidation

(b) Oxidative Cleavage

By using HIO4 : per iodic acid or Pb(OAc) 4
Lead tetra acetate
4 HIO
CH 3 – C H – C H 2  CH 3 – CHO  HCHO
| |
OH OH
Note : (i) ‘trans’ shows cleavage with resistance, whereas ‘cis’ shows cleavage instantly.
O
||
(ii) Special Case : In case when –CHOH and  C  groups are adjacent to each other, HIO4 also
breaks them as follows :
6. Intramolecular Condensation

7. Acid Catalysed “Pinnacol-Pinnacolone” Rearrangement
CH 3 CH 3 CH 3
| | H 2SO 4
|
CH 3 – C – C – CH 3   CH 3 – C – C – CH 3
| | || |
OH OH O CH 3
(Pinnacol) (Pinnacolone)
Methyltert.butylAcetone
Mechanism :
Note : The mechanism follows :

 Protonation of one hydroxyl group.
 Loss of proton.
 Migration of H– /ph– /Me–
 Loss of proton to give ketone.
Important :
1. Watch for the stability of carbocation in case of other diols.
2. Follow the order of migration as : ‘H’ followed by ‘phenyl’, followed by Ethyl followed by Methyl

 Ring expansion or ring contraction may also takes place if possible.
Tri-hydric Alcohol (Glycerol)
Preparations of Glycerol
1. Saponification of oils/fats (glycerides)
2. Synthetic glycerol
CH 2 CH 2Cl CH 2OH CH 2OH CH 2OH

|| Cl 2
| | | |
aq HOCl aq
C H   C H   C H   C HOH   C HOH
500C KOH KOH
| || || | |
CH 3 CH 2 CH 2 CH 2Cl CH 2OH
(propene) allylchloride allylalcohol
Reactions of Glycerol
1. With conc. HNO3

2. Reaction with Oxalic acid
Note : If T = 260°C , allyl alcohol is formed.
3. Action of HI
 If excess of glycerol of used.
 If excess of HI is used.
CH 2 CH 3 CH 3 CH 3
|| | –I 2
| |
HI HI
C H   C HI   C H   CH – I
| | || |
CH 2 I CH 2 I CH 2 CH 3
(Isopropy iodide)
4. Dehydration
CH 2OH CH 2
| KHSO
||
C HOH 4  C H (acrolein)

| |
CH 2OH CHO

Note :  A mixture of glyceryl trinitrate and glycernyl dinitrate absorbed on kieselguhr (Porous earth) is dyna-
mite, an explosive.
 Glycerol is used in the manufacture of polyster called glyptal, in medicines, cosmetics and in textile
processing.
 Glycerol is miscible in water and is sweet in taste.
ILLUSTRATIONS Section - 5
Illustration - 1 An optically active alcohol A(C6H10O) absorbs two moles of hydrogen per mole of A upon
catalytic hydrogenation and gives a product B. The compound B is resistant to oxidation by CrO3 and does
not show any optical activity. Deduce the structures of A and B.
SOLUTION :
2 2H (O)
C6H10O (A)   B  resists oxidation
CrO3
(Optically active)
Clearly, A has a – C  C – bond and B should be a 3° alcohol as they resist oxidation.

Now visualise the structure of A keeping in mind a chiral centre (optically active).
Illustration - 2 3, 3-Dimethylbutan-2-ol loses a molecule of water in the presence of hot conc. H2SO4 to
give tetramethyl ethylene as the major product. Suggest a proper mechanism. Also identify the minor product.
SOLUTION :

Illustration - 3 A compound of molecular formula C7H8O is insoluble in water and dil. Na2CO3 but dissolves
in dil. NaOH solution. On treatment with Br2 / H 2O, it readily gives a precipitate of C7H5OBr3. What is the
structure of compound ?
SOLUTION :
The possible structures of compounds having molecular formula as C7H8O are :
It can not be benzyl alcohol or anisole as alcohols and ether (o, p, m) are insoluble in NaOH. It can be only
be cresol. Note that phenols are soluble in dil. NaOH forming phenoxides.
Now cresol can be o, p or m. How to identify it ?
Observe that it is SE (electrophilic substitution) giving a tri-substituted product as  OH is a strongly activating

group (+M effect). The only possible isomer giving a trisubtituted derivative can be m-cresol.
Note that both – OH and – CH3 activate same positions (i.e. o and p). Though, due to sterie factor,
bromination at the position between  OH and  Me group is quite difficult.

Illustration - 4 A compound X(C5H8O) does not react appreciably with Lucas reagent at room temperature
but gives a precipitate with ammonical AgNO3. With excess of MeMgBr, 0.42 gm of X gives 224 mL of CH4
at STP. Treatment of X with H2 in presence of Pt catalyst followed by boiling with excess HI gives n-pentane.
Suggest the structure of X and give all reactions involved.
SOLUTION :
3 AgNO
X   precipitate
 X contains – C  C – H group, which is confirmed by action of MeMgBr to give CH4.
0.42
mol of X  0.005 mol.
84
224
224 mL CH4 (STP)  mol  0.01 mol of X
22400
 1 mol X  2 mol CH4
Hence X contains two acidic H-atoms.
 
The structure of X should be : HC  CH 2CH 2CH 2 OH
Note that ‘X’ has to be 1° alcohol as it does not give Lucas test. Also note that 2 alcohol react with Grignard
Reapent to give alkanes, hence Lucas test is very important here.
2 H HI
Finally checking : HC  C  CH 2CH 2CH 2OH    H3C  CH 2  CH 2CH 2CH3
Pt
(n  Pentane)
Illustration - 5

SOLUTION :
Illustration - 6 Identify the products in the following reactions and comment on the stereochemistry of the
products.
(i) (ii)
SOLUTION :
(i) Observe that alcohol has a chiral centre.
Et Et Et
| Na
| _ CH3CH 2 Br
|
 (A)
H  C  OH   H  C  O Na   H  C O  CH 2CH3
SN 2
| | |
Me Me Me
Note that here O – H bond breaks to give alkoxide and in SN2 reaction ether is formed retaining the
configuration of alcohol.
Et Et
| TsCl
|
H  C  OH  H  C  OTs ;
| |
Me Me

HS will make an SN 2 attack from the back at   carbon (chiral) to give an inverted configuration.
Note that TsO is a very good leaving group assisting SN 2 reaction.
(ii) Reaction of alcohol with SOCl2 proceed by intramolecular nucleophilie substitution reaction (SN i)
mechanism, hence there is retention in configuration.
In second reaction product B is formed by SN 2 reaction mechanism of necleophilic substitution reaction

hence there is inversion in configuration of chiral carbon atom.
Illustration - 7 Give the possible products in the following reactions. Also comment upon the type of
pathways.
2 4  ? ?? H SO
(a) CH 3CH 2OH  CH 3CH 2CH 2OH 
T ~ 140C
H SO
2 4  ? ??
(b) CH 3CH 2OH   CH 3 3  C  OH 
T ~ 140C
SOLUTION :
2 4 H SO
(a) CH 3CH 2OH  CH3CH 2CH 2OH 
T ~140C
Note that both alcohols are 1 alcohols, so none of these is capable of carbocation formation (1 carbocations
being poorly stable). So here, ethers will be formed via SN2 pathway as temperature is around 140C.

In the first step, either or both of two alcohols can form oxonium ion (R O H 2 ) and then the second step, the
other one will make an SN2 attack on -carbon to give a protonated ether which eventually will give ether as
final product.

Due to absence of steric factors in two alcohols, possible products are :

H 
CH 3CH 2OH 
 CH3CH 2 O H 2
Hence the products (I, II, III) are formed via SN2 path.
H SO
2 4 ?
(b) CH3CH2OH   CH3   C  OH 
3
Note that one of these is tertiary butyl alcohol (3), so it will form stable carbocation which will finally give
ether as the main product via SN1 path.
Note :  A stable carbocation also give alkenes as minor product via E1 path.
H 
 CH3 3  C  CH3  C  CH 2
|
CH3 (E1)
 If T ~ 160 – 170C, E1 will be the major product.

Illustration - 8 Identify the products in the following :
(a) (b)
SOLUTION :
(a)
Note that if reagent is OH–, then visualise its action as a base.

(usually alcoholic KOH is visualised as : OH– as a base)
(b)

Illustration - 9 Identify compounds A, B, C . . . . in the following reaction setup.

CH CO H
3 3  A
CH 3  C  CH 2 
|
CH 3
SOLUTION :
Note :  Observe that Nu– (i.e., H2O18) attaches to more alkylated carbon in an acid catalysed ring opening.
It is SN 1type ring opening
[ CH3O  will attack at least steric hindered carbon atom in an

SN2 attack].
O 
O
| CH3 O H
|
CH3  C  CH 2OCH3   CH 3  C  CH 2OCH3 (C)
| |
CH3 CH3
 Observe that Nu– (CH3O–) attaches to less alkylated carbon in a base catalysed ring opening.
CH3
| conc.
B: CH 3  C  C H 2 
| | H 2 SO4
18OH OH

Visualise Pinnacol - Pinnacolone Rearrangement in glycols.
Note that the wrong answer is : CH 3  C  CH 2CH3

||
18O
Illustration - 10 Identify the products A, B, C and D and describe the pathways.
SOLUTION :
conc. HI solvent in H2O
CH 3 CH3
|  |   _ 
H SN 1 I (Nu )
CH 3  C  O  CH3  CH3  C  O CH3    CH3   C  CH3OH   CH 3  C  I 
3
| | | + (B) (A)
3°C ; stable
CH 3 CH 3 H
When solvent is ether, it being less polar favours SN2 path with I– as a strong nucleophile will make an SN2
attack at –CH3 group (no steric hindrance).

Illustration - 11 Identify A, B, C, . . . . in the following reactions :
ph ph
| | H 2 SO4 conc. LiAlH 4 H 2 SO4  conc.
(a) ph  C  C  Me   A   B  C
170C
| |
OH OH
(b)
NBS KOH  aq. 1. Na HI  conc.

(c) CH 3CH  CH 2 
 A 
 B  C 
DE
CCl4 2. MeBr 
SOLUTION :
C6H5 CH3
| | conc.
(a) C6H 5  C  C  CH3  ? It is a case of Pinnacol-Pinnacolone type of rearrangement.
| | H 2SO 4
OH OH
Observe that first visualise the most stable carbocation and then follow migration in order : H ph  R.
Rewriting (A) as :

(b)
+
Note : In general, R C O does not undergo rearrangement but if R is 3 then it breaks as mentioned below
:
For Example :
Note : If R is 1° or 2° (RCOCl) ; it will be simply Friedal craft acylation.
(c)

Illustration - 12 (a) How will you convert cyclohexanol to 1, 4-Dibromo-2-cyclohexene in not more than
4-steps ?
(b) How will you prepare 2, 3-Dimethyl-2-butanol from 2-Propanol as the only starting organic material ?
SOLUTION :
(a)
CH3 CH3
| |
(b) CH 3 C H  CH3 
 CH3  C  C H  CH3
| |
OH OH
2, 3-Dimethyl-2-butanol
2 alcohol 
 3 alcohol
(Think of Grignard reagent)
CH3 CH3
PCl5 Mg / Et 2 O (CH3 ) 2 CO
| |
CH 3 C H  CH 3   CH3  C H  CH 3   CH3  C H  CH 3   CH3  C  C H  CH3
| | | H 2O |
OH Cl MgCl OH
Illustration - 13 Propose mechanism for the following reactions.
(a)
(b)

SOLUTION :
(a)
Looking at the product . . . . . . Pick the structure II.
(b)

Observe carefully that this step will lead to nowhere as O H 2 is attached to phenyl ring. So think of alternative
path.

Illustration - 14
1. Br / H O
2 2  A 
3 CH C  CH .
3  C  CH I HI ( conc.)
CH3CH  CH 2 

 B   DE
2. OH Na 0C
SOLUTION :
Visualise base catalysed (SN2) ring opening (consider steric factors).
Note : I– as strong Nu– will atack at the least hindered CH3 group.

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My Chapter Notes

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Illustration - 1

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Vidyamandir Classes Surface Chemistry
Surface Chemistry
ABSORPTION & ADSORPTION Section - 1
There are many properties of matter, which are related to their surface. Such properties become predominant
if the substance is in finely divided form or its surface is rough. Under these conditions the surface area
increases enormously and large amount of material is present in the surface. The surface related properties
of matter are adsorption, colloidal state and emulsions.
There are residual forces acting along the surface of liquids and solids. Due to residual forces, the surface of
a solid (or a liquid) has a tendency to attract and retain molecules of other species with which it is brought
into contact. Concentration of these species is more at the surface than in the bulk of the solid or liquid.
The phenomenon of higher concentration of any molecular species at the surface than in the bulk of a solid
(or liquid) is known as adsorption. Solid, particularly when finely divided, have a large surface area, hence
this behaviour is predominant on solid surfaces. The solid that takes up a gas or vapour or a solute from
solution, is called the adsorbent while the gas or the solute, which is held to the surface of the solid is called
the adsorbate.
If the concentration of a substance at the surface of another substance is more than in the bulk of the
adjoining phases, it is called positive adsorption. If the concentration of a substance at the surface of another
substance is less than in the bulk of the adjoining phases, it is called negative adsorption. This type of
adsorption takes place only in case of solutions.
The removal of the absorbed substance from a surface is called desorption. When equilibrium is reached,
Rate of adsorption = Rate of desorption
Difference between Adsorption and Absorption
Adsorption is different from absorption. Absorption of a substance A by a substance B means that A is
uniformly distributed all over B. Adsorption on the other hand, means that A is present on the surface of B,
but the concentration of A in parts of B away from the surface is negligible.
In some cases, adsorption and absorption take place simultaneously and it is difficult to determine the
relative extent of adsorption and adsorption. The term sorption is widely used in such cases.
S.No. Adsorption Absorption
1. It is surface phenomenon. It is bulk phenomenon.
2. Adsorbate is accumulated at the surface. The substance getting absorbed is
uniformly distributed throughout the bulk
of the substance.
3. The rate of adsorption is very rapid in the Absorption proceeds at a steady rate.
beginning. The rate however decreases gradually
until equilibrium is reached.

Surface Chemistry Vidyamandir Classes
Types of Adsorption
Depending upon the nature of forces between the adsorbate (solute) and adsorbent (solvent) molecules,
adsorption can be classified into two groups :
1. Physical adsorption 2. Chemical adsorption
S.No. Physical adsorption Chemical adsorption

1. It is caused by intermolecular van der Waal’s forces. It is caused by chemical bond
formation.
2. It is not specific and is reversible. It is highly specific and is irreversible.
3. It depends on the nature of gas. More easily It also depends on the nature of gas.
liquefiable gases are adsorbed readily. which form compounds with the
adsorbent exhibit chemi-sorption.
4. Heat of adsorption is low and is negative. Heat of adsorption is high and is negative.
5. Low temperature is favourable. It decreases with High temperature is favourable. It
the increase of temperature. increases with the increase of
temperature.
6. No appreciable activation energy is involved. High activation energy is involved.
7. High pressure is favourable. Decrease of pressure High pressure is favourable. Decrease
cause desorption. of pressure does not causes desorption.
8. It depends on the surface area. It increases with It also depends on the surface area. It
the increase of surface area. with increase of surface area.
9. It forms multi-layers on adsorbent surface under It forms uni-molecular layer.
high pressure.
Note : There are mainly two types of adsorption of gases of solids. If accumulation of gas on the surface of a
solid occurs on account of weak van der Waal’s forces, the adsorption is termed as physical adsorption or
physisorption. Chemisorption, on the other hand is when the gas molecules or atoms are held to the solid
surface by chemical bonds. Chemical bonds involved may be covalent or ionic in nature. Chemisorption
involves a high energy of activation and is, therefore, often referred to as activated adsorption. Sometimes
these two processes occur simultaneously and it is not easy to ascertain the type of adsorption. A physical
adsorption at low temperature may pass into chemisorption as the temperature is increased. For example.
dihydrogen is first adsorbed on nickel by van der Waal’s forces. Molecules of hydrogen then dissociate to
form hydrogen atoms which are held on the surface by chemisorption.

Factors affecting adsorption :

The extent of adsorption of a gas on the surface of a solid depends on the following factors :
(i) Nature of gas : Since physical adsorption is non specific in nature, any gas will be adsorbed on the surface
of a solid to some extent or other. However, under any given conditions of temperature and pressure, easily
liquefiable gases such as NH3, CH4, HCl, CO etc. are adsorbed more than permanent gases like O2, N2
etc. Chemisorption is specific in nature. Therefore, only those gases will be adsorbed which form chemical
bonds with it.
(ii) Nature of solid : Activated charcoal is the most common adsorbent for easily liquefiable gases. Poisonous
gases such as CH4 and CO fall in this group. Therefore, it is used in gas masks. Other gases such as O2, H2
and N2 adsorb more on metals such as Ni, Pt and Pd.
(iii) Specific area of solid : Specific area of an adsorbent is the surface area available for adsorption per gm
of adsorbent. Greater the specific area of an adsorbent, greater will be the adsorption. The specific area of
an adsorbent can be increased by making the surface rough. The pores must be large enough to allow
penetrations of gas molecules.
(iv) Pressure of gas : As physical adsorption is reversible, it is accompanied by decrease in pressure. Therefore,
it is expected that at a given temperature the extent of adsorption will increase with the increase of pressure
of the gas. The extent of adsorption is measured as x/m where m is the mass of adsorbent and x that of
adsorbate (can be explained in terms of Le-Chatelior Principle).
1
x
 kp n
m
At low pressure, x/m varies linearly with p
x 1
Or, log  log k  log p
m n
This is called Freundlich adsorption isotherm.
1
The factor can have value between 0 and 1. (probable range 0.1 to 0.5)
n
1 x
When  0,  constant, the adsorption is independent of pressure.
n m
When , 1  1, x  kp, i.e. x  P , the adsorption varies directly

n m m
with pressure.

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(v) Temperature : As adsorption is accompanied by release of heat energy, so in accordance with Le-
Chatelier’s principle, the increase of temperature should decrease the extent of adsorption. This has
indeed been found to be so. A plot of x/m vs temperature at constant pressure is called adsorption isobar.
In the case, physical adsorption x/m decreases with increase of temperature whereas in the case of
chemisorption, x/m initially increases with temperature and then decreases. The initial increase is due to
the fact that chemisorption requires activation energy.
(vi) Activation of solid : Activation of adsorbent means increasing its absorbing power. This is increased by
increasing specific area either by making the surface rough or by breaking the solid into smaller particles.
But care must be taken so that particles do not become very small then inter-particle spaces will be too
small to allow penetration of gas molecules.
Adsorbing power of an adsorbent can be increased by :
(a) By making the surface of the adsorbent rough.
(b) By subdividing the adsorbent into smaller pieces or grains.
(c) By removing gases already absorbed.
Adsorption from Solution :

Solids can adsorb solutes from solutions also. When a solution of acetic acid in water is shaken with
charcoal, a part of the acid is adsorbed by the charcoal and the concentration of the acid decreases in the
solution. The litmus solution when shaken with charcoal becomes colourless.
The following observations have been made in the case of adsorption from solution phase :
(i) The extent of adsorption decreases with the increase of temperature.
(ii) The extent of adsorption increases with the increase of surface area of the adsorbent.
(iii) The extent of adsorption depends on the concentration of the solute in solution.
(iv) The extent of adsorption depends on the nature of the adsorbent and the adsorbate.
The adsorption of a solute from solutions is very similar to the adsorption of a gas on the surface of a solid.
Therefore, Freundilich adsorption isotherm is applicable even in the adsorption from solutions. If C is the
concentration of a solution in mol L1, then extent of adsorptions (x/m) is given by
1
x
 k  C n
m

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x 1
Taking log on both sides we get : log  log k  log C
m n
Graph of log x/m vs log C is a straight line with a slope of (1/n).
Applications of Adsorption
The phenomenon of adsorption finds a numbers of applications. Some of them are:
(i) Activated charcoal is used in gas masks to remove poisonous gases such as carbon monoxide, methane
etc. Animal charcoal is used to remove colouring matter from cane-sugar juice in the manufacture of
sugar.
(ii) Ion exchange resin is used to remove hardness of water.
(iii) Several organic compounds are purified by chromatographic adsorption.
(iv) Silica gel is used for removing and controlling humidity.
(v) The catalytic effect of a number of catalysts, like spongy iron in the manufacture of ammonia and
nickel, platinum or palladium in the reduction of unsaturated hydrocarbons, is based on the principle
of adsorption.
(vi) Due to the difference in degree of adsorption of gases by charcoal, a mixture of inert gases can be
separated by adsorption on coconut charcoal at different low temperatures.
COLLOIDAL STATE Section - 2
Thomas Graham classified the soluble substances into two categories depending upon the rate of their
diffusion through animal and vegetable membranes or parchment paper. He observed that certain substances
diffuse freely through the membrane, whereas others do not diffuse. The former type of substances on
account of their crystalline nature like common salt, sugar, urea, etc., were named crystalloids while the
second type of substances were termed as colloids (Greek word, kola, meaning glue-like). All inorganic
acids, bases and salts and organic compounds such as sugar, urea, etc., were included in crystalloids while
substance such as starch, gelatine, gums, silicic acid, etc., belonged to the colloidal group.
It was soon realised that the above classification was not perfect since many crystalline substances can be
converted into colloidal form by suitable means. The colloidal form of sodium chloride, a crystalloid, can be
obtained in benzene. Thus, the above classification was discarded, i.e., the term colloid does not apply to a
particular class of substances but is a state of matter like solid, liquid and gas. Any substance can be brought
into colloidal state by suitable means.Therefore, there is no separate class of substances called colloidal
substance. It is just a state of matter into which every substance can be obtained by a suitable method.

Surface
Surface Chemistry
Chemistry Vidyamandir Classes
Types Colloidal Solutions

(a) Classification on the basis on the size of the particle of the colloids :
The nature of a substance whether crystalloid or colloid depends upon the size of the solute particles.
When the size of solute particles lies between 1 nm to 100 nm it behaves like a colloid. If size of solute
particles is greater than 100 nm, it exists as suspension and if particle size is less than 1 nm it exists as
a true solution.
S.No. Property Suspension Colloid Solution
1. Particle size >10–5cm or 103Å or 100m10–7cm to 10–5cm or 10Å <10–7cm or 10Å or 1m
to 103Å or 1m to 100m
2. Visibility Visible with naked eye. Visible with ultra microscope. Not visible with any
of the optical means.
3. Diffusion Does not diffuse Diffuse very slowly Diffuse rapidly
4. Settling Settles under gravity Does not settle but it may Does not settle
settle under centrifuge
5. Nature Heterogeneous Heterogeneous Homogeneous
6. Appearance Opaque Generally clear Clear
(b) Classification on the basis on the physical state of dispersed phase and dispersion
medium :
Colloidal solution is heterogeneous in nature and always consists of at least two phases-namely disperse
phase and dispersion medium. The component present in small proportion and consisting of particles
of colloidal dimensions is called disperse phase. The medium in which colloidal particles are dispersed
is called dispersion medium. The two phases can be solid, liquid or gas. There are eight different types
of colloidal solutions.
Disperse Dispersion Common Example
phase medium name
Solid Solid Solid sol Alloys
Solid Liquid Sol Au sol
Solid Gas Aerosol Smoke
Liquid Solid Gels Cheese
Liquid Liquid Emulsion Milk
Liquid Gas Liquid aerosol Mist, Cloud
Gas Solid Solid foam Pumice stone
Gas Liquid Foam Soap lather

Vidyamandir Classes SurfaceChemistry
Surface Chemistry
If colloidal solution has fluid like appearance it is called sol. The dispersion medium in such cases is generally
liquid. Depending upon the nature of medium, colloids are sometimes given special names. For example:
Dispersion medium Name of the sol
Water Hydrosol
Alcohol Alcosol
Benzene Benzosol
Gases Aerosol
Note : Colloidal solutions of solids in liquids are abbreviated as sols.
(c) Classification on the basis of interaction between different phases:

Depending upon the nature of interaction between phase and dispersion medium, colloids are
classified as :
(i) Lyophillic colloids : The disperse phase has great affinity for dispersion medium. In such cases the disperse
phase does not easily get precipitated and the colloids are quite stable. The solids obtained after evaporation
of the medium can be easily brought back to the colloidal state by shaking the solids with the dispersion
medium. The colloides are thus reversible, e.g., gum, gelatin, starch, proteins and certain polymers in organic
solvents. If water is used as the dispersion medium the colloid is called hydrophilic colloid.
(ii) Lyophobic colloids : The disperse phase has little affinity for the dispersion medium. These sols are
relatively less stable. They can be easily precipitated by addition of small amount of electrolyte. Once the sol
is precipitated, it cannot be easily brought back to the colloidal state. They are thus irreversible, e.g., gold
sol and sulphur sol, etc. If water is used as the dispersion medium. The sol is called hydrolyophobic colloid.
S.No. Property Lyophilic Sols Lyophobic Sols
1. Surface tension Lower than that of the medium. Same as that of the medium.
2. Viscosity Much higher than that of the medium. Same as that of the medium.
3. Reversibility Reversible Irreversible
4. Stability More stable Less stable
5. Visibility Particles can’t be detected even under Particles can be detected under
ultramicroscope. ultramicroscope.
6. Migration Particles may migrate in either direction Particles migrate either towards cathode
or do not migrate in an electric field. or anode in an electric field.
7. Action of Addition of smaller quantity of Coagulation takes place.
electrolyte electrolyte has little effect.
8. Hydration Extensive hydration takes place. No hydration takes place.

Surface Chemistry
(d) Classification on the basis of the particles of the dispersed phase
S.No. Multimolecular Colloids Macromolecular Colloids Associated Colloids

1. They are formed by the aggregation They are molecules of large size, They are formed by
of a large number of atoms or e.g., polymers like rubber, nylon, the aggregation of
molecules generally have diameters starch, proteins etc. large no. of ions in
less than 1nm, e.g., sols of gold, conc. solution e.g.,
sulphur. soap sol.
2. Their molecular masses are not They have high molecular masses. Their molecular
very high. masses are generally
high.
3. Their atoms or molecules are held They usually have lyophobic Their molecules contain
together by weak van der character. both lyophillic and
Waal’s forces. lyophobic groups.
Preparation of Colloidal Solutions

Different type of methods are used for the preparation of lyophobic and lyophilic sols:
1. Preparation of lyophilic sols : The colloidal solutions of lyophilic colloids like starch, glue, gelatine,
etc., can be readily prepared by dissolving these substances in water either in cold or on warming.
Solutions of colloidal electrolytes such as soaps and dye stuffs can also be prepared similarly.
2. Preparation of lyophobic sols : To get a substance in colloidal form either the substance in bulk is
broken down into fine particles of colloidal dimension (1Å to 103Å) or increasing the size of molecular
particles as to form larger aggregates. In some cases, a third substance is usually added to increase
the stability of the sol. These substances are called stabilizers. Thus, there are two ways by which the
lyophobic sols can be prepared.
(i) Dispersion methods : By splitting coarse aggregates of a substance into colloidal size.
(ii) Condensation methods : By aggregating very small particles (atoms, ions or molecules)
into colloidal size.
S.No. Dispersion methods Condensation methods

1. Mechanical dispersion Exchange of solvents
2. Electro-dispersion Change of physical state
3. Peptization Chemical methods :
(i) Double decomposition
(ii) Oxidation
(iii) Reduction
(iv) Hydrolysis

Surface Chemistry
Dispersion Methods
1. Mechanical dispersion : Solid material is first finely ground by usual methods. It is then mixed with
dispersion medium which gives a coarse suspension. The suspension is now introduced into the colloid mill.
The particles are ground down to colloidal size and are then dispersed in the liquid. A stabilizer is often
added to stabilize the colloidal solution. Colloidal graphite (a lubricant) and printing ink are made by this
method. Tannin is used as a stabilizer in the preparation of colloidal graphite and gum arabic in lampblack
colloidal solution (Indian ink).
Note : (i) This method is not suitable when the dispersion medium is an organic liquid as considerable charring
occurs.
(ii) This method comprises both dispersion and condensation.
2. Electrical disintegration or Bredig’s arc methods :

This process involves dispersion as well as condensation.
Colloidal solutions of metals such as gold, silver, copper, platinum
etc., can be prepared by this method. In this method electric
arc is struck between electrodes of the metal immersed in the
dispersion medium. The intense heat produced vaporises some
of the metal, which then condenses to form particles of
colloidal size.
3. Peptization : This is a process of converting a precipitate into colloidal solution by shaking it with dispersion
medium in the presence of small amount of electrolyte. The electrolyte used for this purpose is called
peptizing agent. This method is generally applied to convert fresh precipitate into colloidal solutions because
such precipitates are simply aggregates of colloidal particles held by weak forces.
Causes of peptization : During peptization, the precipitate adsorbs one of the ion of the electrolyte on
its surface. The adsorbed ion is generally common with those of precipitate. This causes the development
of positive or negative charge on the precipitates, which ultimately breaks into particles of colloidal
dimensions. For example, when freshly precipitated ferric hydroxide is shaken with aqueous solution of
ferric chloride (peptizing agent) it adsorbs Fe3+. Similarly, a precipitate of AgCl on shaking with dilute
solution of AgNO3 adsorbs Ag+ ion and get peptised to colloidal particles of the type [AgCl]Ag+. In
some cases, peptization can also be achieved by organic solvents. For example, cellulose nitrate is
peptised by ethanol. The colloidal solution of cellulose nitrate in ethanol is called ‘collodion’.
Condensation Methods
1. By exchange of solvent : If a solution of sulphur or phosphorus prepared in alcohol is poured into water,
a colloidal solution of sulphur or phosphorus is obtained due to low solubility in water. Thus, there are a
number of substances whose colloidal solutions can be prepared by taking a solution of the substance in one
solvent and pouring it into another solvent in which the substance is relatively less soluble.

Surface
Surface Chemistry
Chemistry Vidyamandir Classes
2. By change of physical state : Colloidal solutions of certain elements such as mercury and sulphur are
obtained by passing their vapour through cold water containing a stabilizer (an ammonium salt or a citrate).
3. Chemical methods : The chemical method involves chemical reactions in a medium in which the dispersed
phase is sparingly soluble. A condition of super-saturation is produced but the actual precipitation is avoided.
(a) Double decomposition : A colloidal solution of arsenic sulphide is obtained by passing hydrogen
sulphide into solution of arsenic oxide in distilled water.
As2O3 + 3H2O 
 As2S3(yellow sol) + 3H2O
Sols of silver halide are obtained by mixing dilute solutions of silver salts and alkali metal halides in
equivalent amounts.
NaCl + AgNO3 
 AgCl + NaNO3
(b) Oxidation : A colloidal solution of sulphur can be prepared by passing hydrogen sulphide into a
solution of sulphur dioxide in water or through a solution of an oxidising agent like bromine water or
nitric acid.
SO2 + 2H2S 
 2H2O + 3S (sol)
Sulphur sol can also be obtained when H2S is bubbled through an oxidising agent (bromine water or
nitric acid).
(c) Reduction : A colloidal solution of a metal like silver, gold or platinum can be prepared by the
reduction of its salt solution with a suitable reducing agent such as stannous chloride, formaldehyde,
hydrazine etc.
2AuCl3 + 3SnCl2 
 2Au (Gold Sol) + 3SnCl4
4AgCl + N2H4   4Ag (Silver sol) + N2 + 4HCl

(d) Hydrolysis : By this method hydroxide sols of less electropositive metals like Fe, Al or Sn are
prepared. A red sol of ferric hydroxide is obtained by the hydrolysis of ferric chloride with boiling
water.
FeCl3 + 3H2O 
 Fe(OH)3 (Red sol) + 3HCl
Purification of Colloidal Solutions

Colloidal solutions prepared by above methods generally contain excessive amount of electrolytes and
some other soluble impurities. The presence of traces of electrolyte is essential for the stability of the
colloidal solution but larger quantities coagulate it. It is, therefore, necessary to reduce the concentration
of these soluble impurities to a requisite minimum. The process used for reducing these impurities to a
requisite minimum is known as purification of colloidal solution. The purification of colloidal solution is
carried out by the following methods :

(i) Dialysis : It is a process of removing a dissolved substance from a

colloidal solution by means of diffusion through suitable membrane.
Since particles in true solution (ions or smaller molecules) can
pass through animal membranes (bladder) or parchment paper or
cellophane sheet but colloidal particles do not, the above can be
used for dialysis. The apparatus used for this purpose is called
dialyser. A bag of suitable membrane containing the colloidal solution
suspended in a vessel through which fresh water is continuously
flown. The molecules and ions diffuse through the membrane into
the outer colloidal solution are left behind.
(ii) Electro-dialysis : Ordinarily, the process of dialysis is quite slow.
It can be made faster by applying an electric field if the dissolved
substance in the impure colloidal solution is only electrolyte. The
process is then named electro-dialysis. The colloidal solution is placed
between two electrodes while pure water is taken in a compartment
on each side. The ions present in the colloidal solution migrate
out to the oppositely charged electrodes.
(iii) Ultra Filtration : In this method, colloidal solutions are purified by carrying out filtration through special
type of graded filter papers called ultra-filters. These filter-papers are made from ordinary filter paper by
impregnating them with colloidon solution and subsequently hardened by soaking in formaldehyde and
finally drying it. These filter papers allow the electrolytes to pass through them but not the colloidal particles.
The ultra-filtration is generally a slow process and can be hastened by the application of suction. The
colloidal particles left on the ultra-filter paper are then stirred with fresh dispersion medium (solvent) to get
a pure colloidal solution.
(iv) Ultra Centrifugation : In this method, the colloidal solution is placed in a high speed ultracentrifuge. On
centrifuging the colloidal particles settle down. The impurities remain in the dispersion medium and are
removed by decantation. The settled colloidal particles are shaken with water containing peptizing agent to
form the colloidal solution again.
Properties of Colloidal Solutions
The characteristic properties of colloidal solutions are as given below:
(i) Heterogeneous Nature : A colloidal solution is heterogeneous in nature. It consists of two phases namely
the dispersed phase and the dispersion medium.
(ii) Visibility : Colloidal particles are too small to be seen with naked eye. But they become visible as bright
sports against dark background when viewed through an ultra microscope due to scattering of light caused
by them.
(iii) Filterability : The size of solute particles is smaller than the pore size of filter paper and therefore, they can
readily pass through a filter paper. Colloidal particles, however cannot pass through ultra filters, parchment
paper or animal membrane.

Surface Chemistry
(iv) Surface tension and viscosity : The surface tension and viscosity of lyophobic sols are not very different
from those of the dispersion medium. On the other hand, lyophilic sols show higher viscosity and lower
surface tension in comparison to the dispersion medium.
(v) Colligative Properties : A colloidal solution has very small value of mole fraction of dispersed phase due
to high average molecular mass of the colloidal particles. As a result all the colligative properties, colloidal
solutions have quite low values when compared to true solutions, having same concentration. However, the
low osmotic pressure of a colloidal solution is measurable and can be used to determine the molecular
weight of colloidal particles.
(vi) Tyndall Effect : Scattering of light by the colloidal particles present
in a colloidal solution is known as Tyndall effect and is caused by
the scattering of blue part of light by the colloidal particles. If a
strong beam of light is passed through a colloidal solution placed in
a dark place, the path of the beam gets illuminated. The illuminated
path of beam is calledTyndall Cone.
The scattering is caused if the size of particles is of the order of wavelength of light. The same effect is not
observed when the light is passed through a true solution as the size of solution particles is too small to cause
any scattering.
Tyndall effect can be observed during the projection of picture in the cinema hall due to scattering of light by
dust and smoke particles present there. Tyndall effect is observed only when the following two conditions
are satisfied:
(a) The diameter of the dispersed particles is not much smaller than the wavelength of the light used.
(b) The refractive indices of the dispersed phase and the dispersion medium must differ greatly in magnitude.
This condition is satisfied by lyophobic sols. The lyophilic sols show little or no Tyndall effect as there
is very small difference in the refractive indices of the dispersed phase and the dispersion medium.
(vii) Brownian movement : The colloidal particles of a colloidal solution
when viewed through an ultra microscope show a constant zig-zag
motion. This type of motion was first observed by Robert Brown and
hence known as Brownian movement. It is caused by the uneven impacts
of the particles of the dispersion medium on the colloidal particles. As
the size of the particles increases, the probability of uneven impacts
decreases and the Brownian movement becomes slow. When the
dispersed particles acquire the dimensions of suspension, no Brownian
movement is observed.
This motion is independent of the nature of the colloid but depends on the size of the particles and the
viscosity of solution. Smaller the size and lesser the viscosity, faster is the motion. The motion becomes
intense at high temperature.

Chemistry
Importance of Brownian motion

(a) Brownian movement provides a direct demonstration of ceaseless motion of molecules as postulated
by kinetic theory.
(b) It counters the force of gravity acting on colloidal particles and hence helps in providing stability to
colloidal sols by not allowing them to settle down.
(viii) Diffusion : Colloidal particles like solute particles of a true solution diffuse from a region of higher
concentration to that of lower concentration. However, colloidal particles diffuse at a slower rate due
to their large size and high molecular mass.
(ix) Sedimentation : The colloidal particles tend to settle down very slowly under the influence of
gravity. The sedimentation or the rate of settling down can be increased by ultracentrifuge.
(x) Electrophoresis : When electric potential is applied across two platinum electrodes dipping in a
colloidal solution the colloidal particles move towards one or the other electrode. This movement of
colloidal particles under an applied electric field is called electrophoresis. Positively charged particles
move towards the cathode while negatively charged particles move towards anode.
The particles of the colloidal solution carry same type of charge, either positive or negative. The
dispersion medium carries an equal and opposite charge. The colloidal solutions as a whole are
electrically neutral. Due to similar nature of the charge carried by the particles, they repel each other
and do not combine to form aggregates. This makes a colloidal solution stable and the colloidal
particles do not settle down.
Some of the common positively and negatively charged colloids are given below:
Positively charged : Fe(OH)3 sol, Cr(OH)3 sol, Al(OH)3 sol, Ca(OH)2 sol, dyes like methylene
blue and haemoglobin.
Negatively charged : As2S3 sol, Sb2S3 sol, CdS sol, Au sol, Cu sol, Ag sol and acid dyes like
congo red.
When electrophoresis i.e., movement of particles is prevented by some suitable means, it is observed
that the dispersion medium begins to move in an electric field. This phenomenon is termed electro-
osmosis.
Coagulation of Colloidal Solutions

The stability of the lyophobic sols is due to the presence of charge on colloidal particles. If, the
charge is removed, the particles will come nearer to each other and thus, aggregate or flocculate
and settle down under the force of gravity. The flocculation and settling down of the colloidal
particles is called coagulation or precipitation of the sol.

The coagulation of the lyophobic sols can be carried out by following methods:
(i) By mutual precipitation : When two oppositely charged sol such as Cr(OH)3 and Sb2S3 are
mixed in equimolar proportion, they neutralise each other and get coagulated.
(ii) By electrophoresis : During electrophoresis of a sol, the colloidal particles move towards oppositely
charged electrode. The particles touch the electrode, lose charge and get coagulated.
(iii) By boiling : When a sol is boiled, the adsorbed layer is disturbed due to increased collisions with the
molecules of dispersion medium. This reduces the charge on the particles and ultimately they settle down to
form a precipitate.
(iv) By persistent dialysis : On prolonged dialysis, the traces of the electrolyte present in the sol are removed
almost completely and the colloids become unstable.
(v) By addition of electrolytes : When excess of an electrolyte is added. The colloidal particles are
precipitated. The reason is that colloidal particles taken up ions carrying charged opposite to that present on
themselves. This causes neutralisation leading to their coagulation. The ion responsible for neutralisation of
charge on the particles is called the flocculating ion.
It has been observed that, generally, the greater the valency of the flocculating ion added, the greater is its
power to cause precipitation. This is known as Hardy-Schulze Rule.
(a) The ions carrying charge opposite to that of sol particles are effective in carrying the coagulation of the
sol.
(b) Coagulation power of an electrolyte is directly proportional to the fourth power of the valency of the
ions causing coagulation.
In the coagulation of a negative sol, the flocculating power of Na+, Ba2+ and Al3+ ions is in the order of :
Al3+ > Ba2+ > Na+
Similarly, in the coagulation of a positive sol, the flocculation power of Cl–, SO 24 , PO 34 , [Fe(CN)6]4– is in
the order of
[Fe(CN)6]4– > PO 34  SO 24 > Cl–
The minimum concentration of an electrolyte in milli-mole per litre required to cause precipitation of a sol in
2 hours is called flocculation value. The smaller the flocculating value, the higher will be the coagulating
power of an ion.
(vi) Protection of colloids : Lyophilic sols are more stable than lyophobic sols. This is due to the fact that
lyophilic colloids are extensively solvated, i.e., colloidal particles are covered by a sheath of the liquid in
which they are dispersed.
Lyophilic colloids have a unique property of protecting lyophobic colloids. When a lyophilic sol is added to
the lyophobic sol, the lyophilic particles form a layer around lyophobic particles and, thus, protect the latter
from electrolytes. Lyophilic colloids used for this purpose are called protective colloids.
The lyophilic colloids differ in their protective power. The protective power is measured in terms of Gold
Number and is defined as the number of milligrams of a lyophilic colloid that will just prevent the precipitation
of 10 ml of a gold sol on the addition of 1 ml of 10% sodium chloride solution.

Vidyamandir
Vidyamandir Classes
Classes Surface Chemistry
Surface Chemistry
S.No. Protective Colloid Gold number

1. Gelatin 0.005 – 0.01
2. Heamolglobin 0.03
3. Gum arabic 0.15
4. Egg albumin 0.08 – 0.10
5. Potato starch 25
6. Sodium oleate 0.4
7. Gum tragacanth 2
8. Starch 25 – 50
Higher is the gold number, lower will be the protective power.
GELS AND EMULSIONS Section - 3
Certain colloidal systems have the property of setting into a semi-solid, jelly-like form when they are present
at high concentration. Such a process is called gelatine and the colloidal systems with jelly-like form are
called gels. Gel, usually, consists of two components; one is solid, such as gelatine, silicic acid, sodium
oleate, etc., and the other is a liquid such as water.
Gels possess rigid structure formed due to interlocking of particles of disperse phase and create a loose
framework. The particles of dispersion medium are trapped into the loose framework. The degree of
rigidity varies from substance to substance. When gels are allowed to stand for long time, they give out
small quantity of trapped liquid, which accumulates on the surface. This is called syneresis or weeping of
the gel.
Emulsions
Emulsions are colloidal solutions in which both the dispersion phase and the dispersion medium are liquids.
It can be defined as the dispersion of finely divided droplets in another liquid.
Types of Emulsions
There are two types of emulsions.
1. Oil in water type emulsions (O/W type) : In this type of emulsion, oil is the dispersed phase and
water is the dispersion medium. For example milk, vanishing cream etc.

Vidyamandir Classes
2. Water in oil type emulsions (W/O type) : In this type of emulsions water is the dispersed phase and
oil is the dispersions medium. For example butter, cod liver oil, cold cream etc.
Emulsions of oil and water are unstable and sometimes they separate into two layers on standing. For the
stabilization of an emulsion, a third component called emulsifying agent is usually added. The emulsifying
agents form an interfacial film between suspended particles and the medium. The principal agents for O/W
emulsions are proteins, gums, natural and synthetic soaps, etc. For W/O emulsions, the principal emulsifying
agents are heavy metal salts of fatty acids, long chain alcohols, lamp black, etc.
Surfactants
Surfactants are substances which get preferentially adsorbed at the air-water, oil-water and solid-water
interfaces, forming an oriented monolayer where in the hydrophilic groups point towards the aqueous phase
and hydrocarbon chains point towards the air or the oil phase. The surfactants can be cationic, anionic on
non-ionogenic.
Sodium salts of higher fatty acids such as sodium palmitate, C15H31COONa, sodium stearate,
C17H35COONa and sodium oleate, C17H33COONa are anionic surfactants. The salts of sulphonic acids
of high molar mass and general formula (CnH2n+1 M, alkyl sulphonates) or (CnH2n+1 C6H4SO3 M, alkyl
and aryl sulphonates) where M+ is Na+, K+ NH4+, are other anionic surfactants.
Cationic surfactants are those which dissociate in water to yield positively charged ions. Examples are :
  
Octadecyl ammonium chloride  C18H 37 N H3Cl 
 
Cetyl trimethyl ammonium chloride [C16H33(CH3)3N+Cl]
Cetyl pyridinium chloride,
Non-ionogenic surfactants are those whose molecules cannot undergo dissociation. When an alcohol having
a high molar mass reacts with several molecules of ethylene oxide, a non-ionogenic surfactant is produced.
The hydrophilic nature of hydroxyethylated surfactants can be controlled during their synthesis by varying
not only the number of carbon atoms in a hydrophobic chain but also the number of hydroxy ethylene
groups. These surfactants are soluble even in hard water. Hydrophobic surfaces become hydrophilic when
non-ionogenic surfactants are adsorbed from aqueous solutions.

Vidyamandir Classes Surface
Surface Chemistry
Chemistry
Micelles
When the surfactant molecules in the water-air interface become
so packed in the monolayer that no more molecules can be
accommodated with ease, they aggregate in the bulk of the solution
leading to the formation of associated colloids also called micelles.
The formation of micelles takes place only above a particular tem
perature called Kraft temperature (Tk) and above a particular con
centration called critical micelle concentration (CMC). On dillution,
these colloids revert bakc to individual ions. Surface active agents
such as soaps and synthetic detergents belong to this
class. For soaps, the CMC is 10–4 to 10–3 mol L–1.
Mechanism of micelle formation

Let us take the example of soap solutions. Soap is sodium or potassium salt of a higher fatty acid and may
be represented as RCOO–Na+. (e.g.: sodium stearate CH3(CH2)16COO–Na+. When dissolved in water, it
dissociates into RCOO– and Na+ ions. The RCOO– ions, however, consist of two parts - a long hydrocar
bon chain R which is hydrophobic and a polar group COO–which is hydrophilic.
The RCOO– ions are, therefore, present on the surface with their COO– groups in water and the hydrocar
bon chains R staying way from it and remain at the surface. But at critical micelle concentration, the anions
are pulled into the bulk of the solution and aggregate to form a spherical shape with their hydrocarbon chains
pointing towards the centre of the sphere with COO– part remaining outward on the surface of the sphere.
An aggregate thus formed is known as ‘ionic micelle’.

(a) Arrangement of stearate ions on the surface of water at low concentrations of soap.
(b) Arrangement of stearate ions inside the bulk of water (ionic micelle) at critical micelle concentrations
of soap.
Cleansing action of soaps

The cleansing action of soap is due to the fact that soap molecules form micelle around the oil droplet in such
a way that hydrophobic part of the stearate ions is in the oil droplet and hydrophilic part projects out of the
grease droplet like the bristles. Since the polar groups can interact with water, the oil droplet surrounded by
stearate ions is now pulled in water and removed from the dirty surface. Thus soap helps in emulsification
and washing away of oils and fats. The negativity charged sheath around the globules prevents them from
coming together and forming aggregates.
(a) Grease on cloth

(b) Stearate ions arranging around the grease droplet and
(c) Grease droplet surrounded by stearate ions (micelle formed)
1. Why does physisorption decrease with the increase of temperature ?

2. Give reason why a finely divided substance is more effective as an adsorbent.
3. Why is adsorption always exothermic ?
4. Discuss the effect of pressure and temperature on the adsorption of gases on solids.
5. Explain what is observed :
(i) When a beam of light is passed through a colloidal solution.
(ii) an electrolyst, NaCl is added to hydrated ferric oxide solution.
(iii) electric current is passed through a colloidal solution ?
6. Give four uses of emulsions.
7. Comment on the statement that “colloid is not a substance but a state of substance”.
8. What is an adsorption isotherm ? Describe Freundlich adsorption isotherm.
9. What is demulsification ? Name two demulsifiers.

Surface
CATALYSIS Section - 4
Catalysis is the phenomenon by which rate of a chemical reaction is changed due to the participation
of a substance called a catalyst. Unlike other reagents that participate in the chemical reaction, a
catalyst is not consumed by the reaction itself. A catalyst may participate in multiple chemical transfor-
mations.
Characteristics of Catalytic Reactions
(i) The catalyst remains unchanged in amount and chemical composition at the end of the
reaction ; it may, however, undergo considerable change in physical form.
(ii) The reaction of a catalyst is specific to a large extent. Thus, the decomposition of KClO3 is
catalyzed by MnO 2 but not by platinum.
(iii) The catalyst does not initiate a reaction ; it merely accelerates the reaction that is already
occurring.
(iv) A catalyst does not alter the final state of equilibrium in a reversible reaction.
A certain minimum energy must be possessed by the reactants, so that they may react and produce the
products. This is called the activation energy (Ea ) for the reaction. A catalyst is said to lower the
activation energy and thus increase the rate of the reaction. Thus, a catalyst increase the rate of a reaction
by providing a pathway whose activation energy is lower than the activation energy of the uncatalyzed
reaction.
Promoters are substance that increase the catalytic activity, even though they are not catalysts by
themselves. For example, in Haber’s process for manufacture of ammonia, molybdenum acts as a
promoter for iron which is used as catalyst.
Fe(s)
N 2 (g) + 3H 2 (g)  2 NH3 (g)
Mo(s)
Type of Catalysis
(i) Positive Catalysis : The catalyst increases the rate of reaction.
VO
Example : 2 5
2SO2 + O2  2SO3 (Contact process)
Ni
C2 H 4 + H 2 C2 H 6 (Ethane)


(iv) Heterogeneous Catalysis : A catalytic process in which the catalyst and the reactants are in
different phases is called heterogeneous catalysis. This process is also called contact or surface
catalysis.
Example :
Pt
(i) 2 H 2O 2 ()  2 H 2O() + O 2 (g)
(ii) Pt .asbestos
2SO2 (g) + O 2 (g)  2SO3 (g)
(iii) Fe + MO
N 2 (g) + 3H 2 (g) 
 2 NH3 (g)
ZnO + Cr O
2 3  CH OH()
(iv) CO(g) + 2 H 2 (g)  3
General Principle of Catalysis

It is not possible to give a uniform explanation of the mechanism of the phenomenon of catalysis as catalytic
reaction are of varied nature. However, two broad theories of catalytic action have been proposed. First
theory, known as intermediate compound formation theory explains successfully the homogeneous catalysis.
The second theory termed as adsorption theory explains the heterogeneous catalysis.
(i) Intermediate Compound formation Theory :
According to this theory, the catalyst first forms an intermediate compound with one of the reactants.
The intermediate compound is formed with less energy consumption than needed for the actual reaction.
The intermediate compound being unstable combines with other reactant to form the desired product
and the catalyst is regenerated.
C
Consider, a reaction of the type A+ B  AB which occurs in presence of a catalyst C, may take
place as
A + C  AC
(Catalyst) Intermediate (slow reaction)
compound
AC + B  AB + C (fast reaction)
Product Catalyst
Many catalytic reactions can be explained on the basis of this theory. Consider the catalytic oxidation
of SO 2 to SO3 in the lead-chamber process. This occurs as follows,

2 NO + O 2  2 NO 2
Catalyst Intermediate
product
NO 2 + SO 2  SO3 + NO
Product Catalyst
(ii) Adsorption Theory

This theory explains the mechanism of heterogeneous catalysis. The old point of view was that
when the catalyst is in solid state and the reactions are in gaseous state or in solutions, the
molecules of the reactants are adsorbed on the surface of the catalyst. The increased concentra
tion of the reactants on the surface influences the rate of reactions. Adsorption being an exother
mic process, the heat of adsorption is taken up by the surface of the catalyst, which is utilised in
enhancing the chemical activity of the reacting molecules. The view does not explain the speci
ficity of a catalyst.
The modern adsorption theory is the combination of intermediate compound formation theory
and the old adsorption theory. The catalytic activity is localised on the surface of the catalyst.
The mechanism involves five steps :
(a) Diffusion of reactants of the surface of the catalyst.
(b) Some form of association between the catalyst surface and the reactants occurs. This is
as sumed to be adsorption.
(c) Occurrence of chemical reaction on the catalyst surface.
(d) Desorption of reaction products away from the catalyst surface.
(e) Diffusion of reaction products away from the catalyst surface.

Example - 1 What would be the total surface area of a cube of edge length 1 cm. Also what would be the
total surface area of the same material if it were subdivided into colloidal size bubes, each having an edge
length of 107 cm.
SOLUTION :
Surface area of cube of edge length 1 cm 6  1cm2
Surface area of cube of edge length 1107 cm  6 1014 cm 2

Let n cubes of 6  1014 cm 2 are present on breaking the cube of 6 cm 2
 n  volume of cube of edge length 107 cm

= volume of cube of edge length 1 cm.
4 4
n    [107 ]3     (1)3
3 3
 n  1021
 New total surface area  1021  6  10 14  6  107
Example - 2 Calculate the surface area of a catalyst that adsorbs 103 cm3 of nitrogen reduced to STP
per gram in order to form the monolayer. The effective area occupied by N 2 molecule on the surface is
1.62  10 15 cm 2 .
SOLUTION :
103  6.023  1023

No. of N 2 molecules   2.69 1022
22400
Total area covered by N 2 = 2.69  105 cm 2 = 4358 m 2
Example - 3
1 g of activated charcoal has a surface area 103 m2 . If complete monolayer coverage is
assumed and effective surface are of NH 3 molecule is 0.129 nm2 , how much NH 3 in cm3 at STP could be
adsorbed on 25g of charcoal.
SOLUTION :
Total surface area available for adsorption  25 103 m 2
Effective surface area of one NH3 molecule  0.129  1018 m2
25  103
 Number of molecule of NH3 adsorbed   1.94  1023
18
0.129  10
1.94  1023
 Mole of NH3   0.323
6  1023
Volume of NH 3  0.323  22400  7235 cm 3
Example - 4
One gram of activated charcoal has a surface area of 103 m2 . If complete coverage of
monolayer is assumed, how much NH3 in cm3 at STP would be adsorbed on the surface of 25g of the
charcoal. Given diameter of NH 3 molecule = 0.3 nm.
SOLUTION :
Total surface area to be covered  25  103 m

2r for NH3  0.3  109 m
 0.3  109 102 cm  0.3  107 cm

 r  1.5  108 cm
 Surface area of 1 molecule  r 2

 3.14  (1.5  10 8 ) 2  7.065  1016 cm2
Number of NH3 molecules adsorbed
25  103
  3.539  1023
20
7.065  10
3.539  1023
 Mole of NH3 adsorbed   0.5875
6.023 1023
Now using PV = nRT
0.5875  0.0821 273
V
1
 V  13.168litre
Example - 5 20% surface sites have adsorbed N 2 . On heating N 2 gas is evolved from sites and weree
collected at 0.001 atm 298 K in a container of volume 2.46 cm3. Density of surface sites is 6.023  1014 cm 2
and surface area is 1000 cm 2 . Find out the number of surface sites occupied per molecule of N 2 .
SOLUTION :
For adsorbed N 2 on surface sites
PN 2  0.001 atm, V  2.46 cm3  2.46  103 litre,

T = 298 K
PV 0.001 2.46 103

 nN 2    1.0  107
RT 0.0821 298
 Molecules of adsorbed
N 2  1.0  107  6.0  1023  6.023  1016
Total surface sites available = No. of sites per cm2  area

 6.023  1014  1000  6.023  1017
Surface sites on which N 2 is adsorbed
 20%  Available sites
20
  6.023  1017  12.046  1016
100
 Number of sites adsorbed per molecule of
12.046  1016
N2  2
6.023  1016
Example - 6
1g of charcoal adsorbs 100 mL of 0.5 M CH 3COOH to form a monolayer and there by the
molarity of CH 3COOH reduces to 0.49. Calculate the surface area of charcoal adsorbed by each molecule of
acetic acid. Surface area of charcoal  3.01 102 m2 / g .
SOLUTION :
Millimole of acetic acid taken  100  0.5  50
Millimole of acetic acid left  100  0.49  49
Millimole of acetic acid adsorbed  50  49  1
Molecules of acetic acid adsorbed  1 103  6.023  1023  6.023 1020
Total area of 1g charcoal covered by these molecules  3.01102 m2
3.01 102
 Area covered by 1 molecule  ( unilayer adsorption )
6.023  1020
 5  1019 m 2
Example - 7 It is observed that five hours are needed to dissolved a 1cm cube of NaCl in large amount of
water. Calculate the time required for dissolution, if the cube is ground to a powder containing 1016 equal size
spheres. Assume that the rate of dissolution is directly proportional to initial area of contact between NaCl
and water.
SOLUTION :
Volume of cm cube  1 cm3
Volume of powder in spherical shape
4 4 3
 1016  r 3 (Volume of one sphere  r )
3 3
4 3
 r  1016  1 cm3 and r  2.88 106 cm
3
 Total surface area  r 2

22
  (2.88  106 ) 2 1016  2.61 105
7
Initial surface area of cube 6  12  6 cm 2
Rate of dissolution  surface area
ds
or  surface area
dt
1
Thus, time required for dissolution of same amount is t 
surface area
1
 5
6
1
t
2.61 105
 t  1.15  104 hr  1.15 104  3600sec  0.41sec
Example - 8
H 2 gas was adsorbed on 1g powdered copper surface forming monolayer of molecules. On
desorption total H 2 colleted measured 1.36 cm3 at STP. Assuming volume of 1 molecule of H 2
4.742  1023 cm3 , calculate specific area of copper powder..

SOLUTION :
Number of molecules of H 2 in 1.36 cm3
6.023  1023  1.36

  3.66  1019
22400
 Volume of H 2 molecule  4.742  1023
4 3
 r  4.742  1023
3
 r  2.246  108 cm
 Area of cross-section of H 2 molecule
 r 2  3.14  (2.246  10 8 ) 2  1.583  1015 cm2

Area of molecules of adsorbed
 (3.66  1019 ) 1.583 10 15 cm 2
Area of adsorption of Cu powder = specific area of Cu powder, i.e. area/g.
 Specific area of adsorption of Cu
 1.583  1015  3.66  1019  5.79  104 cm2
Example - 9 A solution of palmitic acid ( M  256 g mol 1 ) in benzene contains 4.24 g of acid per litre.
This solution on pouring on water surface forms a monomolecular layer of palmitic acid as benzene gets
evaporated. If 500 cm 2 area of water surface is to be covered by a monolayer, what volume of solution in
2
benzene is needed. Area covered by one molecule of palmitic acid is 0.21 nm .
SOLUTION :
Let V litre of solution be needed to do so
Mass of palmitic acid  V  d  V  4.24 g
V  4.24
Mole of plamitic acid 
256
4.24  V  6.023 1023

 Number of molecules of palmitic acid 
256
 Total area covered

4.24  V  6.023 1023
  0.211018 104 cm2
256
4.24  V 6.023 1023  0.211018 104

or 500 
256
 V  2.386  105 litre
Example - 10 x
A graph plotted between log10 vs. log10 P ( P is pressure of gas in atm) shows a straight
m
line with slope equal to 1 and intercept equal to 0.4771. The extent of adsorption (x/m) of gas at the pressure
2 atm is :
SOLUTION :
x 1
 log  log K  log P
m n
 log K = 0.4711 or K = 3
x 1
 log  log 3   0 ( P = 1)
m n
1
Slope  1
n
 n 1
X
Now  KP1/ n  3  (2)1  6
m
SOLUTIONS TO IN-CHAPTER EXERCISE-A
1. As we know that H < 0 for adsorption. So by Le-chatilier principle physisorption should decrease with
increase in temperature.
2. With each division, surface area available for adsorption increases. E.g. divide a cube into 8 small cubes and
compare old and new surface area.
3. New attraction forces come into picture in case of adsorption. Which leads to lowering in potential energy, so
energy is released.
4. High pressure, low temperature is farourable for adsorption.
5. (i) Tyndall effect.
(ii) Collidal solution of FeCl3 comes into picture.
(iii) When electric current is passed, coagulation occurs and colloidal particles settle down.
6. (i) Pharmaceutical
(ii) Making of cosmetic products such as creams, oils.
(iii) Paints
(iv) Making waxes.
7. Refer theory
8. Refer page No. 33
9. Process which is used to separate emulsions is called demulsification
Examples are Ethylene oxide, Glycerol
28 Solutions INE Self Study Course for IITJEE with Online Support
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes Basic Principle of Extraction
Basic Principle of Extraction
NEEDS FOR EXRACTION OF METALS Section - 1
We all use metals in our day to day life sometimes directly and sometimes indirectly. For example, Iron is
used making electromagnets, chains, etc. Steel is used in making machinery parts, household utensils. Silver
and gold are used in making jewellery. We can find numerous examples where we use metals. Since metals
do not occur in pure form in earth’s crusts, we need to extract metals from their ores or minerals.
Occurrence of Metals :
Metals occur in various forms. Some in native form, some in carbonate form and some in oxide form. Those
metals that are least reactive and have very little affinity for oxygen, moisture and other chemical reagents
occure in free or metallic or native state.
 Natural substances in which metals or their compounds occur in earth are called minerals.
 Those minerals form which metals can be extracted conveniently and proditably are known as ores.
llustration :
A certain metal M occurs in three compounds namely A, B, C. A has 15% of M, B has 66% of M and C has
71% of M. If we extract M from A, it costs Rs 35 per kg, if we extract it from B, it costs Rs 45 per kg and
if we extract from C, it costs Rs 1110 per kg.
Now both A, B, C are minerals as they contain M, but all cannot be called ores. Extraction of M from
mineral A would cost less but would result in a very less amount. Similarly, extraction from C would result in
large amount but it will also cost a large sum. Hence, B is the appropriate mineral from which M should be
extracted as it would give sufficient amount and would not even cost much. In that case, B is the ore of M.
for example : Bauxite (Al2O3 .2 H 2O) and Clay (Al2O3 .2SiO 2 .2 H 2O) both are minerals of Aluminium.
But still Bauxite is appropriate ore but not Clay since we can extract Aluminium more profitably and quan-
titatively from Bauxite.
Commercially Important Ores :
1. Native Ores :
These ores contain metals in the free state. They exist in free state because they are very unreactive.
Some of important metals are :
2. Sulphurised and Arsenical ores :
These ores consists of sulphides and arsenides in simple and complex forms of metals.

Basic Principle of Extraction Vidyamandir Classes
Metal Name of the ore

Pb Galena PbS
Zn Zinc blende ZnS
Hg Cinnabar HgS
Ag Argentite or Silver glance Ag2S
Fe Iron pyrites FeS2
Cu Copper pyrites CuFeS2
Chalcocite or Copper glance Cu2S
3. Oxidised Ores
In these ores, metals are present as their oxides or oxy-salt as carbonates, nitrates, sulphates, phosphates,
silicates, etc.
Oxides : Haematite Fe 2O 3
Magnetite Fe3O4
Bauxite Al2O3.2H2O
Corundum Al2O3
Chromite FeO.Cr2O3
Tinstone (Cassiterite) SnO2
Pyrolusite MnO2
Carbonates : Magnesite MgCO3

Lime stone CaCO3
Dolomite CaCO3.MgCO3
Calamine ZnCO3
Malachite CuCO3.Cu(OH)2
Azurite Cu(OH)2.2CuCo3
Cerussite PbCO3
Siderite FeCO3
Nitrates : Chile saltpetre NaNO 3

Salt petre KNO 3

Sulphates : Epsom salt MgSO4.7H2O

Gypsum CaSO4.2H2O
Glauber’salt Na2SO4.10H2O
Phosphates and Sillicates :

Fluor-apatite 3Ca3(PO4)2.CaF2
Felspar KAlSi3O8
4. Halide Ores :
Metallic halides are very few in nature. Chlorides are most common ores.
Common salt NaCl
Horn silver AgCl
Carnallite KCl.MgCl2.6H2O
Fluorspar CaF2
Cryolite Na3AlF6
Note : You Don’t need to cram all these compounds in one go. As you will read the chapter these com-
pounds will slowly set in your mind.

METALLURGY Section - 2
The complete process of obtaining a pure metal from one of its ores is known metallurgy. The method to
extract a metal is generally not universal, as it depends upon a number of factors such as its chemical nature
and reactivity, nature of ore, nature of impurities and local conditions, etc. But still in general, metallurgy is
divided into following three steps.
I. Concentration of the Ore
II. Obtaining Crude Metal from Concentrated Ore
III. Refining of Crude Metal
Different methods are available for each of these stages. Choice of any method depends upon the nature
of metal and type of impurity present in the ore.
I. Concentration of the Ore :
Concentration of an deals with removal of unwanted impurities. Ores usually contain soil, sand, stones and
other useless silicates. These unwanted impurities are named gangue or matrix. For concentration, metal is
crushed and powdered and then it undergoes concentration. Concentration of ore involves physical as
well as chemical methods. It is also known as Dressing or Benefication of the ore.
(i) Hydraulic Washing (Gravity Separation)
Principle :
It is based on the difference in specific gravity of ore and gangue particles.
Working :
Powdered ore is agitated with running water which carries lighter particles like sand, clay away with
it.

Type of Ore :
The oxides and carbonates type of ores are suitable for this method. For example : Tin’s ore Cassiterite
(SnO 2 ), Iron’s ore Haematite (Fe 2O3 ).
(ii) Magnetic Separation

Principle :
It is based on the magnetic and non-magnetic properties of ore and gangue.
Working :
A magnetic separator consists of a belt which moves on two rollers, one of the roller being a strong
magnet. Now, the powdered ore is dropped on the belt near the non-magnetic roller and as the ore
reaches the magnetic roller the magnetic particles get attracted and fall nearer to the roller while the
non-magnetic particles fall away from the rollers.
Type of Ore :
Separating Wolframite (Tungsten) ore from Cassiterite (Tin) ore, separating transition metal ores such
as Magnetite (Fe3O4 ), Pyrolusite (MnO2 ) and Chromite (FeO, Cr2O3 ) from unwanted gangue.
(iii) Froth Floatation
Principle :
Mineral particles are wetted by oils and the gangue particles are welled by water.
Working :
Collectors, frothing agents and froth stabilisers are added to the ore which mixed water. Collectors
enhance the non-wettability of mineral particles and froth stabilizers stabilize froth. Mineral particles
become wet by oils while gangue particles by water. Liquid mixture is agitated and air blown. Froth
is formed which carries off with it mineral particles. Light froth floats at the surface which is taken off
and from this froth mineral is recovered.

Frothing agents : Pine Oil

Collectors : Fatty acids, Sodium Ethyl Xanthate
Froth Stabilizers : Cresols and Aniline
Depressants :
These are those chemicals that are used to prevent certain type of particles from forming the froth with
the bubbles. For example : NaCN (sodium cyanide) acts as a depressant in preveting ZnS from
forming the froth as it forms a layer of Na 2 Zn(CN)4 on surface of ZnS in concentration of zine
blende (ZnS). This is also known as selective frothing.
Type of Ore :
Sulphide ores eg: Galena (Pbs), Zinc blenda (ZnS), Cinnabar (HgS).
(iv) Chemical Separation (Leaching)
Principle :
It is based on the differences in the chemical properties of the ore and the gangue.
Working :
Ore is made soluble in a solvent and is then separated from the gangue. The solvent’s choice depends
upon the ore and gangue’s chemical properties.
Example :
1. In Bayer’s process, the impurities of iron and silicon are removed from the bauxite ore.
NaOH is added to the ore and as Al is amphoteric it dissolves forming sodium aluminate.
SiO2 being acidicoxide also dissolves as silicate ions. The insoluble iron impurities are re
moved by filtering. Next, CO 2 is bubbled through the solution lowering the pH. This enables
the precipitation of Al(OH)3 (sili-cate ions remain dissolved). The Al(OH)3 precipitated is
calcined (heated strongly) to give concentrated Al2O3 .

 Na[Al(OH) 4 ] + SiO44 
Al2O3 + SiO2 + NaOH 
Na[Al(OH)4 ] + CO2 
 Na 2CO3 + Al(OH)3 ()

Al(OH)3(s)  Al2O3 + H 2 O()
2. Cyanide’s Process
Another example is the cyanide’s process for extraction of Au (from native form) and Ag (from
Ag 2S ore). The ore containing impurities is curshed and then treated with 0.1 – 0.2% soluton of
NaCN or KCN and aerated forming a soluble complex from complex which the metal is extracted
by the addition of Zn power in the solution.
For Au : 4 Au + 8 NaCN + 2 H 2O + O 2 
 4 Na[Au(CN)2 + 4 NaOH
2 Na[Au(CN)2 ] + Zn 
 Na 2 [Zn(CN)4 ] + 2 Au()
For Ag : Ag 2S + 4 NaCN  2 Na[Ag(CN)2 ] + Na 2S
2 Na[Ag(CN)2 ] + Zn 
 Na 2 [Zn(CN)4 ] + 2 Ag()
II. Obtaining Crude Metal :

This step involves reduction of concentrated ore. The concentrated ore i.e. Metal oxides, Metal sulphides,
Metal carbonates etc. are converted to metal in this step. M n+   M reduction occurs in this step.
Metal cabonates and Metal sulphides are difficult to reduce than metal oxides therefore they are first converted
to their oxides and then metal oxides is reduced to metal.
Conversion into Oxide Forms
Metallic ores are converted to metallic oxides by the two processes.
1. Calcination :
It involves heating of the ore below its fusion temperature in absence of air. It can remove moisture
from hydrated oxides or carbondioxide from carbonates. It is suitable for carbonate ores.

CuCO3 .Cu(OH)2 
 2CuO + CO2 + H 2O

ZnCO3 
 ZnO + CO2
Calcination makes the ore porous. The step is generally performed in a reverberatory furnace.

2. Roasting :
It involves heating of the ore strongly in the presence of excess of air below its fusion temperature. It
is suitable for sulphide ores.

2 ZnS(s) + 3O2 (g) 
 2 ZnO(s) + 2SO2 (g)
Sometimes, a part of sulphide may act as a reducing agent as in case of extraction of lead.
PbO formed by roasting is reduced to lead by PbS.
2 PbS + 3O2 
 2 PbO+ 2SO2
PbS + 2 PbO 
 3Pb + SO2
Exception :
O
2  Cu S + Fe O + 3SO
2CuFeS2  2 2 3 2
1400° C
Note : Oxide ores are suitable for reduction. So, if we obtain ore in oxide form just after concentration as in case
of aluminium, then this ore is not required to undergo calcination and roasting as it already exists in oxide
form.
Reduction to Crude Metal

When the oxide form is obtained, then the metal has to be reduced. The choice of the reducing agent is
decided by the factors of energetics and economics.
Three main categories of reduction processes are :
(A) Chemical Reduction (B) Hydrometallurgy (C) Electrolytic Reduction
Now, we will discuss few important points of each category.
(A) Chemical Reduction Process

Carbon, Aluminium, Hydrogen and some other metals are used as reducing agents. These metals replace
less electropositive metals from their oxides.
(i) Reduction by carbon :
Carbon can be used to reduce a number of oxides and other compounds, and because of the low cost
and avilability of coke this methods is widely used. The disadvantages are that a high temperature is
needed, which is expensive and necessitates the use of a blast furance. Also, many metals combine
with caron, forming carbides, some examples are :
blast 1200C
Fe2 O3  C  Fe ; ZnO  C 
 Zn
furnance
electric electric
Ca 3 (PO4 )2  C 
P ; MgO  C  Mg
arc furnance
PbO  C 
 Pb

(ii) Reduction by another metal :

If the temperature needed for carbon to reduce an oxide is too high for economic or practical purposes,
the reduction can be done by another highly electropositive metal such as Al, which liberates a large
amount of energy on oxidation to Al2O3. This is the bases of the thermite process : -
 9Mn  4Al2O3 ;
3Mn 3O4  8Al  B2O3  2Al 
 2B  Al2O3
Cr2O3  2Al 
 2Cr  Al2O3
Magnesium being more electropositive metal as compared to Al is used to reduce halides.
1000C
TiCl4  2Mg 
 Ti  2MgCl2
(iii) Reduction of oxides with hydrogen

This method is not widely used because many metals react with hydrogen at elevated temperatures,
forming hydrides.
Co3O4  4H 2 
 3Co  4H2O
2NH4 [MoO4 ]  7H 2 
 2Mo  8H2O  2NH 3
(iv) Self Reduction Process
The sulphide ore of less electropositive metals like lead, mercury, copper are heated in air as to
convert part of the ore into oxide or sulphate which then reacts with the remaining sulphide ore to
give the metal and SO2 gas.
No external reducing agent is used in this process.
Lead : 2 PbS  3O 2 
 2 PbO  2SO 2 (Extraction of lead from Galena, PbS)
2 PbO  PbS 
 3Pb  SO 2
Copper : 2 Cu 2S  3O 2 
 Cu 2O  2SO 2 (Extraction of copper from copper glance, Cu2S)
Cu 2S  2 Cu 2O 
 6 Cu  SO2
Mercury : 2HgS  3O 2 
 2 HgO  2SO 2 (Extraction of mercury from cinnabar, HgS)
2 HgO  HgS 
 3 Hg  SO 2
Another name for self reduction process is auto reduction process or air reduction process.
(B) Hydrometallurgy
This process is based on the principle that more electropositive metals can displace less electropositive
metals from their salt solution. The ore is treated with such chemical reagents which convert it into soluble
compound. By addition of more electropositive metals to the filtrate, the metal present in the ore can be
precipitated.

Illustration :
Malachite ore is first calcined and the oxide obtained is dissolved in H2SO4. To the solution of CuSO4,
scrap iron is added which precipitates copper.
CuCO3 .Cu(OH) 2 
 2CuO  CO2  H 2O
CuO  H 2SO4 
 CuSO4  H 2O
(soluble)
CuSO4  Fe   FeSO4  Cu 
(soluble)
Similarly, silver can be obtained by cyanide process.
(C) Electrolytic Reduction
Oxide of highly electropositive metals like Na, K etc cannot be reduced with carbon at moderate temperature.
So, for their reduction, a very high temperature is required, at which they may combine with carbon to form
carbide. Thus, they are obtained by electrolysis of their oxides in fused or molten state.
Illustration :
Sodium is obtained by the electrolysis of fused mixture of NaCl and CaCl2 (Down’s Process) or by the
electrolysis of fused NaOH (Castner’s process).
 Na+ + Cl
NaCl (molten) 
Cathode : Na+ + le 
 Na
Anode : 2Cl 
 Cl2 + 2e
Similarly aluminium is obtained by the electrolysis of alumina mixed with cryolite.

(III) Refining of Crude Metal
The crude metal obtained is impure. The impure metal is subjected to some purifying processes
known as refining in order to remove the impurities. The processes used for refining depend upon the
nature of the metal and the nature of impurities.
(A) Distillation (B) Liquation (C) Pyrometallurgical Oxidation
(i) Cupellation (ii) Bessemerisation (iii) Poling
(D) Electrolytic Refining (E) Special Methods
(i) Mond’s Process (ii) Van Arkel Method (iii) Zone Refining
(A) Distillation
This process is used for those metals which are easily volatile such as: Zn, Hg, Cd. The impure metal is
heated in a furnace and its vapours are separately condensed in a receiver. The non-volatile impurities are
left behind in the furnace.

(B) Liquation
This process is based on the difference in fusibility of metal and impurities. When the impurities are less
fusible than the metal, this process is employed. The impure metal is placed on the sloping hearth of the
furnace and gently heated. The metal melts and flows down leaving behind the impurities on the hearth. This
method is used to purify Bi, Sn, Pb and Hg.
(C) Bessemerisation (Pyrometallurgical oxidation)

The impure metal is heated in a furnace and a blast of compressed air is blown through the molten mass.
The impurities get oxidized. For example, the molten pig iron is taken in a Bessemer converter and compressed
air is passed which oxidizes the impurities.
2Mn + O2 
 2MnO ; Si + O2 
 SiO2
2C + O2 
 2CO ; MnO + SiO2 
 MnSiO3 (slag)
(D) Electrolytic Refining

It is different from electrolytic reduction. The impure metal is made anode and a thin sheet of pure metal is
made cathode.
As electrolysis proceeds, pure metal from anode is transferred to the cathode, whereas the impurities settle
down as anodic mud or anodic sludge. For examples Cu, Ag, Au, Pb, Zu, etc. are refined by this method.
(E) Special methods for Refining
(i) Mond’s Process
It is used mainly for refining of nickel. Impure Ni is treated with carbon monoxide at 330K  350K,
when volatile compounds Ni(CO)4 is formed.
The impurities are left behind and the volatile Ni(CO)4 is transferred into another container, where it is
heated more strongly at 450 K to give pure Ni. The CO gas produced is used again.
330  350 K 450K  470K

 Ni  CO 4  Ni  4CO
Ni  4 CO 
Im pure Volatile and (Pure)
highly toxic
(ii) Van Arkel Method

In this method, zirconium (or titanium) is heated in iodine vapour at about 870K to form volatile ZrI4.
The vapours of volatile ZrI4 are then decomposed electrically over tungsten filament to get pure metal,
and iodine is recovered.
870K 2075K
Zr  2 I2  ZrI 4 
 Zr  2 I2
(Im pure) (Vapours) (Pure)
As Van Arkel method and Mond’s process are quite related they are known as Vapour Phase
Refining.

(iii) Zone Refining

This method is used for extracting ultra-pure metals. This method is based upon the principle that
when a molten solution of impure metal is allowed to cool, the pure metal crystallizes out, while the
impurities remain in the melt. A movable heater is fitted at one end of the rod of impure metal. The
heater is slowly moved across the rod. The metal melts at the point of heating and as the heater moves
on from one end of the rod to the other end, the pure metal crystallizes while the impurities pass into
the adjacent melted zone. This process is repeated number of times unless metal of desired purity is
obtained. The process is carried out in an inert atmosphere to prevent the oxidation of metal. For
example, Germanium, Silicon and Gallium for being used in semiconductors are purified by this method.
Important Terms
1. Flux
Flux is a substance which is added to remove non-fusible impurities by forming slag and decrease the
melting point of the melt during reduction. Flux can be of three types :
(a) Acidic flux - It is used to remove basic impurities. Examples of acidic flux include SiO2 (in
smelting of Cu) and borax.
(b) Basic Flux - It is added to remove acidic impurities. Examples include Fe2O3, CaCO3 (in
blast furnance) etc.
2. Furnance
A furnance is a structure built to produce high temperature. Examples of some farnaces are
reverberatory furnance, blast furnance and muffle furance.
3. Refractory materials
These are compounds / mixtures which can withstand very high temperature without melting and are
not affected by slags. They are used in the form of bricks for internal lining of furnaces.
Referectory materials may be of three types :
(a) Acid Refractories - SiO2, quartz.
(b) Basic Refractories - CaO(lime), magnesite, dolomite.(in blast furnance)
(c) Neutral Refractories - Graphite (used in Hall Heroult Process), Chromite, bone ash.

1. List five ores which are smelted and give equations to show what occurs during smelting.
2. Name the process(es) used for concentration of tinstone.
3. Explain the role of collectors and froth stabilisers in Froth floation process.
4. Why is reduction by hydrogen not widely used.
5. Name three ores which undergo autoreduction give balanced equations.
6. Explain thermite process.
EXTRACTION OF IMPORTANT METALS Section - 3
GROUP 1
LITHIUM
Sources :
Lithium occurs mainly as silicate minerals like spodumene (LiAlSi2O6), Lepidolite.
SODIUM
Sources :
Sodium is the most abundant alkali metal. It is found in sea water, as rock salt (NaCl), Saltpetre (NaNO3),
Borax, Glauber’s salt (Na2SO4 . 10H2O), cryolite.
Extraction :
Sodium is obtained on large scale by two processes :
(A) Castner’s process :
In this process, electrolysis of fused NaOH is carried out at 330°C using iron as cathode and nickel
anode.
 Na   OH 
NaOH 
At Fe cathode: Na   e 
 Na
At Ni anode : 4OH   2H 2O  O2  4e

water formed at the anode gets partly evaporeted and is partly broken down to form H2 at cathode.
(B) Down’s process :
Sodium metal is manufactured mainly by this process. It involves the electrolysis of fused sodium
chloride (40%), calcium chloride (60%) and potassium fluoride using iron as cathode and graphite as
anode at about 600C.

 Na+ + Cl
NaCl 
At Iron cathode Na   e 
 Na
At carbon anode 2Cl 
 Cl2  2e 
The electrolysis of pure NaCl presents the following difficulties :

 The fusion temperature of NaCl is high, i.e., 803C. At this temperature both sodium and chlorine are
corrosive.
 Sodium forms a metallic fog at this temperature.
To remove above difficulties, the fusion temperature is reduced to 600C by adding CaCl2 and KF.
POTASSIUM
Sources :
Potassium occurs mainly as deposits of KCl and carnallite (KCl . MgCl2 . 6H2O)
Extraction :
A cell similar to down’s cell can be used to obtain potassium by electrolysing fused KCl.
GROUP 2
MAGNESIUM
Sources : Magnesium salts occur in sea water. Entire mountain ranges (eg Dolomites in Italy) consist of the
mineral dolomite [MgCO3 . CaCO3] . It also occurs as magnesite (MgCO3) and carnallite.
Extraction :
(A) Dow’s sea water process :
Sea water contains MgCl2 . Water is treated with Ca(OH)2 which precipitates MgCl2 as Mg(OH)2.
MgCl2  Ca(OH)2 
 CaCl2  Mg(OH)2 
(in sea water)

This is then converted back to MgCl2 .
 MgCl2   MgCl2 . 6H 2O   2H 2O
Mg(OH)2  2HCl 
dry HCl
MgCl2 . 6H2O  MgCl2 (anhydrous)
The obtained anhydrous MgCl2 is then electrolysed in fused state.
(B) From magnesite

MgCO3 
 MgO  CO2
MgO  C  Cl2 
 MgCl2  CO
(anhydrous)
MgCl2 is then electrolysed.
(C) Electrolysis of Fused Carnallite
Magnesium is prepared by electrolysis of fused MgCl2.

Anhydrous magnesium chloride is first prepared as in (A), (B) above
In order to lower fusion temperature of anhydrous MgCl2 and to increase the conductivity of electrolyte
NaCl or KCl (30%) is added. The electrolysis of MgCl2 is carried out at 700C. An air tight Iron vessel
serves as cathode. A carbon rod serves as anode and is enclosed by a porcelain tube. This arrangement
prevents the contact between magnesium and chlorine. Before starting the electrolysis, air above the electrolyte
is replaced by coal gas. This precaution is necessary because at about 700C magnesium reacts rapidly
with O2, N2 and CO2 present in air.

 Mg2+ + 2 Cl
MgCl2 
At Fe cathode Mg2+ + 2e 
 Mg
At Carion anode 2 Cl 
 Cl2 + 2e
(D) In silico-thermic process / Pidgeon process :

Here calcined dolomite (CaO + MgO) is reduced by ferrosilicon at about 1200C in an electric
furnace working under reduced pressure (3mm) where pure magnesium distils over.

1200 C
CaO  2MgO  Si 
 2Mg  CaSiO3
3mm
CALCIUM
Sources :
It occurs in many common minerals like limestne, marble and chalk (CaCO3), dolomite, gypsum, Fluorspar
and also as coral.
Extraction by Electrolysis :
Calcium is obtained by electrolysis of a fused mass consisting six parts calcium chloride and one part
calcium fluoride at about 700C in an electrolytic cell made of graphite which acts as anode and a water
cooled cathode of iron which is suspended from the top in the fused mass. On passing current, calcium is
discharged at cathode. It gets solidified as cathode is water cooled.
 Ca 2   2Cl
CaCl2 
At graphite anode : 2Cl 
 Cl2  2e 
At Fe cathode : Ca 2   2e  
 Ca
Since metallic calcium is soluble in fused CaCl2 at electrolysis temperature, cathode is raised and Ca is
removed as soon as it is deposited.
Note : Na or K is obtained by electrolysis of fused NaOH or KOH respectively but calcium cannot be obtained in
the same manner as Ca(OH)2 decomposes into CaO (quick lime) which is difficult to fuse.
GROUP 3 - 7
 Ti is refined by Van Arkel - de-Boer method :
Note : TiO2 is very stable and can’t be reduced by C or CO as it forms carbides and hence is reduced by Na or
Mg.

 Zirconium (Zr) is also refined by Van Arkel - de-Boer methods :

 Molybdenum and Tungsten are chemically reduced by H2
MoO3  H2 
 Mo  H2O ; WO3  H2 
 W  H 2O
GROUP 8
IRON
Sources :
Iron is the second most abundant metal and fourth most abundant element in the earth’s crust. It is extracted
from haematite (Fe2O3), magnetite (FeIIFe2IIIO4) and iron pyrites (FeS2) Famously called Fools Gold.
Extraction :
1. Crushing and Concentration :

The ore is crushed and washed with water (i.e., concentrated by levigating in a stream of water-
gravity separation or hydraulic washing) and then concentrated by electromagnetic process.
2. Roasting :
The concentrated ore is roasted in shallow kilns in the presence of excess of air. In roasting,
 Most of the moisture is removed.
 Impurities (like C, S, P, As and Sb) are removed in the form of their volatile oxides.
S + O2   SO
2
; 4As + 3O2   2AS O
2 3
; P + O2  P O
2 3
 Carbonates and sulphides are converted into oxides.
FeCO3   FeO + CO ; 4FeS + 11O 
2 2 2
 2Fe O + 8 SO
2 3 2
 Ferrous oxide is oxidised to ferric and thus avoids formation of slag with sand in further
processing.
4FeO + O2   2Fe O
2 3
(Otherwise FeO + SiO2   FeSiO )
3
 The entire mass becomes porous which makes reduction easy.
3. Smelting or Reduction :
The roasted ore (8 parts) mixed with coke (C), a reducing agent (4 parts) and limestone, a flux (1
part) is smelted (reduced) in a blast furnace lined with dolomite. Hot air blast is introduced near the
bottom of the furnace. Since the blast furnace has different temperature at different zones, different
reactions take place at different zones.
(a) Zone of Combustion : (1500°C -1600°C)
This zone is near the bottom of furnace and little above the tuyeres.
2C + O2 
 2CO + 58 Kcal
C + O2 
 CO + 97 Kcal
2
Both reactions are exothermic, a high temperature of about 1500C 1600C is attained.

FeO  CO 
 Fe  CO2
CO 2  C 
 2CO
FeO  C 
 Fe  CO
(b) Zone of Fusion : (1200°C -1500°C)

It is just above the zone of combustion. Here the iron produced in upper zones melts and trickles
down in hearth while the slag being lighter floats over the molten iron and thus prevents oxidation of
Fe by blast of hot air. The molten metal and slag are removed from different outlets.
(c) Zone of Heat Absorption : (or middle zone) (800°C -1200°C)
In this middle part of furnace, rising CO2 (produced in the zone of combustion) is reduced to carbon
monoxide.
CO2 + C 
 2CO ; H = +39 kcal
The reaction being endothermic lowers the temperature of the zone. In addition to this, following
reactions also take place here.
(i) Limestone decomposes forming CaO which reacts with SiO2 forming slag.

CaCO3   CaO + CO2
CaO + SiO2 
 CaSiO3 (slag)
(ii) Any Fe3O4 which escapes reduction in the zone of reduction is reduced in this zone.
 3FeO + CO 
Fe3O4 + CO  2
(iii) Some impurities are reduced and get mixed up with Iron.
MnO + C   Mn + CO
SO2 + 2C 
 S + 2CO
SiO2 + 2C 
 Si + 2CO
P2O5 + 5C 
 2P + 5CO
Ca3(PO4)2 
 3CaO + P O
2 5
(d) Zone of Reduction : (300°C -700°C)

It is near the top of the furnace. Here the roasted ore is reduced by rising carbon monoxide CO. The
following reactions taking place in this zone are all reversible in nature.
300C  400C
3Fe2O3 + CO   2Fe3O4 (spongy iron) + CO2
680C  700C
Fe3O4 + CO   3FeO + CO2
FeO + CO 
 Fe + CO2
Fe3O 4 + 4 CO 
 3 Fe+ 4 CO 2

 Iron obtained is impure. The product from blast furnace in called as Pig Iron. The net
productof blast furnace consists of Pig Iron, slag and fuel gases.
 The overall process for the extraction of Fe is thus :
3C  Fe 2O3 
 4Fe  3CO2
CaCO3  SiO2 
 CaSiO3  CO2
Cast Iron : The cast iron is specially made by igniting Pig iron with scrap iron and coke in a specially
designed furnace by blast of hot air. It contains 3% carbon in the form of graphite and carbide
and is extremely hard and brittle.
GROUP - 11
COPPER
Sources :
The most common ore is chalcopyrites CuFeS2. Other ores include Cu2S (Copper glance / chalocite),
basic copper carbonate CuCO3 . Cu(OH)2 (called malachite and is green) and cuprite Cu2O (is ruby red)

Extraction :
It is a self reduction method. It can be achieved by two ways.
I. Pyrometallurgical II. Hyderometallurgical
(A) Pyrometallurgical Method :
1. Concentration of Ore : The ore is finely divided and concentrated by froth floatation method.
Here froth is made from pine oil and water by bubbling air into the mixture. Concentrated ore
adheres to the surface of froth leaving behind impurities.
2. Roasting : The concentrated ore is heated strongly in presence of air in a reverberatry furnace.
Sulphur, arsenic and antimony are removed in the form of their volatile oxides while the proper
ore is converted into a mixture of cuprous and ferrous sulphides. These sulphides are partially
oxidised to oxides.
S + O2 
 SO
2
2As2S3 + O2 
 2As O + 6SO
2 3 2
2Sb2S3 + O2 
 2SbO + 6SO
3 2
2CuFeS2 + O2 
 Cu S + 2FeS + SO
2 2
Minor Reaction : 2Cu2S + 3 O2 

 2Cu2O + 2SO2
2FeS + 3O2 
 2FeO + 2SO2
3. Smelting (Auto Reduction) : The roasted ore is mixed with sand (flux) and coke (fuel) and then heated
in water jacketed blast furnace called smelter. The oxidation of ferrous sulphide which started during roasting
now goes up a step further, ferrous oxide, formed reacts with sand to form ferrous silicates (slag). Here
some FeS reacts with Cu2O to form Cu2S again.

FeO + SiO2 (sand) 

 FeSiO3 (Slag)
Cu2O + FeS   Cu2S + FeO
Slag, forming upper layer and molten mass consisting of Cu2S and little FeS, forming lower layer called
‘COPPER MATTE’ are removed from separate holes.
4. Bessemerisation : Molten matte is heated in Bessemer converter and blast of air mixed with sand is
blown through the molten mass. Here Iron (FeS) is completely removed as slag. A part of Cu2S is
oxidised to Cu2O and a part of Cu2S reduces Cu2O to metallic copper.
2Cu2S + 3O2 
 2Cu2O + 2SO2
2Cu2O + Cu2S 
 6Cu + SO2
The molten copper is poured off into sand moulds. As it cools, it gives up dissolved SO2 which forms
blister on the metal surface. The copper thus obtained is called as BLISTER COPPER (98% Cu).
5. Refining of Copper :
(a) Furnace or thermal Refining : Blister copper is melted in a reverberatory furnace provided with
silver lining and air is blown in where the impurities oxidise. Some of oxides escape and other form
a slag with silica.
The slag is removed.
(b) Poling : Molten Cu is stirred with poles of green wood to reduce Cu2O to Cu by CO and H2 from
green wood.
Cu2O + CO 
 2Cu + CO2
Cu2O + H2 
 2Cu + H2O

(c) Electrorefining : The electrolyte bath contains an acidified solution of copper sulphate, impure copper
(blister copper) acts as anode while pure copper strip acts as cathode. The cathode grows in thickness
and pure Cu is scraped off.
Anode : Impure Cu
Electrolyte: 3.55% CuSO4 + 15% H2SO4 :  Cu2+ + 2e
Cu 
Cathode : Pure Cu
Temperature: 50C : Cu2+ + 2e 
 Cu (Pure)
Note : The impurities (Au, Ag, Pb ......) collect below the anode and is called anode mud.
(B) Hydrometallurgical Method :

Low grade ore is crushed and exposed to air and water when copper sulphide is oxidised to copper
sulphate. Some iron sulphate and sulphuric acid is also produced. This process takes one year.
(a) CuFeS2 + 4O2 

 CuSO4 + FeSO4
(b) 2Cu2S + 5O2 

 2CuSO4 + 2CuO
Cu glance
CuS + 2O2 
 CuSO4 (pale green liquid)
In NON-SULPHIDE ores, the crushed ore is leached with dilute H2SO4.

(c) CuCO3.Cu(OH)2 + 2H2SO4 
 2CuSO4 + CO2 + 3H2O
Malachite
The pale green liquor draining from the bottom to the heaps is collected in pans and treated with iron scraps
which precipitate out copper.
CuSO4 + Fe 
 FeSO4 + Cu
The precipitated copper is dried, melted and refined.
SILVER AND GOLD

Sources :
Silver is mainly found as sulphide ore Ag2S (argentite) Gold occurs mainly as grains of metal disseminated in
quartz veins.
Extraction :
Au, Ag are both first crushed and concentrated by froth floatation. Silver then directly undergoes leaching
while gold is leached after roasting.

Leaching is done by Cyanide process.

1. Ag ore is leached with NaCN (or KCN) solution in presence of air when silver and its solt are
converted to soluble complex.
O
Ag 2S  4CN  

2
2[Ag(CN) 2 ]  S2 
Argento Cyanide
(so lub le)
O2(air) is pumped to force the reaction in forward direction.
4S2   5O2  2H2O 

 2SO42   2S   4OH 
Zinc dust is then added to precipitate Ag.
[ Ag(CN) 2 ]  Zn 
 Ag   [ Zn(CN) 4 ]2 
(pure)
2. The leaching process used for Au is called Mac Arthur Forest Cyanide Process :
Concentrated ore is taken in large vats made of cement or iron. It is then treated with dilute (0.5%)
solution of KCN in presence of air to form a soluble complex.
4 Au  8KCN  2H 2O  O 2 
 4 K[Au(CN) 2 ]  4KOH
(ore) Potassium Aurocyanide
(Soluble)
Note : If excess conc. KCN is used then
4Au  1 6CN   O2  2H 2O 
 4[ Au(CN)4 ]3  4OH 
(excess)
Zinc dust is then added :
2K[Au(CN)2 ]  Zn 
 K 2 [Zn(CN)4 ]  2Au 
(pure)
The obtained Gold (or Silver) still contains traces of impurities and thus electrolytic refining is performed.
The electrolyte used is AgNO3 + 10% HNO3(for silver) and AuCl3 + 10% HCl (for gold). Anode is the
impure metal while cathode is made of pure metal.
 Ag is also obtained from argnetiferrous lead (PbS . Ag2S) by Parke’s Process or Pattinson’s
Process :
 Ag, Au can also be extracted from anode mud formed during electrolytic refining of copper.
 Another method of extraction is amalgamation. Powdered ore is first converted to its amalgam and
then distilled to remove Hg in the form of vapour leaving behind pure metal.

GROUP - 12
ZINC
Sources :
Zinc is found as Zinc Blende (ZnS), Colomine (ZnCO3) and zincite (ZnO)
Extration :
1. Concentration
The ore is concentrated first by gravity method and then by froth floatation process. If Fe2O3 is
present as an impurity, it is removed by magnetic separation.
2. Roasting
The concentrated ore is then roasted at 900C  1000C to convert ZnS and ZnSO4 to ZnO.
2ZnS + 3O2   2ZnO + 2SO2
ZnS + 2O2   ZnSO4
ZnSO4   2ZnO + 2SO2 + O2
Note : If calamine is used as the source, only calcination is required at high temperature.

ZnCO3 
 ZnO + CO2
3. Reduction by coke
The oxide, ZnO is reduced with coke at about 1500C to obtain metallic zinc which is distilled of and rapidly
cooled.
ZnO + C 
 Zn + CO
ZnO + CO 
 Zn + CO2
4. Electrolytic Refining
Zn thus produced contains impurities like Pb, Cd, and Fe. These impurities are removed by liquation. The
pure zinc is obtained by electrolysing the Zinc in presence of acidified ZnSO4 (ZnSO4 + dil H2SO4) as
electrolyte. Impure zinc is made the anode and pure zinc, the cathode.
Note : Zinc can also be extracted by electrolytic method. ZnS is first roasted at 700C to produce ZnO. Then, the
oxide ZnO is leached with H2SO4 to convert to sulphate (ZnSO4). After removing impurities by treating with
milk of lime, ZnSO4 is acidified and electrolysed to give pure zinc on cathode.
MERCURY
The most important ore is cinnabar (HgS) which is bright red coloured. The ore is first crushed and
concentrated by froth floatation method. It then undergoes Auto / self reduction
HgS  O2 
 HgO  SO 2
HgO  HgS   Hg  SO2

Refining is done by either liquation or distillation.

GROUP - 13
ALUMINIUM :
Sources :
Aluminium is the most abundant metal and is commercially important. The most important ore of aluminium
is bauxite. This is a generic named for several minerals with formulae varying between Al2O3. H2O and
Al2O3 . 3H2O
Extraction (Electrolytic method from Bauxite) :

1. Purification of Bauxite
Bauxite contains mainly Iron oxide (Fe2O3) and silica as impurity. If iron oxide is the main impurity, it
is called red bauxite and if SiO2 is the main impurity, it is called white bauxite. It is difficult to remove
iron or silicon from aluminium, so the ore is purified before hand. It can be achieved by either of the
following processes.
(a) Bayer’s Process (for ores containing iron oxide as major impurity) :
Finely grounded ore is roasted at a low temperature to convert FeO to Fe2O3 and digested
with a concentrated solution of NaOH in an autoclave. Al2O3 (Amphoteric) dissolves forming
NaAlO2, while Fe2O3 (basic) remains undissolved. Fe2O3 is removed by filtration.
Al2O3.2H2O + 2NaOH 
 2NaAlO2 + 3H2O
The filtrate containing sodium aluminate is diluted, treated with a seed crystal of pure Al(OH)3
and then agitated, when pure Al(OH)3 is precipitated.
NaAlO2 + 2H2O 
 NaOH + Al(OH)3 
The precipitated Al(OH)3 is filtered, washed and ignited to give pure alumina, Al2O3.

2Al(OH)3   Al2O3(pure) + 3H2O
(b) Serpek’s Process (For ores containing silica, SiO2) :

The powdered ore is mixed with carbon and heated to 1800C in a current of nitrogen,
where aluminium nitride is formed. SiO2 is reduced to silicon, which volatilises away.
1800ºC
Al2O3 + 3C + N2 
 2AlN + 3CO
SiO2 + C 
 Si(volaties off) + 2CO
Aluminium nitride is hydrolysed by water to Al(OH)3 which on ignition gives pure alumina.
AlN + 2H2O 
 Al(OH)3 + NH3
1100C
2Al(OH)3  Al2O3(pure) + 3H2O

(c) Hall’s Process [mainly for Red Bauxite] :

Crude bauxite reacts with Na2CO3 at 1000 C to give sodium aluminate and impurities Fe2O3 and
SiO2 form NaFeO2 and Na2SiO3 respectively.
 2NaAlO2 + CO2
Al2O3 + Na2CO3 
CO2 at a temperature of around 60C is passed into sodium aluminate solution producing Al(OH)3.
60C
2NaAlO2 + CO2 + 3H2O  2Al(OH)3  + Na2CO3

2Al(OH)3   Al2O3 (pure) + 3H2O
1100C
2. Electrolytic reduction of alumina (Hall - Heroult Process)

Aluminium can’t be isolated by electrolysis of aqueous solution of Al2O3, since aluminium is more
electropositive than hydrogen, so its electrolysis gives H2 at cathode.
Al2O3 is infusible (M.P. = 2050C), so it can’t be electrolysed. So pure alumina, dissolved in molten
Cryolite (Na3AlF6) containing some CaF2 or NaF is electrolysed at about 800C1000C. Cryolite
decreases melting point and increases conductivity while CaF2 and NaF are added only to increase
conductivity. The electrolysis is carried out in an iron cell lined with graphite (cathode). The anode is a
series of graphite rods.
 Al3+ + 3F
AlF3 
At cathode : Al3+ + 3e 
 Al
At the same time, Al2O3 dissociates into Al3+ and O2–.

Since ‘O’ is below F in the electronegativity series, O2 ions are selectively discharged at the anode as
oxygen.
 4 Al3+ + 6 O2
2 Al2O3 
At anode :  3 O2 + 12 e
6 O2 

The oxygen liberated at anode combines with carbon of anode to form CO and CO2 so anode, which burn
away have to be replaced periodically. Molten Al collects at the bottom of cell (99% pure)
3. Electrolytic Refining
The cells layers contain three fused layers.
(a) The bottom anode layer of an alloy of Al, Cu, Si
(b) The middle layer of Cryolite and BaF2
(c) The top cathode layer of pure aluminium.
When a current is passed, Al3+ ions from the fused middle layer get discharged at the cathode, while an
equivalent amount of aluminium moves into the middle layer. Impurities (Cu etc) remain at the bottom.
GROUP - 14
TIN :
Sources :
It is mainly obtained from Cassiterite (SnO2) which contains Wolfromite (FeWO4 . MnWO4) as an impurity.
Extration :
1. Concentration of ore :
Ore is crushed to a fine powder and concentrated by gravity process. Ore is washed with the stream
of water to remove gangue and other silicon impurities. Tinstone and wolframite are left. Wolframite
is then removed by magnetic seperation.
2. Roasting :
The ore is roasted to remove volatile impurities.
S + O2   SO
2
2As2S3 + 9O2 
 2As O + 6SO
2 3 2
The roasted ore is washed with water to remove soluble impurities and dried. It contains 60 – 70% of
tin as SnO2 called Black Tin.
3. Smelting :
The ore is mixed with 1/5 th of its weight of powdered anthracite and a little limestone and heated in
reverberatory furnace. SnO2 is reduced to metallic state and silica is removed as slag.
SnO2 + 2C 
 Sn + 2CO
4. Refining :
It is refined by any of the following processes.
(a) Liquation : The crude tin is melted on the sloping hearth of a reverberatory furnace when tin
alone melts and flows out. The process is called sweating and the impure tin left is called
dross.

(b) Electrolytic Refining : The electrolyte consists of hydrofluorosilicic acid (H2SiF6) containing
stannic sulphate (SnSO4) and H2SO4. A block of impure tin is anode and a thin strip of pure
tin the cathode.
LEAD
Sources :
Galena (PbS) is the principal ore.
Extraction :
(A) Self Reduction or Air reduction process :
This is used for samples of galena rich in lead. In this process roasting and smelting are done in same
furnace, but at different temperatures.
(i) Crushing and Concentration
The ore is crushed, finely powdered and concentrated by froth floating process. NaCN is
used as a depressant to prevent ZnS (if present) from coming out as froth. The concentrated
ore contains 50  60% of lead.
(ii) Roasting
The concentrated ore is roasted at a moderate temperature in a reverberatory furnace and in
a limited supply of air.
lim e
2PbS + 3O2 
 2PbO + 2SO2
PbS + 2O2 
 PbSO
4
(iii) Reduction (Smelting)

Air supply is cut off, fresh galena is added to roasted ore and the temperature is raised.
Galena reduces lead oxide and lead sulphate to metallic lead.
2PbO + PbS 
 3Pb + SO2
PbSO4 + PbS 
 2Pb + 2SO2
Molten lead is drawn from time to time and purified.
(B) Carbon Reduction Process :

This process is suitable when the ore contains more impurity (silica) and has low amount of lead. Here
roasting and smelting are done in different furnaces.
(i) Crushing and Concentration
This is done as in above process.

(ii) Roasting
Concentrated ore is mixed with lime (CaO) and heated in presence of air when PbS is oxidised
mainly to PbO.
2PbS + 3O2 
 2PbO + 2SO2
Lime performs two important functions.
(a) Being more basic than PbO, lime preferentially reacts with SO2 (formed in the above
oxidation) to form calcium sulphite and thus favours the oxidation of galena in the
forward direction.
(b) It decomposes lead silicate (formed by reaction of PbSO4 with silica present as
impurity) to PbO which would otherwise have gone as slag.
PbS + 2O2   PbSO4
2PbSO4 + 2SiO2 
 2PbSiO3 + 2SO2 + O2
PbSiO3 + CaO 
 CaSiO3 + PbO
(iii) Smelting
The roasted mass is mixed with coke and lime (flux) and smelted in a blast furnace. Following
reactions occur.
PbO + C 
 Pb + CO
PbO + CO  Pb + CO2
CaO + SiO2  CaSiO3 (slag)

PbSiO3 + CaO  CaSiO3 + PbO

Little hematite is added to reduce any unchanged PbS to Pb.
2PbS + Fe2O3 + 3C 
 2Pb + 2FeS + 3CO
(iv) Refining
Impurities are Cu, As, Sb, Fe, Zn, Bi, Ag and sulphur. These are refined by either of flowing
processes :
(a) Oxidation or softening where impure metal is heated in current of air where Cu, Fe, Sn etc are
oxidised before lead.
(b) Desilverisation by Parke’s or Pattinson method to remove Ag.
(c) Electrorefining : Electrolysis of 1-15% Lead silica fluoride (PbSiF6) and 5-10%
(hydrofluorosilicic acid, H2SiF6) is carried out between pure lead sheets serving as cathode,
and crude impure lead as anode.

1. Cinnabar (HgS) and galena (PbS) on roasting often give their respective metals but zinc blende
(ZnS) does not.
Explain :
2. A metal is in combined sate as sulphide. Identify the steps (A), (B) and (C)

3. Why Zinc and not copper is used for the recovery of metallic silver from the complex  Ag  CN  2 
4. Describe the extraction of magnesium from sea water.
NOW ATTEMPT IN-CHAPTER EXERCISE-B REMAINING QUESTIONS IN THIS EBOOK
SOLUTIONS - IN - CHAPTER EXERCISE - A
1. Fe 2O3  C 
 Fe ; ZnO  C 
 Zn  CO 2  CO(gases)
(haematite) (zincite)
PbO  C   Pb ; MgO  C   Mg ; Ca 3 (PO4 ) 2  C  P

2. Tinstone is concentrated first by gravity seperation and then magnetic seperation is used to remove magnetic
impurities like wolframite.
3. Collectors enhance the non wettability of mineral particles and froth - stabilizers stabilize the froth.
4. Reduction by hydrogen is not widely used because many metals react at elevated temperartures, forming
hydrides. There is also a risk of explosion.
5. Galena (PbS), Chalcocite (Cu2S) and cinnabar (HgS).
6. In the thermite process, Al is used to reduce metal oxide to metal while it itself gets oxidised to Al2O3 which
produces a large amount of heat (1675 kJ/mol). This is utilised to join broken railway tracks.
SOLUTIONS - IN - CHAPTER EXERCISE - B

1. This is because HgS and PbS can undergoe self reduction while ZnS doesnot.
2. A = roasting, B = reduction, C = refining
4. Sea water contains MgCl2 which is precipitated as Mg(OH)2 (using Ca(OH)2). This is then converted back
to MgCl2(by HCl) and dried. MgCl2 is then electrolysed.
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes s-Block
s-BlockElements
Elements&&Compounds
Compounds
s-Block Elements & Compounds

PROPERTIES OF s-BLOCK ELEMENTS Section - 1
Group - I
Introduction :
All the alkali metals have loosely held one s-electron in the outermost shell which they can readily lose to
give monovalent (M+) cation having stable noble gas configuration. Due to their tendency of loosing s-
electron easily, they have low ionization energy and high metallic character. The size of atoms and ions of
alkali metals increases down the group.
(i) Electropositive character
Alakali metals are highly electropositive in nature and electropositive character increases down the
group.
(ii) Ionization Energy
Alkali metals have low ionisation energy and it decreases down the group. In fact K and Cs are used
as cathodes in photoelectric cells.
(iii) Density
The density of alkali metals is quite low as compared to other metals. Li, Na and K are even lighter
than water. As we go down the group, the mass and volume of alkali metals increases but mass
increases by larger factor than the volume and the resulatant effect is that the density increases down
the group with an exeption that potassium beigh lighter than Sodium. So, the trend is :
Li  K  Na  Rb  Cs
(iv) Melting Point and Boiling Point :

Melthing point and boiling point of alkali metals decreases down the group. The melting points range
from lithium 181C to caesium 28.5C. These are extremely low values for metals, and contrast with
the melting point of the transition metals, most of which are above 1000C.
(v) Flame Test :
Group I elements give a varied range of colours in their flame test. Li emits crimson light, Na emits
yellow, K emits lilac and Rb and Cs emit violer light.

s-Block Elements & Compounds Vidyamandir Classes
Chemical Properties :
The alkali metals are highly reactive due to low ionization enthalpy and therfore they never occur in free
state. The reactivity of these metals increases down the group.
(i) Reactivity towards air
Li react with air forming oxide Li2O (and some Li2O2) and nitride Li3N. Na react with air forming
oxide (Na2O) and peroxide (Na2O2). Peroxide is formed in large amount. K, Cs and Rb forms oxide
(M2O), peroxide (M2O2) and superoxide (MO2). Superoxide is fromed in large amount. (Where M
is K, Cs, Rb).
You can note here except Li all other alkali metals are forming oxide only, whereas Li form nitride also
on buring in air. Li3N is a ruby red salt which gives LiOH and NH 3  on dissolving in water while Li
and nitrogen on simply heating. The increasing stability of peroxide or super-oxide, as size of the metal
ion increases, is due to the stabilization of large anions by larger cation through higher lattice energies.
(ii) Reactivity towards water
Group 1 metals all react vigorously with water liberating hydrogen. The reaction becomes increasingly
violent on descending the group.
1
M s   M sq  le ; H 2O  le  OH   H2
  2
1
 M   OH  
M  H 2O  H2 (M  Li, Na, K, Rb, Cs)
2
Reaction of sodium is os violent that it catches fire and is thus kept in kerosene in the laboratory.
Standard Reduction Potential

Standard Reduction potential of akali metals M is a value that represents the tendency to gain an electron
M aq  le  M s 

 
If standard Reduction potential is positive it means element desires to gain electrons and if it is negative
it means element desires to loose electron.
Further, lower the standard reduction potential, higher will be the tendency to loose electron.
Standard reduction potential (Eo) for an alkali metal represents the overall change :
M  s   M  g  Sub lim ation enthalpy
M  g   M   le  Ionization enthalpy

g 
M  M
 H 2O  hydration enthalpy
g   aq 

Vidyamandir Classes s-Block Elements & Compounds
Lithium has the most negative standard reduction potential than any other element in the periodic table.
Why ?
a Li  H  159 KJ /mol
ion Li  H  520.2 KJ/ mol
Lis   Li g  
 hydr H Li   520
Li   le  Li   le 
g   aq 
Total energy aborbed  aH Li  ion H Li   hydn H Li  159  520.2  520  159.2 KJ / mol.
a Na  H  107 KJ/ mol

ion Na  H  495.8 KJ/ mol
Na  s  
 Na  g  

 hydr H Na   406 K / mol

Na   le 
 Na   le
g   aq 
Total energy absorbed
 a H Na  ion H Na   hydr HNa   107  495.8  406  196.8 KJ ? mol
Hnece total energy absored in Lis   Li  aq   le  is less and also least as compared to any
other element. Therefore it has most negative standard reduction potential.
Li has most negative standard reduction ptoential (or highest tendency for Li  s   Li   aq   le  ).
It seems that reaction of Li with water should be most vigourous. But it is surprising that Li reacts less
vigorously with water than other alkali metals. The explanation lies in the kinetics (that is the rate at which
the reaction proceeds) rather than in the thermodynamics (that is total amount of energy absorbed). You
will study more about kinetics in upcoming modules.
(iii) Reducing Character
Among alkali metals, Lithium has strongest reducing character and sodium has least reducing
character and rest are almost the same.
[Lower the standard reduction potential (considering the sign also) higher is the reducing character]
(iv) Solution in liquid Ammonia
Liquid Ammonia is also a good polar solvent next the water. Ammonia gas (b.p. = - 33oC) is
condensed to give liquid ammonia. Both water and ammonia undergo self - ionization :


2H 2O  
 H3O  OH

; 

2NH3   
 NH 4  NH 2

When small amount of sodium is added in liquid ammonia (i.e. : Dilute Solutions of Na in liquid
Ammonia), sodium metal looses an electron to give sodium cation, both of these ions are solvated by
liquid ammonia to give a blue coloured solution which is highly conducting.
 
M   x  y  NH3   M  NH3  x   e  NH3  y 
 
The blue colour of the solution is due to the ‘ammoniated electron’ which absorbs energy in the visible
region of light and thus imparts blue colour to the solution. The conducting nature is also mainly due to
solvated electron.
The solution is paramagnetic in nature and on standing slowly liberates hydrogen resulting in the
formation of amide.
1
e  NH3    NH 2 ammoniated   H 2 g 
2
Concentrated solution of Na in liquid ammonia is metallic bronze in colour and diamagnetic in nature
due to formation of metal ion clusters.
Group - II
Introduction :
All the alkaline earth metals have two s-electron in the outermost shell which if they lose, they will give
divalent (M2+) cation having stable noble gas configuration. The size of atoms and ions of alkaline earth
metals increases down the group.
(i) Electropositive character
Alkaline earth metals are highly electropositive in nature and Electropositive character increase down
the group.
(ii) Ionization Enthalpy
Second ionization enthalpy is very high than first ionization enthalpy. It is due to the fact that extracting
an electron from a positive ion bcomes difficult. Both first and second ionization energy decreases
down the group.
(iii) Density
The density of alkaline earth metals is high as compared to alkali metals. And as we go down the
group both the mass and volume of alkali metals increases but the resultant effect that is the density do
not show a regular change. As we move down the group, it first decrease (upto Ca) and then increases.
So, the trend is : Ba > Sr > Be > Mg > Ca

(iv) Melting point and Boiling Point

Melthing point and boiling point of alkaline earth metals is higher than the alkali metals. As we move
down the group,
Melthing point and Boiling point don’t show a regular change.
Chemical propeties :
(i) Reactivity towards air
Alakaline earth metals react with air forming an oxide and a nitride.
air
M s   MO  M 3 N 2  where M  Be, Mg, Ca, Sr, Ba 
The case of above reaction depends on electropositive character and hence increases down the
group. In the case of Mg, it burns with a dazzling white light which is used to provide light in flash
photography using light bulks.
(ii) Reactivity towards water

 M 2aq
OHC : Ms    2e  RHC : 2H 2O    2e 
 H 2  2OH 
 
Now, to check the case of reaction for different metals, we have to check the Oxidation Half Cell
reaction and this reaction refers to the reducing ability (Standard Reduction Potential) of the metal.
And, Since for alkaline earth metals reducing character increases down the group, the case of reaction
of alkaline earth metals with water increases down the group.
Experimentally, it is see that Be reacts only with steam and Magnesium can react with both hot water
and steam and Ca. Sr, Ba ract even with cold water rapidly.
(iii) Solution in liquid ammonia

In liquid ammonia, group II metals form bright blue dilute solutions containing solvated electrons and
metal hexaammoniates. The metal hexammoniates form ammides on heating which further form nitrides
and NH3 concentrated solution are bronze coloured.
(iv) Reducing character

Less is the standard reduction potential more will be reducing character and since the standard reduction
potential decreases down the group, the reducing character of alkaline earth metals increases down
the group.

IMPORTANT CONCEPTS Section - 2
In this section we will discuss some important concepts related to s-block elemets.
Lattice enthalpy
It is the energy required to separate one mole of a solid ionic compound completely in gaseous ions.
Lattice Enthalpy of breaking solid NaCl in gaseous Na+ and Cl– is + 788 KJ/mol.
In a system of + ve and -ve ion the energy required to separate the two ions is inversely proportion to the
distance between the centres of the two ions.
1
 LE 
r  r 
(r+ is the radius of +ve ion and r– is the radius of -ve ion.)
For a given anion and different cations as we move down the group the size of cation increase and conse-
quently the interionic distance between cation and anion increases. Hence, the lattice enthalpy would de-
crease dwon the group.
Also you may not that as the charge of ion increases the Lattice Enthalpy increases. Therefore, Lattice
Enthalpy of group II metal salt is more as compared to corresponding group I metal salts.
Hydration Enthalpy
Hydration Enthalpy refets to the energy released when one mole of gaseous ion is dissolved (or hydrated) in
water. Strictly speacking, value of Hydration Enthalpy is equal to the energy absorbed when one mole of
gaseous ion is dissolved in water. For example, if energy is released on dissolving some ion in water, its
hydration enthalpy will be negative quantity and its magnitude will be equal to the magnitude of energy
released.
When an ion is dissolved in water it attracts water molecules. Thus, a number of water molecules surround
it and a cluster is formed. The number of water molecules surrounded by a cation depend on the ability of
the cation to polarise the water molecule. More the polarizing power of cation, the large the number of
water molecules will surround it. Among alkalie metals cations, Li+ has highest polarising power, hence, a
large number of water molecules will surround it. The numbere is so large that the hydrated Li+ becomes
heavier than hydrated Na+. The hydrated Na+ being lighter moves easily in water as compared to hydrated
Li+, hence Na+ is more conduction than the solution of Li+.
Also, note that more that polarising power of cation, more it will be hydrated and more energy will be
released. And therefore, hydration enthalpy will be more negative. Thus down the group magnitude of
hydration enthalpies of metal ions decreases.

Thermal Stability
Hereby we will discuss the thermal stability of group I and group II metal oxosalts. i.e. carbonates, nitrates,
sulphates etc. For simplicity let us consider metal carbonates and discuss their thermal stability.
Example :
The effect of Heat on the metal carbonates :
All the carbonates undergo thermal decomposition to give the metal oxide and carbon dioxide gas. Thermal
decompostion is the term given to splitting up a compound by heating it.
XCO3  s   XO  s   CO 2  g 
As you go down the group, the carbonates have to be heated more strongly before they will decompose.
i.e. Thermal stability of metal carbonates increase down the group. Let us try to understand the explanation
of this fact.
Explanining the trend the terms of the polarising ability of the positive ion :
A small cation has a lot of charge packed into a small volume of space. It has a high charge density and will
have a marked distorting effect on any negative ions which happen to be near it.
A bigger cation has the same charge spread over a larger volume of space. Its charge denisty will be lower,
and it will cause less distortion to nearby negative ions.
The structure of the carbonate ion :

If you worked out the structure of a carbonate ion, you would probably come up with :
This show two single carbon-oxygen bonds and one double one, with two of the oxygens each carrying a
negative charge. Unfortunately, in real carbonate ions all the bonds are identical, and the charges are spread
out over the whole ion - although concentrated on the oxygen atoms. We say that the charges are delocalised.
The next diagram shows the delocalised electrons. The shading is intended to show that there is a greater
chance of finding them around the oxygen atoms than near the carbon.

Polarisin the carbonate ion :

Now imagine what happens when this ion is placed next to a positive ion. The positive ion attracts the
delocalised electrons in the carbonate ion towards itself. The carbonate ion becomes polarised.
If this is heated, the carbond dioxide breaks free to leave the metal oxide.
How much you need to heat the carbonate before that happens depends on how polarised the ion was. If it
is highly polarised, you need less heat than if it is only slightly polarised.
The smaller the positive ion is, the higher the charge density, and the greater effect it will have on the
carbonate ion. As the positive ions get bigger as you go down the Group, they have less effect on the
carbonate ions near them. To compenstate for that, you have to heat the compound more in order to
persuade the carbond dioxide to break free and leave the metal oxide. In other words, as you go down the
Group, the carbonates become more themally stable.
In case of Nitrates, Group II metal nitrates decompose to give metal oxide, nitrogen dioxide and oxygen gas
while Group I metal nitrates except lithium) decompose to give metal nitrite and oxygen gas. Lithium nitrate
behaves in a way similer to group II metals giving. LiO, NO2 and O2 on decopostion.

Ca  NO3 2  CaO  NO 2  O 2

Li(NO3 ) 2  Li 2O  NO 2  O 2
500C
NaNO3 
 NaNO 2  O 2
800C
NaNO3 
 Na 2O  N 2  O 2
NaNO3 on very strong heating gives Na2O, N2 and O2. Metals sulphates decompose to give metal oxide,
SO2 and O2. Thermal stability of all these oxosalts increases down the group and the explanation lies in a
way similar to as given for metal carbonates.

IMPORTANT COMPOUNDS OF s-BLOCK Section - 3
1. Oxides, Peroxide, Superoxides
Gruop - I
Alkali metals generally burn in air to form oxides, peroxides and superoxides (Lithium forms some nitride
also). Lithium forms Li2O (and some Li2O2 ) and Li3N. Sodium form Na2O2 (and some Na2O), and rest of
the alkali metals form superoxides (major). The increasing stability of oxides, peroxides and superoxides, as
the size of the metal ion increases, is due to the stabilisation of large anions by larger cations through lattice
energy effects. The oxides and peroxides are colourless but the superoxides are orange or yellow. Oxides
and peroxides ae diamagnetic while superoxides are paramagnetic. Alkali metal oxides, peroxides and
superoxides dissove readily in water to give hydroxides along with a lot of heat. Peroxides and superoxides
are good oxidants and generally used in bleaching.
1. Sodium Oxide [Na2O]

Preparation :
(i) Controlled oxidation of sodium in air gives Na2O
(ii) Industrially, Na2O is prepared by heating sodium nitrate of nitrite with sodium.
NaNO3  Na 
 Na 2O  N2 ; 2NaNO2  6Na 
 4Na 2O  N2
(iii) In laboratory pure Na2O is formed by heating mixture of sodium azide and sodium Nitrite.

3NaN3  NaNO2  2Na 2O  5N 2
(pure)
Porperties :
Na2O is a white ionic solid and its aqueous solution is a strong base.
Na 2O  H 2O 
 2NaOH
2. Sodium Peroxide [Na2O2]

The trade name of sodium peroxide is oxone.
Preparation :
Burning Sodium in air mainly forms sodium peroxide.

Properties :
(i) Na2O2 is colourless in pure form and stable at room temperature.
(ii) Na2O2 is diamagnetic. All peroxides are regarded as salts of dibasic acid H2O2.
Na 2O2  2H2O 
 2NaOH  H2O 2
(iii) Cold dilute acids always produce H2O2.
Cold
Na 2 O2  HCl  NaCl  H 2O2
The reaction with CO2 is used to purify air in submarinas but KO2 is even better for this purpose.
(iv) It is strong oxidising agent. It oxidises Al to Al2O3 , Cr 3 to CrO42  and SO 2 to SO 42  .
Na 2O2  Al 
 Al2O3  Na 2O
Na 2O 2  CO 2 
 Na 2SO4
The reaction with CO2 is used to purify air in submarines but KO2 is even better for this purpose.
Uses :
It is a powerful oxidant and used for bleaching wood pulp, paper and fabrics.
3. Potassium Superoxide [KO2]

Preparation :
It is prepared by burning potassium in excess of oxygen.
K  O 2  excess   KO 2
Porperties :
(i) It is paramagnetic and orange coloured solid.
(ii) Potassium superoxide is stronger oxidizing agent and gives both H2O2 and O2 with either water
or acids.
2KO2  2H 2O 
 2KOH  H 2O2  O 2 ; 2KO 2  2HCl 
 2KCl  H 2O 2  O 2
(iii) It readily reacts with CO and CO2 producing Oxygen.
2KO 2  CO 
 K 2CO3  O 2 ; 2KO 2  CO 2  K 2CO3  3 / 2O2

User :
Being oxidant, KO2 produces oxygen and simulataneoulsy it absorbs CO2 and becuase of its above
life supporting properties it is used in space capsules, submarines and breathing masks.
Gruop - II
Alkaline earth metals burn in air to give normal metal nitrides. Generally, there are two methods of forming
oxides, one is buring in air and other decomposing their oxosalts.
Metal oxides and hydroxides of group II are more stable than of group I, that is why oxosalts (carbonates,
sulphates, nitrates,....) of group II are less stable to heat and decompose to give corresponding oxides.
Note : The stability of metal oxides decreases down the group. That is why, down the group metal oxides become
more reactive. Down the group, alkaline earth metal oxide’s basic character increases. BeO is amphoteric
in nature.
1. Magnesium Oxide
Preparation
(i) Magnesium burns in air with a dazzaling flame and forms magnesium oxide.
2Mg  O 2 
 2MgO
(ii) Decomposing the oxosalt MgCO3 also gives magnesium oxide.


MgCO3 
 MgO  CO2
Properties :
(i) It is light infusible (fusibility refers to conversion in liquid form) white powder. It fuses at 2800oC.
(ii) It is reduced by carbon at very high temperature.
2000C
MgO  C 
 Mg  CO
Uses :
(i) Buring of magnesium ribbon is used to initiate the thermite reaction.The thermite reaction goes
as :
Fe 2O3  2Al   2Fe  Al2O3

(ii) MgO being very less reactive and having high m.p., is used as a refractory material. Good
conductivity of MgO towards heat and bad conductivtiy towards electricity also adds to its
usefulness as refractory material.

2. Calcium Oxide [CaO] (Quick lime)

Prepartion :
It is prepared by decompostion of CaCO3 in lime kilns (900oC).

CaCO3  CaO  CO2
Properties
(i) Calcium oxide is a white amorphous solid, having high melting point of about 2870K.
(ii) Being a basic oxide, it combines with acidic oxides at high temperaure.
CaO  SiO 2  CaSiO3 ;  2Ca 3  PO 4 2

6CaO  P4O10 
300C
(iii) CaO  3C 
 CaC2  CO 
Uses :
(i) It is used in metallurgy to remove phosphates and silicates as slag.
(ii) By mixing with SiO2 and alumina or clay it is used to make cement.
(iii) It is used for softening of water.
2. Hydroxides
Gruop - I
Hydroxides of alkali metals are strong base. Their basic character increases down the group. They
dissolve readily in water giving much heat due to intense hydration. If we go down the group solubility
of alkali metal hydroxides increases.
1. Sodium hydroxide [NaOH] (Caustic Soda)

Preparation :
(i) Heating 10%Na2CO3 Sol. with mild of lime (Lime - Caustic Soda process) :


Na 2CO3  Ca(OH)2 
 2NaOH  CaCO3

(ii) Electrolysis of brine :

Commercially, NaOH and Cl2 are manufactured simultaneously by the electrolysis of brine (NaCl
solution).
Reactions occuring at anode and cathode are :


NaCl  
 Na  Cl

At Anode : 2Cl 
 Cl2  2e
At Cathode : Na  le   Na
2Na  2H2O  2NaOH  H2
Another reaction may occur at the anode to a small extent.
4OH  
 O 2  2H 2O  4e 
Electrolysis is carried in either of two types of cell today, diaphragm and mercury cathode cells.
NaOH made in this way always contanins some amount of NaCl.
(a) Diaphragm cell / Nelson : A porous diaphragm of asbestos is used to keep the H 2 and Cl2
gases separated otherwise they react in an explosive chain reaction in dylight. Diaphragm also
seperates the carbon anod and cathod.
(b) Mercury Cathod Cell / Castner - Kellner Cell : The anode is made up of carbon and the
cathode of mercury. The reaction occuring at Hg cathode are thus :
Cathod : Na   e  
 Na
Na  Hg  Na  Hg amalg am 

The amalgam is pumped in a different comartment called denuder where water trickles over.
1
Na  Hg  H 2O 
 NaOH  H 2  Hg  recycled back to electrolysis tan k 
2
Properties :
(i) It is a white crystalline solid, deliquiscent (absorbs moisture from air), soluble in water, good conductor
and gives silky touch like soap.
(ii) It reacts with acid and acidic oxides to form salts
NaOH  HCl 
 NaCl  H 2O
2NaOH  SiO 2 
 Na 2SiO3  H 2O
2NaOH  CO 2 
 Na 2CO3  H 2O
(iii) It reacts with amphoteric metals such as Sn, Al, Zn and amphoteric metal oxides.
Zn  2NaOH   Na 2 ZnO 2  H 2 Sodium Zincate 

3
Al  NaOH  H 2O 
 NaAlO 2  H 2  Sodium Aluminate 
2
Sn  2NaOH 
 Na 2SnO 2  H 2  Sodium Stannate 
SnO  2NaOH 
 Na 2SnO2  H 2O
SnO2  2NaOH 
Al2O3  2NaOH 
 2NaAlO2  H 2O
(iv) It reacts with ammonium salts to give ammonia, whcih serves as a test for ammonia.
NH 4Cl  NaOH 
 NaCl  NH3   H 2 O
The above reaction is double displacement reaction only. NH4OH must be formed as second product.
But NH4OH is never formed as a product. It decomposes to give NH3 + H2O.
(v) Disproportion of some non-metals in NaOH : (Learn these reactions)
X2  NaOH 
 NaX  NaOX  H 2O  X  Cl, Br, I
 Cold & Conc.

X2  NaOH 
 NaX  NaOX3  H 2O
 hot and Conc.
P4  NaOH  
 NaH 2 PO 2  PH 3
 phosphine 
[This reaction is used in the preparation of phosphine gas.]
S  NaOH 
 Na 2S  Na 2S2O3  H2O
(All above reactions can be balanced as Redox Reactions)

(vi) Reactio with salts of transition metals :
 Fe  OH 3  3NaCl
FeCl3  3NaOH 
When hydroxides are unstable, the oxides are precipitated.
 HgO     H 2O  2NaCl
HgCl2  2NaOH 

Hg  OH  2
 Ag 2O     H 2O  2NaNO3
2AgNO3  2NaOH 
  
AgOH
2. Potassium Hydroxide [KOH] (Caustic Potash)

Preparation :
It can be prepared by electrolysis of KCl solution similar to electrolysis NaCl solution (brine)
At Cathode : 2K   2H 2O  2e  
 2KOH  H 2 
At anode : 2Cl  2e 

 Cl2 
Properties :
(i) The properties are similar to those of NaOH but being expensive is less used.
(ii) KOH is more soluble in alcohol than NaOH and produces OC2H5 ions.

 


C2 H5OH  O H 
 OC2 H5  H 2O
This accounts for use of elcoholic KOH in OrganicChemistry which you will study in modules of organic.
Uses :
(i) It is used in organic chemistry
(ii) KOH is used as an absorbent for CO2, for which is perferred over NaOH, since after absorption
of CO2, the KHCO3 formed is solube whereas NaHCO3 being sparingly soluble separates out,
and chokes the absorption bulbs.
Gruop - 2
Alkaline earth metal oxides react with water to form sparingly soluble metal hydroxides.
Alkaline earth metal hydrooxides are less basic and more stable than alkali metal hydroxides. The solubility,
thermal stability and basic character of the hydroxides increases down the group. Beryllium hydroxide is
amphoteric in nature as it reacts with both acids and bases.
Be  OH 2  2NaOH 
 Na 2  Be  OH 4 
Sodium beryllate
Be  OH 2  2HCl  2H 2O 
  Be  OH 4  Cl2
Rest of the alkaline earth metal hydroxide are basic in nature.
1. M agn esi u m H y d r o x id e [ M g(OH ) 2]

Preparation :
Mg(OH)2 is pepared by dissolving magnesium oxide in water.
 Mg  OH 2
MgO  H 2O 
Properties :
(i) It is a white powder extermely insoluble in water.
(ii) It is weakly basic and suspension Mg(OH)2 in water [milk of Magnesia] is used as an antacid.
2. Calcium Hydroxide [CaOH)2]

Preparation :
Calcium hydroxide is prepared by adding water to quick lime (CaO).
 Ca  OH  2
CaO  H 2O 

Properties
(i) It is white powder, sparingly soluble in water.
(ii) The aqueous sturated solution of Ca(OH)2. is known as lime water and the suspension of slaked
lime (solid Ca(OH)2) in water is known as milk of lime.
(iii) Bleaching powder is formed when chloring gas is passed through lime water.
3Ca(OH)2  2Cl2 
 Ca(OCl)2 . Ca(OH)2 . CaCl2 . 2H2O
Uses :
(i) It is used in white wash.
(ii) It is used in the solvay’s process.
(iii) It is used to remove temperaray hardness of water :
Ca(HCO3 ) 2  Ca  OH 2 
 2CaCO 3   2H 2O
Mg(HCO3 )2  Ca(OH)2 
 2CaCO3   Mg(OH)2   2H2O
(iv) When carbon dioxide is bubbled through lime water it turns milky and when excess carbon dioxide is
passed, the precipitate (CaCO3) dissolves forming Ca(HCO3)2.
CO
2  CaCO () 
2  Ca(HCO ) CO
Ca(OH)2(aq)  3 3 2(aq)
white precipitate Excess
soluble
Similaraly, Ba(OH)2 (Baryta water) responds, when CO2 is bubbled through it.
CO
2  BaCO () 
2  Ba(HCO ) CO
Ba(OH)2  3 3 2(aq)
milky so ln. Excess
milkiness disappears
In this reaction Ba(OH)2 is even more sensitive ot CO2 but Ba(OH)2 being more expensive,
Ca(OH)2, is preffered to detect CO2 in laboratory.
Note : The caustic alkalis (NaOH and KOH) are the strongest bases known in aqueous solution. Soda lime is a
mixture of NaOH and Ca(OH)2 and is made from quick lime (CaO) and aqueous NaOH. Soda lime is
much easier to handle than NaOH.

3. Halides
Gruop - I
Alakali metal halides like NaCl and KCl are generally found in sea water. Among Sodium halides,
stability, melthing point and boiling point decreases down the group. Solubility for alkali metal halides
doesnot show a regular trend.
1. NaCl
Preparation :
It occurs in sea water as deposits in mines as rock salt. It is extracted from sea water simply by
solar evaporation. The crystals of NaCl are washed to remove more soluble MgCl2.
Properties :
(i) It is colourless crystalline (in pure form). it is NOT hydroscopic but pressence of MgCl2
makes it deliquescent due to the high polarizing power of MgCl2 (that attracts H2O molecules)
(ii) It is used to produce industrially important compounds like Na2CO3 and Cl2.
(a) Na2CO3 is produced by Solvay’s Process. (discussed later)
(b) Cl2 is produced by :
(i) Electrolysis (NaOH is also a product) of brine.
(ii) Leblanc Process : NaCl  conc. H 2SO4 
 NaHSO4  HCl
heat
NaHSO4  NaCl 
 Na 2SO4  HCl
 Cl2  Mn 2 
HCl  MnO2 
Uses :
(i) Eating salt in food.
(ii) It is used to lower the melting point of ice. Kulfi seller uses NaCl to sustain Kulfi for long time
in summer.
KCl is also extracted from sea water. Its properties are almost similar to NaCl. It has an important
use in producing fertilizers.
Gruop - II
Alkaline earth metal halides are generally made by heating matals with halogen or by action of halogen
acid on metal or metal or metal carbonates. Beryllium halides are covalent while rest of the alkaline
earth metals form ionic halides.
BeCl2 has a chain structure as shown in the figure.

Here Cl bonded to one Be uses a lone pair of e–s to form a coordinate bond to another Be atom.
Dehydration of hydrated chlorides, bromides and iodies of Ca, Sr, Ba can be achieved on heating but the
hydrated halides of Be and Mg suffer hydrolysis on heating. In aqueous solution BeCl2 , Be exists as
2
 Be  H 2O   or  Be  H 2O 4  Cl2 .
 4
heat
 Be  H 2O   Cl2   Be  OH  2  2HCl
 4
1. Magnesium Chloride [MgCl2 . 6H2O]

Preparation
(i) It is prepared by passing dry HCl over Magnesium.
Mg  2HCl 
 MgCl2  H 2 
(ii) Dow’s process :

The extraction of Magnesium from sea water depends on the fact that Mg(OH)2 is very much less
soluble than Ca(OH)2.
Ca(OH)2  MgCl2 
 Mg (OH)2   CaCl2
(in sea water )
acidified
Mg(OH)3  MgCl2(aq) ( MgCl2 . 6H 2O)
with HCl
dry HCl
MgCl 2 . 6H 2 O  MgCl2  6H 2 O
Cl 2 /SOCl 2
Note : If MgCl2 . 6H2O is heated, then the products are MgO and HCl. So water of crystallisation are removed
by passing dry HCl/Cl2 or SOCl2.
Properties
(i) It is colourless solid, highly soluble in water.
(i) When heated, it decomposes


MgCl2 . 6H2O 
 Mg(OH) Cl  HCl  5H2O

Mg(OH) Cl 
 MgO  HCl
Uses :
It is used in electrolytic method for extracting Magnesium.
2. Calcium Chlorid [CaCl2 . 6H2O]
Preparation
It is formed as Solvay’s Process’ by-product.
Properties
(i) It reduces the freezing pt. of water.
(ii) Anhydrous salt is an excellent drying agent. It forms addition compounds with NH3 and CH3OH
(CaCl2 . 8NH2 and CaCl2 . 4CH2OH) and hence cannot be used to dry them.
Uses :
It is sprinkled on roads in hilly areas to remove snow.
4. Carbonates :
Gruop - I
Alakli metal carbonates are basic salts. The stability of alkali metal carbonates towards heat increases
down the gourp. Thye quite stable and melt before they eventually decompose into oxides (at above
1000oC).
1. Sodium Carbonate (Na2CO3) :
Washing soda is Na2CO3 . 10H2O
Soda ash in Na2CO3
Preparation :
Solvays’s Process (Ammonia-Soda Process)
The process is much more complicated than the overall equation and since the reactions involved
are reversible only 75% of the NaCl is converted.
The purified brine (NaCl) solution is first saturated with ammonia and then carbonated with CO2
forming NaHCO3
 HCO3  H 
CO2  H2O  ; NH3  H 
 NH 4
NH 4  HCO3  NaCl 
 NaHCO3  NH 4Cl

The NaHCO3 formed is insoluble in the brine solution becasue of the common ion effect and so can
be filtered off. This is then heated to form anhydrous Na 2CO3 .
150C
2NaHCO3  Na 2CO3  H2O  CO 2
NH4Cl produced above reacts with lime water forming a very good dehydrating agent (CaCl2) and
evolving NH3 gas.
2NH 4Cl  Ca  OH 2 
 CaCl 2  2NH 3  2H 2O
Lime water used above was prepared instantaneously by heating CaCO3 and passing water through
quick lime.

CaCO3  CaO  CO 2 ;  Ca  OH  2
CaO  H 2O 
The materials consumed are NaCl and CaCO3 and the useful product is Na2CO3. CaCl2 which is a
by prodcut is little used and the rest is wasted. CO2 and NH3 formed are used again to continue the
process.
The whole process can be diagrammatically shown as :
Properties :
(i) On passing CO2 through aqueons solution of Na2CO3, NaHCO3 is formed.
Na 2CO3  CO2  H2O 

 2NaHCO3 
(ii) When aqueous solution of sodium carbonate containing sulphur is treated with sulphur dioxide,
sodium thiosulphate is formed.
Na 2CO3  SO2  H2O 

 Na 2SO3  CO2 
Na 2SO3 + S 
 Na 2S2O3

(iii) On heating washing soda (Na 2CO3 10 H 2O) it forms monohydrate called heavy ash or crystal
carbonate.

Na 2CO3 . 10H 2O 
 Na 2CO3 . H 2O  9H 2O
Uses :
(i) Used in water softening and cleaning.
(ii) Used in paper, paint and textile industries
Potassium carbonate (Pearl Ash) is not much important. Its properties resemble closely with
Na2CO3. It is prepared by carbonation of caustic potash.
KOH  CO2 
 K 2CO3  H2O
Note : K2CO3 cannot be prepared by Solvay’s Process because KHCO3 formed in the reaction is highly soluble
and hence cannot be separated form (NH4Cl + KHCO3) mixture easily.
Gruop - II
Carbonates are basic salts. BeCO3 is covalent while other carbonates are ionic. On heating, alkaline earth
metal carbonates forms an oxide and carbon dioxide is evolved.
1. Calcium Carbonate [CaCO3] :
Preparation :
It is mainly extracted from its ores. It can be prepared by these methods also :
(i) It can be prepared by passing limited CO2 through lime water.
Ca(OH)2  CO 2 
 CaCO3  H 2O
(ii) It can be obtained by adding sodium carbonate solution to CaCl2.
CaCl2  Na 2CO3 
 CaCO3  2NaCl
Properties :
(i) It is white powder, almost insoluble in water.
1200 K
(ii) On heating at 1200 K, CO2 is evolved CaCO3   CaO  CO2 (  )
(iii) CaCO3  HCl 

 CaCl2  H2O  CO2 (  )



H2CO3

Uses :
(i) It used in manufacture of cement and quick lime.
(ii) Used in Solvay’s process in the manufacture of Ca(OH)2.
(iii) It is used in toothpaste.
5. Bicarbonates
Gruop - I
Alkali metal are strongly basic and form solid bicarbonates (execpt lithium) while no other melal forms
solid bicarbonates LiHCO3 can exist only in solution. Alkali metal hydrogen carbonates are soulble in
water. On heating, they decompose to give carbonates.
The hydrongen bonding in bicarbonates enhances the stability. In NaHCO3, the HCO3 ions are
linked to form infinite chain while in KHCO3, a dimeric anion is formed.
As the electropositive character increase down the group, the stability of hydrogen carbonates also
increases down the group.
1. Sodium Bicarbonate [NaHCO3] (Baking Soda)
Preparation :
It is an intermediate product of Solvay’s process.
NaCl  NH 4  HCO3 
 NaHCO3  NH 4Cl
Properties :
On heating, it decomposes to give Na2CO3, evolving CO2 which is used to detect bicarbonates.

NaHCO3 
 Na2CO3  H2O(  )  CO2 (  )
Uses :
(i) It used in fire extinguisher.
(ii) It is used as baking powder in manufacturing of cake making it fluffy. Backing powder contains
NaHCO3 and Ca(H2PO4)2

50  100C
2NaHCO3  Na 2CO3  H 2O  CO 2 
Ca  H 2 PO 4  2  NaHCO3 
 CO 2 
The CO2 produced makes cake or bread rise.
6. Sulphates
Gruop - I
Sodium sulphate (Na2SO4 . 10H2O) is named as Glauber’s salt. It is produced as a by-product while
manufacturing HCl.

NaCl  H 2SO 4 
 NaHSO4  HCl  ; NaHSO 4  NaCl 
 Na 2SO 4  HCl 
 conc. salt cake 
Fomation of hydrated salts of Na2SO4 :
T  32C T  12C
Na 2SO4 
 Na 2SO 4 .10H 2O ; Na 2SO 4 
 Na 2SO4 . 7H 2O
It is used in paper industry.
Gruop - II
Sulphates of the alkaline earth metals are all white solids & stable to heat. Be and Mg sulphate are
highly soluble while other alkaline earth metal sulphates are very less soluble. This is due to very high
hydration enthalpy of Be2+ and Mg2+. Thermal stability of alkaline earth metal sulphates increases
down the group while solubility decreases.
1. Magnesium Sulhate [MgSO4]
It is a colourless soluble salt whcih decomposes to MgO, SO2 and O2 on heating.
MgSO4 . 7H2O is called Epsom salt while MgSO4.H2O is called Kieserite.
2. Calcium Sulphate [CaSO4]

Preparation :
It is prepared in lab by adding dil. H2SO4 to the solution of calcium salt.
CaCl2  H 2SO 4  dil  

 CaSO 4  2HCl

Properties :
In nature it occurs as Gypsum CaSO 4 . 2H 2O.
150C 1 200C 1100C 1

CaSO 4 .2H 2O  CaSO4 . .H 2O   CaSO 4   CaO  SO 2  O 2
2 2
gypsum Plaster of paris anhydrite
When powdered plaster of paris CaSO4 . 1/2 H2O is mixed with the correct amout of water it sets
into a solid mass of CaSO4 . 2H2O (gysum). The process is used in plastering walls and plasters for
fractures.
ALUMS
The general representation of alums is [(M1 ) 2 SO 4 ] [(M III ) 2 (SO 4 )3 ]. 24 H 2O where M I represents the
metal with +1 Oxidation state and MIII represents the metal with +3 oxidation state. These alums are double
salts, which dissolve in water to give [M I  H 2O 6 ] , [M III  H 2O 6 ]3 and SO 42 ions and there-
fore., the alums are also represented as [M I  H 2O 6 ], [M III  H 2O 6 ] (SO 4 ) 2 . They form octahedral
crystals.
If MI is K  and M III is Al3 , Then the alum is potash alum  K2SO4 , Al2 (SO4 3 . 24H2O
     III
or [K(H 2O)6 ] [Al(H 2O)6 ] (SO 4 ) 2 M1 can be K , NH 4 , Rb , Cs , TL and M can be
Fe3 , Al3 , CO3 , Ga 3 , Mn 3 .  NH 4  2 SO 4 .Fe2 SO 4 3 .24H 2O is called ferric ammonium alum
while K 2SO4 .Cr2  SO 4 3 .24H 2O is chrome alum. Potash alum on heating dissolves in its own water of
crystallisation and on further heating forms K 2SO 4 .Al2  SO4 3 called burnt alum.
Micro Cosmic Salt [Na(NH4)HPO4]

Microcosmic salt is a white crystallion solid and is prepared NH4Cl and Na2HPO4 as follows :
 Na  NH 4  HPO4   NaCl
NH 4Cl  Na 2HPO 4 
On decomposition the following is obtained :


Na  NH 4  HPO 4 
 NH 4   NaH 2 PO 4

 NaPO3  Calgon   H 2O
NaH 2 PO 4 
Microcosmic salt can be used as a substitue for borax in the Bead Test

Similar salt are also formed by Magnesium :
 Mg  NH 4  PO 4
MgSO 4  NH 4 OH  Na 2HPO4 
 
Mg  NH 4  PO 4 
 NH3  MgHPO 4  Mg 2P2O7  H 2O
IMPORTANT THINGS TO REMEMBER Section - 4
Anomalous properties of Lithium :

The anomalour behaviour of lithium is due to the : (i) exceptionally small size of its atoms and ion, and (ii)
high polarizing power (i.e., charge/radius ratio). As a result, there is increased covalent character of lithium
compounds which is resposible for their solubility in organic solvents. Further, lithium showns diagonal
relationship to magnesium which has been discussed subsequently.
Points of Difference between Lithium and other Alkali Metals :
(i) Lithium is much harder. Its M.P. and B.P. are higher than the other alkali metals.
(ii) Lithium is least reactive but the strongest reducing agent among all the alkali metals. On combustion in
air it forms mainly monoxide, Li2O and the nitride, Li3N while other metals form only oxide.
(iii) LiCl is deliquescent and crystallizes as a hydrate, LiCl.2H2O whereas other alkali metal chlorides do
not form hydrates.
(iv) Lithium hydrogencarbonates being unstable is not obtained in the solid form while all other elements
form solid hydrogencarbonates.
(v) Li2CO3, LiNO3,LiOH all form oxide on gentle heating, throgh the analogus compounds of the rest of
the group are stable.
4LiNO3 
 2Li2O  4NO 2  O 2
2NaNO3 
 2NaNO2  O2
(vi) Li2CO3, LiF and Li2O are comparatively much less soluble in water than the corresponding com-
pounds of other alkali metals.
(vii) Lithium is much heavily hydrated than those of the rest of the group.
Points of Similarities between Lithium and Magnesium :

The similarity between lithium and magnesium is particularly striking and arises because of their similar sizes
: atomic radii, Li = 152 pm, Mg = 160 pm; ionic radii : Li+ = 76 pm, Mg2+ = 72 pm. The main points of
similarity are:

(i) Both lithium and magnesium are harder and lighter than other element in the respective group.
(ii) Lithium and magnesium react slowly with water. Their oxides and hydroxides are much less soluble
and their hydroxides decompose on heating. Both form a nitride, Li3N and Mg3N2, by direct combi-
nation with nitrogen.
(iii) The oxides Li2O and MgO do not combine with excess oxygen to give any superoxide.
(vi) The crbonates of lithium and magnesium decompose easily on heating to form the oxides and CO2.
Solid hydrogencarbonates are not formed by lithium and magnesium.
(v) Both LiCl and MgCl2 are soluble in ethanol.
(vi) Both LiCl and MgCl2 are deliquescent and crystallize from aqueous solution as hydrates. LiCl.2H2O
and MgCl2.8H2O
Anomalour Behaviour of Beryll ium :

Beryllium, the first member of the Group 2 metals, shows anomalous behaviour as compared to magnesium
and rest of the members. Further, it shows diagonal relationship to aluminium which is discussed subse-
quently.
(i) Beryllium has exceptionally small atomic and ionic sizes and thus does not compare well with other
members of the group. Because of high ionization enthalpy and small size it forms compounds which
are largely covalent and get easily hydrolysed.
(ii) The oxide and hydroxide of beryllium, unlike the hydroxides of other elements in the group, are
amphoteric in nature.
Diagonal Relationship between Beryllium and Aluminum :

The ionic radius of Be2+ is estimated to be 31 pm; the charge / radius ration is nearly the same as that of the
Al3+ ion. Hence beryllium resmebles aluminium in some ways. Some of the similarities are :
(i) Like aluminium, beryllium is not readily attacked by acids beacuse of the presence of an oxide film on
the surface of the metal.
(ii) Beryllium hydroxide dissolves in excess of alkali to give a beryllate ion, [Be(OH)4 ]2  just as alu-
minium hydroxide give aluminate ion, [Al(OH) 4 ] .
(iii) BeCl2 and AlCl3 exist in form to chain. BeCl2 form polymeric chain (chain with a large no. of BeCl2
molecules) and AlCl3 forms dimeric chain (chain with two AlCl3 molecules).
(iv) Beryllium and aluminium ions have strong tendency to form complexes, BeF42  , AlF63 .

1. NaHCO3 and NaOH can not exist together in solution. Why ?

2. The hydroxide and carbonates of Na and K are easily soluble in water while the corresponding salts
of Mg and Ca are sparingly soluble in water. Explain.
3. Solvay Process is used to manufacture sodium carbonate but it is not extended to the manufacture of
potassium carbonate. Why ?
4. Why are MgO and BeO used for the lining of steel making furnance.
5. On the treatment with cold water, an element (A) reacted quietly, liberating a colourless, odourless
gas (B) and a compound (C). Gas (B) further reacts with element (A) to yield a solid product (D)
which reacted with water to give a basic solution (E). (E) is found to be same as (C). When carbon
dioxide was bubbled through solution (C) initially a white precipitate (F) is formed, but this redissolved
forming solution (G) when more CO2 was added. Precipitate (F) was heated at 1000C , a white
compound (H) was formed which when heated with carbon at 1000C , gave a solid (I) of some
commercial importance. Name the substances (A) to (I).

HYDROGEN Section - 5
Postion of Hydrogen in the Periodic Table

Hydrogen has electronic configuration 1s1. On one hand, its electronic configuration is similar to the outer
electronic configuration (ns1) of alkali metals, which belong to the first group of the periodic table. On the
other hand, like halogens (with ns2 np5 configuration belonging to the seventeenth group of the periodic
table). it is short by one election to the corresponding noble gas configuration, Helium (1s2). Hydrogen,
therefore, has resemblance to alkali metals, which lose one electron to form uni-positive ions, as well as with
halogens, whcih gain one electron to form uni-negative ion. Like alkali metals, hydrogen forms oxides,
healides and sulphides. However, unlike alkali metals, it has a very high ionization enthalpy and does not
possess metallic characteistics under normal conditions. In fact, in terms of ionization enthalpy hydrogen
resembles more with halogens, i H of Li is 520 kJ mol 1, H of F is 1680 kJ mol1 and i H of H
is 1312 kJ mol 1. Like halogens, if forms a diatomic molecule, combines with elements to form hydrides
and a large number of covalent compounds. However, in terms of reactivity, it is very low as compared to
halogens. It is always a matter of debate in which group hydrogen should be placed. It is best placed
separtely in the periodic table.
Isotpes of Hydrogen
Hydrogen has three isotopes : Protium (11 H), Deuterium (12 H) or D and Tritium (13 H) or T. These isotopes
differ from one another in respect of the presence of neutrons. Ordinary hydrogen, Protium, has no neu-
trons. Deuterium (also know as Heavy Hydrogen) has one and Tritium has two neutrons in the nucleus.
The predominant form is Protium. Terrestrial hydrogen contains 0.156% of Deuterium mostly in the form of
HD. The Tritium concentration is about one atom per 1018 atoms of Protium. Of these isotopes, only Tritium
is radioactiver and emits low energy Particles (t1/2 = 12.33 years).
Since the isotopes have the same electronic configuration, they have almost the same chemical properties.
The only difference is in their rates of reactions, mainly due to their different enthyalpy of bond dissociation.
Property Hydrogen Deuterium Tritium

Relative abundance (%) 99.985 0.0156 10-15
Relative atomic mass (g mol) 1.008 2.014 3.016
Melting point (K) 13.96 18.73 20.62
Boiling point (K) 20.39 23.67 25.0
Density (g L-1) 0.09 0.18 0.27

Prepartion of Dihydrogen, H2
There are a number of methods for preparing dihydrogen from metals and metals and hydrides.
Laboratory Preparation of Dihydrogen
1. It is usually prepared by the reaction granulated zinc with dilute hydrochloric acid.
Zn  2H  
 Zn 2   H 2
2. It can also be prepared by the reaction of zinc with aqueous alkali.
Zn  2NaOH 
 Na 2 ZnO 2  H2
Sodium Zincate
Commercial Production of Dihydrogen :

1. Electroysis of acidified water using platinum electrodes gives hydrogen. This method gives very pure
H2 but it is very expensive
Electrolysis
2H2O 1 
 2H2  g   O2  g 
Traces of acid /base
2. It is obtained as a by product in the manufacture of sodium hydroxide and chlorine by the electrolysis
of brine solutionn. During electrolysis, the reactions that take place are :
At anode : 2Cl  aq  
 Cl2  g   2e
At cathode : 2H 2O  l   2e  
 H 2  g   2OH   aq 
The overall reaction is
2Na   aq   2Cl  aq   2H 2O  l  
 Cl2  g   H 2  g   2Na   aq   2OH   aq 
3. Reaction of steam on hydrocarbons or coke at high temperatures in the presence of catalyst yields
hydrogen.
1270K
 nCO   2n  1 H 2
Cn H 2n  2  nH 2O 
Ni
1270K
CH 4  g   H 2O  g  
 CO  g   3H 2  g 
Ni
The mixture of CO and H2 is called Water gas. As this mixture of CO and H2 is used for the synthesis
of methanol and a number of hydrocarbons, it is also called sythesis gas or ‘Syngas’.Nowadys‘syngas’
is produced from sewage, saw-dust, scrap wood, newspapers etc. The process of producing ‘synags’
from coal is called ‘Coal gasification’.
1270K
C  s   H 2O  g  
 CO  g   H 2  g 

It is difficult to obtain pure H 2 from water gas, since CO is difficult to remove. Still CO may be liquified at
a low temperature under pressure. Thus seperating it from H 2 . One more thing that can be done is the gas
mixture can be mixed with steam, cooled to 400°C and passed over iron oxide to give H 2 and CO2 .
Fe
CO + H 2O  CO2 + H 2
This is called Water - gas shift reacrion. This reaction increases the amount of H2 and gives a method to
extract H2 easily. CO2 in mixture of CO2 and H2 can be removed by dissolving mixture in water under
pressure, or reacting mixture K2CO3 solution giving KHCO3, or by scrubbing mixture with sodium arsenite
solution.
 Dihydrogen is a colouless, odourless, tasteless, combustible gas. It is lighter than air and insoluble in
water.
The chemical behaviour of dihydrogen (and for that mattter any molecule) is determined, to a large extent,
by bond issociation enthyalpy. The H-H bond dissociations enthalpy is the highest for a single bond between
two atoms any element. It is because of this factor that the dissociation of dihydrogen into its atoms is only
 0.081% around 2000K which increases to 95.5% at 5000K. Also, it is relatively inert at room tempera-
ture due to the high H-H bond enthalpy.
1. Reaction with halogens : It reacts with halogens, X2 to give hydrogen haliides, HX.
H 2  g   X 2  g  
 2HX  g   X  F, Cl, Br, I 
While the reaction with fluorine occurs even in the dark, with iodine it requires a catalyst.
2. Reaction with Dioxygen : It reacts with dioxygen to form water. The reaction is highly exothermic.
catalyst of heating
2H 2  g   O 2  g  
 2H 2O  l  ; H   285.9 kJ mol 1
3. Reaction with dinitrogen : It reacts with dinitrogen to form ammonia.
673K, 200atm
3H 2  g   N 2  g   2NH3  g  ; H   92.6 kJ mol1
Fe
This is the method for the manufacture of ammonia by the Haber’s process.
4. Reactions with metals : With many metals it combines at a high temperature to yield the corre-
sponding hydrides.
H 2  g   2M  g  
 2MH  s  ; where M is an alkali metal

5. Reaction with metal ions and metal oxides : It reduces some metal ions in aqueous solution
and oxides of metals (less active than iron) into corresponding metals.
H 2  g   Pd 2   aq  
 Pd  s   2H  (aq)
yH 2  g   M x O y  s  
 xM  s   yH 2O 1
6. React ion w it h organic com pounds : It reacts with many organic compounds in the presence of
catalysts to give useful hydrogenated products of commercial importance. For example :
Hydrogenation of vegetable oils using nickel as catalyst give edible fats (margarine and vanaspathi
ghee).
Uses of Dihydrogen
 The largest single use of dihydrogen is in the synthesis of ammonia which is used in the manufacture of
nitric acid and nitrogenous fertilizers.
 Dihydrogen is used in the manufacture of vanaspati fat by the hydrogenation of polyunsaturated veg-
etable oils like soyabean, cotton seeds etc.
 It is used in the manufacture of bulk organic chemicals, particularly methanol.
cobalt
CO  g   2H 2  g   CH3OH  l 
catalyst
 It is widely used for the manufacture of metal hydrides.
 It is used a rocket fuel in space research.
 Dihydrgoen is used in fuel cells for generating electrical energy. If has many advantages over the
conventional fossil fuels and electric power. It does not produce any pollutions and releases greater
energy per unit mass of fuel in comparison to gasoline and other fuels.
Hydrides
Binary compounds of the elements with hydrogen are called hydrides. The type of hydride which an element
forms depends upon its electronegativity and hence on the type of bond formed. Hydrides are conveniently
studied under three classes.
(i) Ionic or salt like hydrides
(ii) Covalent or molecular hydrides
(iii) Metallic or interstitial hydrides
 Ionic or salt like hydrides : These are formed by metals of low electronegativity, i.e. alkali and
alkaline earth metals by direct reaction with H2 and some highly positive members of lanthanide series
with the exception of Be and Mg whose hydrides show significiant covalent character.

Te stability of the hydrides decreases as the size of the cation increases.
LiH  NaH  KH  RbH  CsH

CaH 2  SrH 2  BaH 2
CaH2 is called Hydrolith.

 Covalent or Molecular hydrides : These hydrides are formed by all the true non-metals (except
zero group elements) and the elements like Al, Ga, Sn, Pb, Sb, Bi. Po, etc., which are normally
metallic in nature. The simple hydride of B and Ga are dimeric materials B2H6 (diborane) and Ga2H6
respectively and the hydride of aluminium is polymeric in nature, (AlH3)n.
 Metallic or interstitial hydrides : Many transition and inner-transition elements at elevated tem-
peratures absorb hydrogen into the interstices of their lattices to yield metal-like hydrides, often called
the interstitial hydrides. These hydrides are often non-stoichiometric and their composition vary with
temperature and pressure. Formulae of some of the hydrides of this class are :
TiH1.73 , CeH 2.7 , LaH 2.8 , PdH 0.60 , ZrH1.92
The interstitial hydrides have metallic appearance and their properties are closely related to those of
the parent metal. They posses reducing properties probably due to the presence of free hydrogen
atoms in the metal lattice.
Water
In the gas phase water is a bent molecule with a bond angle of 104.5o, and O-H bond length of 95.7 pm. It
is a highly polar molecule. Its orbital overlap is shown in figure below. In liquid phase, water molecules are
associated together by hydrogen bonds. In ice each oxygen atom is surrounded tetrahedrally by four other
oxygen atoms at a distance of 276 pm.
Chemical Properties of Water :

Water reacts with a large number of substances. Some of the important reactions are given below.
1. Amphoteric Nature : It has the ability to act as an acid as well as a base i.e., it behaves as an
amphoteric substance. In the Bronsted sense it acts as an acid with NH3 and a base with H2S.


H 2O  l   NH3  aq    
 OH  aq   NH 4  aq 


H 2O  l   H 2S  aq    
 H3O  aq   HS  aq 

The auto-protolysis (self-ionization) of water takes places as follows :


H 2O  l   H 2O  l   
 H3O  aq   OH   aq 
acid 1 base  2 acid  2 base  1
 acid   base   conjugate acid   conjugate base
2. Redox Reactions Involving Water : Water can be easily reduced to dihydrogen by highly electroposi-
tive metals.
2H 2O  l   2Na  s  
 2NaOH  aq   H 2  g 
Water is oxidised to O2 during photosynthesis.
6CO 2  g   12H 2O  l  
 C6 H12O6  aq   6H 2O  l   6O 2  g 
With fluorine also it is oxidized to O2.
 4H   aq   4F  aq   O 2  g 
2F2  g   2H 2O  l  
3. Hydrolysis Reaction : Due to high dielctric constant, it has a very strong hydrating tendency. It dissolves
many ionic compounds. However, certain covalent and some ionic compound are hydrolysed in water.
P4O10  s   6H 2O  l  
 4H3PO 4  aq 
SiCl4  l   2H 2O  l  
 SiO2  s   4HCl  aq 
N3  s   3H 2O  l  
 NH 3  g   3OH   aq 
4. Hydrates Formation : From aqueous solutions many salts can be crystallised as hydrated salts. Water of
hydration are water molecules atttached to a compound that can be removed on heating. Such an associa-
tion of water is of different types viz.,
3
(i) Coordinated water e.g.,  Cr  H 2O   3Cl
(ii) Interstitial water e.g., BaCl2 . 2H 2O
2
(iii) Hydrogen-bonded wate e.e.,  Cu  H 2O 4  SO42  . H 2O in CuSO4 . 5 H 2O
Here in CuSO 4 . 5H 2O, four water molecules of hydration are coordinate bonded and one is hydro-
gen bonded.
Note : You will learn about hyrates later in Coordination Compounds.

*Hard and Soft Water :

Rain water is almost pure (may contain some dissolved gases from the atmosphere). Being a good solvent,
when it flows on the surface of the earth, it dissolves many salts. Presence of calcium and magnesium salts
in the form of hydrogencarbonate, chloride and sulphate in water makes water ‘hard’. Hard water does not
give lather with soap. Water free from soluble salts of calcium and magnesium is called Soft water. It gives
lather with soap easily.
Hard water forms scum/precipitate with soap.Soap containg sodium strearate (C17H35COONa) reacts
with hard water precipitate out Ca/Mg strearate.
2 RCOONa(aq) + M 2+ (aq) 
 (RCOO)2 M  +2 Na + (aq) ; M is Ca/ Mg
Scum
e.g., 2C17 H35COONa  aq   Ca 2   aq  

  C17 H35COO 2 Ca   2Na   aq 
Scum
It is, therefore, unsuitable for laundry.
The hardness of water is of two types :
(i) Temporary hardness, and (ii) Permanent hardness.
Temporary Hardness :
Temporary hardness is due to the presence of magnesium and calcium hydrogen-carbonates. It can be
easily removed by :
1. Boiling : During boiling, the soluble Mg(HCO3)2 is converted into insoluble Mg(OH)2 and Ca(HCO3)2
changed to insoluble CaCO3. These precipitates can be removed by filteration.
Heating
Mg  HCO3 2 
 Mg  OH 2   2CO 2 
Heating
Ca  HCO3 2 
 CaCO3   H 2O  CO 2 
2. Clark’s method : In this method calculated amount of lime is added to hard water. It precipitates out
calcium carbonate and magnesium hydroxide which can be filtered off.
Ca  HCO3 2  Ca  OH  2 
 2CaCO3   2H 2O
Mg  HCO3 2  2Ca  OH 2 
 2CaCO3   Mg(OH)2   2H 2O
Note : Temporary hardness such as Ca(HCO3 )2 can also be removed by adding Na 2CO3 .
Ca(HCO3 )2 + Na 2CO3 
 CaCO3  +2 NaHCO3
Permanent Hardness :
It is due to the presence of soluble salts of magnesium and calcium in the form of chlorides and sulphates in
water. Permanent hardness is not removed by boiling. It can be removed by the following methods:

1. Treatment with washing soda (Sodium carbonate) :
MCl2  Na 2CO3 
 MCO3   2NaCl (M  Mg, Ca)
MSO4  Na 2CO3 
 MCO3   Na 2SO4
(Washing soda)
2. Calogen’s method : Sodium hexametaphosphate (Na6P6O18), commercially called ‘Calgon’ or Graham’

salt’, when added to hard water, the following reactions take place :
 2Na   Na 4 P6O182 
Na 6 P6O18  M  Mg, Ca 
2
M 2   Na 4 P6O182  
  Na 2 MP6O18   2Na 
The complex anion keeps the Mg 2  and Ca 2  ions in solution.

3. Ion-exchange method : This method is also called zeolite/permutit process. Hydrated sodium aluminium
silicate is zeolite/permult prcess. For the sake of simplicity, sodium aluminum silicate (NaAlSiO4) can be
written as NaZ. When this is added in hard water, exchange reactins take place.
2NaZ(s)  M 2  (aq) 
 MZ2 (s)  2Na  (aq) (M  Mg, Ca)
Permutit/zeolite is said to be exhausted when all the sodium in it is used up. It is regenerated for further use
by treating with an aqueous chloride solution.
MZ2 (s)  2NaCl (aq) 

 2NaZ (s)  MCl2 (aq)
4. Synthetic Resins Methods : It is used in the prodcution of deionised water and more efficient than the
Zeolite process.
Water is passed through two differnt ion-exchange columns :
1st Column (Cation Exchange Coloumn) :
The resin exchange H  with Na  , Ca 2  and Mg 2 
resin  SO3H  M  
 resin  SO3M  H 
 
sulphonic acid
resin
2nd Coloumn (Anion Exchange Column) :
The resin exchanges OH  with Cl  , HCO3 , SO 42 
resin  NR 4 OH   X  
 resin NR 4 X   OH 
 
re sin with basic
group

When all reactive sites on resins have been used they can be regenerated by treating first one with dil.
H 2SO 4 and second one with Na 2CO3 solution.
Heavy water, D2O

It is extensively used as a moderator in nuclear reactors and in exchange reactions for the study of reaction
mechanisms. It can be prepared by exhaustive electrolysis of water or as a by-product in some fertilizer
industries. It is used for the preparation of other deuterium compounds, for example :
 C2 D 2  Ca  OD 2
CaC2  2D 2O 
SO3  D2O 
 D 2SO 4
 3CD4  4Al  OD 3
Al4C3  12D 2O 
DEGREE OF HARDNESS Section - 6
Concentration of Solute in Terms of Parts per Million (or ppm) :

Concentration of solute ( in ppm) = mass of solute ( in gms) in 106 ml solution
It is used in determining the hardness of water which is due to the presence of bicarbonates (temporary
hardness), chlorides and sulphates (permanent hardness) of Calcium and Magnesium. Degree of Hardness
is defined as the number of parts of CaCO3 or equivalent to other calcium and magnesium salts present in
a million (106 ) parts of water..

Mass of CaCO3
Degree of Hardness   106 ppm
Mass of water

How to calculate degree of hardness in a water sample containing 111 ppm of CaCl2 ?
100 111
E CaCO3 = = 50 ; E CaCl 2 = = 55.5
2 2
which means 50 gm of CaCO3  55.5 gm CaCl2
or 55.5 gm CaCl2  50 gm of CaCO3
 111.0 gm CaCl2  100 gm of CaCO3  100 ppm

Illustration - 1Calculate the weight of CaO required to remove hardness of 106 L of water contain-
ing 1.62 gm of Ca(HCO3 )2 in 1.0 litre .
Solution :
Consider the reaction between CaO and Ca(HCO3 )2 .  moles of CaO required for 1.0 L of sample
= 0.01 (from stoichiometry)
CaO+ Ca(HCO3 )2 
 2 CaCO3 + H 2O
 moles of CaO required for 106 L of water
From stoichiometry, we have :
1 mole of Ca(HCO3 )2  1mole of CaO  0.01  106  104 moles.
 2 moles of CaCO3  grams of CaO  104  56  5.6  105 gm.
Now moles of bicarbonate in 1.0 L of sample
1.62
  0.01 [ M 0 of Ca(HCO 3 ) 2 = 162]
162
Illustration - 2 A particular water sample is found to contain 96.0 ppm of SO42  and 122.0 ppm of
HCO3 , with Ca 2  as the only cation. How many ppm of Ca 2  does this water contain ?
Solution :
CaSO 4  Ca 2+ + SO 42  96 ppm  96 g SO 24  in 106 mL H 2O
Ca(HCO3 ) 2  Ca 2+ + 2 HCO3  1.0 mol of SO 24   1.0 mol of Ca 2+

Every mol of CaSO 4 has equal mol of 122 ppm = 122 g HCO 3 in 10 6 mL H 2 O
Ca 2+ and SO 24  but every mole of
 2.0 mol of HCO3  1.0 mol of Ca 2+
Ca(HCO3 )2 has Ca 2+ half the mol of HCO3 .
Total Ca 2+ = 1+1 = 2.0 mol of Ca 2+
 80 g in10 6 mL H 2O
 Ca 2+  80 ppm

Illustration - 3 A sample of hard water contains 1 mg CaCl3 and 1 mg MgCl3 per litre. Calculate the
hardness of water in terms of CaCO3 present in per 106 parts of water..
Solution :
50
55.5 gm CaCl2  50 gm CaCO3  1 mg CaCl2  mg CaCO3  0.9 mg CaCO3
55.5
47.5 gm MgCl2  50 gm CaCO3 50

 1mg MgCl2  mg CaCO3  1.05 mg CaCO 3
47.5
(0.9 +1.05)×103 gm
 Hardness in CaCO3 ppm   1.95ppm
1/1000
Illustration - 4 A sample of hard water contains 244 ppm of HCO3 ions. What is the minimum mass of
CaO required to remove ions completely from 1 kg of such water sample ?
Solution :
244 ppm HCO3  244 gm HCO3 in 1000 L  244 mg HCO3 in 1.0 L  4 mmoles HCO3 in 1.0 L
 2 mmoles Ca(HCO3 )2 in 1.0 L
 2CaCO3 + H 2O 
CaO + Ca(HCO3 )2   2 mmoles CaO in 1.0 L  2  56  112 mg CaO
Illustration - 5 250 ml of hard water is treated with 100 ml of 0.1 N Na2 CO3 to remove temporary
hardness. Excess of Na2 CO3 required 40 ml, 0.1 N HCl for complete neutralization. Calculate degree of
hardness of water.
Solution :
Meq of Na 2CO3 = meq of Ca(HCO3 )2 + meq of HCl
in hard water
Meq of CaCO3 formed = meq of Ca(HCO3 )2 = meq of Na 2CO3 + meq of HCl

in hard water
 100  0.1  40  0.1  6

6
mmoles of CaCO3 formed  3 (in factor of CaCO3 = 2 )
2

Mass of CaCO3 formed  3  103  100  0.3 gm

Mass of hard water sample = 250 gm (Assuming density of water = 1 gm/ml)
Mass of CaCO3
Degree of Hardness  106 ppm
Mass of water
0.3
  106 ppm  1.2  103 ppm
250
IN-CHAPTER EXERCISE - E
1. How can the dihydrogen be obtained from coal gasification method ? How is its production enhanced ?
2. Arrange the following :
(i) CaH 2 , BeH 2 and TiH 2 in order of increasing electrical conductance.
(ii) LiH , NaH and CsH in order of increasing ionic character..
(iii) H - H, D - D and F – F in order of increasing bond dissolciation enthalpy.
(iv) NaH, MgH 2 and H 2O in order of increasing reducing property .

SOLUTION TO IN-CHAPTER EXERCISE - D
1. NaHCO3  NaOH   Na 2CO3  H 2O

2. It is because hydration energy of group 1 hydroxides and carbonates is higher than lattice energy where as
in group 2 hydroxides and carbonates lattice energy dominates hydration energy.
3. K2CO3 can’t be prepared from soluay’s process because KHCO3 formed in the reaction is highly soluble
and hence can’t be separated from NH4Cl + KHCO3 mixture easily.
4. MgO and BeO are used for lining of steel making furnance because they are less reactive, have high melting
point, good conductivity towards heat and bad conductivity towards electricity.
5. Note : Read the question as this :
On the treatment with cold water, an element (A) reacted quietly, liberating a colourless, odourless gas (B)
and a compound (C). Gas (B) further reacts with element (A) to yield a solid product (D) which reacted
with water to give a basic solution (E). (E) is found to be same as (C). When carbon dioxide was bubbled
through solution (C) initially a white precipitate (F) is formed, but this redissolved forming solution (G) when
more CO2 was added. Precipitate (F) effervesced when moistened with conc. HCl acid and gave deep red
colouration to the burner flame. When (F) was heated at 1000°C, a white compound (H) was formed
which when heated with carbon at 1000°C gave a solid (I) of some commercial importance. Name the
substances (A) to (I).
SOLUTION :
(A) is calcium metal which reacts with water and evolves hydrogen (B) and Ca(OH)2 solution (C).
Ca  2H 2O 
 Ca(OH)2  H 2
“Colourless and Odourless gas”
(A) (C) (B)
Ca  H 2 
 CaH 2
Solid product
(B) (D)
CaH 2  2H 2O 
 Ca(OH) 2  2H 2
(E)
2  Ca(HCO ) CO
Ca(OH)2  CO2 
 CaCO3  3 2
(F) (G)
CaCO3  2HCl 
 CaCl2  H 2O  CO 2 “Gives deep red colouration to flame”
 C
CaCO3 
 CaO 
 CaC2
(F) (H) (I)
Self Study Course for IITJEE with Online Support Solutions- INE 41
SOLUTION TO IN-CHAPTER EXERCISE - E

1. Reaction of steam on coal at high temperatures in presence of catalyst yields hydrogen. This process is called
as coal gasification.
1270K
C(s)  H 2O(g)   CO(g)  H 2 (g)
Mixing this CO and H2 gas mixture with steam, cooling to 400°C and passing over iron oxide gives CO2 + H2
which finally increases the amount of H2.
Fe
CO  H2  CO2  H2
The above reaction is also called as water gas shift reaction.
2. (i) BeH2(covelent) < TiH2 < CaH2

(ii) LiH < NaH < CsH
(iii) F–F<H–H<D–D
(iv) H2O < MgH2 < NaH
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes p-Block Elements - I
p-Block Elements - I
SOLUBILITY OF SALTS Section - 1
[A] In Aqueous Solvent :

A solvent may be polar (having high dielectric constant such as water or mineral acids) or non-polar (having
low dielectric constant such as benzene and tetrachloromethane). Ionic compounds are usually soluble in
polar solvents while covalent compounds usually dissolve in covalent solvents. This rule may be stated as
‘like dissolves like’.
For a substance to dissolve in an aqueous solvent (water) the energy evolved when the ions are hydrated
(hydration energy) must be larger than the energy required to break the crystal lattice (lattice enthalpy). Thus
solubility in principle depends upon two major factors.
(i) Lattice Enthalpy : The lattice enthalpy is inversely proportional to the distance between the cation
and the anion (i.e. r++r-). Thus the lattice enthalpy decreases as we go down the group due to the
increase in size of cation if the anion being considered is came.
(ii) Hydration Enthalpy : Hydration enthalpy usually varies as the inverse of radius of cation (r+). This
is because as the size of cation increases, the polarizing power of cation decreases and thus the
tendency to attract water molecules decreases. (also known as Dehydration Capacity). This decrease
in dehydrating capacity decreases the hydration energy that is releases when a molecule is hydrated.
The General Solubility Rules in Water are as follows :

1. All nitrates (NO3 ) , chlorates (ClO3 ) are soluble. All sulphates (SO 24  ) are soluble except those
of [Sr 2  , Ba 2  and Pb2  ] which are sparingly soluble and hence are used in qualitative analysis.
2. All the carbonates (CO32  ), suphites (SO32  ) , phosphates (PO34 ) and dichromates (Cr2 O 72  )
are insoluble except of Group I, Na  ,   and NH 4 . Practically almost all salts of Group I,
Na  ,   and NH3 are soluble in water..

3. All simple salts of Group I metals dissolve in water producing ions. The solubility of most salts
(NO3 , CO32  , HCO3 ) decreases down the group. This is because the decrease in hydration energy
of metal ions is much more than the decrease in the lattice energy given.

p-Block Elements
p-Block -I -I
Elements Vidyamandir Classes
Exception : The solubility of alkali metal fluorides, hydroxides and carbonates increases rapidly down the
group. The reason is L. E. is proportional to 1/ (r   r  ) and thus the lattice energy will vary most when

r  is small (as in fluorides) and least when r is longer (with I ). Thus the change in lattice enthalpy
exceeds the change in hydration enthalpy in this case.
4. The solubility of most salts of Group II also decreases down the group. For
example, BeSO4 > MgSO4 >> CaSO4 > SrSO 4 > BaSO4 .(As has been stated, all sulphates
except these of Ca, Sr, Ba, Pb, Ag are very soluble).
Exception : The fluorides and hydroxide of Group II metals show an increase in solubility down
the group. The reason in same as that for Group I salts.
5. All hydroxides are insoluble except those of alkali metals (Group I) leaving LiOH. Those of
Ca 2  ,Sr 2  and Ba 2 are moderately soluble.
6. All sulphides (S2  ) are insoluble except those of alkali metals, alkali earth metals and the ammonium
(NH +4 ) ion.
7. All chlorides, bromides and iodides are soluble except those of Ag  , Hg 22  and Pb 2  which are
used in qualitative analysis.
8. It has been noticed that compounds with large difference in radii of ions are generally soluble while
the least soluble salts are those of ions with similar radii. Thus:
LiOH < NaOH < KOH < RbOH < CsOH
LiF < NaF < KF < RbF < CsF
[Here the difference in size between the cation and anion increases down the group].
while, LiBr > NaBr > KBr > RbBr > CsBr.
BeSO 4  MgSO4  CaSO 4  SrSO 4  BaSO 4
[Here the difference in size between the cation and anion decreases down the group].
[B] In Non-aqueous Solvents :

Important non-aqueous solvents include liquid hydrofluoric acid (HF), liquid NO2 and liquid ammonia
(NH3 ). Liquid ammonia is the most studied non aqueous solvent and it resembles the aqueous system quite
closely.
Thus substances producing NH 4 are acids (like NH 4 Cl) in liquid ammonia and those producing NH 2
are bases (like NaNH 2 )

Vidyamandir Classes p-Block
p-BlockElements
Elements- I- I
Similarly,
Thus in N 2O 4 substances containing NO+ are acid (like NOCl) and those containing NO3 are bases (like
NH 4 NO3 ).
Like in water, acid-base neutralization and precipitation reactions also occur in liquid ammonia. Liquid
ammonia is an extremely good solvent for the alkali metals and the heavier Group II metals Ca, Sr and Ba.
The metals are very soluble and solutions in liquid ammonia have a conductivity comparable to that of pure
metals. Thus solutions are very good reducing agents because of the presence of free electrons.
Liquid ammonia
[Na(NH3 )n ]  e 
Na 
GROUP 13 ELEMENTS Section - 2
Ionisation Energy
The first ionisation energies (IE1 ) of group 13 elements are lower than the corresponding elements of group
2 1
2 (alkaline earth metals). This is due to the fact that group 13 elements have ns , np configuration in their
valence shell and the electron thus has to be removed from the p  orbital. This is much easier than
removing an s  electron of group 2 elements which being nearer the nucleus is more strongly attracted.
Boron is considerable smaller than other elements of the group and thus has a higher ionization energy than
others. The ionization energy is so high that B is always covalent.
Oxidation States
Due to ns2 , np1 configuration of the valence shell, group 13 elements are expected to be trivalent but there
is increasing tendency to form univalent compounds on descending the group. B and Al show an O. S. of +3
while Ga, In, T1 show O. S. of both +1 and +3. This is due to the Inert Pair Effect.
Metallic Character/Reducing Power

The order is : B < Al > Ga > ln > Tl

p-Block Elements - I Vidyamandir Classes
The increase in metallic character from B to Al is the usual trend on descending a group associated with
increasing size. However Ga, In, Tl do not continue the trend. Ga, In and Tl follow immediately after a row
of ten transition elements and thus have ten d electrons which are less efficient at shielding the nuclear charge
than s,p electrons. Thus outer electrons being more firmly held by the nucleus are more difficult to remove
than would be expected. This leads to contraction in size as well as decreases in metallic character than
would be expected. The phenonmenon is know as d-block Contraction. Similarly Tl follows immediately
after 14-f-block elements and the size and metallic character are affected even more. This contraction due
to the f-block elements is called Lanthanide Contraction. Note that the size increases down the group as
usual but is less than that expected.
Acidic Character
On moving down the group acidic character decreases and basic character increases because ionization
energy increases. Thus we find that B(OH)3 , and B2O3 are acidic ; Al(OH)3 and Al2O3 are amphoteric
; Ga(OH)3 and Ga 2O3 are amphoteric ; and In (OH)3 , TIOH are basic.
Boron & its compound :

Physical Properties and Occurrence :
Boron occurs in two allotropic form :
(a) Crystalline – It is black, chemically inert and very hard
(b) Amorphous – It is brown, chemically active, a non – conductor and difficiult to fuse.
All allotropic form contain icosahedral unit with atoms at all 12 corners. The important minerals of boron
are :
Borax (Tincal) Na 2 B4 O2 . 10H 2O Boric aicd H3BO3
Kernite (Resorite) Na 2 B4O7 . 4H 2O Boronatro calcite CaB4O7 . NaBO 2 . 8H 2O
Colemanite Ca 2 B6O11 . 5H 2O Boracite 2Mg3B8O15 . MgCl2
Pandertie Ca 2 B6O11.3H 2O
Extraction of Boron : It includes 2 steps :

1. Preparation of Boric anhydride (B2O3) :
[Method l]
Na 2B4O7  2HCl 
 2NaCl  H 2 B4O7
 powdered Borax   conc.

H 2 B4 O7  5H 2O 
 4H3BO3
(sparingly soluble orthoboric acid)

2 H3BO3 
 B2O3 + H 2O
[Method ll]
Ca 2 B6O11  2Na 2CO3 

 2CaCO3  Na 2 B4O7  2NaBO2
 powdered
colemanite 
fuses
The fused mass is extracted with hot water. CaCO3 remains insoluble and filtrate containing borax and
sodium metaborate is put to crystallisation when borax crystals are obtained. The remaining solution is
treated with carbon dioxide.
4NaBO2  CO 2 
 Na 2 B4O7  Na 2CO3
borax
Then Method I is followed.

[Method lll]
Suspension of colemanite mineral in water is formed and SO 2 gas is passed to obtain crystal of boric acid
on cooling.
Ca 2 B6O11 + 4SO2 + 4 H 2O 
 2Ca(HSO3 ) 2 + H 4 B6O11
H 4B6O11 + 7 H 2O 
 6 H3BO3
Ca 2 B6O11 +11H2O+ 4SO2 

 2Ca(HSO3 ) 2 + 6 H3BO3

Then, 2 H3BO3   B2O3 + 3H 2O
crystals
2. Reduction B2O3 :
[Method 1]
heated in
B2O3  3M  2B  3MO  M  Na, K or Mg 
 crucible
fused
The fused mass is stirred with iron rod so as to oxidise unreacted metal M. The mass is then boiled with
dil. HCl to obtain insolube amorphous boron powder with is 95% pure.

[Method ll] : Modern Mehtod

A fused mixture containing boric anhydride, magnesium oxide and magnesium fluroide at 1100oC is electrolysed
in a carbon crucible (anode). Iron rod is used as cathod.
Cathode : Mg 2  2e  
 Mg
Mg  B2O3 
 B  MgO
amorphous
Anode : 2O2  
 O 2  4e
[Method lll]
To obtain crystalline boron in small amounts, B2O3 is redused with aluminium powder..
B2O3  2Al 
 2B  Al2O3
Aluminium is removed by heating the fused mass with NaOH solution.
Chemical Properties of Boron :

1. Boron is unaffected by water under ordinary conditions but :
2B  3H 2O 
 B2O3  3H 2 
 red hot  Steam 
2. Amorphous boron burns in air at 700oC with a reddish flame forming oxide and nitride.
4B  3O2 
 2B2O3 ; 2B  N 2 
 2BN
3. Boron is unaffected by reducing acids. With oxidising acids it gives boric acid.
B  3HNO3 
 H3BO3  3NO 2 
O.A.
4. Boron dissolves is fused alkalies liberating hydrogen.
2B  6NaOH 
 2Na 3BO3  H 2 
fused
5. Boron often forms non-stoichiometric compounds with metals (not of Group 1)
2B  3Mg 
 Mg3B2

6. Action of non-metals :
 
4B  C   B4C ; 2B  3Cl2 
 2BCl3
electric furnance
Uses : Boron caribide rods are used to control nuclear reactions. Boron has a very high cross-section
to capture the neutorns. Also B absorbs neutrons to make boron having an even number of neutrons.
10 1
 5 B11
5 B  0 n 
[a] Diborance B2H6 :

Sturcutre and Physical Porperties :
The bridge hydrogens form abnormal 3 centre 2 electron ‘banana-shaped’ bonds with two B atoms.
An sp3 hybrid orbital from each boron atom overlaps with the 1s orbital of the hydrogen to give a
delocalized molecular orbital covering all three nuclei.
Diborane is a colorless and highly reactive gas with a disagreeable odour. It is used as a reducing
agent in organic reactions and as a catalyst in polymerization reactions.
Preparation :
(i)
(ii) 8BF3  6LiH 

 B2 H 6  6LiBF4
1. It is instantly hydrolysed by water or aqueour alkali.

B2 H6  6H 2O 
 2H3BO3  3H 2
B2 H 6  2KOH  2H 2O 
 2KBO 2  6H 2
2. It catches fire spontaneously in air and explodes with dioxygen.
B2 H 6  3O2 
 B2O3  3H2O
Thus in the laboratory, it is handled in a vacuum frame.
red heat
3. B2 H 6   2B  3H 2
4. Other reactions :
ether
B2 H 6  2LiH  2LiB4 ; B2 H 6  3Cl2 
 2BCl3  6HCl
anhyd
B2 H 6  HCl  B2 H5Cl  H 2
dry AlCl3 Chlorodiborane
5. Reaction with ammonia and amines :
Borazole is called ‘ inorganic benzene’ due to its similar structure and aromatic character.

Boron nitride (BN) is a white slippery solid called ‘inorganic graphite’ which has a layer structure
similar to graphite.
[b] Orthoboric Acid H3BO3 :

Sturcture and Physical Properties :
Orthoboric acid is a weak monobasic acid, sparigly soluble in water. It is a Lewis acid and better
written as B(OH) .
3
Thus B  OH  alone is not titrated with NaOH as a sharp end point is not obtained. However if a cis-
3
diol is added then B  OH  behaves as a strong monobasic acid and can now be titrated with NaOH
3

using phenolphthalein as indicator Cis-diols form stable complexes with  B  OH  4  thus effectively
removing them and carrying the reaction forward.

1. Effect of heat :
100C 160C red heat

H3BO3  HBO 2  H 2 B4O7  B2O3
orthoboric Metaboric boron
acid acid sesquioxide
Thus, B2O3 is also called boric anhydride as it is the anhydride of boric acid.

 B  OCH3 3  3H 2O
2. H3BO3  3CH3OH 
methyl
borate
H 2O is removed by conc. H 2SO 4 and the mixture boruns with green flame. This is used as a
test for boron compounds.
3. Boric acid dissolves in HF(aq) to give fluorobroic acid HBF4 which is a strong acid. In dry
HF borates give BF3 which burns with a gree colour..
Uses :
Boric acid is used in glass industry and as an antisptic and eyewash under the name ‘Boric Lotion’.
[c] Borax :
Stucture
Borax  Na 2 B4O7 . 10H 2O  is better

written as Na2[B4O5(OH)4] . 8H2O
having 8 water molecules and the ion
2
 B4O5  OH   associated with
 4
Na  .
1. When borax dissolves in water equal amounts of weak acid and its salt are formed. Thus it is used
as a buffer.


2. Borax reacts with 2 moles of acid because only  B  OH  4  formed will react with H  .

2  B  OH 4   2H 3O  
 2B  OH 3  4H 2O
or Na 2 B4O7  2HCl  5H 2O 
 4H3BO3  2NaCl
The indicator used is methyl oranges as it is unffected by the boric acid formed.
3. Borax Bead Test :
Metaborates  M  BO 2   of many
transition elements have characteristic
colours and this provides a means of
identifying the metal through this test.
 
Na 2 B4O7 . 10H 2O 
 Na 2 B4O7 
 NaBO2  B2O3
 glassy bead 
Uses :
(i) It is used a flame retardant for wood and fabric.
(ii) It is used as a flux in brazing and silver soldering.
(iii) Used in glass industry.
(iv) Used in Borax Bead Test in analytical chemistry.
Aluminium :
1. Aluminium metal is moderately soft but much stronger and lighter when alloyed with metals.Some
alloys of Aluminium are :
Alloys Composition Uses
Magnalium Al – 95%, Mg – 5% In construction of airships,
balances.
Duralumin Al – 95%, Cu – 4%, Mg – 0.5%, Mn – 0.5% In areoplanes and
automobile parts
Aluminium bronze Cu – 90%, Al – 9.5%, Sn – 0.5% For making utensils, cheap
artificial jewellery.
Alnico Steel – 77%, Al – 20%, Ni – 2%, Co – 1% For making permanent
magnet.

2. Thermodynamically Al should react with water and air but in fact it is stable in both. The reason is that
a very this oxide film of Al2O3 forms on the surface and protects it. Due to this resistance to corrosion
and high thermal conductivity it is used in making domestic utensils .
3. Reduction of some metal oxides like Mn 3O 4 and Cr2 O3 require temperature high enough for carbon
to be used as a reducing agent. Thus Al, a highly electropositive metal which liberates a large amount
of energy on oxidation to Al2O3 is used as the reducing agent. This is know as thermite process. The
thermite reaction is :
3
2Al  s   O 2  g  
 Al2O3  s   energy H    1670 kJ
2
4. Al is amphoteric and dissolves in both acid and bases.
 2Al3  6Cl  3H 2
2Al  6HCl 
 2Na  Al  OH 4  or 2NaAlO 2 . 2H 2O  3H 2
2Al  2NaOH  6H 2O 
Sodium aluminat
However, con. HNO3 renders it passive due to the formation of a protective oxide layer..
[A] Aluminium Oxide Al2O3 (Alumina)
Aumina is a white crystalline powder, insoluble in water. It is stable, quite unreactive and amphoteric
in nature. The   from of Al2O3 called corundum and found as a mineral in nature.
[B] Aluminium Oxide AlCl3 :
AlCl3 exists as a dimer, thus attaining an octer of electrons. It is largely

covalent when anhydrous or in a non-polar solvent such as benzene.
However, when dissolved in water, the high enthalpy of hydration is suf-
3
ficient to break the covalent dimer into  Al.  H 2O  
 6
and 3Cl ions.
At low temperature, AlCl3 exists as a close packed lattice of
Cl with Al3 occupying octahedral holes.
Crystalline AlCl3 exist as AlCl3 .6 H 2O. This on heating cannot give anhydrous salt just like
MgCl2 .6 H 2O (diagnol relationship). Instead it undergoes hydrolysis on heating :


2AlCl3 . 6H 2O  2Al  OH 3  6HCl  6H 2O

2Al  OH 3 
 Al2O3  3H 2O
The anhydrous compoun is prepared by action of dry chlorine gas on aluminium or alumina :
Al  Cl2 
 AlCl3
Al2O3  C  Cl2 
 AlCl3  CO
IN-CHAPTER EXERCISE-A
1. Give reasons for the following :

(a) Phosphoric acid is preferred to sulphuric acid in the preparation of H 2O2 from barium perox-
ide.
(b) Red phosphorus is less volatile than white form.
(c) Diborane is called an electron-definient compound.
(d) Anhydrous AlCl3 fumes in moisture.
(e) A mixture of NaOH and Al pieces is used to open the drain.
2. Identify the unknown compounds in the following reactions :

2 5 1. C H OH
(a) Na2 B4O7  conc. H 2 SO4 
 A  B
2. Ignite
B is identified by the characteristic colour of the flame. Identify A and B.
(b)
140C Na [ BH ]
4  B  3 HCl
(c) BCl3  NH 4Cl 
 A  C
(d) LiH excess LiH

H 3 BO3  HF (non aqueous ) 
 A 
 B 
C
3. AlF3 is insoluble in anhydrous HF but when little KF is added to the compound it becomes stable.
On addition of BF3 ; AlF3 is precipitated. Write the balanced chemical equations.
4. RCN , RNO2 and RCHO can be reduced by B2 H 6 . What are the products due to reduction ?

GROUP 14 ELEMENTS Section - 3
Oxidation States :
C and Si show oxidation state of +4 while Ge, Sn, Pb show oxidation states of both +2 and +4 due to the
Inert Pair Effect.
Metallic Character :
It decreases down the group. Thus, C and Si are non – metals, Ge is a metalloid and Sn and Pb are metals.
Catenation :
Due to smaller size and higher electron negativity of carbon atom it has the property of linking to other
carbon atoms forming long chains. However as we move down, the tendency for catenation decreases in
the order :
C >> Si > Ge  Sn >> Pb.
Carbon and its compounds
Allotropy : carbon exists in a large number of allotropic forms. Two main form are diamond and graphite
Diamond Graphite
Extremely unreactive, colourless, non conductor Quite reactive and soft.

and shows brilliance due to total internal reflection.
It has a layer structure with layers held together
3 by weak van der wall’s forces. Each sheet
The structure comprises of sp hybrid C atoms
forming   bonds and aranged tetrahedrally.. consists of hybridised carbon atoms which are
covalently bonded to three carbon atoms by

  bonds. The fourth e is in unhybridised ‘p’
orbital and forms a partial '  ' bond
The crystal structure of diamomd.
(a) The structure of a graphite sheet.

(b) Structure of a-graphite
It is used as a lubricant due to slippery layers
and electricity is conducted only alog sheets.

1. Water gas is made by blowing air through red or white hot coke :
red heat
C  H 2O  H 2  CO
 
water gas
2. All allotropes burn in oxygen to form CO 2 .
C  O2   CO 2
Producer gas is made by blowing air through red hot coke.
C
C  O2  4N 2 
 CO2  4N 2 
 CO  N 2
  
red hot
air producer gas
3. Carbon as reducing agent :

C  2 H 2SO4  CO 2  SO 2  H 2O
 R.A  conc.
C  4 HNO3 
 CO 2  4NO 2  2H 2O
conc.
 Artificial Tannin  brown 

C  HNO3 
dil., hot
4. Carbon as Oxygen acceptor :
3C  Fe 2O3 
 2Fe  3CO
2C  SiO 2 
 SiC  2CO
Carborundum
2000C
6C  2Al2O3   Al4C3  6CO

Preparation of CO :
(i) In laboratory it is prepared by dehydrating formic acid with concentrated H 2SO 4
H SO
2 4  CO  H O
HCOOH  2
Conc.
Also,
conc. H SO
2 4  CO  CO  H O
 COOH 2  2 2
CO 2 is removed by passing through soda :
2KOH  CO2 
 K 2CO3  H 2O
(ii) C + oxides of heavy metal 

 CO   metal
(ZnO, Fe 2O3 ,..........)


(iii) K 4  Fe  CN 6   6H 2SO 4  6H 2O  2K 2SO4  2FSO 4  3  NH 4 2 SO 4  6CO 
Potassium conc.
Ferrocyanide
Note : Dil H 2SO 4 is not used, as it gives extremely poisonous HCN.
Prepation of CO2 :
(i) The main industrial source is as a by product from the manufacture of hydrogen for making ammonia :
(ii) It is recovered from alcoholic fermatation :
yeast under
C6H12O6   2C2 H5OH  2CO2
anacrobic condition
(iii) It is obtained by heating crabonates :

CaCO3 
 CaO  CO 2 

2NaHCO3  Na 2CO3  H 2O  CO3
(iv) In laboratory it is prepared by the action of dilute acids on carbonates :
CaCO3  2HCl 
 CaCl2  CO 2  H 2O

[a] Silicones
Silicones are a group of organo - silicon polymers containing Si - O - Si linkages.
Prepartaion :
Silicones are formed by the hydrolysis of alkyl or aryl substituted chlorosilanes (formed by reaction
Grignand regents and silicon tetrachloride) and their subsequent polymerization.

SiCl4  RMgCl 
 RSiCl3  MgCl2
 2RMgCl 
 R 2SiCl2  2MgCl2
 3RMgCl 
 R 3SiCl  3MgCl2
Grignard chlorosilanes
Re agent
(i) Formation of cross - linked silicones :
OH O R R
| | | |
3 3H O H O
2   O  Si  O  Si  O  Si 
R  SiC3  R  Si  OH 
| | | |
OH O O O
O O O
| | |
 O  Si  O  Si  O  Si 
| | |
R R R
(ii) Formation of linear polymers :
(iii) Formation of dimers :

Properties :
1. R 3SiCl is a chin stopping unit and reduces polymer size as it blocks the end of chain. While R SiCl3
is used to produce new cross – links and increase polymerization.
2. Silicones are electrical insulators, water-repellent, strong and inert. Their b.p. and viscosity increase
with increase in chain length.
3. Silicones are stable towards heat (hence used as electrical insulators). The order of stability varies
with R attached in the orders: ph  CH3  Et  Pr .
4. Being water – repellent they are used for treating glass ware and fabrics.
5. They are also used as hydraulic fluids and silicone rubbers.
[b] Silicates
Silicates are derivaties of silicic and Si  OH 4  or H 2SiO4 . They have basic tetrahedral units SiO 44
and Si – O bond may be considered 50% covalent and 50% ionic (suggested by a difference of 1.7
in electronegativities).
Preparation :
Silicates can be prepared by fusing an alkali metal carbonate with sand in an electric furnance at about
1400C.
1400C SiO
2 3  n , ......
Na 2CO3 
 CO 2  Na 2O  2  Na SiO , Na SiO
4 4
 sand   
soluble glass
Classification of Silicate Minerals :

(i) Orthosilicates : These silicates contain single discrete unit of SiO 44 tetrahedral.
For example : Zircon (gemstone) ZrSiO 4

Forestrite or Olivine Mg 2SiO 4
Phenacite Be 2SiO 4
Willemite Zn 2SiO 4

Number of shared oxygen atom = 0
(ii) Pyrosilicates : These silicates contain two units of SiO 44 joined along a corner containing oxygen
atom. These are also called as island silicate.
Pyrosilicate ion Si 2O76  .
For example : Thorteveititie Sc 2Si 2O7
Hemimorphite Zn 3  Si2O7  .Zn  OH 2 .H 2O

2 n
(iii) Cyclic Structure : Cyclic or ring silicates have general formula (SiO3 ) n .
Structure and example of cyclic silicates containing Si3O96  and Si6 O18
12 
ions are given below :

For example : Beryl Be3Al2Si6O18
Wollastonite Ca 3Si3O9
Number of shared oxygen atoms = 2
(iv) Chain silicates : Chain silicates are formed by sharing two oxygen atoms by each tetrahedral.
Anions of chain silicates have two general formula.

(a) SiO3 2n
n

(b) Si4O11 6n
n
Number of shared oxygen atom = 2.5
For example : Spodumene LiAl  SiO3  2
Diposide CaMg  SiO3 2
Tremolite Ca 2 Mg5  Si 4O11 2  OH  2

(v) Two Dimensional Sheet Silicates : In such silicates, three oxygen atoms of each tetrahedral are
shared with adjacent SiO 44 tetrahedral, such sharing forms two dimensional sheet structure with
2n 
general  Si 2O5 n .
For example : Tale Mg  Si2O5 2 Mg  OH 2
Kaolin Al2  OH  4 Si2O5 
(vi) Three Dimensional Sheet Silicates : These silicates involve all four oxygen atoms in sharing with
adjacent SiO 44 tetrahedral. For example, Quartz, Feldspars, Zeolites and Ultramarines. Here all 4
oxygen atoms are shared.
Tin and its compounds :

Tin is a white lustrous, soft, malleable metal. It produces a cracking sound called tinery whenever it is
bent.

Properties :
1. Tin reacts with steam to give SnO 2 and H 2 .
2. It dissolves in dilute HNO3 forming Sn  NO3 

2
 4Sn  NO3 2  NH 4 NO3  3H 2O

4Sn  10HNO3 
(cold dil.)
3. It is slowly attacked by cold alkalies and rapidly by hot alkalies. Thus it is amphoteric.
2
Sn  2OH   4H 2O 
 Sn  OH 6   2H 2  g 
4. Sn is used in tin plating (coting iron or steel sheets with tin) and making alloys like bronze
(75% Cu + 25% Sn) and solder (67% + 33% Pb).
Sn2+ and Sn4+

Tin ion exists in two states +II and +IV with the +IV state being more stable. SnO 2 is known as
cassiterite and found as a mineral in nature. The other oxide SnO is less stable and is obtained by
heating stannous oxalate.

Sn  C 2O 4  
 SnO  CO  CO2
Both SnO and SnO 2 are amphoteric but SnO is slightly more basic than SnO 2 and a good reducing
agent too.
SnO  2HCl 
 SnCl2  H 2O ; SnO 2  4HCl 
 SnCl 4  2H 2O
SnO  2NaOH 
 Na 2SnO 2  H 2O ; SnO 2  NaOH 
Sodium stannite sodium Stannate
Among halides, stannous chloride  SnCl2  and stannic chloride  SnCl4  are the most important.
SnCl2 exists as a di-hydrate which undergoes hydrolysis on heating
 Sn  OH  Cl  HCl  H 2O
SnCl2 .2H 2O 
The anhydrous salt SnCl2 is obtained by reaction of Sn with a calculated quantity of HgCl2 . Excess
of HgCl2 result in the formation of stannic chloride.


Sn  HgCl2  SnCl2  Hg

Sn  2HgCl2  excess  
 SnCl 4  2Hg
Most of the reactions of SnCl2 are due to its reducing character. It reduces
MnO 4 to Mn 2  , Cr2O72  to Cr 3 and itself get oxidized to Sn 4 .
Lead and its Compounds

(i) Lead is a bluish grey soft metal which can be cut with a knife and extremely poisonous.
(ii) Pb often appears more unreactive than expected from its standard electrode potential. The
unreactiveness is due to the surface coating of basic carbonate 2PbCO3.Pb  OH  2 which forms
over lead when exposed to air and moisture. Thus lead is unaffected by water.
(iii) Pb is amphoteric and dissolves in both acids and hot alkalies similar to Sn. In alkali it forms plumbates
like Na 2  Pb  OH 6  or Na 2 PbO3 . However, lead does not dissolve in concentrated HCl because
a surface coating of PbCl2 is formed.
(iv) Lead is used in making lead chamber for H 2SO 4 plant and certain alloys like solider (Sn  Pb)
[a] Oxides
Pb exists as Pb2 and Pb 4 with Pb 2 being more stable. This is due to the inert pair effect which
increases the stability of +II state while going down the group. Oxide formation is shown as :
 380  420C 
PB  O2 
 PbO  yellow    Pb3O4  red   PbO2  brown 
Litharge Re d lead O2
(i) PbO and PbO2 are both amphoteric and dissolve in both acids and bases.
PbO  2HCl 
 PbCl2  H2O ; PbO2  2HCl 
 PbCl2  H2O2
PbO  2NaOH 
 Na 2PbO2  H2 O ; PbO2  2NaOH 
 Na 2PbO3  H2O
(ii) Pb3O4 or Red Lead may be represented as 2PbO . PbO 2 and is used in paint to prevent the
rusting of iron and steel.
(iii) PbO (Litharge) is commercially important and is used in large amounts to make lead glass.
PbO2 is used as a strong oxidising agent and produced in lead storage batteries.

[b] Chlorides
Chlorides are prepared by passing lead through a current of chlorine gas.
2 Cl  excess 
Pb  Cl2 
 PbCl2  PbCl4
 
Dissolving Pb2  salt PbO, PbCO3 , Pb  NO3 2 in HCl produces PbCl2 .
PbCl4 is less stable and decomposes on heating at room temperature and liberates Cl2 .
25C
PbCl4  PbCl2  Cl2
[c] Tetraethyl Lead (CH2CH2)4Pb :

It is produced in large amount and used as an ‘anti-knock’ additive to increase the octane number of
petrol. The commercial preparation uses a sodium/lead alloy.
Na | Pb  4EtCl 
 PbEt 4  4NaCl
Once it was produced in larger tonnages than any other organometallic compound but the production
is declining rapidly as a result of legislation requiring that new cars must run on lead-free petrol.
1. Identify the group 14 element that best fits each of the following description :
(i) Prefers the +2 oxidation state
(ii) Forms the strongest  bonds.
(iii) Is the second most abundant element in the earth’s crust.
(iv) Forms the most acidic oxide.
2. Give reasons for the following observervations/applications :
(i) Solid CO2 is known as dry ice.
(ii) Carbon acts as an abrasive and also as a lubricant.
(iii) Glass toppers stick in NaOH bottles.
(iv) Thermodynamically, graphite is more stable than diamond but still diamond ( the less stable
forms) exists.
(v) CCl4 is unaffected by water whilst SiCl4 is rapidly hydrolysed.
(vi) SnCl4 fumes in moist air..

3. Identify A, B, C,. . . . .
(a)
HNO / HF
3 HF
2 BC H O
(b) Si  A 
 B ; A 
(conc.)
(c) Na2CO3  Si ( fused ) 

A
(d)  dil HCl

Sn(C2O4 ) 
 A  B( g )  C ( g ) ; A 
D
B is measured quantitatively using I 2O5 solution.
4. CO2 goes to the atmosphere (greenhouse effect) and thus gets dissolved in H 2O. pH of the water
increases or decreases and what is the effect on the fertility of the soil ?
5. Starting from SiCl4 prepare the following in steps not exceeding the number given in parenthesis :
(i) Silicon (1)
(ii) linear silicon containing methyl group only (4)
(iii) Na2 SiO3 (3)
6. How are the following compounds detected qualitatively ?
(i) CO (ii) CO2 (iii) silicates (iv) PbCl2

SOLUTION TO IN-CHAPTER EXERCISE - A
1. (a) In B2H6 (diborane), B doesnot have enough valency electrons to form conventional two - electron
bonds between all of the adjacent pairs of atoms and so it is termed as electron - deficient.
(b) AlCl3 hydrolyses in moist air to give fumes of HCl.
AlCl3  3H 2O 
 Al(OH)3  3HCl (white fames)
(c) NaOH reacts with Al and evolves hydrogen. The pressure of the evolved hydrogen opens up the
clogged drain.
2 2 1. C H OH
2. (a) Na 2 B4O7  conc. H 2SO4 
 H3BO3   B(OC2 H 2 )2 .
2. Ignite
(A) (B)
The colour of flam produced is green.
(b)
(c) 140C
BCl3  NH 4Cl  B3 N3H3Cl3
(d) LiH excess LiH

H3BO3  HF 
 HBF4 
 B2 H6  Li[BH4 ]
4. RCN 
 RCH 2 NH 2
RNO2 
 RNH 2
RCHO 
 RCH 2OH
SOLUTION TO IN-CHAPTER EXERCISE - B
1. (i) Pb (ii) C (iii) Si (iv) Sn

2. (i) Solid CO2 is used as dry ice to maintain low temperatures
(ii) Carbon in the form of diamond is used as abrasive and in the form of graphite as a lubricant. This is
due to the hardness of diamond and slipperiness of graphite.
(iii) NaOH reacts with glass (SiO2) forming silicates which block the stopper of the bottle.
(iv) Although thermodynamically it is favourable for diamonds to turn into graphite but this doesnot hap
pen because there is a high energy of activation required for the process. If this energy is available, the
change occurs.
(v) Carbon halides cannot hydrolyse because they donot have d orbitals and cannot form a hydrolysis
intermediate while silicon halides readily hydrolyse.
(vi) SnCl4 forms hydrates in moisture : -
2 H O
SnCl4  SnCl4 .3H2O (fumes)
(lim ite)
3. (a)
HNO |HF HF H O
(b) 3
Si   [SiF6 ]2 
 SiF4  ; 2  Si(OH)  HF
SiF4  4
(c) Na 2CO3  Si(fased) 

 Na 2SiO3  CO2
(d) 
Sn (C2O 4 ) 
 SnO  CO   CO 2 
dil. HCl
SnO  SnCl2
(A)
Among CO and CO2 ; CO is measured quantitatively by I2O5 solution. Thus (B) is CO and (C) is
CO2 .
4. CO2 being an acidic axide decreases the pH of water and thus makes the soil acidic.
5. (i) 2SiCl4  4Al 
 4AlCl3  3Si ; SiCl4  3Mg 
 Si  2MgCl2
(ii) SiCl4  CH3MgCl 
 CH3SiCl3  MgCl2 ;
CH3SiCl3  CH3MgCl 
 (CH3 ) 2 SiCl2  MgCl2
2  2H O
(CH3 )SiCl2    CH3 2 Si(OH) 2
(iii) 3SiCl 4  4Al 

 3Si  4AlCl3
Si  O 2 
 SiO2
SiO2  2NaOH 
 Na 2SiO3  H 2 O
6. (i) CO is detected by flame test. It burns with a blue flame.
(ii) CO2 is detected by lime water test. It tarns lime water milky.
(iii) Silicates are detected by first dissolving them in HF to form SiF4 which when comes in contact with a
water droplet forms silicic acid (seen as floating white solid)
(iv) PbCl2 forms a yellow precipitate of PbCrO4 in presence of K2CrO4 which dissolves in NaOH
forming a yellow solution.
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes p-Block Elements - II
p-Block Elements - II
Group 15 Section - 1
The elements of group 15 have ns2 np3 as their valence shell electronic configuration. They can complete
their octets in two different ways :
(a) Electron Transfer : The atoms of the elements of this group may accept three electrons from more
metallic elements to form triply charged negative ions such as nitride, N3– ion and phosphide, P3– ion
and thereby attain noble gas configuration. Only small atoms can form highly charged negative ions
because of their greater electronegativities. Obviously nitrogen with greater electronegativity and smaller
size, has a stronger tendency to form N3– ion as compared to phosphours to form P3–. The other
members of the family show little tendency to form triply charged negative ions and this tendency
decreases down the group because of increase of size and decrease of electronegativity.
The elements of this group also exhibit oxidation states of +3 and +5 ions are generally not known
because their ionization enthalpy will be very high. As we go down the group, the stability of +3
oxidation state increases while that of +5 decreases.
(b) Electron Sharing : Since the atoms of these elements contain three unpaired p-electrons so these
can pair with unpaired p-electrons in another atom or atoms to form three covalent bonds, e.g. , NH3,
PH3, AsH3, BiH3.
Hydrides :
Stability order : NH3 > PH3 > As H3 > SbH3 > BiH3
Basicity : NH3 > PH3 > As H3 > SbH3 > BiH3
H - E - H bond angle : NH3 > PH3 > As H3 > SbH3
Boiling point : SbH3 > NH3 > As H3 > PH3
Reducing character : BiH3 > SbH3 > As H3 > PH3 > NH3
The bond angle in PH3, As H3 and SbH3 is close to 92° which suggests the orbitals used for bonding
are close to pure p-orbitals.
Oxides :
Oxides with higher oxidation state are more acidic :

I II III IV V
N 2O  NO  N 2O3  NO 2  N 2 O5
 
neutral acidic

p-Block Elements - II Vidyamandir Classes
Moreover, acidity decreases down the group :
N 2O3  P4O6  As 4O6  Sb 4O6  Bi 2O3

   
acidic Amphoteric basic
Halides : NX3 are unstable except NF3.

Ammonia forms NCl3, NBr3.6NH3 and NI3. 6NH3 (used as explosives) with Cl2, Br2 and I2 respectively.
NCl3 was formerly used to bleach flour to make white bread but it was banned when it was suspected that
this bread sent dogs mad !!
Penta halides are more covalent than trihalides because higher oxidation state leads to high polarising power.
Nitrogen and its Compounds :

Nitrogen is present in air to the extent of 78.06 % by volume. N2 is colourless, tasteless, odorless and
diamagnetic. It is lighter than air, sparingly soluble in water and a non-supporter of combustion.
Preparation :
1. In laboratory, nitrogen samples are obtained by warming ammonium nitrite or by oxidising ammonia
by bromine water, sodium hypochlorite (NaOCl) or CuO
NH3  CuO 
 N 2  Cu  H 2O
 NaOCl 
 N2  NaCl  H2O
 Br2 
 N2  NH4 Br.
2. Small quantities of very pure N2 is obtained by carefully warming sodium azide.
300°C
NaN3 
 N 2  Na
3. Heating ammonium salts with more oxidizing anion (Cr2O 72  , NO 2 , NO 3 , ClO 4 )
 
(NH 4 ) 2 Cr2O7  N 2  Cr2O3  4N 2O ; NH4 NO2 
 N 2  2H 2O

(i) It is used to prepare NO in the ‘Birkeland and Eyde process’.
Electric arc
N 2  O 2  2NO
3500°C
(ii) It is used to prepare ammonia by ‘Habers Process’.

Fe/ Mo
N 2  H 2   NH3
500°C
250 atm
(iii) Reaction with metals :
[a] Ammonia NH3

Ammonia is a colourless gas having characteristic pungent smell. It is quite poisonous and brings tears
in eyes. NH3 is highly soluble in water due to extensive hydrogen bonding.
 NH 4 (aq)  OH  (aq)
NH3  H 2O 
Preparation :
1. In laboratory :
NH 4Cl  NaOH 
 NaCl  NH3  H 2O
ammonium
salt
NH3 produced is dried with quick lime CaO. Note that it cannot be dried with H2SO4, CaCl2 or
P4O10 as they react with the gas instead of drying it.
NH3  H2SO4 
 (NH 4 )2 SO4
 CaCl2 
 CaCl2 . 8NH3
 P4O10 
 (NH4 )3 PO4
2. Haber - Bosch Process :
Finely divided Fe + Mo

N 2  H 2   NH3  HΘ   46.1kJ / mol
high pressure (200 atm)
low temp. (500°C)

3. NH3 is prepared by the Cynamide process :
4. Serpeck’s Process :
Al2O2  3C  N2 
 2AlN  3CO
AlN  3H 2O 
 Al(OH)3  NH3 
1. Ammonia is a non supporter of combustion but burns in oxygen with a pale yellow flame if continuous
heat is supplied.
4NH3  3O2 
 2N 2  3H 2O
Also, it undergoes catalytic oxidation.
Pt gauze
4NH3  5O2   4NO  6H 2O
800°C
2. Formation of complex ions used in qualitative analysis :
NH 4OH  AgCl 
 Ag(NH3 )2 Cl  H 2O
excess white colourless
 CuSO 4 
 Cu(OH)2   (NH 4 )2 SO 4 ; 4NH 3  CuSO4 
 [Cu(NH 3 )]4 SO 4
Blue Deep Blue
 ZnSO4 
 Zn(OH)2 
white
3. Reaction with Nessler’s Reagent is used as a test to detect ammonia :

4. Reaction with chlorine :
NH3 (excess)  Cl2 

 NH 4Cl  N 2 . This is also used as a test to detect NH3.
white fumes
NH3  Cl2 (excess) 

 NCl3  HCl
[b] Ammonium Salt (NH4)x B :

All ammonium salts are very soluble in water. They are usually slightly acidic and decompose readily
on heating producing NH3, N2 or N2O.
 If the anion (Bx –) is not particularly oxidising (eg. Cl , CO32  or SO 24  ) then ammonia is
evolved.

NH 4Cl 
 NH3  HCl

(NH 4 )2 SO4 
 2NH3  N 2SO4
 If the anion is more oxidising (e.g. NO 2 , NO 3 , ClO 4 , Cr2O 72  ) then NH 4 is oxidised to

N2 or N2O.

NH 4 NO2 
 N2  2H 2O

NH 4 NO3 
 N 2 O  2H 2O

(NH 4 )2 Cr2O7 
 N 2  4H 2O  Cr2O3
Orange Green
[c] Oxides of Nitrogen :

1. Nitrous oxide N2O [Laughing gas] :
It is colourless, non-combustible gas with a sweatish odour and taste. It is a neutral oxide, and is
dimagnetic.
Preparation :
1. It is prepared by careful thermal decomposition of molten ammonium nitrate at about 280°C

2. 10 HNO3  4Zn 
 4Zn(NO3 )2  N 2O  5H 2O
dil.
HSO3 NH 2  HNO3 
 N 2 O  H 2SO 4  H 2O
sulphamic acid conc.
3. 2 NO  SO 2  H 2O 
 H 2SO 4  N 2O
moist
900°C
(i) 2N2O 
 2N 2  O 2
(ii) Reduction of N2O to N2 :
N 2O  Cu 
 CuO  N 2
hot
 Mg 
 MgO  N2
 C 
 CO 2  N 2
 P4 
 P4O10  N 2
(iii) Oxidation : 5N2O  2KMnO4  3H2SO4 

 K 2SO4  MnSO4  3H 2O  10NO
Uses : It is used an on anaesthetic by dentists and a propellant for whipped ice - cream.
2. Nitric oxide NO/N2O2 :

It is a colourless, neutral gas which is paramagnetic due to the presence of odd electrons. It is sparingly
soluble in water.
Preparation :
1. NO is prepared in the laboratory by the reduction of dilute HNO3 with Cu.
8HNO3  3Cu 
 2NO  3Cu(NO3 )2  4H 2O.
2. Commercial Method :
electric
N 2  O2  2NO (in Birkeland and Eyde Process)
arc
Pt gauze
Or NH3  5O2 
 4NO  6H 2O (Catalytic Oxidation of ammonia)

(i) It is sparingly soluble in water and its solid state forms diamagnetic dimer O = N – N – O.
(ii)  NO2 (brown fumes) Thus it is not possible to detect its smell.
NO  O2 
[This reaction is also used to detect O2]
900C
(iii) Action of heat : NO   N 2  O2
(iv) Reduction (to N2) : NO  S 

 SO2  N 2
1
 Cu 
 CuO  N 2
2
(v) Oxidising / Reducing properties
10NO  6KMnO4  9H 2SO4 

 3K 2SO4  6MnSO4  4H 2O  10HNO3
2NO  Cl2 
 2NOCl
NO  2HNO3 
 3NO2  H2O
(vi) NO is used in Ostwad’s Process (to make HNO3) and Lead Chamber Process (to make H2SO4)
Note : No is colourless gas is readily soluble in cold FeSO 4 solution forming dard-brown colourtion due to formation
of complex [Fe(H 2O)5 NO]SO 4 .
3. Dinitrogen Trioxide N2O3 :

It exists only in solid state at low temperature which is pale blue in colour. N2O3 is an acidic anhydride
of nitrous acid (HNO2). It is diamagnetic.
Preparation :
1. It can be made by condensing equimolar amounts of NO and NO2 together at 253 K.
NO  NO2 
 N 2 O3
2. 2Cu  6HNO3 
 2Cu(NO3 ) 2  NO 2  NO  3H 2O
(5N)

3. As 2O3  2HNO3  2H 2O 
 NO  NO 2  2H 3AsO 4
(50%)

(i) N 2O3 (s) 
 NO 2  NO

(liquid)
(ii) It being the anhydride of nitrous acid forms nitrites with alkalies.
(NO  NO2 )  2KOH 

 2KNO2  H 2O
nitrites
(iii) It forms brown coloured FeSO4.NO with FeSO4. This is used as a test for nitrates called Brown Ring
Test.
IV. Nitrogen Dioxide NO2 :

It is a reddish brown gas and exists at the room temperature. Being an odd electron molecule it is paramagnetic
and dimerises into N2O4 at low temperature. It is acidic.
10C 20C 140C 620C

N 2O 4 
 N 2O 4 
 N 2 O4 
 2NO 2 
 2NO  O 2
solid solid vapour Dark Colour
colourless yellow Reddish Brown less
Brown
Structure :
Preparation :
1. In the laboratory it is prepared by heating dried lead nitrate :
2. It is produced on a large scale by oxidizing NO in the Ostwald’s Process for the manufacture of nitric
acid.
2NO  O2 
 2NO2

(i) NO2  H 2O 
 HNO2  HNO3
Thus NO2 is called as mixed anhydride of nitrous acid and nitric acid. The reaction of NO2 with
aqueous alkalies is similar to that of a mixture of HNO2 and HNO3.
NO2  2NaOH 
 NaNO2  NaNO3  H2O
(ii) Oxidation :
10NO2  3H2SO4  2KMnO4  H 2O 

 K 2SO4  2MnSO4  10 HNO3
NO 2  H 2SO 4 
 HNO3  NO2 .SO2 (OH)
nitrosulphuric acid
(iii) Reduction :
NO 2  SO 2  H 2O 
 H 2SO 4  NO
(here NO2 behaves likeHNO3 )
NO2  H2S 
 N 2O  NO  S
V. Dititrogen Pentoxide N2O5 :

It is a colourless crystalline solid which sublimes readily and is acidic.
The solid form consists of (NO2+ + NO3–) which is ionic and called as nitronium while in solution it is
covalent.
Preparation :
P O
2 5  N O  H O (Dehydration)
1. 2HNO3 
1000 temp. 2 5 2 . Thus N2O5 is the anhydride nitric acid.
60  90C
2. AgNO3  Cl2   AgCl  N 2O5  O 2
3. 4NO2  O2 
 2N 2O5

(i) It dissolves in water with a hissing sound.
N 2O5  H 2O 
 2HNO3
Thus it is called as nitric anhydride and neutralisation reactions similar to HNO3 :
N 2O5  NaOH 
 NaNO3  H2O

(ii) Since N 2O5  NO2  NO  O2 it is a very powerful oxidising agent. It destroys all organic
substances.
5N2O5  I2 
 10NO2  I2O5
[d] Oxoacids of Nitrogen :

Nitrous acid HNO2 :
Nitrous acid is unstable except in dilute aqueous solution. It is considered to be a tautomeric mixture of two
forms :
Preparation :
1. It is easily made by acidifying a solution of a nitrite
Ba(NO2 )2  H 2SO 4 
 2HNO2  BaSO4 
filteredoff
2. Dissolving nitrous anhydride(N2O3) in water of course forms nitrous acid :
N 2O3  H 2O 
 2HNO2
Oxidising Properties :
NO 2 ion is a weak oxidising agent and gets reduced to NO which forms a red complex with haemoglobin
and improves the look of meat.
NO 2  Fe2   2H  
 Fe3 NO  H 2O
2NO2  2I  4H  
 I2  2NO  2H 2O

However it is oxidised by KMnO4, Cl2 forming NO3 (but to NO2 by H2SO4) :
HNO2  Cl2  H 2O 
 HNO3  2HCl
5NO2  2MnO4  3bH  

 2Mn 2   5NO3  3H 2O
2HNO2  H 2SO4 
 SO2  2NO2  2H2O
Reactions with Amines :

HNO 2  NH3 
 [NH 4 NO 2 ] 
 N 2  2H 2O
ammonia unstable
HNO2  EtNH 2 
 EtOH  N 2  H 2O
1° amine
Secondary and tertiary aliphatic amines form nitrosamines with nitrites :
HNO 2  Et 2 NH 
 Et 2  N  O  H 2O
2° amine

HNO2  Et 3 N 
 [Et 3 NH][NO 2 ] 
 Et 2  N  N  O  EtOH
3° amine
Nitrites are used to make diazo compounds used in azo dyes :


 Ph  N  N Cl  2H 2O
PhNH 2  HNO 2 
aniline
Other Reactions :
On standing HNO2 decomposes into NO and NO2 :
2HNO 2 
 NO  NO2  H 2O
While on boiling it disproportionates :
III V II

3 HNO 2 
 HNO3  2 NO   H 2O
Nitric acid HNO3 :

Also called as Aqua fortis, it is colourless fuming liquid with a pungent smell. Yellow colour occurs on
standing due to decomposition into NO2.

Preparation :
1. In laboratory :
distilling in
2NaNO3  H 2SO4  Na 2SO 4  2HNO3 
glass retort
nitrates conc.
HNO3 vapours are then condensed in a water cooled receiver.
2. Birkeland and Eyde Process :
3. Ostwald Process :
Pt gauze
Step (a) : 4NH3 (g)  5O2   4NO  6H 2O (Catalytic Oxidation)
300C
2O 2H 2 O  O 2
Step (b) : 
2
4NO 
 4NO 2 
distillation
4HNO3  4HNO3
50C
(60%) (68%)
azeotrope
Due to the formation of azeotrope, HNO3 cannot be further concentrated by distillation and other methods
are used like dehydrating using sulphuric acid vapours.
dehydration with
HNO3   HNO3 (conc.)
H SO 2 4
68% 98%
Oxidising Properties :
V
N O3 is a very powerful oxidising agent in acidic solution. Cu, Ag which are insoluble in HCl dissolve in
HNO3. Concentrated HNO3 froms NO2 with a reducing agent although. Fe, CO, Al, Ni, Cr and B are
rendered passive by concentrated HNO3 due to the formation of a protective oxide layer (like Fe3O4 with
iron).
Dilute HNO3 forms NO with a poor reducing agent (Cu, Hg) ; N2O with a good reducing agent in hot
3 5
conditions and N H 4 N O3 with a good reducing agent in cold conditions.

Some reactions with non-metals are :
HNO3  N 2 
 no reaction
dil. or conc.

 Only Mg and Mn react with 2% dil. HNO3.

 Mg(NO3)2 + H2
HNO3 (dil.2 %) + Mg (or Mn) 
 Solution of 75% HCl and 25% HNO3 is called Aqua Regia which contains NO+ Cl– ions. Aqua Regia
is capable of dissolving Gold and Platinum by forming soluble HAuCl4 and H2PtCl6 respectively.
Other Oxoacids :
HOONO Pernitrous acid
H2NO2 Hydronitrous acid
HNO4 Pernitric acid
H2N2O2 Hyponitrous acid
Remember that N2O is NOT an anhydride of Hyponitrous acid (H2N2O2)
Phosphorous and its Compounds :

Allotropy :
It exists in many allotropic forms, the important ones being white, red and black phosphorous
300C 
White P 
inert atmosphere
 Re d P 
 Black P
for several days thermodynamically
most stable allotrope

Only white phosphorous reacts with caustic alkalies to undergoe a disproportion reaction.
P4  3NaOH  3H 2O 
 3NaH 2 PO4  PH3 
sodium hypophosphite Phosphine
Uses :
Red phosphorus is used in Match - Industry and white phosphorus as a rat poison.
Preparation :
Phosphorous is obtained by the reduction of calcium phosphate with C in an electric furance. Sand (SiO2)
is added to remove the calcium as a fluid slag.
Ca 3 (PO4 )  SiO 2 
 CaSiO3  P4O10
slag
P4O10  C 
 P4  CO 

Other oxides like P4O8 and P4O9 are intermediate between

P4O6 and P4O10 and form a mixture of phosphoric acid P(+V)
and phosphorous acid P(+III) on hydrolysis.

Oxo Acids of Phosphorous

All oxo acids of phosphosphorous can be categorized into two main acid series namely, phsphorous acid
series and phosphoric acid series.
The Phosphorous acid series :
They contain P(+III) and are generally reducing agents due to the presence of P – H bonds which are
reducing (as they break down easily to loose H+).
[I] Orthophosphorous acid H3PO3 :
H3PO3 is a dibasic acid formed by hydrolysis of P4O6 .
P4O6  6H 2O 
 4H3PO3
1. H3PO3 forms phosphites on hydrolysis which are very strong

reducing agents in basic solutions.
 H   H 2 PO3
H3PO3  Ka1 = 1.6 × 10–2
 H   HPO32 
H 2 PO3  Ka2 = 7 × 10–7
2. On heating orthophosphorous acid disproportionates :

3 5 3

4H3 P O3 
 3H3 P O4  P H3
3. It is a moderotely strong reducing agent and reduces Ag+ to Ag, Au3+ to Au, Cu2+ to Cu and
itself gets oxidised to H3PO4 :
2AgNO3  H3PO3  H 2O 
 2Ag   3HNO3  H3PO4
[II] Hypophosphorous Acid H3PO2 :

It is prepared by alkaline hydrolysis of (white) phosphorous.
P4  3OH   3H 2O 
 PH3   3H 2PO2
Hypophosphite Ion

It is a monobasic acid and a very strong reducing agent.
4Ag   H3PO2  2H2O 

 4Ag  H3PO4  4H 
[III] Pyrophosphorous Acid H4P2O5 :
While reaction with PCl5 is :
H3PO3  3PCl5 
 PCl3  3POCl3  3HCl
Trichloride Oxychloride
The Phosphoric Acid Series :

They usually cortain P(+V) and have oxidising properties. The simplest phosphoric acid is orthophosphoric
acid.
[I] Orthosphoric acid H3PO4 :
Preparation :
1. It is formed by hydrolysis of phosphorous pentaoxide (P2O5 or P4O10). The scheme for its
hydrolysis is :

2. In laboratory
2 I
P4  20 HNO3  4H3PO 4  20NO 2  4H 2O
Catalyst
conc.
3. Impure H3PO4 is prepared in large amounts by ‘Wet Process’.
Ca 3 (PO4 )2  3H 2SO 4 
 2H3PO4  3CaSO 4
Phosphate Rock
CaSO4 is hydrated to gypsum CaSO4.2 H2O and filtered off. H3PO4 thus produced is used to
make fertilizers.
Properties :
1. H3PO4 is hydrogen bonded in aqueous solution and thus the ‘concentrated acid’ is syrupy and
viscous.
2. It forms meta phosphates on heating:
220 320C
H3PO 4 
 H 4P2O7 
8r
  HPO3 n
pyrophosphoric 2
metaphosphoric
acid acid
(Na PO3)n or sodium metaphosphate is called Graham’s salt or Calgon (Commercial name). It is
soluble in water and precipitates Pb2+ , Ag+ but not Ca2+, Mg2+. Thus it is used for softening water.
3. It forms 3 series of salts :
 H   H 2 PO 4
(a) H3PO 4  Ka1 = 7.5 × 10–3
Dihydrogen phosphates are slightly acidic in water.
 H   HPO 42 
(b) H 2 PO 4  Ka2 = 6.2 × 10–8
Monohydrogen phosphates are slightly basic in water.
 H   PO34
(c) HPO24   Ka3 = 1 × 10–12
Normal phosphates are appreciably basic in water.

4 Phosphates are estimated quantitatively by adding a solution containing NH4OH solution of the
phosphate and Mg2+. Magnesium ammonium phosphate precipitated is ignited and weighed as
Mg2P2O7.

2NH4  2Mg 2   2PO34 
 2MgNH4PO4 
 Mg2P2O7  2NH3  H2O

[II] Hypophosphoric acid H4P2O6 :

It contains P(+ IV) and is prepared by hydrolysis and oxidation of red phosphorous by NaOCl.
On hydrolysis it forms both H3PO3 and H3PO4
Phosphine [PH3]
It is a colourless, extremely toxic gas which smells of garlic or rotten fish. It is highly reactive and not very
soluble in water. It’s aqueous solutions are neutral.
The H – P – H bond angle is 93.5° which suggests the presence of almost pure p orbitals.
Preparation :
It can be formed by hydrolysing metal phosphides or hydrolysing white phosphorous in basic media.
Ca 3P2  6H2O 
 2PH3   3Ca(OH)2
 PH3   3NaH2 PO2 (disproportionation)

P4  3NaOH  3H 2O 
The second method also produces small amounts of highly inflammable P2H4 . Thus PH3 is removed in the
following manner:
 KOH
PH3  HI 
 PH 4 I  KI  H 2O  PH3 
Phosphonium (Pure)
Iodide

Properties :
1. PH3 is stable in air but catches fire at 150°C.
150C
PH3  2O2  H3PO4
2. It explodes in contact with traces of oxidising agents like HNO3, Cl2 and Br2.
2PH3  16HNO3 
 P2O5  16NO2  11H2O
3. Solution of PH3 in water decomposes in presence of light giving red phosphorous and H2.
4. Formation of metallic phosphides :
3CuSO 4  2PH3 
 Cu 3P2   3H 2SO4
Black
3AgNO3  PH3 
 Ag3P   3HNO3
Black
5. Phosphine is weakly basic and forms phosphonium salts with anhydrous acids while NH3 readily forms
NH4X in aqueous solutions of the acids.
PH3  HX 
 PH4 X (X = Cl, Br, I)
Uses :
It is used for making ‘Holme’s signals’. Containers containing CaC2 and Ca3P2 are pierced and thrown in
sea when gases evolved, burn and serve as a signal.
Halides :
1. PCl3 is a colourless oily liquid and is widely used in organic chemistry while PCl5 is a yellowish white
powder.

P4  6Cl2 
 4PCl3
White Dry
P4  8SOCl2 
 4PCl3  4SO2
Thionyl
Chloride
P4  10Cl2 
 4PCl5
White Dry, excess
P4  10SO 2Cl2 
 4PCl5  10SO 2
Sulphuryl
Chloride

PCl3  Cl2 (or S2Cl2 ) 

 PCl5
2. PCl3 fumes in moisture.
PCl 3  3H2O 
 H3PO3   3HCl 
While, PCl5  H 2O 
 POCl3  2HCl
Moist Air
 H3PO4  3HCl .
POCl3  3H 2O 
3. In liquid and gaseous state PCl5 is trigonal bipyramidal. While in solid state it is ionic and hence
conducts electricity
 [PCl4 ]  [PCl6 ]

2PCl5 
Tetrahedral Octahedral
4. PF5 forms an unusual trigonal bipyramid where axial and equatorial bonds interchange their positions
in short time. This is called pseudo rotation.
Fertilizers :
Fertilizers are compounds of nitrogen, phosphorus and potassium which are soluble in water and easily
assimilated by plants without being injurious to them.
I. Nitrogenous Fertilizers :
(i) Ammonium sulphate (NH4)2SO4 :
It is made by passing NH3 and CO2 gases into a slurry of CaSO4 in water :
4 CaCO  (NH ) SO  CaSO
2NH3  CO2  H 2O 
 (NH 4 )2 CO3  3 4 2 4
In soil, the action is :

soil nitrifying
(NH 4 ) 2 SO 4  NH3   Nitrates (easily taken up by plants)
bacteria
Excess of this fertilizer makes the soil acidic.
(ii) Calcium Ammonium Nitrate (CAN) :

Ostwalds 3  Ca(NO ) CaCO
NH3   HNO3  3 2
Pr ocess
NH3  HNO3 
 NH 4 NO3
NH4NO3 alone is explosive and is mixed with calcium nitrate to form Ca(NO3)2.NH4NO3
known as Calcium Ammonium Nitrate (CAN). It is more soluble in water and does not make
soil acid.

(iii) Nitrolim Ca NCN

Preparation :
It is a slow fertilizer and produces more permanant effect.
(iv) Urea (NH 2CO NH2) :

It has high nitrogen content (46%) and is very soluble in water. Thus it is quick acting but is easily
washed away.
180  200
2NH3  CO 2   NH 2COONH 4 
 NH 4CONH 2  H 2O
high pressure
Ammonium Urea
Carbamate
In soil, urea slowly hydrolyses to ammonium carbonate :
NH 4CONH 4  2H2O 
 (NH 4 )2 CO3
II. Phosphatic Fertilizers :

Phosphate rocks like fluorapetite [3Ca3(PO4)2.CaF2] are very insoluble and of no use to plants. Thus they
are processed to form useful fertilizers.
Note : Superphosphate consists of the insoluble waste CaSO4 which is of no use to plants being in soluble while
triple phosphate doesnot contain it.

III. Potash Fertilizers KNO3, KCl and K2SO4 are some examples.
IV. NPK Fertilizers They contain N, P and K in suitable proportions. Example is 4 – 8 – 2 mixed
fertilizers which contain 4% N2, 8% P2O5 and 2% K2O.
1. Give balanced equations involved :
(a) effect of heat on
(i) NaNO3 (ii) NH4NO3 (iii) Mixture of NH4Cl and NaNO2
(b) effect of water on
(i) Li3N (ii) AlN (iii) NCl3
(iv) NO2 (v) PCl3 (vi) PCl5
(c) preparation of
(i) nitric oxide from nitric acid (ii) NH3 commercially
(iii) HNO3 commercially
2. Give reasons for the following :
(i) NF3 is not hydrolysed but NCl3 is readily hydrolysed.
(ii) Ammonia has a higher boiling point than phosphine.
(iii) Concentrated nitric acid turns yellow in sunlight.
(iv) (CH3)3N is pyramidal in shape while (SiH3)3 N is planar.
(v) PF5 is known but NF5 is not
(vi) NH3 gas is dried by CaO and not by P2O5 and H2SO4.
(vii) H3PO3 is a dibasic acid
3. Identify the unknown compounds A, B, C, . . . in the following reactions :
(a) P + conc. HNO3 
 A+B
(b) PCl5 + SO2 
 A+B
PCl5 + P4O10 
B
A is a colourless fuming liquid which on reaction with P4 gives SO2(g) and C.
Pt O
2 B (brown fumes ) 
2 C  D H O
(c) NH 3  O2  A( g ) 
(oxo acids)
–
C + I   E (violet vapours)

(d) Colourless salt (A) + NaOH 
 B (g) + C (alkaline solution)
B + HCl 
 white fumes.

 D  g   E l 
A 
  
both triatomic
NaOH , Δ
2  A  H O Al , Δ Δ
(e) 
 C   E ( g ) 
 A or B E is used as an anaesthetic.
 O2  O2  H 2O P4 O10
(f) A  P4 
 P4O10  B  C   D (brown fumes )   F  G
electric arc
cool
C  D  E (blue)
A, B, C, D, E, F are all compounds of nitrogen while A, B, C and D are gases.
4. Give structural formula for the following :
(a) H3PO3 (b) H3PO2 (c) H4P2O5 (d) H3PO4
(e) H4P2O6 (f) H4P2O7 (g) P4 O10
5. (a) Reaction of phosphoric acid with Ca3(PO4)2 yields a fertilizer “triple phosphate”. Represent the
same through balanced chemical equation.
(b) Give reason(s) why elemental nitrogen exists as a diatomic molecules while elemental phosphorus
is a tetratomic molecule.

CHALCOGENS Section - 2
Group 16
Ionization Enthalpy
The first ionization enthalpies of the elements of group 16 are unexpectedly lower than those of correspond-
ing elements of group 15 despite their smaller atomic radii and higher nuclear charge.
Normally as the atomic radii decreases or nuclear charge increases along a period, the ionization enthalpy is
expected to increase. But the ionization enthalpy of these elements is smaller than those of group 15 ele-
ments. This is due to the relatively symmetrical and stable electronic configuration of the elements of group
15 as compared to the elements of group 16 (oxygen family). e.g.
Group 15 element
N(Z = 7)1s2 2s2 2 p1x 2 p1y 2 p1z (more symmetrical, stable)

Group 16 element
O(Z = 18)1s2 2s 2 2 p 2x 2 p1y 2 p1z (less symmetrical, less stable)
Therefore, first ionization enthalpy values of elements of oxygen family are smaller.
Metallic Character
Because of high ionization enthalpy values, the elements of group 16 are less metallic. However, as we
move down the group, the ionization enthalpy decreases and hence the metallic character increases.
Electronegativity
The elements of group 16 have higher values of electronegativity than the corresponding elements of group
15. Oxygen is the second most electronegative element, the first being fluorine.
Bonding
Oxygen can form strong p  p double bonds. The double bonds formed by other elements becomes
weaker as the atomic number increases. Thus CO 2 is stable, CS2 is less stable, CSe 2 polymerises and
CTe2 is unknown.
S, Se, Te, Po can even form 4 or 6 bonds unlike oxygen due to the presence of d-orbitals. S forms strong
d  p bond with O due to its small sized d-orbital which is similar to the p-orbital of O in size.
Hydrogen bonding is important for oxygen compounds.
Hydrides
H 2O , H 2S, H 2Se, H 2Te, H 2 Po
   
liquid colourless toxic gases with foulsmell.

As we go down the group, f H of hydrides becomes more positive and bonding orbitals diffuse on becoming
larger. This decreases stability and thus increases acidity down the goup.
H 2S, H 2Se, H 2Te use almost pure p-orbitals for bonding as is indicated by their H-E-H bond angles
which are close to 90. The boiling points usually increase as the atoms become larger and heavier but
boiling point of H 2O is abnormally high due to extensive hydrogen bonding in solid and liquid state. Thus
the order is :
H 2O >> H 2Te > H 2S > H 2S.
Halides
Elements of this group form dihalides, tetrahalides and hexahalides. Among hexahalids only hexafluoride
are stable.
SF4 is a powerful fluorinating agent.
SCl2 is a foul smelling red liquid. It forms poisonous ‘mustard gas’ which is NOT a gas but a volatile
liquid.
2CH 2 = CH 2 + SCl2 
 S(CH 2CH 2Cl)2
ethene Bis(2-Chloroethyl)sulphide
(Mustard gas)
Oxygen and its Compounds

Preparation :
O2 is a colourless, odourless and tasteless gas which is partially soluble in water. Liquid dioxygen is pale
blue in colour and the solid is also blue. It is paramagnetic due to presence of unpaired electrons.
1. It is prepared industrially by the electrolysis of acidic or alkaline H 2O or by Claud’s Process
(fractional distillation of liquid air)
2. In laboratory it is prepared from thermal decomposition of
MnO
2  2 KCl+ 3O + traces of Cl , ClO
2 KClO3  2 2 2
heat

Pb(NO3 )2   PbO + NO 2 + O2
3. It can also be made by catalytic decomposition of hypochlorites :
Co2
2 HOCl  HCl + O2 
catalyst

CaOCl2  CaCl2 + O2 
bleaching powder

Uses :
Most of the O2 is used in the steel making industry. Some of it is used in oxy-acetylene welding and as an
oxidant in rockets. It is an essential constituent of life.
[a] Oxides and their general properties
Dioxygen reacts with practically all elements to form oxides. The reactions are usually exothermic and
once started often continue spontaneously.
 If an element exists in several oxidation states then generally lower ones are basic and higher ones are
acidic
N 2O, NO , N 2O3 , NO 2 , N 2O5
    
neutral acidic
CrO
 , Cr2O , CrO
 3 3
basic amphoteric acidic

PbO
 , PbO 2
more basic less basic
 The order of acidic strength of oxides can be obtained as follows :
The further apart two oxides are in the series, the more stable the compound formed when they react
together.
Example : CaO + H 2O + SO3 
 more stable CaSO4 (CaO.SO3 )
[b] Ozone O3
O3 is an unstable, dark blue diamagnetic toxic gas. The colour is due to intense absorption of red light, It
also absorbs strongly in the UV region.
2
For each O atom, of the three sp orbitals two are occupied by two lone pairs and one forms   bond.
The remaining 4 electrons form   bonds. The  system is thus 4e 3 centre bond.
Preparation :
O3 is prepared by the action of a silent electric discharge upon dioxygen in an ozoniser..
Bond order = 1.5 for O – O bonds.
Preparation :
O3 is prepared by the action of a silent electric discharge upon dioxygen in an ozoniser..
Silent electric discharge is used because sparking can generate heat and decompose O3 .

1. O3 turns starch iodide paper blue.
2. The amounts of O3 in a gas mixture is determined by passing gas into KI solution buffered with a
borate buffer (pH 9.2)
Iodine liberated is titrated with sodium thiosulphate.
O3 + 2 K + + 2 I  + H 2O   I 2 + KOH + O 2
Alternatively, it is decomposed catalytically and the change in volume measured.
2 O3 
 3O 2
2 volumes 3 volumes
3. Hg in the presence of ozone is oxidized to sub-oxide and starts sticking to glass and loses its meniscus.
This is used as a test for ozone called ‘Tailing of Mecury’
4. O3 is an extremely powerful oxidising agent, second only to F2 .
3PbS + 4O3 
 3PbSO4
2 NO 2 + O3 
 N 2O5 + O 2
2 KOH + 5O3 
 2 KO3 + 5O2 + H 2
Potassium
ozonide
(Orange solid)
5. O3 reduces peroxides
O3 + BaO 2 
 BaO + 2 O2
O3 + H 2O 2 
 H 2O + 2 O2
Uses :
It is used as a disinfectant for water. Its advantage over chlorine is that it avoids unpleasant smell and
taste of chlorine, since any excess O3 decomposes to O2 .
[C] Hydrogen Peroxide H 2O2 :

Pure H 2O2 is a colourless liquid (like water), more hydrogen bonded than water (and thus has highest
boiling point)
Preparation :
1. At one time H 2O2 was obtained by electrolysis of H 2SO4 or (NH 4 )2 SO4 using high current density..
electrolysis
2SO24   S2O82  + 2 e

H 2S2O8 + 2 H 2O 
 2 H 2SO 4 + H 2 O2
Peroxodisulphuric
acid
2. Now, it is produced industrially by a cyclic process.
H 2O2 is extracted with water as 1% solution which is concentrated to 30% solution.

3. In laboratory :
cool
Na 2O 2 + H 2SO 4 
 Na 2SO 4 + H 2O 2 
 Na 2SO4 . 10 H 2O 2 crystals
(dil, cold)
OR BaO2 + CO2 + H2O 

 BaCO3  + H2O2 (Merck's Process)
1. H 2O2 decomposes in presence of impurities like Fe2+ , Fe3+ , Ni 2+ , Pt . to undergoes a
disproportionation reaction :
2 H 2O 2   2 H 2O + O 2
Glycerol or acetanilide is added to check its decomposition.
2. In most of its reactions H 2O2 acts as a strong oxidising agent (slow in acidic medium while fast in
alkaline).
H 2O 2 + 2 Fe2+ 
 2 Fe3+ + 2 H 2O
H 2O 2 + 2[Fe(CN)6 ]4  
 2[Fe(CN) 6 ]3 + 2 OH 
Ferrocyanide Ferricyanide
H2O2 + SO32  
 SO 42  + H 2O

 4 H O + Cr O 2  + 2 H + 
 2 CrO5 + 5 H 2O
 2 2 2 7
Chromium peroxide
 (blue)

 4 CrO5 +12 H +   4 Cr 3+ + 6 H 2O+ 7 O2 

3. H 2O 2 is forced to act as a reducing agent with stronger oxidising agents and O2 is evolved.
5H 2O2 + 2 MnO4 + 6 H + 
 2 Mn 2+ + 8H 2O + 5O 2 
H 2O 2 + KIO 4 
 KIO3 + H 2O + O 2 
H 2O2 is useful to counteract chlorine:
H2O2 + Cl2 
 2 HCl + O2
4. H 2O2 is a mild bleaching agent for hair feathers due to the oxidation reaction :
H 2O 2 
 H 2O [O]
5. Qualitative Analysis : It is detected qualitatively by its action on KI.
H O starch
2 2  I  blue
KI  2
It also forms blue CrO5 with Cr2 O 72  / H + and decolourises KMnO 4 .
Structure :
It is proposed H 2O2 is a tautomeric mixture of two forms :
It shows restricted rotation about O O bond due to repulsion between

two H’s. The structure is same in liquid and gaseous forms but angles
and bond lengths change due to hydrogen bonding.

Sulphur and its Compounds

Allotropy :
Sulphur has the maximum number of allotropic structures. The two common crystalline forms are :
(i)   Rhombic Sulphur :
It is a yellow solid stable at room temperature, m.p. 11.8C and specific gravity 2.06 g/cc.
(ii)   Monoclinic Sulphur :
It is a colourless solid stable above 95.5C , mp 120C and specific gravity 1.98g/cc.
heat
Note :   sulphure    Sulphur..
cool
At 95.5C (transition temperature both forms are stable).

Both  and  forms contain puckered S8 rings in crown
conformation.
Other allotropic forms are :
(iii) Engels Sulphur (  sulphur) :
It is unstable and has S6 rings in chair conformation.
Toluene
Na 2S2O3 + conc.HCl  S
(iv) Plastic Sulphur (  - sulphur) :
It is elastic, dark coloured and obtained liquid sulphure into water. It can be moulded with fingers.
(v) Colloidal Sulphur :
It is prepared by passing H 2S gas into an oxidising solution like HNO3 , FeCl3 ....
2 HNO3 + H 2S 
 S  2 NO 2  H 2O
Note :  ,  ,  - sulphur are soluble in CS2 and insoluble in water while  - sulphur is insoluble in both CS2 and
water.
Extraction :
Sulphur is obtained from natural gas plants (which contain ) and from metal sulphide ores (especially iron
pyrites ) which produce SO 2 .
2 H2S + O 2 
 2SO 2 + 2 H 2O
SO2 + 2 H 2S 
 2 H 2O + 3S

Uses :
Almost 90% of S produced is used to manufacture H 2SO 4 . The rest is used in vulcanizing of rubber,,
making fungicides, gunpowder etc.
[a] Hydrogen sulphide H 2S (Sulphuretted Hydrogen)

It is a colourless, poisonous gas, soluble in H 2O and smells of rotten eggs.
Preparation :
It is easier to make H 2S by the action of mineral acids on metal sulphides.
FeS + H2SO4 
 FeSO4 + H 2S 
Sb 2S3 + 6 HCl 
 2SbCl3 + 3H 2S 
pure
1. It burns with blue flame.
2 H 2S + O2 
 2 H 2O + 2SO2
excess
A saturated solution of H 2S is slowly oxidized by air and Sulphur is deposited.
2 H 2S + O2 (limited) 
 2 H 2O + 2S
2. It is a very weak dibasic acid.
H2S + NaOH 
 NaHS + H2O ; NaHS + NaOH 
 Na 2S + H 2O
The two salts NaHS, Na 2S are basic and soluble in water..
3. H 2S + NH3   (NH 4 ) HS (not ( NH 4 )2 S )

dil solution
Yellow ammonium sulphide is a mixture of ammonium polysulphide and is made by dissolving
sulphur in colourless (NH 4 ) HS/ NH3 solution. This solution is used to precipitate metal sulphides
in qualitative analysis.
4. H 2S is a reducing agent and reduces Cl2 to Cl , H 2SO4 to SO 2 , FeCl3 to FeCl2 and itself gets
oxidized to S.
H 2S + Cl2 
 2 HCl + S
H 2S + H 2SO 4 
 SO 2 + 2 H 2O + S
H 2S + 2 FeCl3 
 2 FeCl2 + 2 HCl + S

[b] Sulphur Dioxide SO 2

It is a colourless poisonous gas with a choking smell. It is highly soluble in water and almost completely
present as SO 2  6 H 2O in water and only 1% as H 2SO3 . Liquid SO 2 has also been used as a non-
aqueous solvent.
Preparation :
1. It is prepared by burning S or H 2S in air..
S + O 2 
 SO 2
2 H 2S + 3O2 
 2SO2 + 2 H 2O
excess
2. It is also prepared by roasting various metal sulphides in smelters.
2 ZnS + O 2 
 2 ZnO + 2SO2
4 FeS2 +11O 2 
 2 Fe2O3 +8SO 2
1. Most of SO 2 is oxidized to SO3 by the contact process and used to manufacture H 2SO 4 .
 r H   196.6 kJ/ mol

2 5 V O
2SO2 + O2  2SO3
2. Bleaching action :
SO 2 + H 2O 
 H 2SO 4 +[H]
Bleaching by SO 2 is temporary as reduced colour is reoxidised by air to give black coloured matter..
Also, H 2SO 4 produced during bleaching may be harmful to fibres.
2  XOH HCl H O
X  OH+ SO2 
 XHSO3 
 XCl 
coloured colourless  HCl coloured
Cl2 although has a permanent effect as it produces [O].

3. It shows reducing properties in presence of moisture.
SO 2 + Cl2 + 2 H 2O 
 H 2SO4 + 2 HCl
5SO 2 + 2 KIO3 + 4 H 2O   K 2SO4 + 4 H 2SO 4 + I2

Although with stronger reducing agents it acts as an oxidising agent.
2 H 2S + SO 2 
 2 H 2O + 3S 
3Fe + SO2 
 2 FeO + FeS

Detection of SO 2 :
It may be detected in three ways in the laboratory :
1. By its choking smell
2. It turns filter paper moistened with K 2Cr2O7 / H + green.
K 2Cr2O7 + 3SO2 + H 2SO4 

 Cr2 (SO 4 )3 + K 2SO4 + H 2O
orange green
3. It turns starch iodate paper blue.
2 KIO3 + 5SO 2 + H 2O 
 I 2 + 2 KHSO 4 + 3 H 2SO4
turns starch
blue
Quantitative Analysis :
SO 2 is determined quantitatively by first converting to H 2SO 4 and then determining H 2SO 4 by titration
or conductimetric titration.
SO 2 + H 2O2 
 H 2SO4
Structure :
3d orbital of S cannot be used to form  bond as its symmetry is
z2
wrong. Instead 3d xz orbital on S is used to make the second  bond
with 2 p z orbital on the second O atom. Although, it is surprising that
both  bonds have the same energy..
[C] Sulphur Trioxide SO3

It is the anhydride of H 2SO 4 and is solid at room temperature. It has three forms :
2
In gaseous state, SO3 has a planar triangular structure involving sp hybrid sulphur atom. The lone pair
of Sulphur atom forms coordinate bond ( ). Therefore, bond angle is exactly 120. Solid SO3 possesses
either cyclic trimer (  form) or infinite helical chains (   form).

Note : Of the three forms :   SO3 is most stable.

 25C dry
  SO3 
   SO3 
   SO3
Preparation :
1. It is manufactured on a huge scale by the Contact Process. Practically all of it is converted to H 2SO 4 in
the same process :
2 5 Pt/V O
2SO2 + O2  2SO3
2. 
Fe2 (SO4 )3 
 Fe2O3 + 3SO3
1. 1000°C
2SO3 
 2SO 2 + O2
2. SO3 + H 2O 
 H 2SO 4
vapour dense mist
It is used to prepare oleum (mainly pyrosulphuric acid H 2S2O7 )
SO3 (g) + H 2SO 4 

 H 2S2O7
98% oleum/fuming sulphuric acid
3. SO3 is used to make sulphamic acid NH 2SO3H (the only strong acid that can exist as a solid at
room temperature).
NH 2CONH 2 + SO3 + H 2SO4 

 2 NH 2SO3H + CO 2
Urea Sulpharic acid
[d] Oxo Acids of Sulphur :

Oxo - acid of Sulphur ending in – ous have S in the oxidation state (+IV) and form salts ending in –ite.
Acid ending in –ic have S in the oxidation state (+VI) and form salts ending in –ate. Four main series
exist which are :
I Sulphurous Acid Series :
The most important acid in this series is sulphurous acid (H 2SO3 ) :

Preparation :
It is only known in solution (like carbonic acid) and as discussed SO 2 solution in water gives 1%
H 2SO3 .
SO 2 + H 2O  H 2SO3
Chemical Properties of SO32  ion.

 
1. H 2SO3 being dibasic forms salt of bisulphites (HSO3 ) and sulphites (SO3 ).HSO3 however
undergoes internal dehydration to form S2O52  ion.

heat
2 HSO3  S2O52   H 2O
disulphite
 
2. S( + IV) in SO3 and HSO3 is a moderately strong reducing agent and forms sulphates on oxidation.
SO32  + H 2O 2 
 SO 42  + H 2O
H 2SO3 + H 2O + 2 FeCl3 
 H 2SO4 + 2 FeCl2 + 2 KCl
while with sulphur, sulphites form thiosulphates :
OH 
SO32  + S  S2O32 
thiousulphate
Sulphites and hydrogen sulphites liberates SO 2 on treatment with dilute acids
H + (dil)
SO32  (or HSO32  ) 
 SO2 
3. SO32  acts as an oxidising agent with a strong RA like H 2S.
SO32  + 2S2  + 6 H + 
 3S  +3H 2O
II Sulphuric Acid Series :

(i) Sulphuric acid [oil of Vitriol] H 2SO 4 :

H 2SO 4 is the most important acid used in the chemical industry. It is a colourless syrupy liquid with
boiling point 338C and freezes into crystals at 10.5C . It is strongly hydrogen bonded.
Preparation
1. In ancient days it was prepared from ferrous sulphate (Green vitriol) and hence called Oil of Vitriol.
heat
2(FeSO 4 .7 H 2O) 
 Fe2O3 + SO 2 + 13 H 2O + H 2SO4
green vitriol (oil of vitriol)
2. Lead Chamber Process
Was used to manufacture H 2SO 4 industrially but the process is now obsolete as it only produced
78% H 2SO 4 . NO 2 is used as a homogeneous catalyst to oxidise SO 2 in the presence of water..
NO produced combines with air to produce NO 2 which is reused. Thus, NO and NO 2 act as
oxygen carriers
3. Contact Process :
It is the most important and widely used commercial process for the manufacture of H 2SO4 .

(i) SO 2 is first collected from burning of Sulphur or sulphide ores.

(ii) SO 2 is then oxidized.
2SO2 (g) + O 2 (g)  2SO3 (g)
The forward reaction is exothermic and is favoured by low temperature, high pressure and
excess of oxygen. A catalyst (activated V2O5 ) is used to obtain a reasonable conversion.
Earlier Pt gauze was used but due to high costs and its susceptibility to poisoning it has been
replaced by V2O5 .
(iii) SO3 is then passed into 98% H 2SO 4 forming pyrosulphuric acid (H 2S2O7 ) called oleum.
Dilution of oleum with water gives concentrated H 2SO 4(98%).
1. H 2SO 4 due to its low volatility is used to manufacture more volatile acids.
2 MX + H 2SO 4 
 2 HX + H 2SO 4
(M=metal; X=F, Cl, NO3 )
2. H 2SO 4 is a powerful dehydrating agent especially for gases.
It dehydrates HNO3 forming NO 2 +
2 H 2SO 4 + HNO3 
 NO 2+ + H 3O + + 2 HSO 4
Nitronium ion
It removes elements of water from organic compounds.
2 EtOH + H2SO4 
 Et  O  Et + H 2SO 4 . H 2O
(COOH)2 + H 2SO 4 
 CO + CO 2 + H 2SO4 . H 2O
Note : H 2SO 4 mixes with water to evolve large amount of heat. If water is poured into concentrated acid, the heat
evolved causes violent splashing. Thus to dilute strong acids like H 2SO 4 , acid is poured into water while
stirring (not water into acid).
3. H 2SO 4 is a quite strong oxidising agent.
conc. H2SO4 + Br  
 SO2 + Br2 + H2O
2conc. H 2SO4 + Cu 
 CuSO4 + SO 2 + 2 H 2O
2conc. H 2SO4 + C 
 CO 2 + 2SO 2 + 2 H 2O

4. Pure H 2SO 4 is a non-aqueous solvent and a sulphonating agent.
C6 H 6 + HO . SO3H 
 C6 H 5SO 2 OH + H 2O
Benzene sulphonic acid
Uses :
1. The largest used is in making superphosphate fertilizer.
2. It is used in Pickling (removal of oxides from the surfaces of metals like Fe, Cu before electroplating
or galvanizing.
3. It is used as a dehydrating agent. O.A. and as strong acid.
(ii) Thiosulphuric acid H 2S2O3 :

The free acid is unstable and decomposes in water into a mixture of S, H 2S, SO 2 and H 2SO4 while
the salts (thiosulphates) are stable. It forms large colourless hexagonal crystals, highly soluble in water.
The most important thiosulphate is sodium thiosulphate (Na 2S2O3 . 5 H 2O) also called hypo.
Preparation :
boiling
SO32  +  S2O32 
S 
Neutral/alkaline
1. Hypo solutions are used for iodine titrations in volumetric analysis.
2 Na 2S2O3 + I2 
 Na 2S4O6 + 2 NaI
Sodium tetrathionate
In iodometric estimation O.A.’s like CuSO4 , K 2Cr2O7 are treated with KI which liberates
I2 which is determined by hypo as above.
2CuSO4 + 4 KI 
 2 K 2SO4 + Cu 2 I2 + I 2
2. Na 2S2O3 is used to destroy excess Cl2 on fabrics after they have been bleached and called as
antichlor.
Na 2S2O3 + 4 Cl2 + 5 H 2O 
 2 NaHSO 4 + 8 HCl
This is also used to remove the taste from heavily chlorinated drinking water.
3. Hypo is used in photography for ‘fixing’ films and prints. It dissolves unreacted
AgNO3 , AgBr salts.
 Na 2S2O3
Na 2S2O3 + AgBr 
 Ag 2S2O3    soluble complexes Na 3[Ag(S2O3 )2 ]

Note :
(iii) Thionic Acid Series :
(iv) Peroxo Acid Series

They contain the peroxo linkage  O O .

1. Write equations for :
(a) preparation of oxygen from (i) KClO3 (ii) Ozoe (iii) Pb( NO3 )2
(b) reaction of H 2O2 with (i) acidified solution of KMnO4 (ii) aqueous HI.
2. State reasons for the following statements

(a) Statues coated with white lead on long exposure to atmosphere turn black and the original
colour can be restored on treatment with H 2O2 .
(b) Presence of water is avoided in the preparation of H 2O2 from Na2O2 .
(c) Hydrogen peroxide acts as an oxidizing as well as a reducing agent.
(d) Ozone destroys mercury meniscus.
(e) A white turbidity is obtained by passing H 2 S in aqueous solution of SO2 .
(f) Conc. H 2 SO4 can’t be used for drying up H 2 S and NH 3.
(g) Liquid oxygen sticks to the poles of a magnet but liquid nitrogen does not.
(h) SF6  is known but OF6 is not.
3. Describe the differences in structure between gaseous and solid SO3.
4. Which of nitric acid and sulphuric acid is the stronger Bronsted acid, i.e., which donates proton to the
other?
5. How are the following gases detected ?
(a) O2 (b) O3 (c) H 2S (d) SO2
NOW ATTEMPT IN-CHAPTER EXERCISE-B REMAINING QUESTIONS IN THIS EBOOK

THE HALOGENS Section - 3
Group – 17
Ionisation Energy
The ionization energies of halogens are very high, next only to the noble gases in each group. On moving
down the group, the ionization enthalpies progressively decrease as the size of halogen increases from
F to I
Electronegativity
Due to small size and higher nuclear charge, each halogen has the highest electronegativity in their respec-
tive periods. F is the most electronegative element (electronegativity of 4.0).
The electronegativity decreases down the group.
Electron Affinity
Halogens have large negative electron gain enthalpies. Down the group, electron affinity decreases as the
size increases.
F < Cl > Br > I > At.
However, Cl is more electronegative than F due to extremely small size of F as a result of which strong
electron repulsions are present in the relatively compact 2p – orbitals of fluorine and thus its tendency to
accept an electron decreases.
Oxidation States
F shows O.S of only – 1 (being most electronegative) often halogens show oxidation states of
1,  5 and  7.
Bond Dissociation Enthalpy

All elements form diatomic molecules. The bond dissociation energy decreases down the group since the
atoms become larger which results in less effective overlap of orbitals.
F2 << Cl2 > Br2 > I2 .
However bond energy of F2 is abnormally low due its very high reactivity. The small size of F atoms
induces e  e repulsion between the lone pairs of electrons on the two fluorine atoms.

Note : I2 is tested by starch indicator which turns blue. The bluish colour produced disappears on titration with
S2 O32  . This colour reappears after 2 – 3 minutes due to atmospheric oxidation.
I2 + 2S2O32 
 2 I + S4O62 
1
2 I + O2 + 2 H + 
 I 2 + H 2O
2

Hydra – Acids
I Hydrofluoric acid [H 2F2 or HF]
1. HF is a colourless, corrosive liquid with pungent smell. It attacks glass and is thus stored in wax
bottles or gutta percha bottles.
 [SiF6 ]2  + 2 H+ + 2 H 2O
SiO2 + 6 HF  (This is also used for etching glass.)
HF is kept in laboratory in KF giving K + [F H  F] ions.

2. H 2 and F2 combine with each other very violently even in dark to form HF. Thus special methods
are employed in its preparation.
Industrially it is made by heating CaF2 with strong H 2SO 4 .The reaction is endothermic : hence the
need for heating. SiO 2 impurities are removed from CaF2 otherwise they consume much of HF
produced.
CaF2 + H 2SO4 
 CaSO4 + 2 HF
SiO 2 + 4 HF 
 SiF4 + 2 H 2O
SiF4 + 2 HF(aq) 
 H 2 [SiF6 ]
3. Two thirds of HF produced are used to make chlorofluoro charbons (Freons) used as refrigerating
fluids.
anhydrous conditions
CCl4 + 2 HF  CCl2 F2 + 2 HCl
SbCl5 freon
4. In liquid form HF is used as a non - aquous solvent.
2 HF()  [H 2 F]+ + F
II. Hydrochloric acid [HCl]

1. At one time HCl was made exclusively by ‘salt cake’ method.

NaCl + conc.H 2SO4  HCl(g) + NaHSO 4
Rock salt
NaHSO 4 + NaCl 
 HCl(g) + Na 2SO 4
2. Highly pure HCl is made by bringing H 2 and Cl2 in a special combustion chamber. (Direct combination
is explosive)
Cl2 + H 2 
 2 HCl

3. In laboratory :
2 NH 4Cl + H 2SO4 
 2 HCl + (NH 4 ) 2 SO 4
conc.
4. HCl cannot be dried over P2O5 or quick lime because it reacts with them :
CaO + HCl 
 CaCl2 + H 2O
P4O10 + 3HCl 
 POCl3 + 3HPO3
Hence it is dried by passing through conc. H 2SO 4
5. HCl(g) is colourless, weak reducing agent (is oxidized by strong oxidising agents like
MnO 2 , KMnO 4 , K 2Cr2O7 ) and highly soluble in water..
6. Aqua Regia :
It is a fuming mixture of HCl and HNO3 in the ratio 3 : 1. It can dissolve both gold and platimum
while no other acid has that capability.
Au + NO3 + 4Cl + 4 H + 
 AuCl4 + NO  + 2 H 2O
Pt + NO3 + 6Cl + 2 H + 
 PtCl62  + NO  + 2 H 2O
3Pt + 4 NO3 + 18Cl + 16 H + 

 3PtCl62  + 4 NO + 8H 2O
III HBr and HI

1. They are prepared by reaction of phosphoric acid on metal bromides or iodides (similar to salt cake
process)
NaI + H3PO 4 
 HI + NaH 2 PO4
NaBr + H3PO4   HBr + NaH 2 PO 4

2. The usual laboratory process is :
+6 H O
2  6 HBr + 2 H PO
2 P + 3Br2 
 2 PBr3  3 3
Red
+6 H O
2  6 HI + 2 H PO
2 P + 3I2 
 2 PI3  3 3
Red
3. HBr is not very stable and acts as a strong reducing agent while HI is least stable and thus a more
powerful reducing agent.
2 HNO3 + 2 HI 
 2 NO 2 + I2 + 2 H 2O
2 HNO3 + 2 HI 
 2 NO + I 2 + 2 H 2O
HIO3 + 5HI 
 3I2 + 3H 2O
H 2SO4 + 2 HI 
 SO 2 + I2 + 2 H 2O

Oxides
There is only a small difference in electronegativity between the halogens and oxygen and thus the bonds in
oxides are largely covalent. Most halogen oxides are unstable and tend to explode when subjected to shock.
Stability of oxides increases down the group and higher oxidation states are more stable than lower oxidation
states.
I Dichloro oxide [Cl2O]
Cl2O is a yellow – brown gas which condenses to an orange liquid (bp = 2°C). It is the anhydride of
hypochlorous acid (HClO).
1. It is prepared by passing dry chlorine over freshly precipitated mercuric oxide.
HgO + 2 Cl2 
 HgCl2 + Cl2O.
dry
2. It is solube in water Cl2O + H 2O  2 HOCl(aq)

Golden solution
3. It explodes in presence of NH3 or a reducing agent or on heating.
3Cl2O + 10 NH3 
 2 N 2 + 6 NH 4Cl + 3H 2O
4. It is a strong oxidising agent.
Cl2O + 2 HCl 
 2Cl2 + H 2O
II Chlorine Dioxide [ClO2 ]

It is a yellow gas, condenses to deep red liquid, explodes above 40° C and in
presence of reducing agents. It is paramagnetic being an odd electron molecule
but DOESNOT dimerises as the odd electron is delocalised.
1. It explodes when mixed with reducing agents. The safest laboratory preparation is form sodium
chlorate and oxalic acid as this automatically dilutes the gas with CO 2 .
2 NaClO3 + 2(COOH)2 
 2ClO 2 + 2CO2 + (COONa) 2 + 2 H 2O
2. ClO2 + H 2O 
 HClO3 + HClO 2 + heat

dark green solution
3. It is used to manufacture NaClO2 which is used for bleaching paper textile.
2ClO 2 + 2 NaOH + H 2O2 

 2 NaClO 2 + O 2 + 2 H 2O
2ClO2 + 2 NaOH 
 NaClO2 + NaClO3 + H 2O
Chlorite Chlorate
4. ClO2 is a powerful oxidising about and a bleaching agent and is used to purify water..

III Dichlorine Hexoxide [Cl2O6 ]

It is a dark red liquid which freeze at 180° C to a yellow solid. It is diamagnetic
in nature due to absence of unpaired electrons and exists as a dimer. The structure
is guessed to be as shown but the exact structure is unknown.
1. It is obtained from ClO2 and O3 .
ClO2 + O3 
 ClO3 + O2
2ClO3  Cl2O6
2. Hydrolysis with water or alkali gives chlorate and perchlorate
Cl2O6 + H 2O 
 HClO3 + HClO 4
Cl2O6 + 2 NaOH 
 NaClO3 + NaClO 4 + H 2O
Chlorate per chlorate
3. It is a strong oxidising agent which explodes on contact with grease.
4. Reaction with anhydrous HF is reversible :
Cl2O6 + HF  FClO 2 + HClO 4
IV Dichlorine Heptoxide [Cl2O7 ]

It is a colourless oily liquid which is moderately stable and less reactive than
others. It is the only exothermic oxide of Cl and the anhydride of perchloric
acid HClO 4 . It is anhydride of perchloric acid and made by dehydrating
perchloric acid with P2O5 or H3PO 4 .
PO
4 10  Cl O
2 HClO 4  2 7
Oxo Acids
Four series of oxo acids are known (HOX, HOX 2 , HOX3 and HOX4 ). The structure of the ions formed from
these oxoacids are :

 In general, for any series of oxoacids, the acid with most oxygen (i.e. highest oxidation state) is most
dissociated. This is because, the most oxygen atoms are bonded, the more the electrons will be pulled

away from the O H bond and thus weaking the bond. [Note that plainly ClO4 ion is larger than

OCl ion and so hydration energy of ClO4 is less than that of OCl . This suggests HOCl to be a
stronger acid but the reverse in true. The reason is the bond energies discussed above]
Thus the acidic character follows the trend :
HClO 4 > HClO3 >> HClO2 > HClO
Similarly,
H 2SO4 > H 2SO3 ; HNO3 > HNO2
 The thermal stability of the oxyhalide ion increase from  OCl to ClO4 .
ClO4 > ClO3 > ClO2 > ClO

This is due to the increase in the number of oxygen atoms.
 Among the hypohalous acids (HXO) stability order is :
HClO > HBrO > HIO >> HFO.
Oxoacids of F are exceptionally unstable because all the oxoacid ions except those of F are stabilised
by p  d  bonding between full 2p orbitals on O and empty d orbitals on the halogen atoms.

Bleaching Powder :
Bleaching powder is actually written as Ca(OCl)2 .Ca(OH)2 .CaCl2 .2 H2 O. It is a pale yellow powder having
a strong smell of chlorine and sobuble in water. However, a clear solution in never formed due to the presence of
impurities.
Preparation :
It is made by passing Cl2 into slaked lime.
3Ca(OH)2 + 2 Cl2 
 Ca(OCl) Cl + H 2O

1. Bleaching action
Coloured matter + [O] 

 Colourless product.
While,
2. Oxidising action
CaOCl2 + H 2S 
 CaCl2 + H 2O+ S
CaOCl2 + Pb(NO3 )2 + 2 NaOH 

 CaCl2 + PbO 2 + 2 NaNO3 + H 2O.
3. It converts acetone into chloroform.
Halogen Halides
I. Inter Halides
A + X 
 AX, AX 3 , AX5 , AX 7 (inter halides) where X is smaller than A.
halogen halogen
Interhalogen compounds are covalent and have physical properties intermediate of A and X. They are
more reactive than halogens (except F2 ) as A – X bond is weaker than X – X bond.
[Draw the structures of all four king of interhalides]
1. ICl(l) is conducting as it ionizes :
3 IC l  [I 2Cl]+ + [IC l 2 ]
Addition of AlCl3 in molten ICI greatly increases conductivity as it increases the ionisation by forming
[AlCl4 ] and [I2Cl]+ ions.
[I2Cl]+ [AlCl4 ]
AlCl3 + 2 ICl 
2. ICl3 exists as dimer I2Cl6 with two Cl bridges
[I2Cl6 ]  [ICl2 ]+ + [ICl4 ]

and is thus conductive.
Square planar

3. Hydrolysis of interhalides :
AX n + H 2O 
 HA + HXO n+1 (n = 1,3,5, 7)
2
II. Poly Halides

The most important polyhalide is I3 . It has very long, weak bonds with bond
order 0.5 and is linear in shape. I2 is only slightly in water. Its solubility is
greatly increased if some iodide ions are present. This is due to the formation
of the polyhalide
I2 + I   I3
III. Pseudo Halides

These are univalent ions with at least one N atom, that have properties similar to those of the halide ions.
   
Example are CN ,SCN , N 3 , OCN .

CN  resemble Cl closely in the following ways :
1. It forms an acid HCN and the dimer (CN)2 just like HCl and Cl2
2. It forms insoluble salts with Ag + , Pb 2+ , Hg 2+ and soluble salts with Na + .
OH _
3. (CN)2  CN  + OCN  .
H+
and 3 ICN  [I2CN]+ +[I(CN) 2 ]
(Replace CN  by Cl  and compare the above reactions with those of Cl  ).

IN - CHAPTER EXERCISE - C
1. Give reason for the following :

(a) HF exists as dimeric molecule i.e. H 2 F2 or HF has higher viscosity or high boiling point.
(b) When blue limus is dipped into a solution of hypochlorous acid, it first turns red and then later
gets decolourised.
(c) In preparation of HI from alkali iodide, H 3 PO4 is preferred in place of H 2 SO4 .
(d) Fluorine is better oxidant than chlorine.
(e) The brown colour of an acidified dilute solution of iodine in aqueous KI is intensified by the
addition of nitrite but it is discharged by the addition of a sulphite.
(f) It is not possible to obtain F2 by electrolysis of acqueous HF, aqueous NaF or anhydrous HF..
(g) A mixture of KF and HF is electrolyzed to increase the conductivity of anhydrous HF.
2. Write balanced equations for :

(a) reaction between HF and (i) CCl4 (ii) SiO2 (iii) KF
(b) reaction between Cl2 and (i) SO2 (ii) H 2 (iii) NaOH
3. Find A, B, C, . . . . in the following reactions :

(a) hot NaOH
MnO2  HCl 
 A( g ) 
BC;
OH 
B  C  D( g ). D is a yellow triatomic gas.

(b) excess CN 
HCN  CuSO4 
 A( g )  B  complex C
Br2 H 2O conc.H 2 SO4
(c) Red phosphorus   A   B( g )   Br2
(d) CH 3  CH  CH 2  ICI 

4. H 2 SO4 is a weaker acid than HCl, yet HCl is evolved when conc H 2 SO4 is added to NaCl. Explain.
5. HF can be prepared by the action of H 2 SO4 on NaF. Explain why HBr cannot be prepared by the
action of the same acid on NaBr.

NOBLE GASES Section - 4
Group 18
Physical Properties of Noble Gases
1. They are monoatomic, colourless, odourless, tasteless and sparingly soluble in water.
2. They have very low m.p. and b.p due to weak dispersion forces. Helium has the lowest known b.p.
(4K) and shows superfluidity.
3. All noble gases can diffuse through glass, rubber, plastic and some metals making them difficult to
handle in the laboratory.
Clathrate Compounds
In the clathrates atoms or molecules of the appropriate size trapped in cavities in the crystal lattice of other
compounds. These atoms donot form any bond. Clathrates provide a convenient means of storing radioac
-tive isotopes of Kr and Xe produced in nuclear reactors.
Chemistry of Xenon
Xe reacts directly only with F2 .Oxygen compounds can be obtained from the fluoride.
1. Xenon fluorides are white solide which are extremely powerful oxidising and fluorinating agents. They
sublime readily at room temperature and are hydrolyzed even by traces of water. Thus they are stored
in Ni or Monel containers.

XeO3 is a hygroscopic white explosive solid. XeOF4 is a colourless volatile liquid.

OH 
 Na + [HXeO4 ]
XeO3 + NaOH   Na 4 XeO6 + Xe + O2 + H2O
Sod.xenate Disproportionate Sod.perxenate
2. All xenon fluorides react with hydrogen and oxidise Cl  to Cl2 . I  to I 2 and Ce(III) to Ce(IV)
3. Xenon fluorides reacts with fluoride ion acceptors to form cationic species and fluoride ion donors
to form fluoro anions.
[XeF]+ [PF6 ]
XeF2 + PF5 
[XeF3 ]+ + [SbF6 ]
XeF4 + SbF5 
 M + [XeF7 ]
XeF4 + MF 
(M = Na, K, Rb, Cs)
4. Xe compounds show a variety of shapes :
XeF2 is linear, XeF4 is square planar,, XeF6 is a capped octahedron, XeO3 is pyramidal, XeOF4 is
square pyramidal, XeO 2 F2 is see saw shaped, XeOF2 is bent T – shaped, XeO 4 is tetrahedral,
XeO3F2 is trigonal bipyramidal and [XeO6 ]4  ion is octahedral. [Draw geometries of all these
compounds].
IN - CHAPTER EXERCISE - D
1. Why xenon does not form fluorides XeF , XeF3 or XeF5 ?

SOLUBILITY OF SALTS Section - 5
[A] In Aqueous Solvent :

A solvent may be polar (having high dielectric constant such as water or mineral acids) or non-polar (having
low dielectric constant such as benzene and tetrachloromethane). Ionic compounds are usually soluble in
polar solvents while covalent compounds usually dissolve in covalent solvents. This rule may be stated as
‘like dissolves like’.
For a substance to dissolve in an aqueous solvent (water) the energy evolved when the ions are hydrated
(hydration energy) must be larger than the energy required to break the crystal lattice (lattice enthalpy). Thus
solubility in principle depends upon two major factors.
(i) Lattice Enthalpy : The lattice enthalpy is inversely proportional to the distance between the cation
and the anion (i.e. r+ + r–). Thus the lattice enthalpy decreases as we go down the group due to the
increase in size of cation if the anion being considered is came.
(ii) Hydration Enthalpy : Hydration enthalpy usually varies as the inverse of radius of cation (r+). This
is because as the size of cation increases, the polarising power of cation decreases and thus the
tendency to attract water molecules decreases. (also known as Dehydrating Capacity). This decrease
in dehydrating capacity decreases the hydration energy that is released when a molecule is hydrated.
The General Solubility Rules in Water are as follows :

1. All nitrates (NO3–) and chlorates (ClO3– ) are soluble. All sulphates (SO42–) are soluble except
those of [Sr2+, Ba2+ and Pb2+] which are sparingly soluble and hence are used in qualitative analysis.
2. All the carbonates (CO32–), suphites (SO32–), phosphates (PO43–) and dichromates (Cr2O72–) are
insoluble except of Group I, Na+, K+ and NH4+ . Practically almost all salts of Group I, Na+, K+ and
NH4+ are soluble in water.
3. All simple salts of Group I metals dissolve in water producing ions. The solubility of most salts
(NO3–, CO32–, HCO3–) decreases down the group. This is because the decrease in hydration
energy of metal ions is much more than the decrease in the lattice energy given.
Exception : The solubility of alkali metal fluorides, hydroxides and carbonates increases rapidly
down the group. The reason is L.E. is proportional to 1/(r+ + r–) and thus the lattice energy will
vary most when r– is small (as in fluorides) and least when r+ is longer(with I–). Thus the change in
lattice enthalpy exceeds the change in hydration enthalpy in this case.
4. The solubility of most salts of Group II also decreases down the group.
For example, BeSO4 > MgSO4 >> CaSO4 > SrSO4 > BaSO4. (As has been stated, all sulphates
except these of Ca, Sr, Ba, Pb, Ag are very soluble).
Exception : The fluorides and hydroxide of Group II metals show an increase in solubility down the
group. The reason in same as that for Group I salts.
5. All hydroxides are insoluble except those of alkali metals (Group I) leaving LiOH. Those of Ca2+,
Sr2+ and Ba2+ are moderately soluble.

6. All sulphides (S2–) are insoluble except those of alkali metals, alkali earth metals and the ammonium
(NH4+) ion.
7. All chlorides, bromides and iodides are soluble except those of Ag+, Hg22+ and Pb2+ which are used
in qualitative analysis.
8. It has been noticed that compounds with large difference in radii of ions are generally soluble while the
least soluble salts are those of ions with similar radii. Thus :
L iOH < NaOH < K OH < RbOH < CsOH
L iF < NaF < K F < RbF < CsF
[Here the difference in size between the cation and anion increases down the group].
while, L iBr > NaBr > K Br > RbBr > CsBr.
BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4
[Here the difference in size between the cation and anion decreases down the group].
[B] In Non-aqueous Solvents :

Important non-aqueous solvents include liquid hydrofluoric acid(HF), liquid NO2 and liquid ammonia
(NH3).
Liquid ammonia is the most studied non aqueous solvent and it resembles the aqueous system quite
closely.
 NH 4  NH 2
2NH3 () 
Thus substances producing NH4+ are acids (like NH4Cl) in liquid ammonia and those producing NH2– are
bases (like NaNH2)
Similarly,
 NO  NO  NO3
N 2O4 
(liquid)
Thus in N2O4 substances containing NO+ are acid (like NOCl) and those containing NO3– are bases (like
NH4N3).
For HF we have :
 [H 2 F]  F
2HF 
Like in water, acid-base neutralisation and precipitation reactions also occur in liquid ammonia. Liquid
ammonia is an extremely good solvent for the alkali metals and the heavier Group II metals Ca, Sr and Ba.
The metals are very soluble and solutions in liquid ammonia have a conductivity comparable to that of pure
metals. Thus solutions are very good reducing agents because of the presence of free electrons.
Liquid ammonia
Na   [Na(NH3 )n ]  e

SOLUTIONS TO IN-CHAPTER EXERCISE - A

1. (a) (i) 2NaNO3  (ii) 
 2NaNO2  O2 NH4 NO3 
 N2O  2H2O

(iii) NH4Cl  NaNO2   N2  2H 2O  NaCl
(b) (i) Li3 N  H2O 
 Li (ii) AlN  3H 2O 
 Al(OH)3  NH3 
(iii) NCl3  4H 2 O 
 NH 4OH  3HOCl (iv) 2NO2  H2O 
 HNO3  HNO2
(c) (i) 8HNO3  3Cu   2NO  3Cu(NO3 )2  4H 2O
(Laboratory preparation)
(ii) Serpeck’s process :
Al2O3  3C  N 2 
 2AlN  CO
AlN  3H2O   Al(OH)3  NH3 

(iii) Using Ostwalds Process :
Pt 2O
2H 2O  O 2
(a) 4NH3 (g)  5O 2  2
 4NO  6H 2O (b) 4NO  4NO2   4HNO3
50C
(60%)
2. (i) NF3 is more stable than NCl3 due to higher bond dissociation enthalpy. Thus it is not readily hydrolysed.
(ii) NH3 has higher b.p. than PH3 molecules due to hydrogen bonding present among NH3 molecules. This
makes it difficult to evaporate solid NH3 than solid PH3.
light
(iii) conc. HNO3   NO2  O2  H2O
The brown colour of NO2 produced makes it look yellow in solution.
(iv) (CH3)3N is pyramidal while (SiH3)3N is planar because in (SiH3)3N[trisilyamine] there sp2 orbitals are used
for  - bonding. The lp of e– occupy a p orbital at right angles to the plane triangle. This overlaps with empty
d orbitals on each of the three silicon atoms resulting in p – d bonding. This is impossible in (CH3)3N
because C does not passes d orbitals.
(v) NF5 cannot exist because there are no d-orbitals to accomodate the 5 electrons coming from five fluorine
atoms. This however can occur in PF5.
(vi) NH3 cannot be dried with H2SO4 for else they will nautralise each other. Similarly P2O5 will react with CaO.
(vii) H3PO3 has the structure :
OH
|
OPH
|
OH
Which shows that it is dibasic due to only 2 OH groups.
Self Study Course for IITJEE with Online Support Solutions INE 59
3. (a) P4  conc. HNO3 

 H3PO4  NO2
(b) PCl5  SO 2 
 POCl3  SOCl2
(A)
6PCl5  P4O10 
 10POCl3
(B)
SOCl2  P4 
 SO 2  PCl3
(A) (C)
Pt
(c) NH3  O2  H2O O2
 NO(g) 
 NO 2   HNO 2  HNO3
(A) (B) (C) (D)
HNO 2  I 
 I2
(C) (E)

(d) NH 4 NO3  NaOH   NH3 (g)  NaNO3
(A) (B) (C)
NH3  HCl 
 NH 4Cl (white fumes)

 N 2O(g)  H 2O()
NH 4 NO3 
(D) (E)
(f) N 2O  P4  O2 O2 H 2O P4O10
 P4O10  N 2   NO   NO2   HNO3   H3PO 4
electric arc (C)
(A) (B) (D) (F) (G)
cool
NO  NO 2 
 N 2O3 (blue)
(C) (D) (E)
4. (a) (b) (c)
(d) (e) (f)
(g)
5. (a) 3Ca 3 (PO 4 ).CaF2  14H 3PO 4 

 10Ca(HPO4 )2  2HF
triple phasphate
(b) This is because N2 can form much stabler triple bond than an unstable tetrahedral structure.
SOLUTIONS TO IN-CHAPTER EXERCISE - B
1. (a) (i) Heat KClO3 in the presence of manganese dioxide.

MnO
2  2KCl  3O
2KClO3  2
(ii) Passing carbon dioxide through oxone releases O2.
1
Na 2O 2  CO2 
 Na 2CO3  O2
2

(iii) Pb(NO3 )2   PbO  NO2  O2
(b) (i) 5H2O2  2MnO4  6H  

 2Mn 2   8H2O  5O2
(ii) H2O2  2I   2H    2H 2O  I2
2. (a) White lead on exposure to atmosphere oxidises to block plumbous oxide. This can be removed by a treatment
with hydrogen peroxide.
 2PbO (black) ;
2Pb  O2  PbO  H 2O 2 
 PbO2  H 2O
(soluble)
(b) Na2O2 gives H2O2 with dilute acids.

Na 2O2  H 2SO4   Na 2SO4  H 2O2
However if water is used (or present), the NaOH formed being basic catalyses decomposition of H2O2 :
(c) In most reactions H2O2 acts as a strong oxidising agent (like with Fe2+, SO32–, Cr2O72–) but however with
sronger oxidising agents it is forced to act as a reducing agent (like with MnO4–, IO4–).
(d) Hg in the presence of ozone is oxidied to suboxide and starts sticking to glass and loses its meniscus.
(e) Passing H2S in aqueous solution of SO2 precipitates sulphur which produces turbidity in the solution.
2H 2 S  SO 2 
 2H 2 O  3S 
(f) NH3 cannot be dried with H2SO4 as they nutralise each other. NH3  H 2SO 4   (NH 4 )SO 4 . Ammonia is
thus best dried with quick lime (CaO).
(g) Liquid oxygen is paramagnetic due to presence of unpaired electrons which liquid nitrogen being diamagnetic
doesnot stick to a magnet.
(h) OF6 cannot exist because their are no d orbital in an oxygen atom to accomodate incoming electrons from
fluorine atoms.
3. Gaseous SO3 has a planar triangular strucure with sp2 hybridised s atom while solid SO3 exists in a cyclic
trimer form (or hetical chains)
4. H2SO4  HNO3   HSO4  H 2 NO3
Thus H2SO4 is the stronger Bronsted acid.
5. (a) O2 burns with a blue flame which serves as a test for it. (b) O3 turns starch iodide paper blue.
(c) H2S can be detected by its small of rotten eggs.
(d) SO2 can be detected by its choking small. It also turns filter paper moistened with K2Cr2O7/H+ green.
IN - CHAPTER EXERCISE - C
1. (a) There is hydrogen bonding among HF molecules which increases its viscosity and boiling point. Its existence
as a dimer is also due to very strong hydrogen bond between two HF molecules (which is due to the larger
electronegativity difference).
(b) HOCl is an acid [H+ + OCl–] which turns blue litmus red. HOCl is also an oxidising agen [HCl + O] and thus
bleaches the colour of litmus solution. Thus this involves acidic as well as bleaching action of HOCl.
(c) NaI  H2SO4 
 NaHSO4  HI
HI thus formed being a strong reducing agent reduces H2SO4 to SO2.
2HI  H2SO4  H 2SO4 
 SO2  I2  2H2O
H3PO4 is not reduced by HI.
(d) F2 is better O.A. than Cl2 because it has a very low value of bond dissociation energy (though its electron
affinity is lower than Cl–)
 NO
2  I  I  KI
(e) I  2 3 will lead to intensification of colour while,
SO 2
3  2I  will not.
I2 
(f) Water must be excluded otherwise F2 produced will oxidize it to dioxygen and itself will get reduced to F–.
While anhydrous HF is only slightly ionized and therefore a poor conductor of electricity.
(g) A mixture of KF and HF is used to increase conductivity and lower the m.p.. The mixture exists in the ionic
form K+[F – H – F]–
2. (a) (i) 2HF  CCl4 

 CC2 F2  2HCl (ii) 4HF  SiO2 
 SiF4  2H2O
(freon)
 K  [F  H  F]
(iii) HF  KF 
(b) (i) Cl2  SO2 

 SO2Cl2 (ii) Cl2  H 2 
 2HCl
(iii) Cl2  2NaOH 

 NaOCl  NaCl  H2O
hot NaOH
3. (a) MnO 2  HCl 
 Cl2 (g)   NaClO3  NaCl
(A) (B) (C)
OH 
NaClO3  NaCl  O 2
 (C)
(B) (D)
(b) HCN  CuSO 4 

 Cu 2 (CN)2  (CN)2 (g)
(B) (A)
excess CN 
Cu 2 (CN)2  [(Cu(CN) 4 ]3
(C)
3Br
2  2PBr 
2  6H O
(c) 2P(red)  3  6HBr(g)  2H3PO3
(A) (B)
conc. H SO
2 4  Br
HBr  2
(d) CH 3  CH  CH 2  ICl 
 CH 3  C H  C H 2
| |
Cl I
 I   Cl )
(Iodination occurs : ICl 
4. NaCl  H 2SO4 
 NaHSO4  HCl(g)
(Weaker acid) (Stronger acid)
This occurs because HCl gas escapes taking equilibrium tothe right.
5. H2SO4 oxidises HBr formed to Br2 while this is not the case with HF.
SOLUTIONS TO IN-CHAPTER EXERCISE - D
1. By unpairing of one paired orbital,two singly occupied orbitals come into existence. Thus either two or four or
six singly occupied orbitals can be formed instead of one or three or five singly occupied orbitals.
Vidyamandir Classes
My Chapter Notes

Vidyamandir Classes
Illustration - 1

Vidyamandir Classes

Vidyamandir Classes

Vidyamandir Classes d-Block Elements
d-Block Elements
There are six sections, Section 1 discusses general properties of d-Block Elements, Section 2 discusses
chromium, Section 3 discusses Manganese, Section 4 discusses Iron, Cobalt Nickel groups, Section 5 discusses
Copper and Section 6 is on Zinc group.
GENERAL PROPERTIES OF TRANSITION ELEMENTS Section - 1
Three series of elements are formed by filling the 3d, 4d and 5d shells of elements, together called the d-
block elements (Group 3-12). They are often called ‘transition elements’ because their position is be-
tween the s-block and p-block. Strictly speaking, a transition element is the one which has incompletely
filled d-orbitals in its ground state or in any one of its oxidation states. Thus Zn, Cd, Hg of group 12 having
full d10 configuration are not regarded as transition metals. Compounds of these elements are thus not
typical and show some differences from the others. In general the electronic configuration of these elements
is (n – 1) d1–10ns1–2. In the case of Cr and Cu, the configuration is d5s1 and d10s1 instead of d4s2 and d9s2
respectively. This is because of the additional stability when the d-orbitals are exactly half filled or com-
pletely filled.
Oxidation states and their stability

Transition elements show a great variety of oxidation state. The prominant oxidation states are shown in the
following table:
The various oxidation states show a difference in stability. In general the second and third row elements
exhibit higher coordination numbers and their higher oxidation states are more stable than the corresponding
first row elements. This is interesting because in p-block elements the lower oxidation states are favoured by
the heavier elements (due to inert pair effect).

d-Block Elements Vidyamandir Classes
Atomic and Ionic Sizes

The covalent radii decreases from left to right across the period in d-block until near the end when the size
increases slightly.
On going down the group the size increases as expected. But it is noticed that the increase in radius between
the second and third member of a group is virtually negligible. This is due to the intervention of the 4f orbitals
which must be filled before the 5d series begins. The f-shells shield the nuclear charge poorly as compared
to s, p, d shells and thus lead to a decrease in radii called Lanthanoid contraction or f-block contraction
which compensates for the expected increase in atomic size with increasing atomic number.
Melting and boiling points

The transition metals (except Zn, Cd and Hg) are very much hard and have high m.p. and b.p.. They
typically melt over 1000°C. Zn, Cd and Hg behave abnormally (Hg is in fact a liquid with m.p. –38°C)
because they have a complete d shell and d dectrons donot participate in metallic bonding.
Density
Due to low atomic volumes as compared with Group 1 and 2 metals, they have high densities (almost all
have greater than 5gcm–3). To get a feel of high densities of Os (22.57g/cc) and Ir (22.61g/cc), a football
of Os or of diameter 30cm would weight 320kg !
Colour
Many ionic and covalent compounds of transition elements are coloured (In contrast those of s and p block
are generally white). Colour arises when a compound is able to absorb some wavelength in the visible
region of the spectrum. The colour of the compound is then that of the transmitted light i.e. the complementary
colour to the colour of the light absorbed. Ions having d10 or d0 configuration are usually uncoloured. Thus
ZnSO4 and TiO2 are colourless because in Zn2+(d10) and Ti4+(d0) it is not possible to promote electrons
within the d-level.
Another reason for colour can be charge transfer from one atom to another as occurs in MnO4– (intense
purple).

Magnetic Properties
When an external magnetic field H is applied on a substance, the intensity of field inside it may be greater
than or less than H. If the field is greater than H, the substance is paramagnetic and if the field is less than H
it is diamagnetic. Ferromagnetic materials are a special case of paramagnetism in which the moments on
individual atoms become aligned and all point in the same direction increasing the magnetic susceptibility
drastically. Fe, Co and Ni are ferromagnetic. Antiferromagnetism is just opposite to ferromagnetism when
the moments on individual atoms are aligned in the opposite direction to that of H. It occurs in several simple
salts of Fe3+, Mn2+ and Gd3+. Since ferromagnetism and antiferromagnetism depend on orientation they
disappear in solution.
Paramagnetism arises from the presence of unpaired electrons each having a magnetic moment due to its
spin and due to its orbitals angular momentum. The ‘spin only’ formula is :
 s  n  n  2  , where n is the number of unpaired electrons. The unit is Bohr Magneton (BM). For
the 3-d series effect of orbitals angular momentum is effectively negligible.
Catalytic Properties
Transition elements and their compounds are important catalysts. In some cases they form variable valency
unstable intermediates and in other cases they provide a suitable reaction surface. For example, TiCl3 is
used as ‘Zieger-Natta catalyst’ in the production of polythene, MnO2 is used as a catalyst to decompose
KClO3 to give O2, Pd is used for hydrogenation and V2O5 converts SO2 to SO3 in the Contact Process for
which Fe was formerly used.
Complexes
The transition elements have an unparalleled tendency to form coordination compounds with lewis bases
called ligands. Some example are [Co(NH3)6)3+, [Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+. The reason
for this is that transition elements have small, highly charged ions and vacant low energy orbitals to accept
lone pairs of electrons donated by other groups.
1. Why do second and third rows of transition elements resemble each other more closely than the first
raw?
2. Give reasons :
(i) Most transition metals show paramagnetic behaviours.
(ii) Transition metal and their many compounds are coloured.

CHROMIUM & ITS COMPOUNDS Section - 2
Chromium metal is produced on a large scale from the ore chromite (FeO. Cr2O3 or FeCr2O4). It is
unreactive or passive at low temperature due to the formation of a protective coating of oxide, Cr2O3. Thus
it is used in electroplating to prevent corrosion of iron articles. For Cr the +II, +III, +VI states are well
known. Cr(+II) is reducing, Cr(+III) is the most stable and important, and Cr(+VI) is strongly oxidising.
Cr+II state (Chromous Compounds)

Cr+2 is one of the strongest reducing agent known in aqueous solution. The Cr+2 ion is blue coloured in
aqueous solution.
aqueous
Cr 2  [Cr(H 2O)6 ]2  (sky blue)
Important compounds are CrCl2 and Cr2(CH3COO)4.
Cr+III state (Chromic Compounds)

It is the most stable and important state of chromium.Chromic Oxide (Cr2O3) is used as a green pigment in
paint, rubber, cement and prepared in the well known volcano experiment :

(NH 4 )2 Cr2O7 
 Cr2O3 (green)  N 2  4H 2O
ammonium settleslike
dichromate volcano dust
The heat produced continues the above reaction on its own. Also,

4Cr  3O2 
 2Cr2O3
Chromic chloride (CrCl3) is a solid which forms red-violet flakes and dissolves in water to form violet
coloured solutions.
aq
Cr 3  [Cr(H 2 O)6 ]3 (violet)
Cr+VI State
Few Cr+6 compounds are known. These are very strong oxidising agents and include chromates [CrO4]2–
, dichromates [Cr2O7]2– and chromiun trioxide CrO3.
Sodium chromate (Na2CrO4) is a yellow solid prepared by fusing chromite with Na2CO3.
Na CO
2 3 Na CrO  Fe O  CO
FeCr2O4  2 4 2 3 2
O2  
chromite
On acidifying sodium chromate, an orange coloured solid sodium dichromate (Na2Cr2O7) is obtained while
this sodium dichromate turns orange in basic solutions due to reformation of CrO42–. The reversible reaction
is thus represented by :
 Cr2O72  (aq)  OH  (aq)
CrO24  (aq)  H  (aq) 
Yellow Orange

Potassium dichromate [K2Cr2O7]

To prepare potassium dichromate, Na2Cr2O7 is first prepared from chromite as discussed above and then
it is converted to K2Cr2O7 by a KCl solution.
Na 2Cr2O7  2KCl 
 K 2Cr2O7  2NaCl

1. Action of heat : K 2Cr2O7  K 2CrO 4  Cr2O3  O 2 
Green solid
2. Potassium dichromate is widely used as an oxidizing agent and a primary standard. The orange coloured
K2Cr2O7 solution gets declourised and Cr2+ is formed.
Cr2O72   14H   6e 

 2Cr3  7H2O
Thus it oxidises HCl to Cl2, KI to I2, and FeSO4 to Fe2(SO4)3. Note that K2Cr2O7 is preferred to
Na2Cr2O7 for use in volumetric analysis because the Na compound is hydroscopic whilst the K
compound is not.
3. The Chromyl Chloride Test is used to detect Cr2O72– when treated with conc. HCl or any chloride
in conc. H2SO4, reddish brown vapours of chromyl chloride are obtained.
K 2Cr2O7  4KCl  6H 2SO4 

 2CrO 2Cl2   6KHSO4  3H2O
4. When hydrogen peroxide is added to K2Cr2O7/H+, a deep blue - violet peroxo compound CrO5 is
formed. This decomposes rapidly into Cr3+ and O2 in aqueous solution.
Note : Chromic acid (CrO3) is a bright orange solid used to clean laboratory glassware. It is obtained by adding
conc. H2SO4 to a saturated solution of sodium dichromate.
Na 2Cr2O7  H 2SO4 
 2CrO3  Na 2SO4  H 2O

MANGANESE & IT’S COMPOUNDS Section - 3

Maganese is mined as the ore pyrolusite (MnO2) and is obtained by electrolysis of aqueous solution of
MnSO4 . 95% of it is used in the steel industry to produce alloys.
Mn+II State (Manganous)

The (+II) state is the most stable and common state. Manganous salts like MnCl2, MnSO4 are soluble in
water and form pink coloured solutions of [Mn(H2O)6]2+ while MnCO3 is sparingly soluble.
Mn+IV State
Very few Mn(+IV) compounds are known. MnO2 is the most important oxide in the group and is commercially
important. It occurs naturally as black coloured pyrolusite ore.
1
MnO 2  H 2SO 4 
 MnSO4  O 2  H 2O
(hot, conc.) 2

MnO2  4HCl 
 MnCl2  Cl2  2H2O
(Scheele discovered Cl2 using this reaction)
Mn+VI State
The only example in this category is dark green coloured manganate ion MnO42–. It is a strong oxidising
agent and only stable in very strong alkali solutions. In dilute alkali, water (neutral) or acidic solution it
disproportionates.
MnO24  
 MnO4  MnO2
Mn+VII State
Mn+7 state is obtained when all the electrons of d5s2 in Mn are used for bonding. It is not common but very
well known as the purple coloured permanganate ion (MnO4– ). The colour arises despite the d° configuration
due to charge transfer.
Potassium Permanganate [KMnO4]

KMnO4 exists as deep purple black prism with greenish lustre and is moderately soluble in water at room
temperature. It is manufactured on a large sale as follows :
fused with KOH electrolysis or  Cl

 MnO42  
MnO 2  2 MnO 
4
oxidised with air or  O3
Green mass purple
1. KMnO4 is stored in dark bottles as its decomposition to MnO2 is catalysed by sunlight.

2. KMnO4 is widely used as an oxidising agent in both preparative and qualitative chemistry. In acidic
solution it is reduced to Mn2+ , to MnO24– in alkaline solutions and to MnO2 in neutral or slightly basic
solutions thus oxidising Fe2+ to Fe3+, I – to I2 and H2S to S.
3. With larger amounts of KMnO4, an explosive oil Mn2O7 is formed. (Do not try this)
The following diagram will help you to memorize the interconnection between various manganese
compounds :
1. Complete and balance the following equations.

(i) K 2Cr2O7  . . .  4H 2 SO4 
 K 2 SO4  Cr2 ( SO4 )3  7 H 2O  3I 2
Δ
(ii) K 2Cr2O7 

400C
Δ
(iii) KMnO4 

200C
(iv) MnO4  AsO3  H  


4 NH Cl Δ A
(v) K 2Cr2O7  
 ( gas )  ( green)  (metal )  (oxide)
Δ
2. Account for the following observations and write balanced chemical equations for them.
(i) The yellow colour of solutions change to orange an acidification.
(ii) Acidified solution of ions form a deep blue colour with H2O2.
3. When a white crystalline compound X is heated with K2Cr2O7 and concentrated H2SO4, a reddish
brown gas A is evolved. On passing A into caustic soda solution, a yellow coloured solution of B is
obtained. Neutralising the solution of B with acetic acid and on subsequent addition of lead acetate, a
yellow precipitate C is obtained. When X is heated with NaOH solution, a colourless gas is evolved and
on passing this gas into K2HgI4 solution, a reddish brown precipitate D is formed. Identify A, B, C, D
and X. Write the equations of reaction involved.

4. Pyrolusite on heating with KOH in the presence of the air gives a dark brown compound A. When
ozonized oxygen is passed through a solution of A, a purple coloured compound B is formed.Write
balanced chemical equations for the formation of B.
5. Acidified K2Cr2O7 solution turns green when sodium sulphite is added to it. Explain.
IRON, COBALT & NICKEL GROUPS Section - 4
Group 8 Group 9 Group 10

Fe Co Ni
Ru Rh Pd
Os Ir Pt
These nine elements earlier made up Group VIII in the old Mendeleev periodic table. The horizontal similarities
between these elements are greater than anywhere else in the periodic table. Fe, Co and Ni are together
called ‘Ferrous metals’ and Ru, Rh, Pd, Os, Ir, Pt are known as ‘platinum metals’.
[A] Iron and Its Compounds

Fe is a silvery metal which is not very hard and quite reactive. It is used in large quantities in steel
making. Its biological importance is as an electron carrier in plants and animals, as haemoglobin in
mammals, as nitrogenase to fix bacteria and many more. Fe is strongly ferromagnetic but the
ferromagnetism is lost above the Curie Temperature which is 700°C for Fe.
Iron is passivated by strong oxidising agents like conc. HNO3, K2Cr2O7 due to the formation of a
protective coat of oxide (Fe2O3) while with dilute acids Fe is oxidised to Fe2+. Finely divided iron
combines with the ligand CO forming [Fe(CO)5] which is liquid at room temperature.
Rusting of iron is a special case of corrosion and is of great importance. Rusting occurs in the presence
of O2, H2O and H+ due to the formation of an oxide film of Fe2O3 which is not protective and the
corrosion continues. To prevent corrosion, O2 and H2O must be excluded. This is done by electroplating
Fe with a thinlayer of Sn (tin plating), dipping the Fe in molten zinc (hot dipping), electroplating with
Zn (galvanising) or painting with red lead.
I. Fe+II State (Ferrous)
It is the most stable state of Fe and salts are called ferrous salts. In aqueous solutions, ferrous
salts are pale green and contain the [Fe(H2O)6]2+ ion.
(a) Green Vitriol [FeSO4 . 7H2O]
It is a pale green crystalline solid soluble in water. It is efflorescent and isomorphous with
Epsom salt (MgSO4 . 7H2O) and white vitriol (ZnSO4 . 7H2O). It is prepared by adding
dilute H2SO4 to iron or to FeS in the kipp’s apparatus.

Fe  dil. H2SO4 
 FeSO4  H2
FeS  dil. H 2SO4 

 FeSO4  H2S
140C 300C 
1. FeSO 4 . 7H 2O  FeSO 4 . H 2O  FeSO 4 
 Fe 2O3  SO 2   SO3 
2. FeSO 4  (NH 4 )2 SO 4  6H 2O 
 FeSO4 . (NH 4 ) 2 SO4 . 6H 2O
(Mohr's salt)
Mohr’s salt is double salt used as a primary standard compound in volumetric analysis for
titrations with oxidising agents such as dichromate, permanganate and ceric solutions where
Fe2+ is oxidised to Fe3+.
3. FeSO4  2KCN 
 Fe(CN)2  K 2SO 4
Fe(CN)2  4KCN 
 K 4 [Fe(CN)6 ]
Potassium ferrocyanide
4. FeSO4 and H2O2 are used as Fenton’s reagent for producing hydroxyl radicals, for example oxidising
alcohols to aldehydes.
(b) FeO
It is a non stoichiometric, metals deficient compound more precisely written as Fe0.95O. It dissolves
in acids and is completely basic.
II. Fe+III State (Ferric)

It is a very important oxidation state. Salts are often called ferric salts and solution are usually yellow brown.
The colour is due to the presence of colloidal iron oxide (FeO.OH)
(a) Ferric Oxide (Fe2O3)
It is also a non stoichiometric red - brown compound prepared in the laboratory by strongly heating
FeSO4 .

FeSO4 
 Fe2O3  SO2   SO3 
Igniting Fe2O3 at 1400°C produces Fe3O4 or FeII Fe2III O4 (a black solid). It is largely basic and
when fused with Na2CO3 gives ferrites (NaFeO2). Ferrites hydrolyse with water forming NaOH.
Fe2O3  Na 2CO3 
 2NaFeO2  CO2
2NaFeO2  H2 O 
 2NaOH  Fe 2O3

(b) Ferric Chloride (FeCl3)

It exists as yellow deliquescent solid FeCl3 . 6H2O. It is very soluble in water, alcohol and ether.
moisture
Fe  Cl2 
 FeCl3 (anhydrous) 
 FeCl3 .6H 2 O
Blackish Yellow
Hydrolysis of FeCl3 does not produce Fe(OH)3 but gives a red-brown gelatinous precipitate of the
hydrous oxide Fe2O3(H2O)n. On heating FeCl3 at 500°C FeCl2 and Cl2 are obtained.
Uses :
FeCl3 is used as an oxidising agent and in the manufacture of CCl4.
Fe 2  Sn 2 
 Fe 2   Sn 4   as an 
 
Fe3  SO 2 
 Fe 2   SO 24   Oxidising Agent 
FeCl3 catalyst
CS2  3Cl2   CCl4  S2Cl2 (manufacture of carbon tetrachloride).
Cyanide Complexes
Iron forms two impartant complexes with the cyanide ion namely hexacyanoferrate (II) {FeII(CN)6]4–}
and hexacyanoferrate(III) {[FeIII(CN)63–] }. Hexacyanoferrate(II) is also know as ferrocyanide ion
while hexacyanoferrate (III) is also known as ferricyanide ion. Both these ions from coloured salts with
metal ions like K+, Cu2+, Fe2+ which are used in qualitative analysis. Potassium ferrocyanide K4[Fe(CN)6]
is a yellow coloured solid which is famously used to defect Fe2+ (and Fe3+) ions in solution. It forms a white
coloured precipitat e with Fe(+II) and a Prussiun blue solut ion with Fe(+III) ions.
Potassium ferricyanide K3[Fe(CN)6] can also be used for the same purpose as it gives Turnbull’s blue
colour with Fe(+II) and a brown colour with Fe(+III). The reactions are :
Fe2  K 4[Fe (CN)6 ] 

 Fe2II [FeII (CN)6 ] 
Ferro Ferrocyanide (White)
 Fe3II [FeIII (CN)6 ] 

 K 3[Fe (CN)6 ] 
Ferro Ferricyanide (Tuenbull’s blue)
Fe 3  K 4[Fe (CN)6 ] 
 Fe 4III [FeII (CN)6 ]
Ferri Ferrocyanide (Prussian Blue)
 FeIII [Fe III (CN)6 ]

 K 3[Fe (CN)6 ] 
Ferri Ferricyanide (Brown)
One of the best tests for Fe(+III) is to add aqueous solutions containing SCN– ions. A blood red colour is
produced due to a mixture of Fe(SCN)3 and [Fe(SCN)(H2O)5]2+.

[B] Cobalt & Its Compounds

Cobalt is a very tough metal which resembles iron. It is bluish white and lustrous in appearance. Like
iron it is ferromagnetic (Curie temperature = 1000°C) but relatively unreative as it doesnot react with
H2O, H2 or N2. However, it forms the most number of complexes and more compounds than any
other element except carbon.
I. Co +II State
+II state is the most important oxidisation state for simple compounds of cobalt. Some compounds
in this state are CoO, CoCl2, CoSO4, CoCO3 . The hydrated salts are all pink or red due to the
hexahydrate ion [Co(H2O)6]2+ while CoO is olive green. Thus CoCl2 is used as a test for water
and as an indicator added to the drying agent ‘silica gel’. CoO in combination with ZnO is used
as a green pigment in paints called Rinnmann’s green.
II. Co+III State
This state is the most important state for complexes of cobalt. Since the (+II) state is common
for simple compounds, it is difficult to oxidise Co+2 to Co+3 and Co+3 are less stable and are
reduced by water. In contrast many Co(+II) complexes are readily oxidised to Co(+III)
complexes, Co(+III) complexes being more stable.
[C] Nickel & its Compounds
Nickel, a silvery white metal which does not tarnish in air is produced in large quantities and used in a
wide variety of alloys both ferrous and non-ferrous. All three metals (Ni, Pd, Pt) of Group 10, are
used as catalysts in many reactions. For example, ‘Raney Nickel’ is very finely divided nickel used in
reduction processes and Pd is used for hydrogenation.
Nickel is predominantly divalent in both its simple compounds and complexes. The hydrated salts are
bright green coloured due to the hydrated ion [Ni(H2O)6]2+. Complexes are commonly square planar
or octahedral. The red colourd complex precipitated by Ni2+ and dimethylglyoxime from slightly
ammonical solution is square planar. This reaction is used both for detection and quantitative estimation
of Ni.

1. Write the chemical reactions associated with the Brown Ring Test.
2. A hydrated metallic salt A, light green in colour, gives a white anhydrous residue B after being heated
gradually. B is soluble in water and its aqueous solution reacts with NO to give a dark brown compound
C. B on strong heating gives a brown residue D and a mixture of two gases E and F. The gaseous mixture,
when passed through acidified KMnO4 discharges the pink colour, when passed through acidified BaCl2
solution, gives a white precipitate. Identify A, B, C, D, E and F.
COPPER GROUP [COINAGE METALS] Section - 5
Group 11 consists of the metals coper, gold and silver, all having a completely filled d-shell and one s-
electron. They have been known since prehistoric times when they were used to moke coins and hence
called Coinage Metals. They conduct electricity and heat particularly well and tend to be noble (unreactive).
The reason for their noble character is higher ionisation energy and enthalpy of sublimation.
[A] Copper & its Compounds

Copper is a reddish coloured, lustrous and soft metal produced on large scale from its ores like
chalcopyrite (CuFeS2), malachite (CuCO3.Cu(OH)2), cuprite (Cu2O). The metals is used in the
electrical industry because of its high conductivity, electroplating, in manufacture of coins and also as
a catalyst.
(i) Reaction with air :
A green coating of basic copper carbonate CuCO3.Cu(OH)2 called ‘Verdigris’ is formed in
presence of moisture and CO2 in air (O2) .
2Cu  H 2O  CO 2  O 2 
 CuCO3 . Cu(OH)2
While, when heated it forms two oxides :
1100C
Cu  O 2 
 CuO
Cupricoxide(black)
 1100C
 Cu 2O
Cuprous oxide (red)
(ii) Copper is inert towards non-oxidising acids (HCl, dil. H2SO4) but reacts with concentrated
HNO3 and H2SO4.
Cu  2H2SO4 (conc.) 
 CuSO4  SO2  2H 2O
3Cu  8HNO3 (dil.) 

 3Cu(NO3 )2  4H2O  2NO

Cu  4HNO3 (conc.) 
 Cu(NO3 )2  2H 2O  2NO2
(iii) Copper reduces oxides of nitrogen to N2 and ferric ion to ferrous ion.
1
Cu  NO   CuO  N 2
2
Cu  2Fe3  
 Cu 2   2Fe 2 
The etching of designs on copper plates using ferric chlorides is based on this property.
Cu  2FeCl3 
 CuCl2  2FeCl2
I. Cu+I State
The configuration of copper in (+I) state is 3d10 to 4s° which is known as ‘pseudo-noble gas
configuration’. It might thus be expected that the (+I) state would be the most stable but surprisingly
this is not so. In fact is disproportionates in aqueous solution as :
 Cu 2 (aq)  Cu(s)

2Cu  (aq)  K eq  1.6  106
The only Cu+ compounds stable in water are either insoluble (CuCl, CuBr, CuI, CuCN) or present
as complexes.
(a) Cuprous Oxide (Cu2O) :

Cu2O is a red coloured basic oxide found as the ore cuprite in nature. It is prepared by heating
cupric oxide and copper or by reduction of Cu2+ by mild reducing agents (as in the Fehling’s Test for
reducing sugars).

CuO  Cu 
 Cu 2O
CuO  glucose (or aldehyde or HCOOH) 

 Cu 2O  gluconic acid
(reducing agent) (red)
[Fehling's test]
(i) Cu2O reacts with halogen acids HCl, HBr and HI giving insoluble CuCl(white), CuBr(yellow)
and CuI(yellow). CuF is unknown.
(ii) Cu2O is reduced to copper when heated in a current of H2 or CO or with carbon.
Cu 2O  C 
 2Cu  CO
Cu 2  H 2 
 2Cu  H 2O
Cu 2  CO 
 2Cu  CO 2

(iii) Oxidation of Cu2O :


2Cu 2O + O 2 
 4CuO
Cu 2O  3H 2SO 4 
 2CuSO4  3H2O  SO2
(hot. conc.)
3Cu 2O  14HNO3 (dil.) 

 6Cu(NO3 )2  7H2O  2NO
(iv) Reaction with aqueous ammonia :

no air
Cu 2O  NH 4OH  [Cu I (NH3 )2 ] OH
O
2
Cu 2O  NH 4OH  [Cu II (NH 3 )4 (OH)2 ]
Deep blue
II. Cu+II State

It is the most important and stable state of copper. Since the electronic configuration is d9, the
compounds are typically coloured due to d-d spectra and paramagnetic. The hydrated salts are
blue due to [Cu(H2O)6)]2+ ions. Cu2+ compounds are detected by adding a KI solution which
forms yellow precipitate of Cu2I2.
2Cu 2   4I 
 Cu 2I2   I2 (CuI is not formed)
Yellow
This is also used in the volumetric analysis of Cu+II. Another test is adding the salt to NH4OH solution.
NH OH excess NH OH
Cu 2  (aq)  4  [Cu(NH ) ]2 
4  Cu(OH)  
2 3 4 (aq)
Light blue Deep blue
(a) Copper sulphate [CuSO4 . 5H2O] :

Also known as blue vitriol, copper sulphate solutions are blue coloured. The anhydrous salt is
however white.
It is prepared by dissolving CuCO3.Cu(OH)2 or CuO in sulphuric acid.
CuO 
 H 2SO4
Cu  O2    CuSO 4

Cu(OH)2 .CuCO3 
(i) Hydrated copper sulphate crystals are blue coloured and thus this can be used as a
test for the presence of water on heating, the water of crystallisation is lost.
100C 230C 750C 1200C
CuSO4 .5H 2O 
 CuSO4 .H 2O 
 CuSO4   CuO  O2  Cu 2O
' SO , O ' 2 2

(ii) CuSO 4  KCN 

 CuCN   (CN) 2
Cyanogen
(extremely poisonous)
 K3[Cu(CN)4 ] (a complex is formed)

CuSO4  KCN(excess) 
(iii) A mixture of CuSO4 and Ca(OH)2 (milk lime) is used as Bordeaux Mixture used for
preventing fungus attack on potato leaves and vines. CuSO4 is also used to make
fehling solution.
(b) Cupric Chloride [CuCl2.2H2O] :

Cupric chloride can be obtained by dissolving Cu(OH)2.CuCO3 or CuO or the metal in
conc. HCl.
CuO 
Cu  O2  
conc. HCl
 CuCl2 (hydrated)

Cu(OH)2 .CuCO3 
The hydrated crystals are green coloured. Anhydrous salt can be obtained by heating in HCl
gas.
150C
CuCl2 .2H 2O  HCl(g) 
 CuCl2  2H 2O
Dark brown mass
(i) It is a deliquescent compound readily soluble in water. Dilute solutions are blue while
concentrated solutions are green. It changes to yellow if added to conc. HCl or Cl2
current is passed.
The blue colour is due to [Cu(H2O)4]2+ and yellow colour due to complex ion
[CuCl4]2–
(ii) CuCl2  NaOH 

 Cu(OH) 2   2NaCl
Light blue

(iii) CuCl2  Cu 
 Cu 2Cl2
(c) Cupric Oxide [CuO] :

It is black coloured and formed by heating cuprous oxide or copper in air (O2). In fact, all
oxosalts, such as Cu(NO3)2 decompose into black CuO on strong heating.

Cu(OH)2 
 CuO  H 2O


Cu(NO3 )2 
 CuO  O2  NO2

Cu(CO3 )2 . Cu(OH)2 
 CuO  CO2  H 2O
[B] Silver & its Compounds

Silver is a white lustrous, ductile and malleable metal. It is the best known conductor of electricity and heat.
The chemical properties of silver are :
(i) It is quite unreactive and has no effect of air and alkalies. However, air contaminated with H2S
tarnishes silver due to formation of black Ag2S.
4Ag  2H2S  O 2 
 2Ag 2S  2H 2O
(ii) On heating the molten mass of silver absorbs oxygen which is again released on cooling. This is called
as ‘SPITTING OF SILVER’.
(iii) Ag dissolves in conc. HNO3 and conc. H2SO4 producing NO2 and SO2 respectively. Dilute H2SO4
has no effect on silver but dilute HNO3 react to from NO (Ag being a poor reducing agent). In each
case Ag is oxidised to Ag+ ion.
(iv) Cyanide complexes are used in the extraction of silver.
4Ag  8KCN  2H 2O  2H 2O  O2 
 4K[Ag(CN)2 ]  4KOH
Argentocyonide
Complex
[Ag(CN) 2 ]  2CN  
 [Ag(CN) 4 ]3
(i.e. exces KCN)
(v) Silver finds its use as AgCl and AgBr in photographic emulsions. Other uses include in making jwellery
and ornaments, silver mirrors and for batteries.
The most stable and common oxidation state of silver is the (+I) state. Some compounds in this state
are :
(a) Silver oxide [Ag2O] :

Ag2O is mainly basic and prepared from silver salts like AgNO3
2AgNO3  2NaOH 
 Ag 2O   H 2O
(Brown)
(i) On heating silver oxide decomposes to silver and oxygen at 160°C.

(ii) Aqueous solutions of Ag2O consist of Ag(OH) making the solution strongly basic. Thus the moist
Ag2O can hydrolyse alkyl halides.

C2 H5Br  AgOH 
 C2 H5OH  AgBr
Moist Ag2O also abosorbs carbon dioxide and forms Ag2CO3.
3. Ag2O forms black coloured AgO with sodium thiosulphate. This oxide actually exists as
AgI[AgIIIO2] and hence is diamagnetic not paramagnetic.
(b) Silver Nitrate [AgNO3] (Lunar Caustic) :
Silver nitrate is one of the most important salts of silvers. It can be formed by simply dissolvingAg in
nitric acid.
3Ag  4HNO3 
 3AgNO3  2H2O  NO
1. In crystalline form it is colourless. Heating AgNO3 dissociates it into Ag, NO2 and O2.
2. All simple compounds of Ag+ (Ag2O, AgCl, AgBr, AgNO3) from complexes with alkali cyanide
and sodium thiosulphate.
O excess CN

Ag   CN  
2
[Ag(CN) 2 ] 
 [Ag(CN) 4 ]3
Ag   S2O32  
 [Ag(S2O3 )2 ]3  [Ag3 (S2O4 )4 ]5 + other complexes.
3. A solution of AgNO3 and alkaline aqueous ammonia is used as Tollens Reagent (ammonical
AgNO3 or [Ag(NH3)2]OH–)
4. 5AgNO3  3H 2O  I2 (excess) 
 HIO3  5AgI   5HNO3
6AgNO3 (excess)  3I 2  3H 2O 
 AgIO3  5AgI   6HNO3
(c) Silver Halides :

Silver halides (AgX) are insoluble solids used in photography. AgCl is white, AgBr pale yellow and
AgI yellow. Presence of halide ions in solutions is tested by adding AgNO3 solution and dil. HNO3
which forms silver halide precipitates. The colour indicates the type of halide ion present. This can be
confirmed by testing solubility of these precipitates in ammonium hydroxide. AgCl is soluble in dilute
NH4OH. AgBr fully dissolves only in strong ammonia solution while AgI is insoluble in NH4OH.(AgCl
and AgBr form the soluble ammine complex Ag(NH3)2+ which is linear).
(d) Silver thiosulphate [Ag2S2O3] :

It forms white needle like crystals precipitated when Ag2S or AgNO3 reacts with hypo.
Ag 2S  S2O32  
 Ag 2S2O32  
White
On adding excess of sodium thiosusphate, it dissolves.

Ag 2S2O2  3Na 2S2O3 

 2Na 3[Ag(S2O3 )2 ]
 Ag2S2O3 is decomposed by water giving a variety of colours changing from black through yellow and
brown.
Ag 2S2O3  H 2O 
 H2SO4  Ag 2S 
[C] Gold
Gold(Au) is a soft, heavy and yellow metal with high lustre. It is inert to air and all acids except aqua regia
(a 3 : 1 mixture of concentrated HCl and HNO3). The HNO3 acts as an oxidising agent and the chloride
ions as a complexing agent.
2Ag  9HCl  3HNO3 

 2AuCl3  6H 2O  3NOCl
 H AuCl4 (Chloroauric acid)

AuCl3  HCl 
The most stable oxidation state for gold is Au(+III)
1. Explain the following facts :

(i) Silver nitrate is kept in dark coloured bottles :
(ii) Copper hydroxide is soluble in ammonium hydroxide but not in sodium hydroxide.
(iii) Cuprous chloride is insoluble in water and dilute HCl but dissolves in concentrated HCl.
(iv) The species [CuCl4]2– exists but [CuI4]2– does not .
(v) Addition of an alkali to cuprous chloride solution gives a yellow precipitate which gradully
changes to a red colour.

ZINC GROUP - GROUP 12 Section - 6
The elements of group 12 have a d10s2 configuration and they typically form divalent ions. Since they have a
fully filled orbital in native as well as any other state, they donot behave as typical transition metals (like they
are very soft).
The members of this group are zinc (Zn), cadmium (Cd) and mercury (Hg).
Zinc & its Compounds

Zinc is bluish white crystalline metal which shows some similarities to Mg. It is brittle at ordinary temperature,
malleable and ductile at 100° - 150° C and again becomes brittle at 220°C. Some properties are :

1. 2Zn  O 2   2ZnO
2. Zn(red hot)  H 2O(g) 

 ZnO  H 2
3. Reaction with acids :

(i) Zn  2H 2SO 4 (conc.) 
 ZnSO4  H 2O  SO2
(ii) 4Zn  10HNO3 (very dil.) 

 4Zn(NO3 )2  NH 4 NO3  3H2O
(iii) 3Zn  8HNO3 (moderately conc.) 

 3Zn(NO3 )2  2NO  4H2O
(iv) Zn  4HNO3 (hot conc.) 

 Zn(NO3 )2  2NO2  2H 2O
4. Reaction with NaOH : Zn  2NaOH(hot) 

 Na 2 ZnO2  H 2
Sodium zincate(soluble)
5. Uses : Zinc is used in larger amounts for coating iorn to prevent it from rusting, make alloys (brass is Zn +
Cu), sheets used for roofing and as a reducing agent. It also has an important role inbiological systems.
(a) Zinc oxide (ZnO) : ZnO is a white, light powder insoluble in water and made by heating zinc salts.
Zn(NO3 )2 
 heat
Zn(OH)2    ZnO
Zn  O 2 
1. ZnO is white when cold and becomes yellow on heating. The colour occurs due to loss of O atoms on
heating. creating defects in structure.
2. ZnO is amphoteric. In acids it forms salts and in alkali, zincates such as [Zn(OH)4]2–.
ZnO  2HCl 
 ZnCl2  H 2O

ZnO  2NaOH 
 Na 2 2NO 2  H 2O (or NO2 [Zn(OH)4]2–.
Sodium zincate (soluble)
3. ZnO is the only important commercial oxide in this group. It is used mainly in vulcanization of rubber. It is
also used as white shoe polish and manufacture of glass.
(b) Zinc Sulphide (ZnS) :

ZnS is also white and insoluble in water. It turns yellow on exposure to light. Zinc oxide or zinc sulphate
or other zinc salts form zinc sulphide in the presence of H2S gas.
ZnSO4  H 2 
 ZnS  H2SO4
1. It shows phosphorescence due to impurities of Mn, Cu, Ag etc. and hence is used as a phosphorecsent.
2. On heating in oxygen at high temperature ZnO is formed while ZnSO4 is the major product at how
temperature.
3 O
ZnS  ZnO  ZnSO 4 .

(c) Zinc Sulphate [ZnSO4.7H2O] (White vitriol) :

White vitriol is isomorphous with epsom salts and green vitriol. It is highly soluble in water and prepared
as follows:
ZnCO3  H 2SO4 
 ZnSO4  H 2O  CO2
100C 280C 800C

1. ZnSO 4 . 7H 2O   ZnSO 4 . 6H 2O   ZnSO 4   ZnO  SO 2  O 2
2. It is used in medicine as an eye lotion and in manufacture of white point.
(d) Zinc Chloride (ZnCl2) : It is a white deliquescent solid very soluble in water.
Zn  Cl2 (or HCl) 

 ZnCl2 (anhydrous)
ZnO 
ZnCO3  
HCl
 2nCl2 . 2H 2O (crystals)
Zn(OH)2 
Heating hydrated ZnCl2 simply decomposes it to ZnO instead of dehydrating to anhydrous form.
1. Aqueous solutions of Zn2+ are acidic because of hydrolysis.
H O
Zn 2   6H 2O 
 [Zn(H 2O)6 ]2 
2  [Zn(H O)OH]  H O 
2 3

2. ZnCl2  H2S 
 ZnS   2HCl
NaOH NaOH
3. ZnCl2 
 Zn(OH)  (White gelationus precipitate) 
 Na 2 ZnO2
Sodium zincate
NH OH
4  Zn(OH)  
4 NH OH / NH Cl
4  [Zn(NH ) ]Cl
4. (i) ZnCl2  2 3 4 2
Tetramminezinc Chloride
4 NH 3
(ii) ZnCl2  ZnCl2 . 4NH 3
5. Concentrated solutions of zinc chloride are corrosive and dissolve paper. It is used for treating textiles.
ZnCl2 is also used as a flux for soldering.
Mercury & its Compounds

Mercury is a silvery liquid which doesnot tarnish readily. All mercury (and cadmium) compounds are toxic.
It has two oxidation state +I and +II. Hg(I) compounds (mercurous compounds) are few in number and
contain the ion (Hg – Hg)2+ and Hg+. Hg(II) compounds (mercuric compounds) are more covalent and
stable.
Hg is used in thermometers, barometers and mercury vapour street lights.
I. Hg+I State (Mercurous)
Mercurous compound can be made by reducing the Hg(II) salts with the metal.
HgCl2  Hg   Hg 2Cl2  (white)

Calomel
Alternatively, mercury (I) nitrate can be made by dissolving Hg in dilute HNO3.
Hg  HNO3 (dil.) 
 Hg 2 (NO3 )2  NO
 Hg2Cl2 also known as calomel is used in calomel electrodes. It is a white powder which turns black in
NH3 (which is used in detection of mercurous ion).
Hg 2Cl2  NH 3 
 Hg NH 2Cl  Hg  NaCl2

black
II. Hg+II State (Mercuric)

Salts are usually anhydrous. Mercuric chloride (HgCl2) is called ‘Corrosive Sublimate’ and prepared as
follows :

HgSO4  NaCl 
 HgCl2  Na 2SO4
It is a colourless crystalline highly poisonous solid used as an antiseptic since the middle Ages. It is also
used to make Nessler’s Reagent which is used to detect NH3.
KI excess KI
HgCl2  HgI2  K 2 [HgI4 ] (Called Nessler’s reagent in alkali medium)

IN-CHAPTER EXERCISE - E
1. Write balanced equations for the reaction of alkaline perbromate with zinc giving tetrahydraoxozincate
anion.
2. Excess of dilute sodium hydroxide solution is gradually added with shaking to an aqueous solution of
zinc sulphate. What would you observe?
3. Explain the following:
(i) The addition of NaOH solution to a solution of zinc chloride produces a white precipitate which
dissolves on further addition of NaOH.
(ii) The addition of NH4OH to ZnSO4 solution produces white precipitate but no precipitate is formed if
it contains NH4Cl.
4. Mercurous chloride turns black on adding NH4OH to it. Explain.
5. A while substance A reacts with dilute H2SO4 to produce a colourless gas B and a colourless solution C. The
reaction between B and acidified K2Cr2O7 solution produces a green solution and a slightly coloured precipitate D.
The substance D burns in air to produce a gas E which reacts with B to yield D and a colourless liquid. Anhydrous
copper sulphate is turned blue on addition of this colourless liquid. Addition of aqueous NH3 or NaOH to C
produces first a precipitate, which dissolves in the excess of the respective reagent to produce a clear solution in
each case. Identify A, B, C, D and E. Write the equations of the reactions involved.

SOLUTIONS - IN - CHAPTER EXERCISE - A

1. Due to lanthanoid contraction, the difference between the radius of second and third group elements is negligible.
As a result, they have similar lattice energies, solvation energies, ionization energies and other properties.
2. (i) Many transition metals contain partially filled electrons shell. The unpaired electrons produce spin
magnetic moments which result into paramagnetism.
(ii) Colour arises from the ability of a compound to absorb particular wavelengths of white light and emit
the rest. This can occur when their is/are electrons / charge which can be transferred from an energy
level to another which is the case with transition elements and their compounds.
SOLUTIONS - IN - CHAPTER EXERCISE - B
1. (i) K 2Cr2O7  2KI  4H 2SO 4 

 K 2SO4  Cr2 (SO4 )3  7H 2O  I2
(ii) 
K 2Cr2O7 
 K 2CrO4  Cr2O3  O 2
(iii) 
 K 2 MnO4  MnO2  O2 (disproportionation)
2KMnO4 
(iv) 2MnO4  5AsO3  6H 
 2Mn 2   3H 2O  5AsO34
(v) K 2Cr2O7  2NH 4Cl 
 (NH4 )2 Cr2O7  2Kcl
 
(NH 4 )2 Cr2O7 
 Cr2O3  N 2  4H 2O ; Cr2O3  2A 
 2Cr  A 2O3
(green) (gas) (metal) (oxide)
2. X is NH4Cl.
4Cl  K 2Cr2O7  6H 2SO4 
 2CrO 2Cl2  2KHSO 4  4HSO4  3H 2O
(from NH 4Cl) (gas A)
CrO2Cl2  4NaOH 
 Na 2CrO 4  2NaCl  2H 2O
(B)
Na 2CrO 4  (CH3COO)2 Pb 
 PbCrO4   2CH3COONa
(C)

NH 4  NaOH 
 NH3  Na   H 2O
(From NH 4Cl) (gas)
NH3  2HgI42   H 2O 
 H 2 N  Hg  O  Hg  I   7I   3H 
(D)
3. The process described is that of preparation of potassium permanganate from pyrolusite ore.

2MnO2  4KOH  2[O]   2K 2 MnO4  2H 2O ; 2K 2MnO4  Cl2 
 2KMnO4  2KCl
4. Cr2O72   3S2   14H 
 2Cr3  3S  7H 2O
SOLUTIONS - IN - CHAPTER EXERCISE - C
1. Nitrates produce NO which coordinates with Fe2+ to give a brown ring.
FeSO4  NO  5H 2O 
 [Fe(H 2O)5 NO]SO4
 H O
2  [Fe(H O) NO]SO
2. FeSO4 . 7H 2O 
 FeSO4 (white) ; FeSO4  NO  2 5 4
(A) (B) (C)

FeSO4 
 Fe 2O3  SO 2  SO3
(D) (E) (F)
 Mn 2  (pink solution)
SO2  SO3  KMnO4  ;
SO2  SO3  BaCl2 

 BaSO4 (white precipitate)
SOLUTIONS - IN - CHAPTER EXERCISE - D
1. (i) AgNO3 decomposes to Ag2O and NO2 in presence of slight heat (due to light) and is thus kept in
dark bottles.
(ii) This is because Cu2+ can form many complexes with NH4+ which are soluble in water.
(iii) Cuprous halides form soluble complexes in presence of excess of halide ions in solution.
Cu 2Cl2  2HCl 
 2H[CuCl2 ]
(iv) I– ion is a stronger reducing agent than Cl– ion. It reduces Cu2+ ion into Cu+ ion. Hence, cupric iodide
is converted into cuprous iodide. Thus the species [CuI4]2– doesnot exist.
(v) Cu 2Cl2  2NaOH   Cu 2O   2NaCl  H2O
Precipicate changes colour from yellow to red due to formation of Cu2O
SOLUTIONS - IN - CHAPTER EXERCISE - E
1. BrO4  Zn  2OH   H 2O 
 BrO3  Zn(OH)42 
NaOH
2. ZnSO 4  2NaOH 
 Na 2SO 4  Zn(OH)2  
 Na 2 ZnO2
(white)  so lub le 
 and 
 colourless 
 
3. (i) First a white precipitate of Zn(OH)2 is formed which on further addition of NaOH forms soluble
zincate Na2ZnO2.
(ii) NH4OH is a weak hydroxide. It is ionized slightly furnishing OH– ions which are suflicient to precipitate
Zn(OH)2 because its low solubility product. However, in presence of NH4Cl, the ionization of NH4OH
is further suppressed and suficient OH– are not available to cause precipition.
4. Hg 2Cl2  NH 4OH 
 Hg  NH 2Cl  Hg This is used to detect mercurous ions.
 
black
5. ZnS  dil.H2SO4 
 H2S  ZnSO4 ;
(A) (B) (C)
3H 2S  Cr2O72   8H  
 2Cr3  3S  7H 2 O
(green) (D)
SO 2 + H 2S 
 S + H2O
S  O2 
 SO2 (E) ;
(E) (B) (D) (colourless liquid)
OH 
Zn 2   2OH  
 2n(OH)2   Zn(OH)42  (clear solution)
(C)
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VIDYAMANDIR MODULES

Concept of Gram Atom :

Mass of 1 atom of an element

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

Illustrating the Concept :

Self Study Course for IITJEE with Online Support Section 1 1

Concept of Gram Mole :

Illustrating the Concept :

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

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

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

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

2 Section 1 Self Study Course for IITJEE with Online Support

Concept of Gram Equivalents :

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

Atomic weight of an element

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

Self Study Course for IITJEE with Online Support Section 1 3

Basicity of CH3COOH (Acetic acid) = 1

This can be deduced from its structure shown ( 

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

(Ans: Basicity of H3PO2 = 1)

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

Molecular weight of base

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

4 Section 1 Self Study Course for IITJEE with Online Support

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

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

Illustrating the Concept :

Self Study Course for IITJEE with Online Support Section 1 5

Relationship between Moles and Gram Equivalents :

Concentration of solute  Amount of solute

6 Section 1 Self Study Course for IITJEE with Online Support

Illustrating the Concept :

Illustrating the Concept :

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

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

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

Self Study Course for IITJEE with Online Support Section 1 7

Illustrating the Concept :

Important Concepts in Stoichiometric Calculations :

8 Section 1 Self Study Course for IITJEE with Online Support

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

Illustrating the Concept :

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

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

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

Self Study Course for IITJEE with Online Support Section 1 9

Illustrating the Concept :

How to calculate E when Strength is given ?

Important Concepts in Stoichiometric Calculations :

10 Section 1 Self Study Course for IITJEE with Online Support

Illustrating the Concept :

2. When Solute is Solid :

Illustrating the Concept :

Self Study Course for IITJEE with Online Support Section 1 11

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

Illustrating the Concept :

12 Section 1 Self Study Course for IITJEE with Online Support

Important Concepts in Stoichiometric Calculations :

Self Study Course for IITJEE with Online Support Section 1 13

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