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Chapter- 13: S & P-BLOCK ELEMENTS


Elements of group I-A (Alkali Metals) and Group II-A
constitute s-block. They have their valence electrons in sorbital. S-block has only metals however hydrogen and
helium are exceptions, these two are non-metals.
Elements of group III-A, IV-A, V-A, VI-A, VII-A and VIII-A
constitute p-block. They have their valence electrons in porbital. P-block consists of metals as well as non metals. Up
till now more than 100 elements are discovered so chemists
felt to classify them into groups of similar properties.
(i)

Blocks:

The elements are divided into four blocks.


(a)

(b)

(c)

(d)

The elements having their valence electrons in


s-sub shell are called s-block elements. Two
vertical columns on extreme left of periodic
table i.e. Group-IA and Group-IIA constitute sblock.
The elements having their valence electrons in
p-sub shell are called p-block elements. Six
vertical column on extreme right of periodic
table i.e. Group-IIIA, IVA, VA, VIA, VIIA and
Group-VIIIA constitute p-block.
The elements having their valence electrons in
d-sub shell are called d-block elements. Ten
vertical columns in between s-block and pblock of periodic table i.e. Group-IB to VIIIB
constitute d-block.
The elements having their valence electrons in
f-sub shell are called f-block elements. Two
horizontal rows on the bottom of periodic table
i.e. Lanthanides and Actinides series constitute
f-block.

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(ii)

Transition and Representative Elements:


The elements of d-block and f-block are called
transition elements. The d-block elements are
called outer transition elements while f-block
elements are called inner transition elements.
Their groups are called B-groups.
On other hand elements of s-block and p-block
are called representative elements. Their
groups are called A-groups.

(iii)

Metals and Non-metals:


In the periodic table a diagonal line separates
metals and non-metals. The elements on left
side of this line are metals while those present
on right side of the line are non-metals.

(iv)

Periods:
The horizontal rows in the periodic table are
called periods. In a period a shell starts from
the first member and completes at the last
member of the period. There are seven
periods in the periodic table.
Period-I:
It is the shortest period. It
consists of only two elements both are
representative elements and belong to s-block.
Period II & III: These are short periods. Each
consists of eight elements two from s-block
and six from p-block.
Period IV & V: These are long periods. Each
consists of eighteen elements out of which
eight representative and ten transition
elements. Out of eight representative elements

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two belongs to s-block and six to p-block.
Where as all the ten transition elements belong
to d-block.
Period VI:
It is longest period. It consists of
Thirty two elements, out of which eight
representative and twenty four transition
elements. Out of eight representative elements
two belongs to s-block and six to p-block. Out
of twenty four transition elements ten belong to
d-block while fourteen belong to f-block (i.e.
Lanthanides).
Period VII:
It is incomplete period. It is also
long period. Actinides are also member of this
period.
(v)

Groups:
The vertical columns in the periodic table are
called groups or families. In a group all
members have same number of electrons in
their valence shell; however their number of
shells is different. There are eight groups in the
periodic table, each group consists of two sub
groups A and B.
Some of important groups are
Group-IA:
It consists of Li, Na, K, Rb, Cs
and Fr and is also called Alkali metal group.
Group-IIA:
It consists of Be, Mg, Ca, Sr, Ba
and Ra and is also called Alkaline Earth metal
group.
Group-VIIA: It consists of F, Cl, Br, I and At
and is also called Halogen group.

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Group VIIIA: It consists of He, Ne, Ar Kr, Xe
and Rn. It is also called Zero group, Inert
gases, Noble gases group.
Group-IB:
It consists of Cu, Ag and Au and
is also called Coin age metals group.
Group-VIIIB: It consists of three vertical
column or three triads.
Fe
Co
Ni
Ru
Rh
Pd
Os
Ir
Pt
(vi)

Lanthanides and actinides:


Fourteen elements that follow Lanthanum are
called Lanthanide while fourteen elements that
follow Actinium are called Actinide. They
belong to f-block and are present in two
horizontal rows at the bottom of periodic table.
They are inner transition elements.

Periodicity in Physical Properties:


Properties vary with increasing atomic number but are
repeated after regular intervals and this is called
periodicity in properties. Periodicity occurs in
properties due to periodic variation in electronic
configurations.
Electronic Configuration:
The third period contains eight
magnesium, aluminium, silicon,
chlorine, and argon. The first
magnesium, are members of

elements: sodium,
phosphorus, sulfur,
two, sodium and
the s-block of the

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periodic table, while the others are members of the pblock
Chemical element
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Na

Sodium

Chemical

Electron

series

configuration

Alkali

[Ne] 3s1

metal
12 Mg Magnesium

Alkaline

[Ne] 3s2

earth
metal
13 Al

Aluminium

Post-

[Ne] 3s2 3p1

transition
metal
14 Si

Silicon

Metalloid

15 P

Phosphorus Polyatomi

[Ne] 3s2 3p2


[Ne] 3s2 3p3

c
nonmetal
16 S

Sulfur

Polyatomi

[Ne] 3s2 3p4

c
nonmetal
17 Cl

Chlorine

Diatomic

[Ne] 3s2 3p5

nonmetal
18 Ar
(1)

Argon

Noble gas

[Ne] 3s2 3p6

Atomic Radii:
It is difficult to state exact atomic size as atom has no
fixed boundaries also it is difficult to isolate atom.
Therefore, atomic radius is defined as half of the

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distance between nuclei of two identical atoms
bonded together through single covalent bond.

Going across Period 3:

the number of protons in the nucleus increases so ...


the nuclear charge increases ...
there are more electrons, but the increase in shielding
is negligible because each extra electron enters the
same principal energy level ...
therefore the force of attraction between the nucleus
and the electrons increases ...
so the atomic radius decreases.

As the number of electrons in each atom increases going


across Period 3, you might expect the atomic radius to
increase. This does not happen, because the number of
protons also increases and there is relatively little extra
shielding from electrons in the same principal energy level.
(2)

Ionic Radii:
The distance of place of maximum probability of outer
most shell from the nucleus of an ion is called ionic
radius.
The ionic radius of cation is much smaller than atomic
radius of the element while ionic radius of anion is
much larger than atomic radius of the element.
During formation of cation loss of outer shell occurs
and also hold of nucleus increases on remaining
electrons so cation is much smaller than neutral atom.
On other hand in anion due to addition of extra
electron(s) repulsion increases among electrons so
the electronic cloud expands and thus size of anion
become larger than neutral atom.
Periodicity in ionic radii occurs within the same period.
Elements on the left of a period forms cation so their
size is smaller, further, across the period positive

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charge increases so ionic radii decrease. Elements on
the right of a period forms anion so size increases and
then across the period ve charge decreases so size
decreases.
I
II
III
V
VI
VII
Period-3

Na

Ionic radius
(in pm)

95

Mg

+2

65

Al

+3

50

-3

212

-2

Cl

184 181

In group from top to bottom ionic radii increase.


(3)

Melting and Boiling Points:


Periodicity in melting and boiling points occurs within
the same period. Moving from group I to group IV
melting and boiling point increase then moving from
group V to group VIII they decrease as number of
binding first increase and then decrease.
Down the group in metals, melting and boiling points
decrease while in non-metals increase.

(4)

Metallic Character (Electro-positivity):


The electron giving ability of an element is called
metallic character or electro-positivity.
Across the period from left to right electro-positivity
decreases due to increasing nuclear charge. While
down the group it increases due to increasing atomic
sizes.

(5)

Electronegativity:
The electron puling ability of an element is called
electronegativity.

9
Across the period from left to right electronegativity
increases due to increasing nuclear charge. While
down the group it decreases due to increasing atomic
sizes.
Na
Mg
Al
Si
P
S
Cl
Ar
0.93 1.31 1.81 2.02 2.19 2.58 3.16 -It should be kept in mind that Ar has not assign any
E.N value as Ar does not form any covalent bond.
(6)

Ionization Energy/Potential:

The energy required to remove the most loosely


bound electron from an isolated atom (gaseous atom) to
make cation is called Ionization Potential or Ionization
Energy.
This is an endothermic process in which energy is absorbed
so sign for this energy is +ve. This energy is required to
overcome the force of attraction of nucleus on the electron.
After removal of first electron hold of nucleus on remaining
electrons increases so Second I.P is greater than First I.P
because more energy is required to remove the second
electron and so on.
+
e.g (i) Na

Na
+ e (I.E)1 = +496 kJ/mol
(2,8,1)
(2,8)
+
e.g (i) Mg

Mg
+ e (I.E)1 = +738 kJ/mol
(2,8,2)
(2,8,1)
+
2+
Mg

Mg
+ e
(I.E)2 = +1451 kJ/mol
(2,8,1)
(2,8)
Trend in Periodic Table:
Generally I.E increase in a period from left to right due
to decreasing atomic size and increasing nuclear
charge. But anomalies are observed at group 1A, IIA
and VIIIA they have extra ordinary high I.E. This is due

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to the reason that they have completely filled or half
filled outer orbitals which are more stable and thus
their electrons are difficult to remove so their I.E are
high.
e.g. trend of 2nd period is
Groups
IA
IIA IIIA IVA VA VIA VIIA VIIIA
Elements Li Be B
C
N
O
F
Ne
I.E
520 900 801 1086 1402 1314 1681 2081
On other hand in a group I.E decrease from top to
bottom due to increasing atomic size.
(7)
Elec

tron Affinity:
The energy released (with few exception) when an
electron is added to the outer most shell of an isolated
(gaseous atom) to make anion is called Electron Affinity.
1st electron affinities are energy released so they have ve
values. But second electron affinities are energy absorbed so
have +ve values.
e.g(i) Cl + e

Cl (E.A)1=-348.8 kJ/mol
(2,8,7)
(2,8,8)
e.g(ii) O + e

O (E.A)1 = -141 kJ/mol


(2,6)
(2,7)
2O
+
e

O
(E.A)2 = +844 kJ/mol
(2,7)
(2,8)

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When first electron is added to an isolated atom, nucleus
provides attraction for this additional electron so energy is
released. But when second electron is added then energy is
required to overcome repulsion between anion and electron
so energy is absorbed. In case of groups IIA, VA and VIIIA
even first electron affinities have +ve values.

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Name of Element
Symbol

Sodium Magnesium Aluminium


Na
Mg
Al

Silicon
Si

Phosphorus
P

Sulfur Chlorine
S
Cl

Argon
Ar

Atomic Number, z

11

12

13

14

15

16

17

18

Electronic
Configuration

2,8,1

2,8,2

2,8,3

2,8,4

2,8,5

2,8,6

2,8,7

2,8,8

186

160

143

118

110

102

99

192

502

744

584

793

1017

1006

1257

>1526

Electronegativity
(Pauling)

0.93

1.31

1.61

1.9

2.19

2.58

3.16

Melting Point (oC)

98

639

660

1410

44

113

-101

-189

Atomic
(picometers)

Radius

1stIonization
(kJ/mol)

Energy

13
Boiling Point (oC)

883

1090

2467

2680

280

445

-35

-186

Metallic Character

metal

metal

metal

semi-metal
(metalloid)

non-metal

nonmetal

non-metal

nonmetal

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Trends across Period 3 of the Periodic Table

The modern Periodic Table is arranged in order of


increasing atomic number. As one moves from one
element to another on the right, one more proton is
found in the nucleus, and one more electron is found
in the same electron 'shell' (energy level). For this
reason, all the elements in Period 3 have the first
electron 'shell' (energy level) filled with 2 electrons and
the second electron 'shell' (energy level) filled with 8
electrons (the electronic configuration of Neon).
Sodium begins a new electron 'shell' ( 3rdenergy level)
with 1 electron, Magnesium has 2 electrons in the
third electron 'shell' (energy level), Aluminium has 3
electrons in the third electron 'shell' (energy level) etc,
until finally the third electron 'shell' (energy level) is
filled with 8 electrons and the stable electronic
configuration of the Noble Gas Argon is reached
(2,8,8).
Atomic radius of the elements decrease across the
Period from left to right. As we move from left to right
across the period one more proton is added to the
nucleus of each successive atom, and one more
electron is added to the same electron 'shell' (energy
level) of each successive atom. The increased
positive charge in the nucleus of each successive
atom attracts all the electrons in the atom more
strongly, so they are drawn in more closely towards
the nucleus.
1st Ionization Energy (the energy required to remove
an electron from the gaseous atom) increases across
the Period from left to right. The further away from the
positively charged nucleus that a negatively charged
electron is, the less strongly the electron is attracted to
the nucleus and so the more easily that electron can
be removed. So, as the atomic radius decreases from

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left to right across the Period so the 1 st Ionization


Energy increases.
Electronegativity (the relative tendency shown by an
atom to attract electrons to itself) increases across the
Period from left to right. Typically, metals have low
electronegativity, little ability to attract electrons, while
non-metals have high electronegativity, greater ability
to attract electrons. As we move from left to right
across the Period, the elements become less metallic
in nature (more non-metallic).
In general metals are hard (EXCEPT Group 1 (IA)
metals which are quite soft), have metallic lustre, high
melting and boiling points (Except for mercury which is
a liquid at room temperature, and the Group 1 (IA)
metals which have low melting/boiling points
compared to other metals) and good electrical
conductivity. In general, non-metals are dull, brittle,
have low melting and boiling points and are electrical
insulators (non-conductors of electricity). Elements to
the left of Period 3 exhibit metallic properties,
elements to the right show non-metallic properties.
Silicon is a semi-metal (metalloid).

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Properties of Oxides and Chlorides of Period 3 Elements
Element

Sodium Magnesium Aluminium Silicon Phosphorus Sulfur

Chlorine

NaCl
Na2O

MgCl2
MgO

AlCl3*
Al2O3

SiCl4
SiO2

PCl3
P4O6

SCl2
SO2

Cl2
Cl2O7

Chloride melting point (oC)


Oxide melting point (oC)

801
920

712
2800

193
2045

-68
1700

-92
420

-80
17

-101
-92

Chloride bonding
Oxide bonding

Ionic
Ionic

Ionic
Ionic

Covalent
Ionic

Covalent
Covalent

Covalent
Covalent

Chloride conductivity of liquid


Oxide conductivity of liquid

Good
Good

Good
Good

Poor
Good

Nil
Nil

Nil
Nil

Nil
Nil

Nil
Nil

Chloride acid-base behaviour


Oxide acid-base behaviour

Neutral
Basic

Neutral
Basic

Acidic
Acidic

Acidic
Acidic

Acidic
Acidic

Chloride formula
Oxide formula

Acidic
Acidic
Amphoteric Acidic

Covalent Covalent
Covalent Covalent

Aluminium forms a covalent anydrous aluminium chloride, Al2Cl6, which forms ions in aqueous solution. Ionic aluminium
chloride, AlCl3.6H2O, can be crystallised out of this solution.

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Reactions with water
Sodium
Sodium has a very exothermic reaction with cold water
producing hydrogen and a colourless solution of sodium
hydroxide.

Magnesium
Magnesium has a very slight reaction with cold water, but
burns in steam.
A very clean coil of magnesium dropped into cold water
eventually gets covered in small bubbles of hydrogen which
float it to the surface. Magnesium hydroxide is formed as a
very thin layer on the magnesium and this tends to stop the
reaction.

Magnesium burns in steam with its typical white flame to


produce white magnesium oxide and hydrogen.
Aluminium
Aluminium powder heated in steam produces hydrogen and
aluminium oxide. The reaction is relatively slow because of
the existing strong aluminium oxide layer on the metal, and
the build-up of even more oxide during the reaction.

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Silicon
There is a fair amount of disagreement in the books and on
the web about what silicon does with water or steam. The
truth seems to depend on the precise form of silicon you are
using.
The common shiny grey lumps of silicon with a rather metallike appearance are fairly unreactive. Most sources suggest
that this form of silicon will react with steam at red heat to
produce silicon dioxide and hydrogen.

But it is also possible to make much more reactive forms of


silicon which will react with cold water to give the same
products. Phosphorus and sulphur
These have no reaction with water.
Chlorine
Chlorine dissolves in water to some extent to give a green
solution. A reversible reaction takes place to produce a
mixture of hydrochloric acid and chloric(I) acid (hypochlorous
acid).
In the presence of
sunlight, the chloric(I) acid slowly decomposes to produce
more hydrochloric acid, releasing oxygen gas, and you may
come across an equation showing the overall change:

Argon
There is no reaction between argon and water.

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Reactions with oxygen
Sodium
Sodium burns in oxygen with an orange flame to produce a
white solid mixture of sodium oxide and sodium peroxide.
For the simple oxide:

For the peroxide:

Magnesium
Magnesium burns in oxygen with an intense white flame to
give white solid magnesium oxide.
Aluminium
Aluminium will burn in oxygen if it is powdered, otherwise the
strong oxide layer on the aluminium tends to inhibit the
reaction. If you sprinkle aluminium powder into a Bunsen
flame, you get white sparkles. White aluminium oxide is
formed.

Silicon
Silicon will burn in oxygen if heated strongly enough. Silicon
dioxide is produced.

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Phosphorus
White phosphorus catches fire spontaneously in air, burning
with a white flame and producing clouds of white smoke - a
mixture of phosphorus(III) oxide and phosphorus(V) oxide.
The proportions of these depend on the amount of oxygen
available. In an excess of oxygen, the product will be almost
entirely phosphorus(V) oxide.
For the phosphorus(III) oxide:

For the phosphorus(V) oxide:

Sulphur
Sulphur burns in air or oxygen on gentle heating with a pale
blue flame. It produces colourless sulphur dioxide gas.

Chlorine and argon


Despite having several oxides, chlorine won't react directly
with oxygen. Argon doesn't react either.
Reactions with chlorine
Sodium
Sodium burns in chlorine with a bright orange flame. White
solid sodium chloride is produced.

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Magnesium
Magnesium burns with its usual intense white flame to give
white magnesium chloride.

Aluminium
Aluminium is often reacted with chlorine by passing dry
chlorine over aluminium foil heated in a long tube. The
aluminium burns in the stream of chlorine to produce very
pale yellow aluminium chloride. This sublimes (turns straight
from solid to vapour and back again) and collects further
down the tube where it is cooler.

Silicon
If chlorine is passed over silicon powder heated in a tube, it
reacts to produce silicon tetrachloride. This is a colourless
liquid which vaporises and can be condensed further along
the apparatus.

Phosphorus
White phosphorus burns in chlorine to produce a mixture of
two chlorides, phosphorus(III) chloride and phosphorus(V)
chloride
(phosphorus
trichloride
and
phosphorus
pentachloride).
Phosphorus(III) chloride is a colourless fuming liquid.

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Phosphorus(V) chloride is an off-white (going towards yellow)


solid.

Sulphur
If a stream of chlorine is passed over some heated sulphur, it
reacts to form an orange, evil-smelling liquid, disulphur
dichloride, S2Cl2.

Chlorine and argon


It obviously doesn't make sense to talk about chlorine
reacting with itself, and argon doesn't react with
chlorine.
Phosphorus(V) oxide
Phosphorus(V) oxide is also a white solid, subliming (turning
straight from solid to vapour) at 300C. In this case, the
phosphorus uses all five of its outer electrons in the bonding.
Solid phosphorus(V) oxide exists in several different forms some of them polymeric. We are going to concentrate on a
simple molecular form, and this is also present in the vapour.
This is most easily drawn starting from P 4O6. The other four
oxygens are attached to the four phosphorus atoms via
double bonds.

23

ACID-BASE BEHAVIOUR OF THE PERIOD 3 OXIDES


The oxides
The oxides we'll be looking at are:
Na2O

MgO

Al2O3

SiO2

P4O10

SO3

Cl2O7

P4O6

SO2

Cl2O

The trend in acid-base behaviour


The trend in acid-base behaviour is shown in various
reactions, but as a simple summary:

The trend is from strongly basic oxides on the lefthand side to strongly acidic ones on the right, via an
amphoteric oxide (aluminium oxide) in the middle. An
amphoteric oxide is one which shows both acidic and
basic properties.

For this simple trend, you have to be looking only at the


highest oxides of the individual elements. Those are the ones
on the top row above, and are where the element is in its

24
highest possible oxidation state. The pattern isn't so simple if
you include the other oxides as well.
For the non-metal oxides, their acidity is usually thought of in
terms of the acidic solutions formed when they react with
water - for example, sulphur trioxide reacting to give sulphuric
acid. They will, however, all react with bases such as sodium
hydroxide to form salts such as sodium sulphate.
These reactions are all explored in detail on the rest of this
page.
Chemistry of the individual oxides
Sodium oxide
Sodium oxide is a simple strongly basic oxide. It is basic
because it contains the oxide ion, O2-, which is a very strong
base with a high tendency to combine with hydrogen ions.
Depending on its concentration, this will have a pH around
14.

As a strong base, sodium oxide also reacts with acids, it


would react with dilute hydrochloric acid to produce sodium
chloride solution.

Magnesium oxide
Magnesium oxide is again a simple basic oxide, because it
also contains oxide ions. However, it isn't as strongly basic as
sodium oxide because the oxide ions aren't so free.

25
In the sodium oxide case, the solid is held together by
attractions between 1+ and 2- ions. In the magnesium oxide
case, the attractions are between 2+ and 2-. It takes more
energy to break these.
However, if you test the pH of the liquid, you find that it is
somewhere around pH 9 - showing that it is slightly alkaline.

it reacts with warm dilute hydrochloric acid to give magnesium


chloride solution.

Aluminium oxide
Aluminium oxide is amphoteric. It has reactions as both a
base and an acid.
Aluminium oxide doesn't react in a simple way with water in
the sense that sodium oxide and magnesium oxide do, and
doesn't dissolve in it. Although it still contains oxide ions, they
are held too strongly in the solid lattice to react with the water.
Aluminium oxide will react with hot dilute hydrochloric acid to
give aluminium chloride solution.

In this (and similar reactions with other acids), aluminium


oxide is showing the basic side of its amphoteric nature.
With hot, concentrated sodium hydroxide solution, aluminium
oxide reacts to give a colourless solution of sodium tetrahydroxo-aluminate.

26

Silicon dioxide (silicon(IV) oxide)


Silicon dioxide has no basic properties - it doesn't contain
oxide ions and it doesn't react with acids. Instead, it is very
weakly acidic, reacting with strong bases.
Silicon dioxide doesn't react with water, because of the
difficulty of breaking up the giant covalent structure.
Silicon dioxide reacts with sodium hydroxide solution, but only
if it is hot and concentrated. A colourless solution of sodium
silicate is formed.

In Blast Furnace extraction of iron - in which calcium oxide


(from the limestone which is one of the raw materials) reacts
with silicon dioxide to produce a liquid slag, calcium silicate.
This is also an example of the acidic silicon dioxide reacting
with a base.

The phosphorus oxides


phosphorus(III) oxide, P4O6, and phosphorus(V) oxide, P4O10.
Phosphorus(III) oxide
Phosphorus(III) oxide reacts with cold water to give a solution
of the weak acid, H3PO3 - known variously as phosphorous
acid, orthophosphorous acid or phosphonic acid. Its reaction
with hot water is much more complicated.

27
The pure un-ionised acid has the structure:

Phosphorous acid has a pKa of 2.00 which


makes it stronger than common organic acids
like ethanoic acid (pKa = 4.76).
sodium hydroxide solution depending on the proportions
used.

In the first case, only one of the acidic hydrogens has reacted
with the hydroxide ions from the base. In the second case
(using twice as much sodium hydroxide), both have reacted.
If you were to react phosphorus(III) oxide directly with sodium
hydroxide solution rather than making the acid first, you would
end up with the same possible salts.

Phosphorus(V) oxide
Phosphorus(V) oxide reacts violently with water to
give a solution containing a mixture of acids, the
nature of which depends on the conditions. We
usually just consider one of these, phosphoric(V) acid,
H3PO4 - also known just as phosphoric acid or as
orthophosphoric acid.
This time the pure un-ionised acid has the structure:

28

Phosphoric(V) acid is also a weak acid


with a pKa of 2.15. That makes
it fractionally weaker than phosphorous
acid. Solutions of both of these acids of
concentrations around 1 mol dm-3 will
have a pH of about 1.

The sulphur oxides


Sulphur dioxide
Sulphur dioxide is fairly soluble in water, reacting with it to
give a solution of sulphurous acid (sulphuric(IV) acid), H2SO3.
This only exists in solution, and any attempt to isolate it just
causes sulphur dioxide to be given off again.

Sulphur dioxide will also react directly with bases such as


sodium hydroxide solution

Sulphur trioxide
Sulphur trioxide reacts violently with water to produce a fog of
concentrated sulphuric acid droplets.

29
The acid reacts with water to give a hydroxonium ion
(a hydrogen ion in solution, if you like) and a
hydrogensulphate ion. This reaction is virtually 100%
complete.
The second hydrogen is more difficult to remove. In
fact the hydrogensulphate ion is a relatively weak acid
- similar in strength to the acids we have already
discussed on this page. This time you get an
equilibrium:

Sulphuric acid, of course, has all the reactions of a strong


acid that you are familiar with from introductory chemistry
courses. For example, the normal reaction with sodium
hydroxide solution is to form sodium sulphate solution - in
which both of the acidic hydrogens react with hydroxide ions.

Chlorine(VII) oxide
Chlorine(VII) oxide is the highest oxide of chlorine - the
chlorine is in its maximum oxidation state of +7. It continues
the trend of the highest oxides of the Period 3 elements
towards being stronger acids.
Chlorine(VII) oxide reacts with water to give the very strong
acid, chloric(VII) acid - also known as perchloric acid. The pH
of typical solutions will, like sulphuric acid, be around 0.

30
Chloric(VII) acid reacts with sodium hydroxide solution to form
a solution of sodium chlorate(VII).

Chlorine(VII) oxide itself also reacts with sodium hydroxide


solution to give the same product.

Chlorine(I) oxide
Chlorine(I) oxide is far less acidic than chlorine(VII) oxide. It
reacts with water to some extent to give chloric(I) acid, HOCl also known as hypochlorous acid.

Chloric(I) acid reacts with sodium hydroxide solution


to give a solution of sodium chlorate(I) (sodium
hypochlorite).
Chlorine(I) oxide also reacts directly with sodium
hydroxide to give the same product.

Electronic Configuration of Group IA elements

31

Atomic Radii:
It is difficult to state exact atomic size as atom has no
fixed boundaries also it is difficult to isolate atom.
Therefore, atomic radius is defined as half of the
distance between nuclei of two identical atoms
bonded together through single covalent bond.
Atomic radii decrease in a period from left to right due
to increasing nuclear charge and increase in a group
from top to bottom due to addition of new shells.

Melting and Boiling Points:


Periodicity in melting and boiling points occurs within the
same period. Moving from group I to group IV melting and
boiling point increase then moving from group V to group VIII
they decrease as number of binding first increase and then
decrease.
Down the group in metals, melting and boiling points
decrease while in non-metals increase.
Metallic Character (Electropositivity):
The electron giving ability of an element is called metallic
character or electropositivity.

32
Across the period from left to right electropositivity decreases
due to increasing nuclear charge. While down the group it
increases due to increasing atomic sizes.
Electronegativity:
The electron puling ability of an element is called
electronegativity.
Across the period from left to right electronegativity increases
due to increasing nuclear charge. While down the group it
decreases due to increasing atomic sizes.
Reactions of Alkali Metal with Chlorine
All of the alkali metals react vigorously with chlorine gas.
Each reaction produces a white crystalline salt. The reaction
gets more violent as you move down Group 1, showing how
reactivity increases down the group.
Lithium
If a piece of hot lithium is lowered into a jar of chlorine, white
powder is produced and settles on the sides of the jar. This is
the salt lithium chloride.
lithium + chlorine lithium chloride
2Li(s) + Cl2(g) 2LiCl(s)
Sodium
If a piece of hot sodium is lowered into a jar of chlorine, the
sodium burns with a bright yellow flame. Clouds of white
powder are produced and settle on the sides of the jar. This is
the salt sodium chloride.
The reaction of sodium with chlorine is similar to the reaction
with lithium, but more vigorous.
sodium + chlorine sodium chloride

33
2Na(s) + Cl2(g) 2NaCl(s)
Potassium
Potassium reacts more violently with chlorine than sodium
does.
potassium + chlorine potassium chloride
2K(s) + Cl2(g) 2KCl(s)
Heating the nitrates
Most nitrates tend to decompose on heating to give the metal
oxide, brown fumes of nitrogen dioxide, and oxygen.
For example, a typical Group 2 nitrate like magnesium
nitrate decomposes like this:

In Group 1, lithium nitrate behaves in the same way producing lithium oxide, nitrogen dioxide and oxygen.

The rest of the Group, however, don't decompose so


completely (at least not at Bunsen temperatures) - producing
the metal nitrite and oxygen, but no nitrogen dioxide.

All the nitrates from sodium to caesium decomposes in this


same way, the only difference being how hot they have to be
to undergo the reaction. As you go down the Group, the
decomposition gets more difficult, and you have to use higher
temperatures.
Heating the carbonates

34
Most carbonates tend to decompose on heating to give the
metal oxide and carbon dioxde.
For example, a typical Group 2 carbonate like calcium
carbonate decomposes like this:

In Group 1, lithium carbonate behaves in the same way producing lithium oxide and carbon dioxide.

The rest of the Group 1 carbonates don't decompose at


Bunsen temperatures, although at higher temperatures they
will. The decomposition temperatures again increase as you
go down the Group.
The thermal stability of the hydrogencarbonates
The Group
2 hydrogencarbonates
like
calcium
hydrogencarbonate are so unstable to heat that they only
exist in solution. Any attempt to get them out of solution
causes them to decompose to give the carbonate, carbon
dioxide and water.

By contrast, the Group 1 hydrogencarbonates are stable


enough to exist as solids, although they do decompose easily
on heating. For example, for sodium hydrogencarbonate:
The thermal stability of the hydrogencarbonates
The Group
2 hydrogencarbonates
like
calcium
hydrogencarbonate are so unstable to heat that they only

35
exist in solution. Any attempt to get them out of solution
causes them to decompose to give the carbonate, carbon
dioxide and water.

By contrast, the Group 1 hydrogencarbonates are stable


enough to exist as solids, although they do decompose easily
on heating. For example, for sodium hydrogencarbonate:

Explaining the trend in terms of the polarising ability of


the positive ion
A small positive ion has a lot of charge packed into a small
volume of space - especially if it has more than one positive
charge. 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 positive ion has the same charge spread over a
larger volume of space. Its charge density will be lower, and it
will cause less distortion to nearby negative ions.
If you worked out the structure of a carbonate ion using "dotsand-crosses" or some similar method, you would probably
come up with:

This shows 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 -

36
although concentrated on the oxygen atoms. We say that the
charges are delocalized.
This is a rather more complicated version of the bonding you
might have come across in benzene or in ions like ethanoate.
For the purposes of this topic, you don't need to understand
how this bonding has come about.
Polarising 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. The diagram shows what happens with
an ion from Group 2, carrying two positive charges

Flame Test
Flame tests are used to identify the presence of a relatively
small number of metal ions in a compound. Not all metal ions
give flame colors. For Group 1 compounds, flame tests are
usually by far the easiest way of identifying which metal you
have got. For other metals, there are usually other easy

37
methods which are more reliable - but the flame test can give
a useful hint as to where to look.

Practical details in carrying out a flame test

Clean a platinum or nichrome (a nickel-chromium


alloy) wire by dipping it into concentrated hydrochloric acid
and then holding it in a hot Bunsen flame. Repeat this until
the wire produces no color in the flame.
When the wire is clean, moisten it again in the acid
and then dip it into a small amount of the solid to be tested so
that some sticks to the wire. Place the wire back in the flame.
If the flame color is weak, it is often helpful to dip the
wire back in the acid and put it back into the flame as if
cleaning it. This should produce a very short but intense flash
of color.

The colors
The table below gives a rough color guide for the elements.
As people see and describe colors differently, it is impossible
to provide a definitive guide.
flame color
Li

red

Na

strong, persistent orange

lilac (pink)

Rb

red (red-violet)

38
Cs

blue/violet (see below)

Ca

orange-red

Sr

red

Ba

pale green

Cu

blue-green (often with white flashes)

Pb

gray-white

If a red flame is produced, the flame test must be repeated


with known samples of lithium, strontium, etc, comparing the
colors of the unknown and the samples.
Group II-A Elements (Alkaline Earth Metals):
Electronic Configuration
Alkaline Earth Metals
2
2
4Be
1s , 2s
2
2
6
2
12Mg
1s , 2s , 2p , 3s
2
2
6
2
6
2
20Ca
1s , 2s , 2p , 3s , 3p , 4s
Sr

38

Ba

56

Ra

88

2
2
6
2
6
2
1s , 2s , 2p , 3s , 3p , 4s ,
6
2
4p , 5s
2
2
6
2
6
2
1s , 2s , 2p , 3s , 3p , 4s ,
6
2
10
6
2
4p , 5s , 4d , 5p , 6s
2
2
6
2
6
2
1s , 2s , 2p , 3s , 3p , 4s ,
6
2
10
6
2
4p , 5s , 4d , 5p , 6s ,
10
6
2
5d , 6p , 7s

Beryllium:
The principal ore of
aluminosilicate ore Beryl [Be3Al2(SiO3)6]

[He]2s

2
[Ne]3s
2
[Ar]4s
3d

10
2
, [Kr]5s

3d

10
2
, [Xe]6s

10
2
, [Rn]7s
14
4f ,

3d

beryllium

is

an

39
Magnesium:

It is very abundant in rocks of earths crust. It is


found in sea water and springs water. Its
mineral
are
Dolomite
(MgCO3.CaCO3),
Magnesite
(MgCO3),
Epsom
salt
(MgSO4.7H2O),
Soap
stone
(Talc)
[Mg2(Si2O5)2.Mg(OH)2],
and
Asbestos
[CaMg3(SiO3)4].

Calcium:

Strontium:

It is very abundant in rocks of earths crust. It


is present in sea shells. Its important mineral
are Calcite or Lime stone or Marble (CaCO 3),
Gypsum (CaSO4.2H2O).
Its important ore is Strontianite (SrCO3).

Barium:

Its important ore is Barite (BaSO4).

Radium:

It is radioactive and is of great importance. It is


found in all uranium ores but in low
concentration, as product of radioactive decay.

General Physical Properties of Alkaline earth metals


(group IIA):
(i)

They are harder than alkali metals.


Beryllium is hard enough to scratch glass.
(ii)
They are grayish white colour metals.
(iii)
They are malleable.
(iv)
Their melting and boiling points are higher
than alkali metals.
(v)
They give characteristic colours to Bunsen
burner flame.
Ca = Brick red
Sr = Crimson red
Ba
=
Green
Ra = Crimson red
General Chemical Properties of Alkali metals and Alkaline
earth metals (group IA & IIA):

40
Due to low ionization energies both alkali and
alkaline earth metals are reactive and they form
ionic compounds.
(ii)
Oxidation state of alkali metals in their compounds
is +1 while that of alkaline earth metals is +2.
(iii)
They have strong reducing ability and this ability
increases down the group.
(iv)
Reaction with Oxygen:
They react readily with
oxygen and produce their oxides.
Lithium forms normal oxide
4Li
+
O2

2Li2O
Sodium forms peroxide
2Na
+
O2

Na2O2
K, Rb & Cs forms super oxide
K +
O2

KO2
Alkaline earth metals form normal oxides
2Ca + O2 2CaO
(v)
Reaction with Hydrogen: All s-block elements
except Be react directly with hydrogen to form
hydride. The hydrides are ionic except BeH2 and
MgH2 these two are covalent.
2Na +
H2

2NaH
Ca
+
H2

CaH2
(vi)
Reaction with Chlorine:
All
s-block
elements react directly with chlorine to produce
chlorides. All their chlorides are ionic however
BeCl2 is covalent MgCl2 is intermediate.
2Na +
Cl2

2NaCl
Ca
+
Cl2

CaCl2
(vii)
Reaction with Water:
Alkali
metals
react
vigorously with water to produce their hydroxide
and liberate hydrogen. Reaction is highly
exothermic so the hydrogen produced catches fire.
Vigorousness of reaction increases down the
group.
Beryllium does not react with water even at
strong heating, Magnesium react with
boiling water the rest react with cold water.
(i)

41
2Na

2H2O

2NaOH

H2

Ca

2H2O

Ca(OH)2

H2

o
Mg
+
2H2O 100 C
Mg(OH)2
+H2
(viii) Reaction with Nitrogen:
Alkali metals do
not react with nitrogen Only Lithium reacts with
nitrogen however all alkaline earth metals react
with nitrogen on heating and produce their nitrides.
6Li
+
N2

2Li3N
3Mg +
N2

Mg3N2
(ix)
Reaction with Carbon:
Alkali metals do
not react with carbon Only Lithium reacts with
carbon however all alkaline earth metals react with
carbon on heating and produce their carbides.
4Li
+
C

Li4C
4Mg +
2C

Mg4C2
(x)
Reaction with Sulphur:
Alkali
and
Alkaline earth metals react with molten sulphur to
produce sulphides.
2Na +
S

Na2S
Mg
+
S

MgS
Hydroxides:
Hydroxides are produced either by reaction of metals
with water or metal oxide with water.
2Na +
2H2O
2NaOH
+
H2
CaO +
H2O
Ca(OH)2
2Na2O2 +
2H2O
4NaOH
+
2O2

Hydroxides of both groups are ionic and are white


crystalline solids.

Solubility of hydroxides in water increases down the


group. Among alkali metals, LiOH is sparingly soluble
in water, the rest are soluble. Among alkaline earth
metals Be(OH)2 is insoluble, Mg(OH)2 forms

42
suspension in water known as milk of magnesia. It is
used for the treatment of acidity in stomach. Ca(OH) 2
is soluble in water and its aqueous solution is called
lime water. It is used for qualitative and quantitative
analysis for CO2.

The hydroxides of alkali metals are stable to heat


except that of lithium. While hydroxides of Lithium and
that of alkaline earth metals are unstable and they
decompose on heating forming metal oxides.
2LiOH
Mg(OH)2

(3)

Li2O
MgO

+
+

H2O
H2O

The basic strength of hydroxides increases down the


group. All are strong base except LiOH. Being base
they react with acid to form salts and water.
NaOH
+
HCl

NaCl +
H2O
Ca(OH )2 + 2HCl
CaCl2 +
2H2O
Carbonates:

Carbonates are either produced by reacting metal


hydroxides with carbon dioxide
2NaOH + CO2
Na2CO3
+
H2O
Ca(OH)2 + CO2
CaCO3
+
H2O
Or they are produced by reacting metal oxides with
carbon dioxide
MgO
+
CO2
MgCO3
2Na2O2+
2CO2
2Na2CO3
+
O2
4KO2
+
2CO2
2K2CO3
+
3O2

Carbonates of both groups are white weakly alkaline


solids.

The solubility of carbonates increases down the


group. Carbonates of alkali metals except that of
lithium are soluble in water. Where as carbonates of

43
alkaline earth metals as well as that of lithium are
insoluble.

Carbonates of alkali metals are stable except that of


Lithium, while that of alkaline earth metals decompose
on heating. Ease of decomposition of carbonates
decreases down the group. Smaller is the metal ion
more is the lattice energy of the resulting metal oxide
and hence higher the stability of the oxide and vice
versa.
Li2CO3

Li2O +
CO2
CaCO3

CaO +
CO2

Carbonates of alkali metals are hydrolyzed by water to


produce alkalis.
Na2CO3
+
2H2O
2NaOH +
H2CO3

Some Important carbonates:


Na2CO3:
It is an important industrial chemical. Its
hydrated form i.e. Na2CO3.10H2O is used as washing
soda in laundry while its anhydrous form i.e Na 2CO3 is
called Soda ash and is used in glass industry and
o
many more. At temperature below 35.2 C it
crystallizes as Na2CO3.10H2O and is called washing
soda. It is efflorescent so loses water on standing in
air and slowly converts to Na2CO3.H2O. In aqueous
solution it hydrolyses by water to NaOH.
Na2CO3 +
2H2O
2NaOH + H2CO3
MgCO3:
It is called magnesite. It on heating
decomposes to give MgO (Magnesia). Magnesia and
clay are mixed, pressed and dried to make refractory
bricks for furnace lining.
CaCO3:
It is called lime stone, marble and also
called calcite. It on strong heating decomposes to give

44
CaO (Quick lime).Quick lime is used for cement and
glass industries.
(4)

Bicarbonates:

Bicarbonates are produced by passing Carbon dioxide


through solution or suspension of metal carbonates.
Na2CO3
+
H2O +
CO2
2NaHCO3
CaCO3
+
H2O +
CO2
Ca(HCO3)2
Bicarbonates of alkali metals are sparingly soluble in
water while that of alkaline earth metals are soluble in
water.

Bicarbonates of alkali metals are stable at room


temperature however they decompose on heating. On
the other hand bicarbonates of alkaline earth metals
are unstable even at room temperature, thus they
cannot be isolated from solution.
2NaHCO3
Heating
Na2CO3
+
H2O +
CO2
Ca(HCO3)2
CaCO3 +
H2O +
CO2
Sodium bicarbonate is baking soda and is source of
carbon dioxide in baking process as well as in fire
extinguishers.

Nitrates:
Nitrates are produced by neutralization of metal
oxides or metal hydroxides with nitric acid.
NaOH + HNO3 NaNO3 + H2O
Nitrates of both groups are colorless, soluble, neutral
crystalline salts.
Nitrates of alkali metals except lithium on heating
decompose to give metal nitrite while nitrates of
lithium and alkaline earth metals give metal oxide.
2NaNO3

2NaNO2 + O2

45
4LiNO3
2Mg(NO3)2

2Li2O + 4NO2 + O2
2MgO + 4NO2 + O2

Peculiar Behaviour of Beryllium:


Beryllium being 1st member of the family shows some
differences with rest of the members of its family.
(i)
Beryllium atom is very small so according to
Fajans rule which states that small highly charged
cations tend to form polar covalent compounds
thus its compounds are some what covalent.
(ii)
It is as hard as iron while other members of the
family are soft.
(iii)
Melting and boiling point of Beryllium are much
higher than other members of its family.
(iv)
Halides of Beryllium are soluble in organic
solvents while that of other are soluble in water.
(v)
Oxide of Beryllium is amphoteric while that of
others are basic in nature.
(vi)
It is the only member of the family which on
reaction with alkalies liberate hydrogen.
Be

2NaOH

Na2BeO2

H2

(Page-4)
(vii)

Beryllium is resistant to complete oxidation due to


its BeO coating.

Why BeCl2 is covalent not Ionic?


The polarising power of beryllium is high and the polarisability
of chlorine is high so beryllium essentially pulls the donated
electrons back so they are effectively shared. Beryllium is a
small atom and forms a 2+ charge so it has a high
electronegativity value, and chlorine is fairly large with a low
charge (-) so electrons are easily pulled away from it.
Or

46
Beryllium has quite a high electronegativity compared with the
rest of the Group. That means that it attracts a bonding pair of
electrons towards itself more strongly than magnesium and
the rest do. In order for an ionic bond to form, the beryllium
has to let go of its electrons. It is too electronegative to do
that
Beryllium hydroxide
Beryllium hydroxide reacts with acids, forming solutions of
beryllium salts. For example:

But it also reacts with bases such as sodium hydroxide


solution. Beryllium hydroxide reacts with the sodium
hydroxide to give a colourless solution of sodium
tetrahydroxoberyllate.

This contains the complex ion, [Be(OH)4]2-. The name


describes this ion. Tetra means four; hydroxo refers to the OH
groups;beryllate shows that the beryllium is present in a
negative ion. The "ate" ending always shows that the ion is
negative.
Group IV-A Elements:
This group consists of metals and non metals. Carbon and
Silicon are non-metals while other are metals. The electronic
configuration of group IV-A is:
Group IV-A
2
2
2
4C
1s , 2s , 2p
2
2
6
2
2
14Si
1s , 2s , 2p , 3s , 3p

2
2
[He]2s , 2p
2
2
[Ne]3s , 3p

47
Ge

32

Sn

50

Pb

82

2
2
6
2
6
2
10 2
2
1s , 2s , 2p , 3s , 3p , 4s , [Ar]3d ,4s , 4p
10
2
3d , 4p
2
2
6
2
6
2
10 2 2
1s , 2s , 2p , 3s , 3p , 4s , [Kr]4d ,5s ,5p
10
6
2
10
2
3d , 4p , 5s , 4d , 5p
2
2
6
2
6
2
14 10 2 2
1s , 2s , 2p , 3s , 3p , 4s , [Xe]4f ,5d ,6s ,6p
10
6
2
10
6
3d , 4p , 5s , 4d , 5p ,
2 14
10
2
6s , 4f , 5d , 6p

General Characteristics:
Their general electronic configuration is ns2, np2.
They are in the middle of periodic table so they show
intermediate electronegativities, ionization potentials,
electropositivities etc.
Their metallic character increases down the group. So
carbon and silicon are non-metals, germanium is
metalloid while tin and lead are metals.
Oxides of carbon and silicon are acidic while that of
germanium, tin and lead are amphoteric.
Carbon and silicon form covalent compounds.
Tetra valency is common in elements of this group.
Inert pair effect increases down the group so carbon
shows tetra valency while lead shows di valency in
mostly compounds.
They all form hydride and chloride of formulae XH 4
and XCl4.
+2
+2
They form divalent cations e.g. Sn and Pb but no
tetravalent cation due to high ionization potential.
Thus bonds in such cases are covalent.
Atomic radii increase down the group.
Oxidation States of Group IV-A

48
The typical oxidation state shown by elements in Group 4 is
+4, found in compounds like CCl4, SiCl4 and SnO2.
However, as you go down the Group, there are more and
more examples where the oxidation state is +2, such as
SnCl2, PbO, and Pb2+. With tin, the +4 state is still more stable
than the +2, but by the time you get to lead, the +2 state is
the more stable - and dominates the chemistry of lead.
Inert Pair Effect
The inert pair effect is the tendency of the electrons in the
outermost s atomic orbital to remain un-ionized or unshared
in compounds of post-transition metals. The term "inert pair"
was first proposed by Nevil Sidgwick in 1927.
The inert pair effect in the formation of ionic bonds
If the elements in Group 4 form 2+ ions, they will lose the p
electrons, leaving the s2 pair unused. For example, to form a
lead(II) ion, lead will lose the two 6p electrons, but the 6s
electrons will be left unchanged - an "inert pair".
This first chart shows how the total ionisation energy needed
to form the 2+ ions varies as you go down the Group. The
values are all in kJ mol-1.

Notice the slight increase between tin and lead.

49
This means that it is slightly more difficult to remove the p
electrons from lead than from tin. The reasons for all this lie in
the Theory of Relativity. With the heavier elements like lead,
there is what is known as a relativistic contraction of the
electrons which tends to draw the electrons closer to the
nucleus than you would expect. Because they are closer to
the nucleus, they are more difficult to remove. The heavier the
element, the greater this effect.
This affects s electrons much more than p electrons.
In the case of lead, the relativistic contraction makes it
energetically more difficult to remove the 6s electrons than
you might expect. The energy releasing terms when ions are
formed (like lattice enthalpy or hydration enthalpy) obviously
aren't enough to compensate for this extra energy. That
means that it doesn't make energetic sense for lead to form
4+ ions.
The inert pair effect in the formation of covalent bonds
You need to think about why carbon normally forms four
covalent bonds rather than two.
Using the electrons-in-boxes notation, the outer electronic
structure of carbon looks like this:

There are only two unpaired electrons. Before carbon forms


bonds, though, it normally promotes one of the s electrons to
the empty p orbital.

50

That leaves 4 unpaired electrons which (after hybridisation)


can go on to form 4 covalent bonds.
It is worth supplying the energy to promote the s electron,
because the carbon can then form twice as many covalent
bonds. Each covalent bond that forms releases energy, and
this is more than enough to supply the energy needed for the
promotion.
One possible explanation for the reluctance of lead to do the
same thing lies in falling bond energies as you go down the
Group. Bond energies tend to fall as atoms get bigger and the
bonding pair is further from the two nuclei and better
screened from them.
For example, the energy released when two extra Pb-X
bonds (where X is H or Cl or whatever) are formed may no
longer be enough to compensate for the extra energy needed
to promote a 6s electron into the empty 6p orbital.
This would would be made worse, of course, if the energy
gap between the 6s and 6p orbitals was increased by the
relativistic contraction of the 6s orbital.

51

Fajans' Rules
In inorganic

chemistry, Fajans'

Rules,

formulated

by Kazimierz Fajans in 1923, are used to predict whether


a chemical bond will be covalent or ionic, and depend on the
charge on the cation and the relative sizes of the cation
and anion. They can be summarized in the following table:
Ionic

Covalent

Low positive charge

High positive charge

Large cation

Small cation

Small anion

Large anion

THE CHLORIDES OF CARBON, SILICON AND LEAD


Carbon, silicon and lead tetra-chlorides
These all have the formula XCl4.
They are all simple covalent molecules with a typical
tetrahedral shape. All of them are liquids at room
temperature. (Although at room temperature, lead(IV) chloride
will tend to decompose to give lead(II) chloride and chlorine
gas.

52
Lead(II) chloride, PbCl2
Lead(II) chloride is a white solid, melting at 501C. It is very
slightly soluble in cold water, but more soluble in hot water.
You can think of lead(II) chloride as being mainly ionic in
character.
Stability
At the top of Group 4, the most stable oxidation state shown
by the elements is +4. This is the oxidation state shown by
carbon and silicon in CCl4 and SiCl4. These therefore have no
tendency to split up to give dichlorides.
However, the relative stability of the +4 oxidation state falls as
you go down the Group, and the +2 oxidation state becomes
the most stable by the time you get to lead.
Lead(IV) chloride decomposes at room temperature to give
the more stable lead(II) chloride and chlorine gas.
Reaction with water (hydrolysis)
Carbon tetrachloride (tetrachloromethane)
Carbon tetrachloride has no reaction with water. If you add it
to water, it simply forms a separate layer underneath the layer
of water.
Suppose a water molecule is going to react with the carbon
tetrachloride. The reaction would have to start by the water
molecule's oxygen attaching itself to the carbon atom via the
oxygen's lone pair. A chlorine atom would get pushed off the
carbon in the process.

53
First, the chlorines are so bulky and the carbon atom so
small, that the oxygen can't easily get at the carbon atom.

. . . and even if it did, there will be a stage where there is


considerable cluttering around that carbon atom before the
chlorine atom breaks away completely. There is going to be a
lot of repulsion between the various lone pairs on all the
atoms surrounding the carbon.
That cluttering is going to make this half-way stage (properly
called a "transition state") very unstable. A very unstable
transition state means a very high activation energy for the
reaction.
The other problem is that there isn't a convenient empty
orbital on the carbon that the oxygen lone pair can attach to.
If it could attach before the chlorine starts to break away, that
would be an advantage. Forming a bond releases energy,
and that energy would therefore be readily available for
breaking a carbon-chlorine bond. But in the case of a carbon
atom, that isn't possible.
Silicon tetrachloride
The situation is different with silicon tetrachloride.
The silicon atom is bigger, and so there is more room around
it for the water molecule to attack, and the transition state will
be less cluttered.

54
But silicon has the additional advantage that there are empty
3d orbitals available to accept a lone pair from the water
molecule. Carbon doesn't have 2d orbitals because there are
no such things. There are no empty 2-level orbitals available
in the carbon case.
This means that the oxygen can bond to the silicon before the
need to break a silicon-chlorine bond. This makes the whole
process energetically easier.
So . . . silicon tetrachloride reacts violently with water to give
white solid silicon dioxide and steamy fumes of HCl.

Liquid SiCl4 fumes in moist air for this reason - it is reacting


with water vapour in the air.
Lead tetrachloride (lead(IV) chloride)
The reaction of lead(IV) chloride with water is just like the
silicon tetrachloride one. You will get lead(IV) oxide produced
as a brown solid and fumes of hydrogen chloride given off.
(This will also, of course, be confused by the decomposition
of the lead(IV) chloride to give lead(II) chloride and chlorine
gas - see above.)

Lead(II) chloride
Unlike the tetrachlorides, lead(II) chloride can be thought of
as ionic. It is sparingly soluble in cold water, but more soluble
in hot water. Looked at simply, solubility in water involves the
break-up of the ionic lattice and the hydration of the lead(II)
and chloride ions to give Pb2+(aq) and Cl-(aq).

55
Oxides of Carbon:
Structure of carbon dioxide (CO2):
It is most stable oxide of carbon. It has linear structure
having two carbon-oxygen double covalent bonds.
o
-10
The bond length is 1.15 A or 1.15 x 10 . Carbon
dioxide molecule is non-polar due to its linear
structure having zero dipole moment.

O C O
In solid state (i.e. dry ice) carbon dioxide has face-centered
cubic structure.
Structure of carbon suboxide (C3O2):
Structure of carbon suboxide is the resonance hybrid
of the following contributing structures.
+
OCCCO OCCCO OCC
+
CO
Oxide of Silicon:
The oxide of silicon i.e. silicon dioxide (SiO 2) is the most
important compound of silicon. Silicon dioxide is also called
Silica. Silica occurs in nature as Sand and Quartz. In it every
silicon atom is attached tetrahedrally to four oxygen atoms
and each oxygen atom is attached to two silicon atoms. Each
silicon atom is at the centre of tetrahedron with oxygen atoms
lying on the four corners of the tetrahedron. SiO2 differs much
from CO2 as the silicon dioxide exists as polymer (SiO2)n while
carbon dioxide exists as monomer.
Vitreous (glass like) silica has following characters.

56
(i)
(ii)
(iii)
(iv)
(v)

High transparency to light.


Very low thermal expansion.
Excellent insulator.
Hard, brittle and elastic.
Insoluble in water and inert towards many
reagents.
Resistant to all acids except HF.
Very refractory (stubborn) does not soften bellow
o
1500 to 1600 C.

(vi)
(vii)

Si
O

Si
O

Si
O

Si
O

Si
O

O
O

Si

O
O
O

Quartz is the most common crystalline form of silicon dioxide.


It has following characteristics:
(i)
It is hard.
(ii)
It is brittle.
(iii)
It is refractor.
(iv)
It is colourless.
(v)
It is crystalline solid.
Carbon can form Multiple Bonds while Silicon Cannot?
The size of carbon atom is small. The partially filled Py and
Pz orbitals of carbon are close to each other. These orbitals
can overlap side wisely and can form the Pi bonds. While
Silicon has bigger size as compare to carbon. Its Py and Pz

57
orbitals are far away and cannot overlap side wisely so they
cannot form the multiple bonds.
The acid-base behaviour of the Group 4 oxides
The oxides of the elements at the top of Group 4 are acidic,
but acidity of the oxides falls as you go down the Group.
Towards the bottom of the Group, the oxides become more
basic - although without ever losing their acidic character
completely.
An oxide which can show both acidic and basic properties is
said to be amphoteric.
The trend is therefore from acidic oxides at the top of the
Group towards amphoteric ones at the bottom.
Carbon and silicon dioxides
These are both weakly acidic.
With water
Silicon dioxide doesn't react with water, because of the
difficulty of breaking up the giant covalent structure.
Carbon dioxide does react with water to a slight extent to
produce hydrogen ions (strictly, hydroxonium ions) and
hydrogencarbonate ions.
Overall, this reaction is:

The solution of carbon dioxide in water is sometimes known


as carbonic acid, but in fact only about 0.1% of the carbon

58
dioxide has actually reacted. The position of equilibrium is
well to the left-hand side.
With bases
Carbon dioxide reacts with sodium hydroxide solution in the
cold to give either sodium carbonate or sodium
hydrogencarbonate solution - depending on the reacting
proportions.

Silicon dioxide also reacts with sodium hydroxide solution, but


only if it is hot and concentrated. Sodium silicate solution is
formed.

You may also be familiar with one of the reactions happening


in the Blast Furnace extraction of iron - in which calcium oxide
(from the limestone which is one of the raw materials) reacts
with silicon dioxide to produce a liquid slag, calcium silicate.
This is also an example of the acidic silicon dioxide reacting
with a base.

Gernamium, tin and lead oxides


The monoxides
All of these oxides are amphoteric - they show both basic and
acidic properties.
The basic nature of the oxides

59
These oxides all react with acids to form salts.
For example, they all react with concentrated hydrochloric
acid. This can be summarised as:

. . . where X can be Ge and Sn, but unfortunately needs


modifying a bit for lead.
Lead(II) chloride is fairly insoluble in water and, instead of
getting a solution, it would form an insoluble layer over the
lead(II) oxide if you were to use dilute hydrochloric acid stopping the reaction from going on.

However, in this example we


using concentratedhydrochloric acid.

are

talking

about

The large excess of chloride ions in the concentrated acid


react with the lead(II) chloride to produce soluble complexes
such as PbCl42-. These ionic complexes are soluble in water
and so the problem disappears.

Unfortunately, it means that you have more to remember!


The acidic nature of the oxides
All of these oxides also react with bases like sodium
hydroxide solution. This time we can generalise without
exception:

60
Lead(II) oxide, for example, would react to give PbO22- plumbate(II) ions.
Halogens
The word halogen means salt former. Halogens belong to
group VII-A. This group consists of the elements which are
given in the following table.
Group VII-A
2
2
5
9F
1s , 2s , 2p
2
2
6
2
5
17Cl
1s , 2s , 2p , 3s , 3p
2
2
6
2
6
2
35Br
1s , 2s , 2p , 3s , 3p , 4s ,
10
5
3d , 4p
2
2
6
2
6
2
53I
1s , 2s , 2p , 3s , 3p , 4s ,
10
6
2
10
5
3d , 4p , 5s , 4d , 5p
2
2
6
2
6
2
85At
1s , 2s , 2p , 3s , 3p , 4s ,
10
6
2
10
6
3d , 4p , 5s , 4d , 5p ,
2 14
10
5
6s , 4f , 5d , 6p
General Properties:
(i)
(ii)
(iii)
(iv)

2
5
[He]2s , 2p
2
5
[Ne]3s , 3p
10 2
5
[Ar]3d ,4s , 4p
[Kr]4d
[Xe]4f

10 2 5
,5s ,5p

14 10 2 5
,5d ,6s ,6p

2
5
Their general electronic configuration is ns , np .
All halogens are non-metals.
They exists as discrete diatomic molecules F2, Cl2, Br2,
I2, At2.
Their melting and boiling points increases down the
group. Thus from top to bottom they change from gas
to solid. Astatine is radioactive and its half life is
8.3hrs.
Element
State B.P
Colour
o
Fluorine
gas
-188 C
pale yellow

61
Chlorine
green

(v)
(vi)
(vii)
(viii)

FCl
(ix)

(x)

(xi)
(xii)

gas

o
-34 C

yellowish

o
Bromine
liquid 59 C
dark red
(vapours reddish brown)
o
Iodine
solid 184 C
dark
crumbly (vapours violet)
o
Astatine
solid 380 C
black
(vapours dark)
Halogens have irritating odours and they attack skin.
Bromine causes burns that heal slowly.
They have seven electrons in their valence shell.
They have high ionization energies, electron affinities
and electronegativities.
They form binary compounds among themselves,
called interhalogens. Their capacity to combine with
number of other halogen atoms increases down the
group. This is due to availability of more orbitals with
increasing atomic number. Thus one other halogen
atom combines with fluorine combine while seven
other halogen atoms combine with iodine.
ClF3
BrF5
IF7
Common oxidation state for halogens is -1, but they
also show +1, +3, +5, and +7 oxidation states in their
compounds. However fluorine does not show positive
oxidation state as it has highest electronegativity.
Halogens are good oxidizing agent, however their
oxidizing power decreases down the group. Their
oxidizing power depends upon (a) dissociation energy
and (b) electron affinity (c) reduction potential.
They form ionic compounds with group I-A and group
II-A elements.
Halogens directly reacts with hydrogen under different
conditions to produce their hydrides (Hydrogen
halides).
H 2 + F2
2HF
vigorous reaction

62
H2 + Cl2

2HCl
in presence of sunlight
H2 + Br2

2HBr
in presence of sunlight
H2 + I2

2HI
in presence of sunlight
The order of reactivity of halogens towards this
reaction is
F2 > Cl2 > Br2 > I2
As the size of halogen increases, the bond energy
of H X bond decreases and thus stability of
halide decreases also polarity of the bond
decreases.
The order of stability and polarity is
HF > HCl
> HBr > HI
While order of reactivity of halogen acids is
HI
> HBr >HCl > HF
Bond enthalpies (bond energies or bond strengths)
Bond enthalpy is the heat needed to break one mole of a
covalent bond to produce individual atoms, starting from the
original substance in the gas state, and ending with gaseous
atoms.
So for chlorine, Cl2(g), it is the heat energy needed to carry
out this change per mole of bond:

For bromine, the reaction is still from gaseous bromine


molecules to separate gaseous atoms.

Bond enthalpy in the halogens, X2(g)

63
A covalent bond works because the bonding pair is
attracted to both the nuclei at either side of it. It is that
attraction which holds the molecule together. The size
of the attraction will depend, amongst other things, on
the distance from the bonding pair to the two nuclei.
As with all halogens, the bonding pair will feel a net
pull of 7+ from both ends of the bond - the charge on
the nucleus offset by the inner electrons. That will still
be the same whatever the size of the halogen atoms.
As the atoms get bigger, the bonding pair gets further
from the nuclei and so you would expect the strength
of the bond to fall.
he bond enthalpies of the
Cl-Cl, Br-Br and I-I bonds
fall just as you would
expect, but the F-F bond is
way out of line!
Because fluorine atoms are
so small, you might expect
a very strong bond - in fact,
it is remarkably weak.
There must be another
factor at work as well.
As well as the bonding pair of
electrons between the two
atoms, each atom has 3 nonbonding pairs of electrons in
the outer level - lone pairs. Where the bond gets very short
(as in F-F), the lone pairs on the two atoms get close enough
together to set up a significant amount of repulsion.
In the case of fluorine, this repulsion is great enough to
counteract quite a lot of the attraction between the bonding
pair and the two nuclei. This obviously weakens the bond.

64

Bond enthalpies in the hydrogen halides, HX(g)


Where the halogen atom is attached to a hydrogen atom, this
effect
doesn't
happen. There are no
lone pairs on a
hydrogen atom!
As the halogen atom
gets
bigger,
the
bonding pair gets
more
and
more
distant
from
the
nucleus.
The
attraction is less, and
the bond gets weaker - exactly what is shown by the data.
There is nothing complicated happening in this case.
This is important in the thermal stability of the hydrogen
halides - how easily they are broken up into hydrogen and the
halogen on heating.
Hydrogen fluoride and hydrogen chloride are very stable to
heat. They don't split up into hydrogen and fluorine or chlorine
again if heated to any normal lab temperature.
Hydrogen bromide splits slightly into hydrogen and bromine
on heating, and hydrogen iodide splits to an even greater
extent.
As the bonds get weaker, they are more easily broken.
The acidity of the hydrogen halides
Hydrogen chloride as an acid

65
We are going to use the Bronsted-Lowry definition of an acid
as a proton donor. Hydrogen chloride is an acid because it
gives protons (hydrogen ions) to other things. We are going to
concentrate on its reaction with water.
Hydrogen chloride gas is very soluble in water, reacting with it
to produce hydrochloric acid. The familiar steamy fumes of
hydrogen chloride in moist air are caused by the hydrogen
chloride reacting with water vapour in the air to produce a fog
of concentrated hydrochloric acid.
A proton is donated from the hydrogen chloride to one of the
lone pairs on a water molecule.
A co-ordinate (dative covalent) bond is formed between the
oxygen and the transferred hydrogen ion.

The
equation

for

the

reaction is:

The H3O+ ion is the hydroxonium ion (also known as the


hydronium ion or the oxonium ion). This is the ion that we are
actually talking about when we write H+(aq).
When hydrogen chloride dissolves in water (to produce
hydrochloric acid), almost 100% of the hydrogen chloride
molecules react in this way. Hydrochloric acid is therefore a
strong acid. A strong acid is one which is fully ionised in
solution.
Hydrobromic acid and hydriodic acid as strong acids

66
Hydrogen bromide and hydrogen iodide dissolve in (and react
with) water in exactly the same way as hydrogen chloride
does. Hydrogen bromide reacts to give hydrobromic acid;
hydrogen iodide gives hydriodic acid. Both of these are also
strong acids.

Hydrofluoric acid as an exception


By contrast, although hydrogen fluoride dissolves freely in
water, hydrofluoric acid is only a weak acid - similar in
strength to organic acids like methanoic acid. The reason for
this is quite complicated.
Halide Ions as Reducing Agents
The bromide ions are strong enough reducing agents to
reduce the concentrated sulphuric acid. In the process the
bromide ions are oxidised to bromine.

The bromide ions reduce the sulphuric acid to sulphur dioxide


gas. This is a decrease of oxidation state of the sulphur from
+6 in the sulphuric acid to +4 in the sulphur dioxide.

You can combine these two half-equations to give the overall


ionic equation for the reaction:

What you see in this reaction are the steamy fumes of


hydrogen bromide contaminated with the brown colour of

67
bromine vapour. The sulphur dioxide is a colourless gas, so
you couldn't observe its presence directly.
With iodide ions
Iodide ions are stronger reducing agents than bromide ions
are. They are oxidised to iodine by the concentrated sulphuric
acid.

The reduction of the sulphuric acid is more complicated than


before. The iodide ions are powerful enough reducing agents
to reduce it

first to sulphur dioxide (sulphur oxidation state = +4)


then to sulphur itself (oxidation state = 0)
and all the way to hydrogen sulphide (sulphur
oxidation state = -2).

The most important of this mixture of reduction products is


probably the hydrogen sulphide. The half-equation for its
formation is:

Combining these last two half-equations gives:

68
Chapter- 14: d & f Block Elements:
The elements of d or f block which form one or more stable
ions with partially filled d or f orbitals are called transition
elements. As they have properties between s-block and pblock so they are called transition elements. They are divided
into two categories:
a) Main transition elements or outer transition metals: dblock elements are called main or outer transition
elements.
They have partially filled (n-1) d orbitals in ground
state.
They are further divided into
1st transition series or 3d series which consist of
21Sc to 29Cu
2nd transition series or 4d series which consist of
39Y to 47Ag
3rd transition series or 5d series which consist of
57La to 79Au
4th transition series or 6d series which consist of
89Ac to 109Mt (Metnerium)
b)

Inner transition elements or metals:


f-block
elements are called inner transition elements.
They have partially filled (n-2) f orbitals in ground state
They consist of two horizontal rows at the bottom of
periodic table.

Distinguishing Properties of Transition Metals:


1.
2.

They are hard metals and have high melting


and boiling points.
They are good conductor of heat and
electricity.

69
3.
4.
5.
6.
7.
8.

They show variable oxidation states and


valencies.
Their compounds are mostly coloured in solid
state as well as in aqueous state.
Some of these form paramagnetic compounds.
They form complexes or coordination
compounds.
They form alloys.
These elements and some of their compounds
act as solid catalysts.

General Characteristics:
1.

Atomic and Ionic Radii:


The atomic radii across period, decrease rapidly at
the start then remains almost same and then for
last elements it increases. This increase
is probably due to the filled 3 d orbitals give more
shielding to outer shell so atomic radii increases.
Changes in ionic radii across period are irregular.

Radii

Sc
Ti
V

Zn

Cu
Cr Mn Fe Co
Ni
Atomic Number
1.

Melting and Boiling Points:


Melting and boiling points of transition
metals are very high due to strong
binding forces among their atoms. M.P & B.P
increase in a series up to middle of the series and
then decreases up to end of the series. This is due

70
to the reason that up to middle of series number of
unpaired electrons increase so binding forces
increases thus MP & BP increase, the unpaired d
electrons also participate in binding. Then onward
pairing of electrons take place so binding forces
decrease thus MP & BP decrease.
V
Cr
Ti
Fe Co
Ni

Sc

M.P
Mn
Cu
Ca
Zn
K

1.

(Period-3)
Atomic Number
Ionization Energy:
Their ionization energies are intermediate of sblock and p-block. Thus they are capable of
forming both ionic as well as covalent compounds.
2. Oxidation states:

They show variable oxidation states and this is


due to the reason that beside outer s-electrons delectrons also participate in bonding. In series up
to middle, number of oxidation states increases
and then decreases as can be seen in 3-d series.
Sc Ti V
Cr
Mn
Fe
Co
Ni
Cu
Zn
+1
+2 +2 +2
+2
+2
+2
+2
+2
+2
+3 +3 +3 +3
(+3) +3
+3
(+3) +3
+4 +4 (+4) +4
(+4) +4
+5 +5
+5
+5
+6
(+6) (+6) +7
-

71
Oxidation numbers in parenthesis are uncommon.
Highest oxidation state i.e 8, is of Os (Osmium) of 5-d series
and also Ru (Ruthenium) of 4-d series has (+8) but it is rare.
2. Colour:
The compounds of transition metals are mostly coloured. The
colour is due to d-d transition. The d-orbitals during bonding
split up into two energy levels, one set high energy than the
other. The electrons present in low energy
d-orbitals jumps to higher energy d-orbital
E
by absorbing some visible radiations and
transmit other that gives different colours
to ions e.g. Ti+3 ions absorb yellow light
and transmit other 6 so it appears violet. Cu+2 absorbs red
light and transmit other so it appears blue. Co +2 absorb blue
and green light and transmit other so it appears pink.
3. Magnetic Properties:
Substances which are attracted by magnetic field are called
paramagnetic and phenomenon is called paramagnetism.
Substances which are strongly attracted by magnetic field are
called ferromagnetic.
Substances which are repelled by magnetic field are called
diamagnetic and the phenomenon is called diamagnetism.
Most of transition metals have unpaired electrons in their dorbitals. Due to spin motion of electrons, magnetic moment is
generated. The magnetic moments of unpaired electrons are
in same direction so they will reinforce each other and thus
substance will act as tiny magnet and is called paramagnetic.
On other hand if electrons are paired their spins are in
opposite directions and cancel each others effect so

72
substance will not be attracted by magnetic field and will be
slightly repelled, such substance is called diamagnetic.
The substances which have more number of unpaired
electrons will be strongly attracted by magnetic field and are
called ferromagnetic. They can be magnetized as they remain
permanent magnet even in absence of magnetic field e.g.
Iron, cobalt, Nickel.
The magnetic moment is related to number of unpaired
electrons and is given as
=

n(n + 2)

where = magnetic moment


n = number of unpaired electrons
It shows that more is number of unpaired
electrons more is magnetic moment.
Magnetic moment is practically measured by
Gouys balance. Its unit is B.M (Bohr
magneton).
When n = 1
When n = 2
When n = 3

then = 1.73 B.M


then = 2.83 B.M
then = 3.87 B.M

4. Alloy Formation:
Due to similarities in their sizes and structure,
some transition metals are able to replace one
another in the metallic lattice and thus form alloys
e.g. steel (alloys of iron with other metals are
called steel). Other examples are brass, bronze
etc. They are non-stoichiometric.
5. Catalytic properties:
Transition metals show variable oxidation states,
therefore, they form unstable intermediate products with
various
reactants.
These
intermediate
products
decompose to give final products, regenerating the
catalyst.

73
In other cases the finally divided metals or their
compounds provide a large surface area for adsorption and
the adsorbed reactants react faster due to closer contact.
Some of examples of these catalysts are
Finally divide Fe(iron) is used as catalyst in
Haber process (formation of ammonia).
V2O5 is used as catalyst in Contact process for
oxidation of SO2 to SO3.
Pt is used as catalyst in Oswald process for
oxidation of NH3 to NO.
FeSO4 + H2O2 (Fentons reagent) is used as
catalyst for oxidation of alcohols to aldehydes.
Cu is also used as catalyst for oxidation of
alcohols to aldehydes.
Pd is used as catalyst for hydrogenation of
phenol to cyclohexanol.
Pt/PtO (Adams catalyst) is used as catalyst for
reduction.
TiCl4 (Ziegler Natta catalyst) is used as catalyst
for polymerization of ethylene to polythene
(Polyethylene).
Ni is used as catalyst for hydrogenation of
unsaturated hydrocarbons to convert them in
saturated hydrocarbons.
Finally divided Ni is used as catalyst for
hydrogenation of vegetable oil to get vanaspati
ghee.
Pt is used as catalyst for hydrogenation of
unsaturated hydrocarbons to convert them in
saturated hydrocarbons.
9. Complex formation:
Transition elements have great tendency to form
coordination compounds or complexes. A compound
which has one or more coordinate covalent bonds is
called coordination compound or complex.

74
Components of complexes Or the terms used in
complexes:
Different terms used in study of complexes are

(a) Central metal atom or ion:


Transition metal atom or ion to which ligands are attached
due to coordinate covalent bonds is called central metal atom
or ion respectively.
e.g.(i) In K4[Fe(CN)6], Fe is central metal ion
e.g. (ii) In [Ni(CO)4], Ni is central metal atom

(b) Ligand:
The atoms or molecules or anions which make coordinate
covalent bonds with central transition metal and donate
electron pairs(s) to it, are called ligands. The ligands are
electron pair donor while transition metal is electron acceptor.
Ligands could be anionic, cationic or neutral.
e.g.(i) In K4[Fe(CN)6], CN is anionic ligand.
e.g. (ii) In [Ni(CO)4], CO is neutral ligand.
Ligands could be classified on the basis of number of
electron pairs which they donate to the central transition
metal, into three types.
(i) Monodentate Ligands:
Ligands which donate only one lone pair of electrons to
form coordinate
covalent bond with central transition metal are called
monodentate ligands
e.g Cl , Br , NO2 ,OH , CN , RCOO , CO, NH3, H2O
(ii)

Bidentate Ligands:
Ligands which donate two lone pairs of electrons to
form coordinate covalent bond with central transition metal
are called bidentate ligands.
e.g. SO4-2, CO3-2, COO- , S2O3-2, H2N CH2 CH2 NH2

75

COO-

Ethylene diamine

(iii)

Polydentate Ligands:
Ligands which donate more than two lone pairs of
electrons to form coordinate covalent bond with central
transition metal are called polydentate ligands.
e.g. Ethylene diamine tetra acetic acid (EDTA) ion
-

OOC

CH2

N
CH2
OOC
CH2
COO It is a hexadentate ligand
-

CH2
CH2

COO -

N
CH2

(c) Coordination Number:


Number of monodentate ligands attached to central
transition metal or number of coordinate covalent bonds that
are made by transition metal, is called coordination number.
Known coordination numbers are 2,3,4,5,6,7,8 and 9.
e.g. (i) In K4[Fe(CN)6], coordination number of Fe is 6.
e.g. (ii) In [Ni(CO)4], coordination number of Ni is 4.
Complexes with 4 and 6 coordination number are very
common while complexes with coordination number 5 are
less common.
Ag usually shows coordination number 2
Ni, Cu, Pt usually show coordination number 4
Fe, Co usually show coordination number 6

(d) Coordination Sphere:


The central metal atom along with ligands is called
coordination sphere. It is placed in square brackets. It may be
anionic, cationic or neutral e.g. K4[Fe(CN)6], [Cu(NH3)4]SO4
and [Ni(CO)4] are anionic, cationic and neutral respectively.

76
(e) Charge on Coordination Sphere:
It is the algebric sum of the charges present on the central
metal ion and ligands e.g. In [Fe(CN) 6]-4 the charge on Fe is
+2 and that on each CN is -1, so the charge on coordination
sphere is
(+2) + (-1 x 6) = + 2 -6 = -4.

(f) Chelates:
A complex in which all donor atoms of a bidentate or
polydentate ligand get coordinated with the same metal ion
such that the complex formed contain one or more rings, such
a complex is called chelate.
e.g. (i)
-2

Bisoxalato platinate (II) ion


e.g. (ii)
+2

Bisethylenediamine copper (II) ion


Formation of Complexes:
Transition elements have marked tendency to form
coordination compounds or complexes. This is due to high
positive charge on transition metal cation and availability
of vacant hybrid orbitals with them.
-4
e.g.
[Fe(CN)6]
2
2
6
2
6
2
6
Fe 1s , 2s , 2p , 3s , 3p , 4s , 3d
2
2
6
2
6
0
6
Fe+2 1s , 2s , 2p , 3s , 3p , 4s , 3d

77

3d
4s
4p
Due to strong interaction with ligands the unpaired d electrons
are paired up and as a result two orbitals of d sub-shell
become vacant. Two vacant d-orbital, one vacant s-orbital
2 3
and three vacant p-orbital hybridize and give six vacant d sp
hybridized orbital.
Unhybridized d-orbitals

d2sp3 hybrid oribtals


.. ..
..
.. .. ..
CN CN
CN
CN- CN- CNLigands donate their lone pairs of electrons to the vacant
hybrid orbitals and thus form coordinate covalent bonds with
central transition metal and as a result complex is formed.
Nomenclature:
IUPAC names of coordination compounds follow following
sequence
Cation ligand transition metal anion
(i)
Name of cation is written first if any.
(ii)
Then name of ligand is written. Prefixes di, tri,
tetra, penta are used with the name of
monodentate ligand and prefixes bis, tris,
tetrakis etc are used with the name of
bidentate or polydentate ligands to show the
number of ligands. If ligand is anion suffix O
and for cationic ligand suffix ium is used with
its name, while no suffix for neutral ligand just
its Latin name is written.
If more than one kind of ligands are there then
first the negative, then the neutral and at the
end the positive ligands are written. If more
than one kind of ve ligands are there then

78
alphabetical order is followed among
themselves, Same practice will be followed for
+ve and neutral ligands if they are of more
than one kind.
Prefix is used with the names of bridging
ligands and they are written after normal
ligands.
Anionic ligands:
CN Cyano
SCN Thiocyanato
NO2 Nitro
-2
Cl Chloro
SO4
Sulphato
-2
-2
S2O3 Thiosulphato
C2O4 Oxalato
OH
-2
Hydroxo
CO3 Carbonato NH2 Amido
Neutral ligands:
NH3
Ammine
H2O Aqua
CO
Cabonyl
NO
Nitrosyl H
H2N CH2 CH2 NH2
Ethylene diamine (en)
Cationic ligands:
+
+
Hydrazinium N2H5 (:NH2 NH3),
Nitrosonium NO+, Pyrazinium
(iii)

Now name of transition metal is


written. If coordination sphere is
anion then N suffix ate is used with the
Latin name of transition metal, otherwise just
English name is written.
(iv)
Following the name of transition metal,
oxidation state of the metal is written in Roman
numeral in parenthesis.
(v)
Anion is written at the end if any.
Some examples:
K4[Fe(CN)6]
Potassium hexacyano ferrate
(II)
[Co(NH3)4Cl2]Cl Dichloro tetraammine Cobalt

79
(III) chloride
K3[Fe(CN)6]

Potassium hexacyano ferrate (III)

[Ag(NH3)2]Cl
Diammine silver (I) chloride
Na3[Ag(S2O3)2]Sodium dithiosulphato argentate (I)
[Ni(CO)4]
Tetracabonyl nickel (0)

Octa aqua--dihydroxo di Iron (III) sulphate


[PtCl(NO2)(NH3)4]SO4Chloro nitro tetraammine platinum (IV)
sulphate
Na3[Co (NO2)6]
Sodium hexanitro cobaltate (III)
[Cr(H2O)Cl2]NO3
Dichloro aqua
chromium (III)
K3[Al(C2O4)3] Potassium
trisoxalato aluminate (III)
Octa ammine--amido--nitro di cobalt (III) sulphate
Geometries of Coordination Compounds:
Coordination compounds have definite geometrical shapes
because the coordinate covalent bonds formed between
ligands and central transition metal is directional. Hence, the
ligands are arranged around central metal atom in clear
spatial geometries.
The geometry depends on type of hybridization shown by
central transition metal.

80

81
The chromate(VI)-dichromate(VI) equilibrium
You are probably more familiar with the orange
dichromate(VI) ion, Cr2O72-, than the yellow chromate(VI) ion,
CrO42-.
If you add dilute sulphuric acid to the yellow solution it turns
orange. If you add sodium hydroxide solution to the orange
solution it turns yellow.

The equilibrium reaction at the heart of the inter-conversion


is:

If you add extra hydrogen ions to this, the equilibrium shifts to


the right. This is consistent with Le Chatelier's Principle.

82
If you add hydroxide ions, these react with the
hydrogen ions. The equilibrium tips to the left to
replace them.

Making potassium dichromate(VI) crystals


Starting from a source of chromium(III) ions such as
chromium(III) chloride solution:
Add potassium hydroxide solution to give first a greygreen precipitate and then the dark green solution
containing [Cr(OH)6]3-ions. This is all described in
detail further up the page. Notice that you have to
use potassium hydroxide. If you used sodium
hydroxide,
you
would
end
up
eventually
with sodium dichromate(VI).
Potassium dichromate will react with any excess
hydrogen peroxide to give initially an unstable deep
blue solution and it eventually gives the original
chromium(III) ions again.
This is done by boiling the solution. Hydrogen
peroxide decomposes on heating to give water and
oxygen. The solution is boiled until no more bubbles of
oxygen are produced. The solution is heated further to
concentrate it, and then concentrated ethanoic acid is
added to acidify it. Orange crystals of potassium
dichromate are formed on cooling.

83
The reduction of dichromate(VI) ions with zinc and
an acid
Dichromate(VI) ions (for example, in potassium
dichromate(VI) solution) can be reduced to
chromium(III) ions and then to chromium(II) ions using
zinc and either dilute sulphuric acid or hydrochloric
acid.
Hydrogen is produced from a side reaction between
the zinc and acid. This must be allowed to escape, but
you need to keep air out of the reaction. Oxygen in the
air rapidly re-oxidises chromium(II) to chromium(III).
An easy way of doing this is to put a bit of cotton wool
in the top of the flask (or test-tube) that you are using.
This allows the hydrogen to escape, but stops most of
the air getting in against the flow of the hydrogen.

The equations for the two stages of the reaction are:


For the reduction from +6 to +3:

For the reduction from +3 to +2:

84
Using potassium dichromate(VI) as an oxidising agent in
organic chemistry
Potassium dichromate(VI) solution acidified with dilute
sulphuric acid is commonly used as an oxidising agent in
organic chemistry.
It is used to:

oxidise secondary alcohols to ketones;


oxidise primary alcohols to aldehydes;
oxidise primary alcohols to carboxylic acids.

For example, with ethanol (a primary alcohol), you can get


either ethanal (an aldehyde) or ethanoic acid (a carboxylic
acid) depending on the conditions.

If the alcohol is in excess, and you distil off the


aldehyde as soon as it is formed, you get ethanal as
the main product.

If the oxidising agent is in excess, and you don't allow


the product to escape - for example, by heating the
mixture under reflux (heating the flask with a
condenser placed vertically in the neck) - you get
ethanoic acid.

In organic chemistry, these equations are often simplified to


concentrate on what is happening to the organic molecules.
For example, the last two could be written:

85
The oxygen written in square brackets just means "oxygen
from an oxidising agent".
Manganese
It is a chemical element, designated by the symbol Mn. It has
the atomic number 25. It is not found as a free element in
nature; it is often found in combination with iron, and in
many minerals. Manganese is a metal with important
industrial metal alloy uses, particularly in stainless steels.

Oxidation states of manganese

Mn2(CO)10

+1

MnC5H4CH3(CO)3

+2

MnCl2

+3

MnF3

+4

MnO2

+5

K3MnO4

+6

K2MnO4

+7

KMnO4

86
Potassium manganate as oxidizing agent:
Potassium manganate (VII) (potassium permanganate) is a
powerful oxidising agent.
Using potassium manganate (VII) as an oxidising agent in
organic chemistry
Potassium manganate(VII) is usually used in neutral or
alkaline solution in organic chemistry. Acidified potassium
manganate(VII) tends to be a rather destructively strong
oxidising agent, breaking carbon-carbon bonds.
The potassium manganate(VII) solution is usually made
mildly alkaline with sodium carbonate solution, and the typical
colour changes are:

In
testing
for a C=C
double
bond

Potassium
manganate(VII) oxidises carbon-carbon double bonds, and so
goes through the colour changes above.
Ethene, for example, is oxidised to ethane-1,2-diol.

87
In the oxidation of aromatic side chains
Alkaline potassium manganate(VII) solution oxidises any
hydrocarbon side chain attached to a benzene ring back to a
single -COOH group. Prolonged heating is necessary.
For example: In the case
of the ethyl side chain,
you will also get carbon
dioxide. With longer side
chains, you will get all
sorts of mixtures of other
products - but in each
case, the main product
will be benzoic acid.

Using potassium manganate(VII) as an oxidising agent in


titrations
Potassium manganate(VII) solution is used to find the
concentration of all sorts of reducing agents. It is always used
in acidic solution.
For example, it oxidises

iron(II) ions to iron(III) ions

hydrogen peroxide solution to oxygen

ethanedioic acid to carbon dioxide (This reaction has


to be done hot.)

88

sulphite ions (sulphate(IV) ions) to sulphate ions


(sulphate(VI) ions)

In each case, the half-equation for the manganate(VII) ions in


acidic solution is:

Doing the titration


The potassium manganate(VII) solution always goes into the
burette, and the other solution in the flask is acidified with
dilute sulphuric acid.
As the potassium manganate(VII) solution is run into the flask
it becomes colourless. The end point is the first faint trace of
permanent pink in the solution showing that there is a tiny
excess of manganate(VII) ions present.
Iron:
It is an important and useful metal. It was known to
ancient Egyptians since 4000 BC. But its extraction started
since 2000 BC. In India its extraction started since 600 BC. It
belongs to group VIII-B of periodic table.
Occurrence:
After Aluminum it is most abundant metal on the earth
crust. It is found in the form of meteor, rocks, mineral, soils,
plants and animals etc. Broken piece of rock that comes from
stars and burn in earths atmosphere is called meteor.

89
Some important ores of iron are:
1.
Magnetite (Ferroso ferric oxide) Fe3O4. It is found
in Chaghi (Baluchistan), Chitral
2.
Haematite (Ferric oxide) Fe2O3. It is found in
Mazazri tang (Kohat), Langrial(Hazara) and huge
deposits of low grade ore are found in Kalabagh.
3.
Limonite (Hydrated ferric oxide) 2Fe2O3.3H2O.
4.
Siderite (Ferrous carbonate) FeCO3.
5.
Iron Pyrite (Ferrous sulphide) FeS
6.
Copper Pyrite (Fools Gold) CuFeS2.
Commercial forms of Iron:
Iron is available commercially in following three forms.
They differ in their carbon contents.
1.
Pig iron or Cast iron. It contains 2.5 4.5 %
carbon.
2.
Wrought iron. It contains 0.12 0.25 % carbon.
3.
Steel. It contains 0.1 1.5 % carbon.
4.
Iron and its ions as catalysts
Iron as catalyst in the Haber Process
The Haber Process combines nitrogen and hydrogen into
ammonia. The nitrogen comes from the air and the hydrogen
is obtained mainly from natural gas (methane). Iron is used as
a catalyst.

Iron ions as a catalyst in the reaction between


persulphate ions and iodide ions
The reaction between persulphate ions (peroxodisulphate
ions), S2O82-, and iodide ions in solution can be catalysed
using either iron(II) or iron(III) ions.

90
The overall equation for the reaction is:

For the sake of argument, we'll take the catalyst to be


iron(II) ions. The reaction happens in two stages.

If you use iron(III) ions, the second of these reactions


happens first.
This is a good example of the use of transition metal
compounds as catalysts because of their ability to change
oxidation state.
Reactions of iron ions in solution
The simplest ions in solution are:

the hexaaquairon(II) ion - [Fe(H2O)6]2+.


the hexaaquairon(III) ion - [Fe(H2O)6]3+.

They are both acidic, but the iron(III) ion is more strongly
acidic.
Reactions of the iron ions with hydroxide ions
Hydroxide ions (from, say, sodium hydroxide solution) remove
hydrogen ions from the water ligands attached to the iron
ions.
When enough hydrogen ions have been removed, you are left
with a complex with no charge - a neutral complex. This is
insoluble in water and a precipitate is formed.

91
In the iron(II) case:

In the iron(III) case:

In the test-tube, the colour changes are:


In the iron(II) case:

Iron is very easily oxidised under alkaline conditions.


Oxygen in the air oxidises the iron(II) hydroxide precipitate to
iron(III) hydroxide especially around the top of the tube. The
darkening of the precipitate comes from the same effect.
In the iron(III) case:

92
Reactions of the iron ions with carbonate ions
There is an important difference here between the behaviour
of iron(II) and iron(III) ions.
Iron(II) ions and carbonate
ions
You simply get a precipitate of
what you can think of as iron(II)
carbonate.

Iron(III) ions and carbonate ions


The

hexaaquairon(III) ion is sufficiently acidic to react with the


weakly basic carbonate ion.
If you add sodium carbonate solution to a solution of
hexaaquairon(III) ions, you get exactly the same precipitate
as if you added sodium hydroxide solution or ammonia
solution.
This time, it is the carbonate ions which remove hydrogen
ions from the hexaaqua ion and produce the neutral complex.
Depending on the proportions of carbonate ions to
hexaaqua ions, you will get either hydrogencarbonate ions

93
formed or carbon dioxide gas from the reaction between the
hydrogen ions and carbonate ions. The more usually quoted
equation shows the formation of carbon dioxide.

Apart from the carbon dioxide, there is nothing new in


this reaction:
Testing for iron(III) ions with thiocyanate ions
This provides an extremely sensitive test for iron(III) ions in
solution.
If you add thiocyanate ions, SCN-, (from, say, sodium or
potassium or ammonium thiocyanate solution) to a solution
containing iron(III) ions, you get an intense blood red solution
containing the ion [Fe(SCN)(H2O)5]2+.

Copper:
Copper is a chemical element with the
symbol Cu (from Latin: cuprum) and atomic number 29. It is
a ductile metal with very high thermal and electrical
conductivity. Pure copper is soft and malleable; a freshly
exposed surface has a reddish-orange color. It is used as a
conductor of heat and electricity, a building material, and a
constituent of various metal alloys.

94
The reaction of hexaaquacopper(II) ions with hydroxide
ions
Hydroxide ions (from, say, sodium hydroxide solution) remove
hydrogen ions from the water ligands attached to the copper
ion.
Once a hydrogen ion has been removed from two of the
water molecules, you are left with a complex with no charge a neutral complex. This is insoluble in water and a precipitate
is formed.

In the test-tube, the colour change is:

Reactions of hexaaquacopper(II) ions with ammonia


solution
The ammonia acts as both a base and a ligand. With a small
amount of ammonia, hydrogen ions are pulled off the
hexaaqua ion exactly as in the hydroxide ion case to give the
same neutral complex.

95
That precipitate dissolves if you add an excess of ammonia.
The ammonia replaces water as a ligand to give
tetraamminediaquacopper(II) ions. Notice that only 4 of the 6
water molecules are replaced.

The colour changes are:

The reaction of hexaaquacopper(II) ions with


carbonate ions
You simply get a precipitate of what you can think of
as copper(II) carbonate.

96
Chapter 15:
Organic Compounds
Branch of chemistry which deals with the scientific
study of structure, properties, composition, reaction and
preparation of compounds containing carbon like
Hydrocarbons and their derivatives are called organic
chemistry.
Hydrocarbons are those compounds which exclusively
containing carbon and Hydrogen in their structure.
According to Vital Force Theory organic compounds were
believed to be the compounds prepared by living organisms.
But later on , in 1828, Friedrick Wholer ( a German
chemist), prepared Urea (an organic compound) in laboratory
by heating Ammonoium cyanate. It proved the vital force
theory to be wrong.
O

NH4CNO
H2N C NH2
(Urea)
Now-a-days organic compounds are defined as compounds
of carbon with few exceptions. These exceptions are CO,
-2
CO2, CS2, Carbonates (CO3 ), Bicarbonates (HCO3 ),
-4
Cyanides (CN ), Cyanates (CNO-), Carbides C ) etc.
Sources of Organic Compounds:
The major sources of organic compounds are Plants, Coal,
Petroleum and Natural Gas.

97
(i)

Plants:
Plants are one of the important source of organic
compounds. They absorb CO2 from air, water and minerals
from soil and then prepare various organic compounds. They
are actually factories of organic compounds. They produce
Carbohydrates, Oils, Vitamins, Dyes, natural fibers (Cotton &
Jute) etc.
The other three sources are also plant in origin.
(ii)
Coal:
It is a black colour mineral found under earth crust.
Plants, which were buried under, earth crust million of years
ago, they under the influence of temperature and pressure
were slowly converted to coal.
Coal deposits are found at Lakhra of Sind, Dandot and
Katha hills of Punjab, Mach and various other parts of
Baluchistan, Dara Adam Khel of Khyber Pakhtunkhaw.
Coal on the basis of its carbon contents is divided into
four types.
(a) Anthracite: Its carbon contents are 92-98%. It has
high calorific values.
(b) Bituminous Coal: Its carbon contents are 80-90%. It is
the most abundant form of coal.
(c) Sub-bituminous Coal:
Its carbon contents are 65-80%.
It is

used as commercial fuel.

(d) Lignite or Peat:

Its carbon contents are 50-60%. It is

soft and is of brown colour. Its calorific values are very


low so it is not used as fuel.
(iii)

Petroleum:
Petr means rock and oleum means oil. So
petroleum is also called rock oil. It is thick viscous
liquid of brown or greenish black colour.It is produced

98
by the decay of living organisms burried in the earth
crust. Petroleum in unrefined form is called crude oil. It
has un- pleasant, irritating smell due to presence of
sulpher contents.
Petroleum reserves are found in Sanghar and Badin
of Sind, Dera Ghazi Khan district of Punjab province,
and Karak area of KPK province.
(iv)

Natural Gas:
It is found in porous rocks and it is blend of
hydrocarbons. Mostly it was fond where petroleum
occurs. It contains Methane, Ethane, Propane and
butane. Previously it was believed that natural gas
was found only at marshy places so it is also known
as marsh gas. In Pakistan it was first discovered at
SUI (Baluchistan).
The only difference between
natural gas and petroleum is the no of hydrocarbons
( C1- C4). In Natural gas it is low chain hydrocarbons
while in petroleum the hydrocarbon is of larger chain
(C5- C40)

S,No

Fraction

Refinery
Gas

Petroleum
ether

Petrol
or 70-120
o
Gasoline
C
Benzine
120o
150 C

Boiling
range
Below
o
20 C

Composition

Uses

C1-C4

30-70
o
C

C5-C6

Fuel, making
other organic
compounds
Solvent
for
fats, oil for
varnish
Fuel
for
automobiles

C6-C8
C9-C10

Dry cleaning,
solvent
for
varnish and

99
5

Kerosene
150oil
or
o
Paraffin oil 250 C
or jet oil

C11-C12

Diesel oil or 250Gas oil or


o
400 C
Heavy oil
Residue
Above
o
400 C

C13-C18

Lubricating
oil
Paraffin
wax

C17-C20

(i)
(ii)

(iii) Pitch
Asphalt

or

C17
higher

C20-C30

C30-C40

fats
Fuel in oil
stoves,
illuminant in
lamps
and
lantern,
jet
fuel
Fuel in Diesel
engines
and Its
vacuum
distillation
Gives
following
Lubrications
Candles,
boot polish,
wax
paper,
Ointments,
Vaseline
Road
surfacing

Natural Products:
Those compounds which are produce naturally or
obtained from plants and animal sources are called natural
products.
It is well established fact that plants are the major
sources of production of numerous organic
compounds.
Natural products may also extracted from plant parts
like leaves, stem, roots etc. by the process of
extraction.
Natural products are most useful in terms of its
medicinal use.

100

Clinically useful drugs includes , Anticancer palliate


(Texol) from the YEW tree, and the antimalarial agent
Artemisinin form Artemisia annual.

Partial and Total Synthesis:


The study of process by which organic compounds
can be prepared in the laboratory from either living or nonliving sources is called synthetic organic chemistry.
Partial synthesis: Mostly organic reactions occurs in multi
steps. Sometimes, an intermediate product is used in the
synthesis of targeted product. This is called partial synthesis.
While starting material after passing through multistep process to get targeted product is called total synthesis.
In organic chemistry, a total synthesis is, in principle, the
complete chemical
synthesis of
complex organic molecules from simpler pieces, usually
without the aid of biological processes. The target molecules
can be natural products, medicinally important active
ingredients, or organic compounds of theoretical interest in
chemistry or biology.
The first demonstration of organic total synthesis
was Friedrich Whler's synthesis of urea in 1828, which
demonstrated that organic molecules can be produced from
inorganic precursors, and the first commercialized total
synthesis was Gustaf Komppa's synthesis and industrial
production of camphor in 1903. Early efforts focused on
building chemicals which were extracted from biological
sources, and using them to verify their biological activitiesin
this fashion, total synthesis was associated with disproving
the existence of a vital force.

101
Destructive distillation of Coal:
When coal is heated in absence of air, its destructive
distillation or carbonization occurs. Destructive distillation of
coal produces following products.

102
It is the chemical process involving
the decomposition of feedstock by heating to a high
temperature; the term generally applies to processing
of organic material in the absence of air or in the presence of
limited amounts of oxygen or other reagents, catalysts,
or solvents, such as steam or phenols. It is an application
of pyrolysis. The process breaks up or 'cracks' large
molecules. Coke, coal gas, gas carbon, coal tar, Buckminister-fullerene, ammonia liquor, and "coal oil" historically,
are examples of commercial products of the destructive
distillation of coal.
Coal Tar:
It is mixture of more than 200 organic compounds, which can
be separated by fractional distillation. It is a brown or black
liquid of extremely high viscosity. Coal tar is among the byproducts when coal is carbonized to make coke or gasified to
make coal gas. Coal tars are complex and variable mixtures
of
phenols, polycyclic
aromatic
hydrocarbons (PAHs),
and heterocyclic compounds.
Coal Gas:
It is mixture of carbon mono oxide and Hydrogen also called
as water gas and town gas. It is a flammable gaseous
fuel made from coal and supplied to the user via a piped
distribution system. Town gas is a more general term referring
to manufactured gaseous fuels produced for sale to
consumers and municipalities.
Ammonical Liquor:
It is
a concentrated solution of ammonia, ammonium compounds,
and

103
sulfur compounds, obtained as a byproduct in the destructive
distillation of bituminous coal. It is used in the synthesis of
fertilizers like ammonium sulphate, ammonium super sulphate
etc.
How coal can be converted into Petroleum?
Coal gasification is the process of producing syngasa
mixture
consisting,
primarily
of methane (CH4) carbon
-monoxide (CO), hydrogen (H2), carbon dioxide (CO2) and
water vapor (H2O)from coal and water, air and/or oxygen.
Historically, coal was gasified using early technology to
produce coal gas (also known as "town gas"), which is a
combustible gas traditionally used for municipal lighting and
heating before the advent of industrial-scale production of
natural gas. In current practice, large-scale instances of coal
gasification are primarily for electricity generation, such as
in integrated gasification combined cycle power plants, for
production of chemical feedstocks, or for production of
synthetic natural gas. The hydrogen obtained from
coal gasification can be used for various purposes such as
making ammonia, powering a hydrogen economy, or
upgrading fossil fuels. Alternatively, coal-derived syngas can
be
converted
into
transportation
fuels
such
as gasoline and diesel through additional treatment via
the Fischer-Tropsch process or into methanol which itself can
be used as transportation fuel or fuel additive, or which can
be converted into gasoline by the methanol to
gasoline process.
Importance of Organic Compounds:
Organic compounds have great importance in our
daily life e.g.
i.

Our body is made up of organic compounds.

ii.

Our food is mostly organic.

104
iii.

Clothes we wear are made up of organic


compounds.

iv.

Leather we use is organic in nature.

v.

Paper we use for writing is organic in nature.

vi.

Fuels we use in automobiles are organic


compounds

vii.

Woolen products, rubber, plastics, cosmetics,


paints, medicines, shoe polish, and many other
daily use items are mainly organic in nature.

Characteristics of Organic Compounds:


Organic compounds have following common
characteristics
1.
They must contain Carbon.
2.
They have low melting and boiling points.
3.
They decompose at low temperature.
4.
They are mostly flammable.
5.
They are covalent compounds.
6.
Their reactions are usually slow.
7.
They mostly show isomerism.
e.g. CO2 is not organic compound as it has some of the
above mentioned characteristics but not all on the other hand
sucrose (C12H22O11) is an organic compound as it possesses
all of the above mentioned characteristics.
Reasons for very large number of organic compounds:
Due to following reasons number of organic
compounds is very large.
1. Tetra valency of Carbon: As carbon has tetra valency so it
can give various combinations with other atoms e.g.
carbon gives 5 combinations with H and Cl i.e. CH4,
CH3Cl, CH2Cl2, CHCl3, CCl4.

105
2. Catenation: Self linkage of atoms of an element is called
catenation, this ability is maximum in carbon. Due to this
reason carbon can form long chains, branched chains and
rings.
3. Isomerism: Organic compounds have various isomers
e.g (i) Pentane C5H12 shows 3 isomers i.e. n-pentane,
iso pentane, neo pentane etc.e.g (ii) molecular formula
C2H6O represents two isomers CH3-O-CH3 & C2H5OH.
4. Multiple Bonds: Carbon is capable of forming multiple
bonds among its own atoms as well as with other atoms
e.g. CH3-CH3, CH2=CH2, CHCH etc.
Bucky Balls:
Buck minster fullerene (or bucky-ball) is a
spherical fullerene molecule

with

the

formula C60. It has a cage-like fused-ring


structure

(truncated

icosahedron)

which

resembles a soccer ball, made of twenty hexagons and


twelve pentagons, with a carbon atom at each vertex of each
polygon and a bond along each polygon edge.
It was first generated in 1985 by Harold Kroto, James R.
Heath,

Sean

O'Brien, Robert

Curl,

and Richard

Smalley at Rice University. Kroto, Curl and Smalley were


awarded the 1996 Nobel Prize in Chemistry for their roles in
the discovery of buckminsterfullerene and the related class of
molecules,

the fullerenes. The name is a reference

to Buckminster

Fuller,

as

C60 resembles

his

trademark geodesic domes. Buckminsterfullerene is the most


common naturally occurring fullerene molecule, as it can be

106
found in small quantities in soot. Solid and gaseous forms of
the molecule have been detected in deep space.
Buckminsterfullerene is one of the largest objects to have
been shown to exhibit waveparticle duality, as stated in the
theory every object exhibits this behaviour. Its discovery led to
the exploration of a new field of chemistry, involving the study
of fullerenes.
The structure of a buckminsterfullerene is a truncated
icosahedron with 60 vertices and 32 faces (20 hexagons and
12 pentagons where no pentagons share a vertex) with a
carbon atom at the vertices of each polygon and a bond along
each polygon edge.

Vertex

Edge 5-6

Edge 6-6

Face Hexagon

Classification of Organic Compounds:


Organic compounds are usually divided on two basis.
(i) Classification on the basis of arrangement of carbon atoms
(Old Classification):
Classification of Organic Compounds:
Organic compounds are usually divided on two basis.
(i) Classification on the basis of arrangement of carbon atoms
(Old Classification):
On this basis following classification is made.

107

108

109
Homologous Series:
A series of compounds in which there is a constant
difference of methylene (-CH2-)
group between any two successive members of the family.
e.g.

General characteristics of Homologous Series:


1. There is a constant difference of methylene (-CH2-)
group between any two successive members of a
homologous series.
2. All the members of a homologous series can be
represented by a general formula e.g. general
formulae for alkanes, alkenes, alkynes, alcohols, alkyl
halides are CnH2n+2, CnH2n, CnH2n-2, CnH2n+1OH, CnH2n+1X
respectively.
3. All the members of a homologous series have same
functional group.
4. All the members of a homologous series have same
general chemical properties.
5. There is a gradual change in physical properties in a
homologous series from lower members to higher
members.
6. All the members of a homologous series can be
prepared by same general methods of preparations.
7. All families of organic compounds form a homologous
series.
Primary, Secondary and Tertiary Carbons and Hydrogens:

110
The carbon attached to one other carbon or no other
carbon is called primary carbon, while hydrogens attached to
primary carbon are called primary hydrogens e.g in following
compound Carbon No.1,5 and that of methyl group are
primary carbons and their hydrogens are primary hydrogens.

3Methyl pentane
The carbon attached to two other carbons is called
secondary carbon, while hydrogens attached to secondary
carbon are called secondary hydrogens e.g in above
mentioned compound Carbon No.2,4 are secondary carbons
and their hydrogens are secondary hydrogens. The carbon
attached to three other carbons is called tertiary carbon, while
hydrogen attached to tertiary carbon is called tertiary
hydrogen e.g in above mentioned compound Carbon No.3 is
tertiary carbon and its hydrogen is tertiary hydrogen.
Alkyl Group:
A group obtained after the loss / removal of hydrogen atom
the an alkane is called an alkyl group. It is represented by R.
R means remainders, as alkyl group is always attached with
any functional group.
Alkane--------(-H)-------------- Alkyl group.
(1)

Detection of elements:-

INTRODUCTION:

111
Carbon is an essential constituent of all organic compounds.
Majority of organic compounds also contain hydrogen. Other
elements which are generally present in organic compounds
are oxygen, nitrogen, sulphur and halogens.
Oxygen cannot be detected by any direct method. Rest of the
elements are detected by performing various tests. Organic
compounds are covalent in nature and in this state nitrogen,
sulphur and halogen could not be detected as it is difficult to
ionize them. Therefore compounds containing these elements
are converted into water soluble ionic compounds before the
detection is carried out. This is done very carefully as further
analysis is largely based on the type of element present in it.
I)

Detection of Carbon:Apparatus:
Test tubes, delivery tube, cork, beaker,

burner.
Chemicals:or thiourea )

(1)
(2)

Given organic compound ( usually urea

Procedure:Take a little amount of organic compound and


comparatively larger amount of dry CuO in a test tube.
Heat the test tube strongly.

112
(3)

The gas produced as a result of heating is passed


through the lime water taken in a test tube.
Reaction:C + 2CuO

CO2 +
2Cu
Ca (OH)2 + CO2
CaCO3
+ H2O
Aqueous calcium hydroxide (lime water)
Calcium carbonate (white ppt)
Observation and inference:
If lime water turns milky then carbon is present in the
compound.
II)

Detection of Hydrogen:-

Apparatus:
Chemicals:or thiourea)

Test tubes, delivery tube, burner, stand.


Given organic compound ( usually urea

113
Procedure:(1)
(2)
(3)

Take a little amount of organic compound and


comparatively larger amount of dry CuO in a test tube.
Heat the test tube strongly.
The gas and vapours produced as a result of heating
are passed over anhydrous copper sulphate.

Reaction:CuO +
Cupric oxide

2H
H2O+ Cu
Organic compound

CuSO4 +
5H2O
CuSO4.5H2 O
Anhydrous copper sulphate
hydrated
copper
sulphate
(white)
(blue)
Observation and inference:
If water drops appeared on cooler parts of the test
tube or anhydrous copper sulphate turned blue then
hydrogen is present in the compound.
III)

Detection of Oxygen:Oxygen cannot be detected by any direct method but


for its detection some indirect methods are used.
1. The given organic compound is heated alone in a dry
test tube usually in Nitrogen atmosphere. Formation of
water droplets on the cooler part of test tube clearly
indicates the presence of oxygen.
2. Different tests are applied for the detection of oxygen
containing functional group like, alcohol, aldehyde,
ketone and carboxylic acid. If any functional group is
detected, it shows the presence of oxygen.
3. The most important test for the presence of oxygen is
combustion analysis, in which percentage of carbon
and hydrogen are determined. Then sum of carbon

114
and hydrogen percentage is subtracted from 100. The
remaining percentage will be oxygen.
% Oxygen = 100 ( % Carbon + % Hydrogen).
Combustion Analysis:
It is one of the estimation techniques. A weighed
amount of sample is placed in combustion tube. The tube is
connected to cylinder of oxygen gas and the gas is passed for
some time to remove air from the combustion tube.
CO2, H2O, O2
CO2, O2

O2
unreacted
O2
Sample boat

Mg(ClO4)2
50% KOH
Magnesium per chlorate
aq Potassium hydroxide
(Water absorber) (CO2 absorber)
The two u-shaped tubes, one containing water
absorber and other containing CO2 absorber are weighed and
connected to the combustion tube as shown in fig. The
compound in the combustion tube is strongly heated to
burning. Carbon and hydrogen (if any) of the compound will
be converted to CO2 and H2O respectively. The increase in
the weight of absorbers will give the mass of CO2 and H2O
produced. From the mass of CO 2 percentage of Carbon is
calculated while from the mass of H2O percentage of
Hydrogen is calculated.

115
IV)

Detection of Nitrogen, Sulphur and Halogens:Various tests are performed to detect nitrogen, sulphur
and halogens in the given organic compounds.

To detect these elements in the organic compound


first Lassaignes solution is prepared.
Preparation of Lassaignes solution:
It is based upon the fact that when organic compound
containing nitrogen, sulphur and halogen is strongly heated
with metallic sodium, its nitrogen converts to ionic NaCN
(sodium cyanide), sulphur to ionic NaS (sodium sulphide) and
halogen to ionic NaX (sodium halide) if they are present.
(i)

Put a small piece of sodium metal in a fusion

tube.
(ii)
Heat the tube until the sodium melts.
(iii)
Drop a pinch of organic compound on molten
sodium in the fusion tube.
(iv)
Again heat the tube strongly till the tube
becomes red hot.
(v)
Break the red hot tube in distilled water
contained in a china dish.
(vi)
Stir the solution with a glass rod and boil it.
(vii) Now filter the solution, the filtrate is called
Lassaignes solution.
Reactions:
When Nitrogen without Sulphur is present:
Carbon and nitrogen from organic compound react
with sodium to form sodium cyanide.
Na + C + N

NaCN
Sodium cyanide (ionic)

When both Nitrogen and Sulphur are present:

116
Carbon, Nitrogen and Sulphur from organic compound
react with the sodium to form sodium thiocyanide.
Na + C + N + S

NaCNS

Sodium thiocyanide (ionic)


When Sulphur without Nitrogen is present:
Sulphur from organic compound reacts with sodium to
form sodium sulphide.
Na

NaS

Sodium sulphide (ionic)


When Halogen is present:
Halogen from organic compound reacts with sodium
to form sodium halide.
Na + X

NaX

Where X = (Cl, Br, I)


Sodium halide (ionic)

(A)

Detection of Nitrogen:

(i)
(ii)

Take a few mls of Lassaignes solution in a test tube.


Add a few drops of NaOH solution and then few mls of
freshly prepared FeSO4
solution.
Boil and cool the solution.
Add a few drops of FeCl3 solution.
Acidify the solution by adding dil HCl.

(iii)
(iv)
(v)

Observation and inference:


(a)
A Prussian blue or green colouration or precipitate
confirms presence of Nitrogen.
Reactions:
Na + C + N
FeSO4 + 2NaOH
Fe(OH)2 + 6NaCN

NaCN
Na2SO4 + Fe(OH)2
Na4[Fe(CN)6]+ 2NaOH

117
Sodium ferrocyanide
Sodium hexa cyano ferrate (II)
3Na4[Fe(CN)6] +4FeCl3
Fe4[Fe(CN)6]3+12NaCl
Ferri ferrocyanide
(Prussian blue or green)
(b)
Blood red precipitate indicates presence of
Nitrogen and Sulphur together.
Reactions:
Na + C + N+

FeSO4 + 2NaOH
Fe(OH)2 + 2NaCNS
Fe(CNS)2 + 4NaCNS
3Na4[Fe(CNS)6]+4FeCl3

3NaCNS + FeCl3

NaCNS
Sodium thiocyanide
Na2SO4 + Fe(OH)2
Fe(CNS)2+ 2NaOH
Na4[Fe(CNS)6]
Fe4[Fe(CNS)6]3+12NaCl
Ferri ferrothiocyanide
(blood red colouration)
Or

Fe(CNS)3 + 3NaCl
Ferric thiocyanide (reddish colour)

Note:
(i)
Sometimes when amount of nitrogen present is small,
the Prussian blue ferri ferro cyanide is present in
colloidal form and the solution looks green.
(ii)
When the alkaline solution is acidified with HCl, the
yellow colour of FeCl3 makes the blue colour to
appear green.
(iii)
Li and K cannot be used in place of Na because Li
reacts slowly where as K reacts vigorously and cannot
be handled properly. Moreover lithium compounds are
covalent.
The presence of nitrogen in an organic compound can also
be detected by the following methods:
(1)

Ignition Test:

118
When a small amount of the organic compound is
burnt smell of burning feathers indicates the presence
of nitrogen however ignition test is not a sure test.
(2)

Soda Lime Test:


The given organic compound (1 parts) is heated with
soda lime (2 Parts). Evolving of ammonia indicates the
presence of nitrogen.

Limitation:
Many classes of nitrogen compounds like nitro and
diazo derivatives do not respond to this test.
(B)

Detection of sulphur:
To detect sulphur two tests could be performed.
Test-1

(i)Take a few mls of Lassaignes solution in a test tube.


(ii)
Add acetic acid solution.
(ii)
Then add lead acetate solution.
Observation and inference:
Appearance of black precipitate of lead sulphide
indicates presence of sulphur in the compound.
2Na

Na2S

Na2S + (CH3COO)2Pb
PbS + 2CH3COONa
Sodium sulphide Lead acetate
Lead sulphide
sodium acetate
(Black ppt)
Note:

119
Sulphuric acid is not used for acidification of Lassaignes
solution because if it is used then on adding lead acetate,
lead sulphate will precipitate. Moreover, addition of acetic acid
also increases the precipitation of PbS due to common ion
effect.
Test-2
(i) Take a few mls of Lassaignes solution in a test tube.
(ii) Add freshly prepared sodium nitroprusside solution
Observation and inference:
Appearance of deep violet colouration indicates presence of
sulphur in the compound.
2Na

Na2S

Na2S + Na2 [Fe (CN)5 NO] Na4[ Fe (CN)5 NOS]


Sodium pentacyano nitosyl ferrate (III)
(Sodium nitroprusside)
(Purple Colouration)
(C)

Detection of Halogens:
The presence of halogens in an organic compound
can be shown by silver nitrate test with Lassaignes
solution.
(i)
(ii)
(iii)
(iv)

Take a few mls of Lassaignes solution in a test


tube.
Add 1-2 drops of conc HNO3.
Boil and cool the solution.
Add silver nitrate solution.

Observation and inference:

120
(a)
Appearance of white precipitate of silver chloride
soluble in NH4OH solution indicates presence of chlorine
in the compound.
Reactions:
Na + Cl
NaCl + AgNO3

NaCl
AgCl + NaNO3
Silver chloride
(White precipitate)

(b)
Appearance of pale yellow precipitate of silver
bromide partially soluble in NH4OH solution indicates
presence of bromine in the compound.
Reactions:
Na + Br
NaBr + AgNO3

NaBr
AgBr + NaNO3
Silver bromide
(Pale yellow precipitate)

(c)
Appearance of yellow precipitate of silver iodide
insoluble in NH4OH solution indicates presence of iodide
in the compound.
Reactions:
Na + I
NaI + AgNO3

NaI
AgI + NaNO3
Silver iodide
(Yellow precipitate)

Note:
If S-2 and CN- ions are not removed from the solution,
precipitate of sodium sulphide and sodium cyanide will
be formed with silver nitrate solution and interfere with
the test.

121
NaCN +

AgNO3

Na2S

2AgNO3

AgCN +

NaNO3
(White ppt)

Ag2S +
(Black ppt)

2NaNO3

So to remove sulphide and cyanide, conc HNO3 is added


before addition of silver nitrate.
NaCN + HNO3
NaNO3
+
HCN
Na2S + 2HNO3
2NaNO3 +
H2S
Beilsteins Test:
Friedrich K. Beilstein-a Russian chemist introduce this
test. A copper wire is cleaned and flattened at one end is
heated in a Bunsen burner flame till it ceases to impart any
green or blue colour to the flame. It is touched with the
organic compound and reheated in the flame. A volatile,
copper halide is formed which imparts green or blue colour to
the flame. It indicates the presence of a halogen in the
organic compound.
Limitations:
(i)
Compounds like pyridine, urea and thiourea
which do not contain halogens also respond to
this test.
(ii)
It does not tell about the particular halogen
present in the organic compound.
Nomenclature:
There are two systems of naming organic compounds.
(i)

Common system or Trivial Names:


In this system names are derived from source or
their property or their structure etc.
e.g Urea from urine (source), Citric acid from citrus
plant (source).

122
Glucose from the greek word meaning sweet
(property, Valyric acid from Greek word valyr
meaning powerful (property).
Pentane from Greek word penta meaning five
(structure).
The common system failed as it is not systematic.
(ii)

IUPAC System:
To develop a systematic system of naming
compounds International Chemical congress met
in Geneva in 1892 and formulated a system of
naming called Geneva System.
Geneva System was revised by International
Union of Chemistry at Liege in 1930 and is known
as IUC System.
IUC later change its name to IUPAC i.e.
International Union of Pure and Applied Chemistry
and modified the rules in 1957 and revised in
1967. This system now called IUPAC System.

Rules of IUPAC System:


It involves following steps:

Step-I Chain selection:


Select the longest possible continuous carbon chain
containing the carbon of functional group and if functional
group has no carbon in it then the carbon to which it is
attached should be in the chain.
If more than one longest chains of equal number of
carbons are there then the one which has more branches
or side chains is selected.
Step-II Numbering:
Carbon atoms of the selected chain (parent chain) are
numbered from one end to other end such that the locant
or sum of locants of the functional group should be
smaller.

123

If the locant or sum of locants of the functional group is


same for both ends then numbering is carried out from
that end which gives smallest locant or sum of locants to
the substituents. But first point of difference must get
smaller locant.
Next preference is given to more electronegative group
and last preference is given to larger alkyl group.
Step-III Naming:
Substituents are named before parent name and names
of substituents are preceded by their locants. At end
parent name is written and it is preceded by its locant(s).
If same substituent is occurring more than one time then
prefixes di, tri, tetra, penta etc are used with its name and
locant of each is written each time.
If substituents of more than one kind are there then their
names are written in alphabetical order.
Two numbers are separated by comma between them, a
number and a name are separated by a hyphen between
them while two names are separated by a space between
them.

124
Chapter 16: HYDROCARBONS
The binary compounds consisting of carbon and hydrogen
only are called hydrocarbons. They are classified as follows:

125

A. Saturated Hydrocarbons:
Those hydrocarbons in which all the carbon atoms have
single covallent bond with hydrogen or with other atoms are
called saturated hydrocarbons. Carbon atom valency is fully
satisfied. Here each carbon is bonded to four other atoms.
These are also known as alkanes, which may be branched
chain or straight chain molecules.
B. Un-saturated Hydrocarbons:
Hydrocarbons which contains at-least one double or triple
bond in their structural formula are called un-saturated
hydrocarbons.
Unsaturated hydrocarbon where carbon and carbon atom
contain at least one double bond are called alkenes, having

126
general formula of CnH2n. while those having at least one
triple bond between carbon and carbon atoms are called
alkynes having general formula of CnH2n-2. Both alkenes and
alkynes may be branched or straight chain molecules.
Cycloalkanes:
Hydrocarbons having fused ring or
closed ring of carbon atoms are
called cyclic hydrocarbons, cyclo
alkanes. They have two hydrogen
atoms less than open chain alkanes.
Examples are cyclobutane, cyclo
hexane etc.
Aromatic Hydrocarbons
Those hydrocarbons which contain at-least one benzene ring
in their structure are called aromatic hydrocarbons. The term
aromatic was first introduced by Kekule, who wanted to
classify benzene and its derivatives.
Characteristics of Aromatic Hydrocarbons:
These are cyclic compounds which contains conjugate
double bonding system like in benzene.
They resist to undergo addition type of reactions.
They favor the electrophilic substitution reactions.
They never favor the elimination reactions.

127
Alkanes:
Alkanes are open chain saturated hydrocarbons
having general formula CnH2n+2. They are less reactive and
hence are also called Paraffins.
General Methods of Preparation of Alkanes:
1) By Hydrogenation of unsaturated hydrocarbons (Sabatier
Senderns reaction):
Alkanes can be prepared by passing alkenes or alkynes
over finely divided nickel or platinum or palladium catalyst.
The catalyst changes molecular hydrogen to atomic hydrogen
which can break pi-bonds of alkenes or alkynes and will be
added to them. Addition of hydrogen to alkenes or alkynes is
called hydrogenation and is also called Sabatier-Senderns
Reaction or S-S Reaction.
o
While using Nickel, heating is required from 250-300 C
but in case of Platinum and palladium no heating is required.

128
2) By Reduction of Alkyl Halides:
Molecular hydrogen can not reduce alkyl halides,
however atomic hydrogen can reduce alkyl halides and gives
alkanes. Therefore alkyl halides are treated with Zinc in
presence of dil HCl, nascent hydrogen is produced which
reduces alkyl halides to corresponding alkanes.

3) By Hydrolysis of Grignard Reagent:


Alkyl Magnesium Halides (R Mg X) are called
Grignard reagents. These are organo-metallic
compounds.
Hydrolysis
of
grignard
reagents
produce
corresponding alkanes.

4) By Wurtzs Reaction:
Wurtz discovered this method in 1885. The reaction of alkyl
halides with sodium metal in presence of anhydrous ether
produces alkanes and is called Wurtzs reaction.
In this method higher alkanes are produced.

129

General Physical Properties of Alkanes:


1. At room temperature and pressure 1st four alkanes
(i.e. from C1 to C4) are colourless and odourless
gases. Alkanes from C5 to C17 are colourless and
odourless liquids while alkanes from C18 and onward
are colourless and odourless solids.
2. The melting and boiling points of alkanes are lower
than alcohols of comparable molecular masses.
3. The melting and boiling points of alkanes show
gradual increase with increasing molecular masses.
However the higher alkanes show no marked change
in melting and boiling point.
4. More is the number of branches in alkanes lower will
be the boiling points.
5. Alkanes are non-polar so are soluble in non-polar
solvents like ether, acetone, benzene, carbon tetra
chloride etc.
6. Specific gravity, viscosity of alkanes increases with
increasing molecular masses.
Structure of Alkanes
The hybridization in which one s-orbital and three p-orbitals
are mixed to form four identical hybrid orbitals is called sp 3
hybridization. The four sp3 hybrid orbitals are degenerated
(have equal energy) and they are directed in space to four
o
corners of tetrahedron having an angle of 109.5 . Each sp3
hybrid orbital has 25% s-character and 75% p-character.

130

Methane
(CH4):
In methane and all other alkanes, carbon atoms are sp 3
hybridized. The electronic configuration of carbon is 1s2, 2s2,
2p2. Its valence shell has 2 electrons in s-orbital and one
electron in each of two p-orbitals while the third p-orbital is
lying vacant.
(Page-9)

By absorption of
energy one of
electron of 2s promotes to vacant p-orbital and atom
becomes in excited state, which is not stable state. Thus to
gain a state of stability mixing of atomic orbitals take place
and energy is lowered. One s-orbital and three p-orbitals are
mixed together and gives four sp3 hybridized orbitals. These
four sp3 hybrid orbitals are identical in shape and energy and
each has a single electron in it. So carbon is tetravalent and
not divalent.
Four half-filled s-orbitals of four hydrogen
atoms overlap with half-filled sp3 hybrid
orbitals of carbon forming four C-H
sigma-bonds. These bonds are formed

131
due to sp3-s overlapping. As overlapping have taken place on
bond axis so sigma bonds are formed.
Shape of methane molecule is tetrahedral. Bond angle
o
between any two C-H bonds is 109.5 . Whereas C-H bond
-10
length is 1.11x10 m or 1.11 Ao. In other alkanes C-H bond
-10
length is 1.11x10 m or 1.11 Ao while C-C bond length is
-10
1.54x10 m or 1.54 Ao. The deviation of angle from the
normal tetrahedral angle of 109.5 to 60 degree is called angle
strain.
Relative stability and Reactivity of Alkanes and cycloalkanes:
In open chain alkanes the carbon atoms are fully satisfied so
they are inert. There are few reasons as well:
E.N difference of carbon & hydrogen is less which
is 0.4. due to this less difference there is no clear
cut poles created in alkane molecule.
Carbon-carbon bond is purely non-polar.
All the bonds are sigma bond which is stronger
bond.
While in cyclo alkanes their chemical behavior is similar to
alkane except cyclobutane and cyclopropane due to
formation of angle strain. There are few other reasons as
well:
In case of cyclopropane and cyclobutane the extant of
overlapping of orbitals is not maximum due to which
greater angle strain is created which leads to
instability.
Cyclo butane has less angle strain than that of cyclo
propane , so its is stable.
Higher members of cycloalkanes are even more
stable. Still they resemble open chain alkanes and
gives substitution reactions.

132
Types of bond fussion:
Chemical reaction involves the breaking of existing
bond and formation of new bonds. This process of bond
breaking is of two types hemolytic and homolytic.
Homolytic
In homolytic bond fission of a bond each bonded atom
takes one electron of the bond pair of electron and forms the
free radicals. Breaking of Cl-Cl bond by U.V light is homolytic
fission
A free radical is a specie with an unpaired of electron
and highly reactive.
Hemolytic
Un like homolytic fission one of the bonded atom takes the
paired electron pair and from anion and cation. Carbon
having +ve charge is called carbo cation and having ve
charge called
carbo anion.

Chemical Properties of Alkanes:


Alkanes are less reactive i.e they are comparatively inert and
are hence called paraffins. It is from Latin word parum
meaning little and affin meaning affinity.
The low reactivity of alkanes is due to
(i)
the reason that they are saturated compounds
having strong covalent bonds which are difficult to
break.
(ii)
The reason that they are non-polar so electrophile
as well as nucleophile can not attack them.
Due to these reasons alkanes are inert towards acids, bases,
oxidizing and reducing agents at ordinary conditions.

133
However at elevated temperatures they react with these
reagents.
Alkanes being saturated compounds mostly show substitution
reactions. Their oxidation is very difficult thus even strong
oxidizing agents like KMnO4, K2Cr2O7 etc can not oxidize
them.
1. Halogenation:
Halogens replace hydrogen from alkanes and it is
called halogenation of alkanes. The order of reactivity
of haogens with alkanes is
F2>Cl2>Br2>I2
Fluorine shows reaction with explosive violence.
Reaction of iodine is slow and reversible.
Halogenation is a substitution reaction and it proceeds
through free radical mechanism.
a)
In dark no reaction occurs

Mechanism:
It is a free radical substitution reaction. Its steps are
divided into three categories.
Step-I Reaction Initiating Step:

134
The step in which free radical is generated and due to
which then reaction starts is called initiation step.
Step-II
Reaction Propagation Step:
The step in which one free radical give birth to another
free radical is called propagation. Following are reaction
propagation steps.

135
Step-IIIReaction Terminating Step
The step in which two free radicals combine to give a
molecule is called termination step.

1. Nitration:
Nitration like halogenation is also a substitution
reaction. When alkanes and vapours of nitric acid are
passed through metal tube at 400-450 oC, nitration of
alkanes occurs.

1. Combustion:
Alkanes on strongly heating in air starts burning.
Combustion reaction is an oxidation reaction.

136
Alkanes on burning in sufficient supply of air produce
carbon dioxide and water vapours and heat is
liberated.
CH4 + 2O2

CO2 +
2H2O + 891kJ
But in limited supply of air carbon monoxide and
carbon soot is produced and less heat is liberated.
2CH4 +
3O2

2CO +
4H2O
CH4
+
O2

C
+
2H2O
Overall reaction 3CH4 +4O2 C + 2CO + 6H2O
2C2H6 +
7O2

4CO2 +
6H2O
H = - 3081 KJ or -1540.5 KJ/mol
2. Catalytic Oxidation:
Lower alkanes on heating in air in presence of copper
catalyst and applying pressure, oxidize to mixture of
useful products.
Alkanes first oxidize to corresponding alcohols

Carboxylic acids other than methanoic acid do not


further oxidize, however methanoic acid further oxidizes to
carbon dioxide

137

Uses of Alkanes:
(i)
(ii)
(iii)

Alkanes are used as fuel. e.g. refinery gas, gasoline,


kerosene oil, diesel oil all are mixture of alkanes and
are used as fuel.
Alkanes are used in the synthesis of many valuable
organic compounds like chloroform, carbon tetra
chloride, methanol, formaldehyde etc.
Cracking of methane produce carbon soot and
hydrogen.
CH4
500-700oC
C
+
2H2

Carbon soot
The carbon soot is used in automobile tyre industries
for vulcanization of rubber. While hydrogen is used for
hydrogenation of vegetable oil to get ghee and also for
reduction of tungsten oxide to get tungsten. Tungsten
filaments are used in electric bulbs.
Alkenes:
Alkenes are open chain unsaturated hydrocarbons
having general formula CnH2n. They have at least one carboncarbon double bond. Lower members of alkene family on
reaction with halogens produce oily products hence alkenes
are also called olefins (meaning oil producing).

138
General Methods of Preparation of Alkenes:
1.
By Dehydration of Alcohols:
Removal of water is called dehydration. Alcohols when
heated with H2SO4 or H3PO4 or Al2O3 or P4O10 (also written as
P2O5) they lose water so they are dehydrated to
corresponding alkenes.
The ease of dehydration in alcohols is in the order of
Tertiary alcohols > Secondary alcohols > Primary alcohols

Thus
prialcohols on dehydration gives their corresponding 1-alkenes
(terminal alkenes). Pri-alcohols are less reactive so they need
high concentration of acid and also more heating.

Sec-alcohols are comparatively more reactive so they


need lower concentration of acid and also less heating.

Ter-alcohols
are most reactive among alcohols so they need

139
still lower concentration of acid and also least
heating.
2.

Dehalogention of vicinal dihalides:


Removal of halogens is called dehalogenation. Vicinal
means adjacent. When alkyl halides having two halogens
on adjacent vicinal carbons (known as vicinal dihalides or
vicinal dihaloakanes) are heated with zinc dust in
anhydrous alcohol, dehalogenation occurs and alkenes
are obtained.

3.
By Hydrogenation of Alkynes:
Controlled addition of hydrogen to alkynes produces
alkenes. When alkynes are heated with hydrogen in
presence of palladium catalyst poisoned by heavy metal
salts, partial hydrogenation occurs and alkenes are
produced.

140

Structure of Alkenes:
In ethene the doubly bonded carbon atoms are sp 2
hybridized. The electronic configuration of carbon is 1s2, 2s2,
2p2. Its valence shell has 2 electrons in s-orbital and one
electron in each of two p-orbitals while the third p-orbital is
lying vacant.

By
absorption of energy one of electron of 2s promotes to vacant
p-orbital and atom becomes in excited state, which is not
stable state. Thus to gain a state of stability mixing of atomic
orbitals take place and energy is lowered. One s-orbital and
two p-orbitals are mixed together and gives three sp 2
hybridized orbitals. These three sp2 hybrid orbitals are
identical in shape and energy and each has a single electron
in it. Also the unhybridized p-orbital has single electron. So
carbon is tetravalent and not divalent.
Two half-filled s-orbitals of two hydrogen atoms
overlap with half-filled sp2 hybrid orbitals of one carbon while
half-filled s-orbitals of two other hydrogen atoms overlap with
half-filled sp2 hybrid orbitals of second carbon forming total
four C-H sigma-bonds, two with each carbon. As overlapping
have taken place on bond axis so four C-H sigma bonds are
produced. These bonds are formed due to sp2-s overlapping.

141
The remaining third sp2 hybrid of one carbon overlaps with
the third sp2 of other carbon on bond axis thus forming C-C
sigma bond. This bond is formed due to sp2-sp2 overlapping.
The unhybridized p-orbitals (one of each carbon) are
parallel to each other so they overlap side wisely (i.e.
laterally) and form pi-bond. Pi-bond is a week bond and is
easy to break hence ethene is reactive.
Bond angle between
any two C-H bonds is
o
116.7 . Bond angle
between C=C and Co
H bond is 121.6 .
The C-H bond length
-10
is 1.10x10 m or 1.10 Ao. While C=C bond length is
-10
1.34x10 m or 1.34 Ao.
General Physical Properties of Alkenes:
1. At room temperature and pressure 1st three alkenes
(i.e. from C2 to C4) are colourless gases. Alkenes from
C5 to C18 are colourless liquids while alkenes from C18
and onward are colourless solids.
2. They are odour-less except ethene which has
pleasant smell.
3. The melting and boiling points of alkenes increase
with increase of molecular weight.
4. They are less volatile than corresponding alkanes.
5. More is the number of branches in alkenes lower will
be the boiling points.
6. Alkenes are insoluble in water but dissolve freely in
organic solvents.

142
Chemical Properties of Alkenes:
The reactivity order of aliphatic hydrocarbons is
Alkenes
>
Alkynes
>
Alkanes
It means that alkenes are most reactive in this series.
They have a double bond which consists of a strong sigma
() bond (bond energy = 83 Kcal/mol) and a weak pi ( )bond (bond energy = 63 Kcal/mol). The density of -electrons
is high above and below the bond axis. In other words electrons are away from the nuclei of the carbon atoms so
hold of nuclei is less on them. Thus they are exposed to
electrophilic attack. Thus an electrophile can easily attack and
can break bond by using less energy and therefore alkenes
are more reactive.
Alkenes being unsaturated compounds mostly shows
addition reactions. Beside addition reactions they also show
oxidation reactions. An oxidizing agent can remove their
loosely bound -electrons.
The reactions of alkenes can be divided into three
categories.
A.

Addition Reactions:
Alkenes being unsaturated compounds mostly show
addition reactions and the addition is electrophilic addition.
Mechanism:
A polar or temporarily polarized molecule approaches
to alkene and +ve end of the molecule pulls its -electrons as
a result reagent molecule breaks up and its +ve ion
(electrophile) forms a temporary bond with two multiple
bonded carbons.

143
The elecrophile makes permanent bond with one of the
carbon and leaving +ve charge on other carbon.

The ve ion (nucleophile) attacks carbonium ion and


offers its electrons to positively charged carbon and makes
bond with it.

Some addition reactions of alkenes are following.


1.
Hydrogenation:
Addition of hydrogen is called hydrogenation.
Molecular hydrogen cannot break -bond however
atomic hydrogen can break it. Therefore to
dissociate molecular hydrogen into atomic
hydrogen either heating (from 240-300oC) is
carried out in presence of Nickel catalyst. If
platinum catalyst is used then without heating
hydrogen dissociates.

Hydrogention is an exothermic process.

144
2.

Halogenation:
Addition of halogens is called halogenation. It is
carried out in presence of inert solvent like CCl 4.
Halogenation of alkenes produces vicinal
dihaloalkanes.

Halogenation of alkenes with chlorine and bromine


is carried out but not with fluorine because it is too
reactive to control while iodine does not react.
Bromine water (bromine dissolved in water) is
used to detect presence of carbon-carbon multiple
bond (i.e double or triple bond). Bromine adds to
multiple bonded carbons thus reddish colour of
solution disappears. This test is called bromine
water test.
Mechanism:
When halogen molecule approaches to alkene it is
polarized. The +ve end of the halogen molecule pulls electrons and as a result halogen molecule breaks up and
+ve halogen ion (chloronium or bromonium acts as
electrophile) forms a temporary bond with two multiple
bonded carbons.

145
The elecrophile (Bromonium) makes permanent bond with
one of the carbon and leaving +ve charge on other carbon.

The ve ion (nucleophile i.e bromide) attacks


carbonium ion and offers its electrons to positively charged
carbon and makes bond with it.

3.

Hydrohalogenation:
Addition of hydrogen and halogen is called
hydrohalogenation. When alkenes are treated with
halogen acids hydrohalogenation take place.
The order of reactivity of halogen acids towards
this reaction is
HI >
HBr
>
HCl
>
HF

If alkene is unsymmetrical then addition take place


according to Markownikoffs rule. If alkene is symmetric then
only one addition product is possible.

146

Two products are possible.


But
actually only 2-haloalkane will be obtained as
major product. This shows that when alkene is
unsymmetrical then addition take place according
to Markownikoffs rule. Which states
When an asymmetric molecule is added to an
asymmetric alkene or alkyne then the negative
part of the molecule to be added goes to that
multiple bonded carbon which has less number of
hydrogens and vice versa.
In above mentioned later case addition took place
according to Markownikoffs rule. In case-I primary
carbonium ion will be formed while in later case
secondary carbonium ion will be formed. The
stability of carbonium ions is
Ter-carbonium ion > Seccarbonium ion > Pri-carbonium ion
As in case-II stable carbonium ion is formed so
addition takes place according to Markownikoffs rule.

147
Mechanism:
When halogen acid molecule approaches to alkene its
+ve end pulls -electrons and as a result halogen acid
molecule breaks up and
+ve hydrogen ion (acts as
electrophile) forms a temporary bond with two multiple
bonded carbons.

The elecrophile (Hydrogen) makes permanent bond with one


of the carbon and leaving +ve charge on other carbon.

4.
Addition of Hypohalous Acid:
When alkenes are treated with aqueous solution of
hypohalous acids HOX addition reaction take
place to give halohydrins (haloalcohols).
The order of reactivity of halogen acids towards this
reaction is
HOF >
HOCl
>
HOBr
>
HOI
Hypofluorous acid
Hypoclorous
acid
Hypobromous acid Hypoiodous acid
Hypoiodous acid is nonreactive in this reaction and
will not show this reaction.

148
If alkene is unsymmetrical then addition take place
according to Markownikoffs rule. If alkene is symmetric then
only one addition product is possible.

Both possibilities gave same product.


But if alkene is asymmetric then two addition products
are possible.

Two products are possible.


But actually only 1- Chloro2propanol will be obtained as major product. This
shows that when alkene is unsymmetrical then
addition take place according to Markownikoffs
rule.

149
5.

Addition of Sulphuric Acid:


When alkenes are treated with cold concentrated
H2SO4 addition of acid take place.

In
asymmetric
alkenes addition takes place according to
Markownikoffs rule.
The alkyl hydrogen sulphates on dilution with
water and boiling give alcohols

Alkyl hydrogen sulphate


Alcohol
As acid is replaced by water so actually addition of
water has taken place, therefore, the reaction is
called Hydration of alkenes.
6.

B.

Reaction with dilute Sulphuric acid:


When ethene is treated with dilute (10%) H2SO4 in
presence of mercuric sulphate hydration occurs.

Oxidation Reactions:

The -bond in alkenes is a weak bond and .electrons are loosely bound to carbon nuclei hence are
susceptible for the attack of oxidizing agents. Therefore

150
oxidizing agents can easily oxidize alkenes. Some oxidation
reactions of alkenes are following.
1.

Combustion:
Alkenes on burning produce CO2 and H2O vapours
along with liberation of heat.
This is oxidation reaction.

2.

Ozonolysis:
Ozone is highly reactive so it reacts vigorously
with alkenes and produce corresponding alkylene
ozonide. This is oxidation reaction. Alkylene
ozonide then on reaction with Zinc dust in
presence of water reduces to some aldehyde or
ketone or mixture of the two.

As water is recovered so it is acting as catalyst.


3.

Epoxide Formation:

When a mixture of alkene and air is passed over


heated silver oxide catalyst, an atom of oxygen adds to
alkene molecule and alkylene epoxide is formed. This is
oxidation reaction.

151

From these epoxides


glycols can be prepared.
4.

Hydroxylation:
When alkenes are treated with dilute alkaline
KMnO4 solution hydroxylation of alkenes occurs
and as a result vicinal glycols (Vicinal dihydroxy
alcohols) are produced. This is also an oxidation
reaction. This reaction could be used as
identification for presence of carbon-carbon
multiple bonds and is known as
Baeyers test. Decolourization of pink colour of
KMnO4 indicates the presence of carbon-carbon
double or triple bond.

C.

Polymerization:
When ethene is subject to a pressure of 1000 atm
it liquefies. Then on heating liquid ethane to a
temperature of 100-300oC it polymerizes to
polyettylene or polythene. If catalysts like
aluminium
triethyl
Al(C2H5)3
or
titanium
tetrachloride TiCl4 are used a good quality
polythene is obtained.

152

Polythene is a plastic.
Uses of Ethene:
Ethene is an important member of alkene family and it
has many uses.
1. On burning mixed with oxygen gives oxyethylene
flame which is used for welding and cutting metals
2. For artificial ripening of green fruits.
3. For making mustard gas which is used in chemical
weapons. It was used in first world war.

Actually it is not gas but liquid that disperse as mist in air.


It has mustard like odour. It is a powerful vesicant i.e. causes
blisters.
4. It is used as general anaesthetic.
5. For manufacturing polythene, a plastic used for bags,
boxes, cables, toys etc.
6. For making glycol used as antifreeze.
7. For making ethylene dichloride used as solvent.
8. For making ethylene oxide used as fumigant.
9. For making ethyl alcohol.
Isomerism:
It is a Greek word, Iso means same and mer means
molecular unit.

153
The phenomenon of existence of different compounds with
same molecular formula but different structural formulae is
called isomerism and the compounds are called isomers.
Isomers differ in physical or chemical or in both properties.

Chiral Center
A structural feature within a molecule that is responsible for its
chirality is called chiral center of molecule. A carbon atom
which is bonded to four different groups is called chiral carbon
or asymmetric carbon atom. For example lactic acid here
carbon is chiral which is attached to four different groups like
left side methyl, upper hydrogen, lower hydroxyl and right
carboxylic group.
Optical Isomerism
Those organic compounds which have the same structural
formula but they can rotate the plan of plane polarized light to
any direction are called optical isomers. While the activity to
rotate the plan of polarized light in opposite direction by
compound is called optical activity. If the light is rotate to right
or clockwise it is called dextro rotatry denoted with positive

sign and if to the

154
left side than it is called levo rotatry and denoted with
negative sign.
Types of Isomerism:
There are two major types of isomerism.
A)

Structural Isomerism:

The phenomenon of existence of different


compounds with same molecular formula but different
arrangements of atoms or group of atoms in structural
formulae is called structural isomerism and the compounds
are called structural isomers.
It is further divided into four types.
(i)

Chain Isomerism:

The phenomenon of existence of different


compounds with same molecular formula but different carbon
chains or skeletons is called chain isomerism and the
compounds are called chain isomers.

Alkanes usually show chain isomerism. Lower alkanes


having 3 or less carbons do not show isomerism.

155
(ii)

Position Isomerism:

The phenomenon of existence of different


compounds with same molecular formula but different
positions of the functional groups is called position isomerism
and the compounds are called position isomers.

(iii)
Functional Group Isomerism:
The phenomenon of existence of different
compounds with same molecular formula but different
functional groups is called functional group isomerism and the
compounds are called functional group isomers.
e.g (ii)
Glucose

and

Fructose

(iv)

Metamerism:
The phenomenon of existence of different
compounds with same molecular formula but having unequal
number of carbons on two side of functional group is called
metamerism and the compounds are called metamers.
rs,
and amines often show metamerism.

Ethe
ketones

156
(V)

Tautomerism:

It is special type of isomerism which is functional


group isomerism, in which the isomers are in dynamic
equilibrium with each other.
B)

Geometric Isomerism (Cis-trans isomerism):

The phenomenon of existence of different


compounds with same molecular and structural formula but
differ only in position of identical groups in space is called
geometric isomerism or cis-trans isomerism and the
compounds are called geometric isomers or cis-trans
isomers.
Carbon atoms joined by single bond are capable of free
rotation about the bond. But carbon atoms joined by double
bond are not capable of free rotation about double bond as it
need first to break pi-bond which requires energy comparable
to that which needs in chemical reactions. This lack of
rotation about double bond gives rise to geometric isomerism.

157
Alkynes:
Alkynes are open chain unsaturated hydrocarbons
having general formula CnH2n - 2. They have at least one
carbon-carbon triple bond. First member of this family is
acetylene, the other members of the family are considered as
derivatives of acetylene and are hence called acetylenes.
General Methods of Preparation of Alkynes:
1.

By dehydrohalogenation of vicinal dihaloalkanes:


Removal of hydrogen and halogen is called
dehydrohalogenation. When vicinal dihalides are
heated with alcoholic solution of KOH, hydrogen
and halogen atoms are removed from adjacent
carbons and in two steps alkynes are produced.

2.
Dehalogenation of Tetrahaloalkanes:
Tetrahaloalkanes on treating with active metals
produce alkynes. Usually Zinc dust is used for
delaogenation.

158

3.

4.
(i)

By Haloforms:
By heating haloforms (chloroform or iodoform) with
silver powder acetylene is produced.

Commercial preparation of Acetylene:


By hydrolysis of Calcium carbide:
Acetylene is commercially prepared by
hydrolysis of calcium carbide. For this purpose
calcium carbide is added to water.

159

General Physical Properties of Alkynes:


1. At room temperature and pressure 1st three alkynes (i.e.
from C2 to C4) are colourless gases next eight members i.e
from C5 to C12 are colourless liquids while alkynes from C 13
and onward are colourless solids.
2. They are odourless except ethyne which has garlic like
smell.
3. The melting and boiling points of alkynes increase with
increase of molecular weight.
4. More is the number of branches in alkynes lower will be the
boiling points.
5. Alkynes are insoluble in water but dissolve freely in organic
solvents like ether, benzene, carbon tetrachloride etc.

Structure of Alkyne
Ethyne has triply bonded carbon atoms are sp hybridized.
The electronic configuration of carbon is 1s2, 2s2, 2p2. Its
valence shell has 2 electrons in s-orbital and one electron in
each of two p-orbitals while the third p-orbital is lying vacant.

160
By absorption of energy one of electron of 2s
promotes to vacant p-orbital and atom becomes in excited
state, which is not stable state. Thus to gain a state of stability
mixing of atomic orbitals take place and energy is lowered.
One s-orbital and one p-orbital are mixed together and give
two sp hybridized orbitals. These two sp hybrid orbitals are
identical in shape and energy and each has a single electron
in it. Also two unhybridized p-orbitals each have single
electrons in it. So carbon is tetravalent and not divalent.
The half filled s-orbitals of one hydrogen atom overlap with
half filled sp hybrid orbital of one carbon while half filled sorbitals of other hydrogen atom overlap with half filled sp
hybrid orbital of second carbon forming total two C-H sigmabonds, one with each carbon. As overlapping have taken
place on bond axis so two C-H sigma bonds are produced.
The two C-H sigma bonds are formed due to sp-s
overlapping.
The remaining one sp hybrid of each carbon overlaps among
themselves on bond axis thus forming C-C sigma bond. This
bond is formed due to sp-sp overlapping.
The two unhybridized p-orbitals (one of each carbon) are
parallel to each other so they overlap side wisely (i.e.
laterally) and form pi-bond. Similarly the other two
unhybridized p-orbitals (one of each carbon) are also parallel
to each other so they also overlap side wisely (i.e. laterally)
and form another pi-bond. The two pi-bonds are formed due
to p-p overlapping. Pi-bonds are week bonds and are easy to
break hence ethyne is reactive.
Bond angle between CC
o
and C-H bond is 180 . The
C-H
bond
length
is
-10
1.08x10 m or 1.08 Ao.
While CC bond length is
-10
1.20x10 m or 1.20 Ao.

161
Chemical Properties of Alkynes:
The reactivity order of aliphatic hydrocarbons is
Alkenes
>
Alkynes
>
Alkanes
It means that alkenes are most reactive in this series.
They have a double bond which consists of a strong sigma
() bond (bond energy = 83 Kcal/mol) and a weak pi ()-bond
(bond energy = 63 Kcal/mol). The density of -electrons is
high above and below the bond axis. In other words electrons are away from the nuclei of the carbon atoms so
hold of nuclei is less on them. Thus they are exposed to
electrophilic attack. Thus an electrophile can easily attack and
can break bond by using less energy and therefore alkenes
are more reactive. Alkynes are also reactive due to same
reason but less than alkene. In alkynes electron density
between two triply bonded carbon nuclei is more than that in
doubly bonded carbons in alkene so triple bond is shorter
than double bond and hold of carbons nuclei on pi-electrons
is more in alkynes and thus alkynes are less reactive than
alkenes.
Alkynes being unsaturated compounds mostly shows
addition reactions. Beside addition reactions they also show
oxidation reactions. An oxidizing agent can remove their
loosely bound -electrons.
The reactions of alkynes can be divided into four
categories.
A.

Addition Reactions:

Alkynes being unsaturated compounds mostly show


addition reactions and the addition is electrophilic addition.
Mechanism:
A polar or temporarily polarized molecule approaches
to alkyne and +ve end of the molecule pulls its -electrons as

162
a result reagent molecule breaks up and its +ve ion
(electrophile) forms a temporary bond with two multiple
bonded carbons.

The elecrophile makes permanent bond with one of the


carbon and leaving +ve charge on other carbon.

The ve ion (nucleophile) attacks carbonium ion and offers its


electrons to positively charged carbon and makes bond with
it.

Similarly addition of second molecule talk place.


Some addition reactions of alkynes are following.
1. Hydrogenation:

163
Addition of hydrogen is called hydrogenation.
Molecular hydrogen cannot break -bond however
atomic hydrogen can break it. Therefore to

dissociate molecular hydrogen into


atomic hydrogen either heating (from 240-300oC)
is carried out in presence of Nickel catalyst. If
platinum catalyst is used then without heating
hydrogen dissociates.
But if palladium poisoned by heavy metal salt is used as
catalyst its catalytic ability is less hence concentration of
atomic hydrogen will be less and hydrogenation will be
stopped at production of alkene.

2. Halogenation:
Addition of halogens is called halogenation. It is
carried out in presence of Ferric chloride catalyst.
Halgenation of alkynes produces vicinal tetrahaloalkanes.

164
If Cl2 is taken in excess than 2,2,3,3- tetrachloro
butane will be major product but if 2-butyne is in excess then
2,3- dichloro-2- butene will be major product.
Chlorine and bromine add readily while iodine reacts slowly.

Mechanism:
Ferric chloride
chlorine or bromine.

(catalyst)

polarizes

halogen

i.e.

The +ve end of the halogen molecule pulls electrons and as a result halogen molecule breaks up and
+ve halogen ion (chloronium or bromonium acts as
electrophile) forms a temporary bond with two multiple
bonded carbons.

The elecrophile (halonium ion) makes permanent bond with


one of the carbon and leaving +ve charge on other carbon.

The ve ion (nucleophile i.e halide ion) attacks carbonium ion


and offers its electrons to positively charged carbon and
makes bond with it.

3. Hydrohalogenation:

165
Addition of hydrogen and halogen is called
hydrohalogenation. When alkynes are treated with
halogen acids hydrohalogenation take place. In
case of asymmetric alkynes addition follows
Markownikoffs rule. However in case of symmetric
alkynes only second addition is according to
Markownikoffs rule.
The order of reactivity of halogen acids towards
this reaction is
HI >
HBr
>
HCl
>
HF

Mechanism:
It follows same mechanism as in other addition
reactions of alkynes.

4. Addition of Water (Hydration):


When ethyne is treated with dilute (10%) H 2SO4 in
presence of mercuric sulphate hydration occurs.
Addition of water take place at about 80oC. In
asymmetric alkynes Markownikoffs rule is
followed.

Vinyl alcohol is unstable so it undergoes rearrangement to


form aldehyde.

166

Alkynes other than ethyne on hydration give ketones

The unsaturated alcohol is unstable so it undergoes


rearrangement to form ketone..

B.

Oxidation Reactions:

The -bond in alkynes is a weak bond and .electrons are loosely bound to carbon nuclei hence are
susceptible for the attack of oxidizing agents. Therefore
oxidizing agents can easily oxidize alkynes. Some oxidation
reactions of alkynes are following.
1. Combustion:
Alkynes on burning produce CO2 and H2O vapours
along with liberation of heat.
This is oxidation reaction.
2. Oxidation by KMnO4:
When alkynes are treated with dilute alkaline
KMnO4 solution hydroxylation of alkynes occurs
and as a result polyhydric alcohol is produced.
This is an oxidation reaction.

167

This A polyhydric alcohol is not stable so it undergoes


dehydration to produce aldehyde.

KMnO4 further oxidizes aldehyde to carboxylic acid.

This reaction could be used as identification for presence of


carbon-carbon multiple bonds and is known as Baeyers test.
Decolourization of pink colour of KMnO4 indicates the
presence of double or triple bond.

C. Acidic Reactions:
All the terminal alkynes show acidic behaviour. In these
alkynes Hydrogen is bonded to carbon due to sp-s
overlapping. The sp-hybrid orbital has more s-character
as compared to sp2 and sp3 hybrid orbitals. So sp-hybrid
orbital is shorter and thus shared pair of electrons is
shifted more towards carbon rendering more ve charge

on it and consequently more +ve charge on hydrogen as


compared to that in alkenes and alkanes. Therefore

168
terminal alkynes are capable of donating H+ ion (proton)
and are acidic in nature. Alkynes other than terminal
alkynes have no hydrogen attached to sp-hybridized
carbon so they are not acidic.
So terminal alkynes acting as acid donates proton (s) and
react with strong bases.
Alkynes are very weak acids, which is clear from acidic
strength order given below
H2O > HCCH > NH3
Some of the acidic reactions of alkynes are
(i)

When terminal alkynes are treated with sodium


amide or potassium amide (strong bases) alkynes
donate proton and form acetylide or alkynides.
+
R C C- H ++ NaNH2
R C C Na + NH3
Alkyne
Sodium amide Sodium acetylide
- +
R C C- H + +KNH2
R C C K + NH3
Alkyne Potassium amide Potassium acetylide
Acetylides can be used for making higher alkynes.
R C C Na + CH3I R C C CH3 + NaI
(ii)

On passing terminal alkynes over molten sodium


acid base reaction occurs and acetylides or
alkynides are produced.
+ +
H + C - C - H + + 2Na Na C C Na + H2
Disodium acetylide
Terminal alkynes show acidic reaction with
ammonical silver nitrate and produces white
precipitate of disilver acetylide.
H C C H + 2AgNO3 + 2NH4OH
Disilver acetylide
AgC CAg + 2NH4NO3+ 2H2O
(iii)

169
(White precipitate)
Unlike sodium and potassium acetylides silver
acetylide is a covalent compound.
(iv)

Terminal alkynes show acidic reaction with


ammonical cuprous chloride and produces reddish
brown precipitate of dicopper acetylide.

H C C H + Cu2Cl2 + 2NH4OH
Dicopper acetylide
Cu+C- C-Cu+ + 2NH4Cl + 2H2O
(Reddish brown precipitate)
Copper and silver acetylides on reaction with dilute
mineral acids reproduce alkynes
Ag C C Ag + H2SO4 (dil) HC CH + Ag2SO4
Ag C C Ag + 2HNO3 (dil) HC CH + 2 AgNO3
The reaction of terminal alkynes with ammonical cuprous
chloride and ammonical silver nitrate could be used for
identification of these alkynes.
Uses of Ethyne:
Ethyne is an important member of alkyne family and it has
many uses.
1. On burning mixed with oxygen gives oxyacetylene
flame which is used for welding and cutting metals
2. It is used for artificial ripening of fruits.
3. It is used for manufacturing of alcohol, acetic acid and
acetaldehyde.
4. It is used for manufacture of polymers like poly vinyl
chloride (PVC), poly vinyl acetate (PVA), polyvinyl
ethers etc.
5. It is used for preparing acetylene tetra chloride which
is a solvent for varnishes, resins and rubber.

170
6. It is used for making vinyl acetylene which in turn is
used for preparing synthetic rubber.
Benzene and Substituted Benzenes
Benzene was first discovered by Michael Faradey in
1825. Similarly in 1845 Hoffmann found benzene in coal
tar.Molecular formula of Benzene has been found to be
C6H6. This formula shows that benzene is highly
unsaturated compound having four double bonds,
therefore, benzene should take 4 H2 molecules to become
completely saturated hydrocarbon. But in actual practice
benzene takes 3 H2 molecules to become saturated
compound. Similarly benzene adds on 3 Cl2 molecules to
become saturated. Addition of 3 H2 or 3 Cl2 suggests that
benzene has 3 double bonds and not 4 double bonds. But
open chain structure with 3 double bonds for benzene
does not satisfies the valency.
It is further found that benzene gives only one mono
substituted compound which shows that all Hydrogen
atoms in benzene are equivalent so no matter which
hydrogen is replaced, product will be the same.
These facts led Kekule, a German chemist in 1865 to
givecyclic structure for benzene. He suggested a
hexagonal ring for benzene with alternate double and
single bonds between carbons.
Although Kekule structure can explain many facts about
benzene but there are some objections which cannot be
explained by Kekule structure e.g. according to Kekule
structure we should get two isomers of vicinal disubstituted derivative of
benzene. In one isomer the two carbon atoms having
substituents are linked through double bond while in 2nd
isomer the carbons are linked through single bond. But in
actual practice we get only one vicinal (or 1,2) disubstituted derivative of benzene.

171

Molecular Orbital Theory:


According to this theory each carbon in benzene is sp 2
hybridized. So each carbon has three sp2 hybrid
orbitals and one unhybridized
p-orbital. The sp2 hybrid orbitals
are coplanar having an angle of
o
120 between them. Where
as unhybridized p-orbital is
perpendicular to the plane of
hybridized orbitals. Each of
sp2 hybrid as well as unhybridized
p-orbital has single electron in it.
One sp2 hybrid orbital of each carbon overlaps with s-orbital
of hydrogen, on bond axis forming C-H sigma bond while
other two sp2 hybrid orbitals overlap with sp2 hybrid orbitals
of two neighbouring carbons on the bond axis forming C-C
sigma bond with each carbon. Thus six carbons and six
hydrogen atoms form a coplanar hexagonal ring. Bond angle
between any two sigma bonds is 120o
Each carbon has an unhybridized
p-orbital which is at right angle to
plane of hexagonal ring having one
lobe above the plane and other
below the

172

Plane. The p-orbitals are parallel to each other so each porbital overlaps equally to the p-orbitals of two adjacent
carbons forming a special -bond system. The overlapping is
laterally i.e. -overlapping. Each -electron is attracted
equally by six carbon nuclei, therefore -bond in benzene is
delocalized -bond. As the lobe of p-orbitals are above and
below the plane of hexagonal ring so two electron clouds are
formed above and below. Thus benzene molecule resembles
a sandwich, the two electronic clouds are like two slices of
bread and hexagonal ring is like meat etc between slices.
Molecular orbital picture of benzene can explain all the
properties of benzene which otherwise could not be explained
on the basis of Kekule or other structures. As each -electron
is attracted by six carbon nuclei so it is very much resistant to
oxidizing agents and same is the reason for not occurrence of
addition reactions in benzene. Further according to this
picture all carbons are equivalent and bond length of any C-C
o
bond is 1.39A . This picture also account for lower energy
than the one calculated by Kekule structure. The difference
between energy of molecular orbital structure of benzene and
Kekules structure is called delocalization energy and it is
36kcal/mol or 151kJ/mol. It is same as is resonance energy.
As delocalization energy is high so benzene is stable. In short
molecular orbital picture is best description of benzenes
structure.
Resonance Theory:
According to this theory some molecules are represented by
two or more structures and the actual structure is hybrid and
weighed average of these. There are certain molecules which
cannot be represented by single structure, so we write

173
various possible structures for such molecules. These
possible structures are called resonating structures. The real
structure is weight average of these resonating structures and
is called resonance hybrid.
Each resonating structure contributes to real structure. Some
structures contribute more (Major contributors) and other
contributes less (Minor contributors). More is the stability of a
resonating structure more is its contribution to resonance
hybrid (real structure).
All structures proposed for benzene by different people
contributes but Kekules structures are major contributing

structures
for resonance hybrid of
benzene. Kekules structures contribute about 80% to
resonance hybrid.
It should be clear in mind that neither half benzene molecules
have one Kekules structure and half have other nor benzene
molecules have for some time one structure and for some
time other structure. But in fact all benzene molecules have
only one structure for all the time and that is resonance
hybrid. The resonance hybrid is imaginary structure which is
obtained by mental combination of resonating structures.
Greater is the contribution of resonating structure more is its
resemblance with resonance hybrid.
The resonance hybrid is always lower in energy than
resonating structures, therefore, it is stable. The difference in
energy of resonance hybrid and that of most stable
resonating structures (Kekules structures) is called
resonance energy. This resonance energy is the same as is
delocalization energy in Molecular orbital theory. Resonance

174
energy of benzene is 36 k cal/mol or 151 kJ/mol, which is
high and thus benzene is stable compound.
Stability of Benzene:
Benzene has extraordinary stability and it is due to
delocalization of pi-bonds.
Cyclohexane is when hydrogenated to get cyclohexane, 28.6
kcal/mol or 119.5 kJ/mol heat is liberated.
+ H2

H = -28.6 kcal/mol or -119.5 kJ/mol

1,3-Cyclohexadiene is when hydrogenated to get


cyclohexane, double amount of heat is liberated.
+ 2H2

H = -57.4 kcal/mol or -239 kJ/mol

1,3,5-Cyclohexatriene is when hydrogenated to get


cyclohexane, triple amount of heat is liberated.
+ 3H2

H = -85.8 kcal/mol or -358.5 kJ/mol

But when Benzene is hydrogenated, 49.8 k cal/mol or 208


kJ/mol heat is liberated. It means that benzene shows 36
kcal/mol or 150 kJ/mol less energy than expected. The lower
heat of hydrogenation of benzene than the calculated one is
the cause of stability of benzene and is called resonance
energy
+ 3H2

H = -49.8 kcal/mol or -208 kJ/mol

Preparation/Extraction of Benzene:
Benzene is obtain by two natural sources and can also be
prepared from acetylene.

175

From Coal:
Coal is a black color mineral found under earth crust. It is a
mixture of organic and in organic substances. Its destructive
distillation gives four fractions. Then on fractional distillation of
coal tar again four fractions are obtained. These are shown
below. Coal tar contains about 1.6% benzene and about 0.5%
homologues of benzene.
Light oil contains Benzene. Further fractional distillation gives
benzene and its homologues.
Benzene obtained from light oil is 70% pure and is suitable for
commercial use but for analytical purposes its purification is
needed.
Purification of benzene: For this purpose benzene is frozen at
o
5 C, mostly impurities are left as liquid and are removed by
filtration. But still sulphur impurities known as thiophenes are
left. Benzene is again liquefied and is mixed with
concentrated sulphuric acid and is shaken well. The sulphur
impurities are get dissolved in the acid. The mixture on
standing separates into two layers which are separated by
separating funnel.

176

Physical Properties of Benzene:


(i)
Benzene is a colourless liquid.
(ii)
It has a characteristic smell.
o
(iii)
Its boiling point is 80 C and melting point is 5.5
o
C.
(iv)
Its density is 0.879 g/cm3.
(v)
It is immiscible with water.
(vi)
It is highly flammable.
(vii)
It is a good organic solvent.
Chemical Properties of Benzene:
Benzene like alkanes is less reactive. It is difficult to
break its pi bond system. Mostly reactions of benzene like
that of alkanes are electrophilic substitution reactions. Also its
oxidation at ordinary conditions is very difficult. In electrophilic
substitution reactions its aromaticity is retained however in
oxidation, reduction and addition reactions its aromaticity is
lost.
Reactions of benzene are divided into four categories.
(A)

Electrophilic Substitution reactions:

Electron loving species or reagent is called


electrophile. It could be some cation or a molecule which is
+
+ +
+
+
+
electron deficient e.g. H , NO2 , R , R3C , HSO3 , CH3CO ,
AlCl3 etc.
Electron donating species or reagent is called
- - nucleophile e.g. CN , X , OH , OR, SR, H C C , NH3,
H2O etc.

177
Benzene and other aromatic compounds mostly shows
electrophilic substitution reactions. Electrophilic substitution
reactions in benzene take place through following mechanism
involving three steps.
Step-I Generation of strong electrophile:
Only strong electrophile can attack the -electrons of
benzene and cations are strong electrophiles.
Therefore catalysts are used to dissociate reagent
molecules for producing cations.
E Nu

C Nu

Step-II Attack of Electrophile on Aromatic Ring:


In this step electrophile attacks the aromatic ring
producing phenonium ion. The positive charge on phenonium
ion is delocalized over the benzene ring thus the ion is stable.
However this ion is less stable than aromatic ring.
Furthermore this ion is non aromatic.

Step-III:
Approach of Nucleophile
When nucleophile approaches phenonium ion then
there are two possibilities of giving final product.
(a)

One possibility is that nucleophile gets attached to


phenonium ion and gives addition product.

(b)

Second possibility is that phenonium give a proton


and form aromatic compound.

178
For phenonium ion, it is energetically more preferable to
lose proton to give an aromatic substitution product than
to give a non-aromatic addition product. Thus this reaction
will occur.
(i)

Nitration:

o
Benzene on reaction with conc HNO 3 at 50-60 C
in presence of sulphuric acid produces Nitro benzene.

Nitration of benzene gives mono substituted product.


Mechanism:
Step-I Generation of strong electrophile:
Nitric acid on reaction with sulphuric acid produces
nitronium ion which act as strong electrophile.
+
+ +
HO NO2 + H OSO2OH NO2 +
OSO2OH + H2O
Step-II Attack of Electrophile on Aromatic Ring:
+
In this step electrophile (NO2 ) attacks the aromatic
ring producing phenonium ion. The positive charge on
phenonium ion is delocalized over the benzene ring thus the
ion is stable. However this ion is less stable than aromatic
ring. Furthermore this ion is non aromatic.

179
Step-III:

Approach of Nucleophile or Removal of proton


When nucleophile ( OSO2OH) approaches
phenonium ion it gives a proton and form
nitrobenzene. While sulphuric acid i.e. catalyst is
reproduced.

(ii)
Halogenation:
Benzene reacts with halogens in two different ways
under two different conditions i.e. in presence of direct
sunlight and in diffused sunlight using catalyst.
When benzene is treated with halogens in
presence of FeBr3 or AlCl3 it gives substitution product i.e.
halo benzene.

Halogenation of benzene gives mono substituted product.


Mechanism:
Step-I Generation of strong electrophile:
Chlorine on reaction with AlCl3 produces Chloronium
ion which act as strong electrophile.
+
+
Cl Cl + AlCl3

Cl
+ AlCl4
Step-II Attack of Electrophile on Aromatic Ring:
+
In this step electrophile (Cl ) attacks the aromatic ring
producing phenonium ion. The positive charge on phenonium
ion is delocalized over the benzene ring thus the ion is stable.

180

However this ion is less stable than aromatic ring.


Furthermore this ion is non aromatic.
Step-III:

Approach of Nucleophile
When nucleophile (AlCl4 ) approaches phenonium ion it gives
a proton and form Chloro benzene. While AlCl 3 i.e. catalyst is
reproduced.

(iii)

Sulphonation:
Benzene reacts with fuming sulphuric acid and
gives benzene sulphonic acid, the process is called
sulphonation.

Sulphonation of benzene gives mono substituted product.


Mechanism:
Step-I Generation of strong electrophile:
Sulphuric acid molecule dissociates in presence of
other molecule to produce cation which act as strong
electrophile.

181
- +
+ +
HO SO2OH + H OSO2OH HOSO2
+ OSO2OH + H2O
Step-II Attack of Electrophile on Aromatic Ring:
+
In this step electrophile (HOSO2 ) attacks the
aromatic ring producing phenonium ion. The positive charge
on phenonium ion is delocalized over the benzene ring thus
the ion is stable. However this ion is less stable than aromatic
ring. Furthermore this ion is non aromatic.

Step-III:

Approach of Nucleophile
When nucleophile (HOSO2O ) approaches
phenonium ion it gives a proton and form benzene
sulphonic acid.

(iv)

Friedel-Crafts Reactions:
The alkylation and acylation of benzene are called
Friedel Crafts reactions.
(a) Alkylation:

When benzene is treated with alkyl halide in


presence of FeBr3 or AlCl3 it gives substitution product i.e.
alkyl benzene.

182
Alkylation of benzene does not stop at the stage of mono
alkylation rather further alkylation will occur.
Mechanism:
Step-I Generation of strong electrophile:
Alkyl halide on reaction with AlCl 3 produces Cabonium
ion which act as strong electrophile.
+
+
CH3 Cl + AlCl3
CH3
+
AlCl4
Step-II Attack of Electrophile on Aromatic Ring:
+
In this step electrophile (CH3 ) attacks the aromatic
ring producing phenonium ion. The positive charge on

phenonium ion is delocalized over the benzene ring thus the


ion is stable. However this ion is less stable than aromatic
ring. Furthermore this ion is non aromatic.

Step-III:

Approach of Nucleophile
When nucleophile (AlCl4 ) approaches phenonium ion it gives
a proton and form Alkyl benzene. While AlCl 3 i.e. catalyst is
reproduced.

183
(b) Acylation:
When benzene is treated with acyl halide in
presence of FeBr3 or AlCl3 it gives
substitution
product i.e. aromatic ketone.

Acylation of benzene gives mono substituted product.


Mechanism:
Step-I Generation of strong electrophile:
Acyl halide on reaction with AlCl3 produces acylium
ion which act as strong electrophile.

Step-II Attack of Electrophile on Aromatic Ring:


+
In this step electrophile (CH3CO ) attacks the
aromatic ring producing phenonium ion. The positive charge
on phenonium ion is delocalized over the benzene ring thus
the ion is stable. However this ion is less stable than aromatic
ring. Furthermore this ion is non aromatic.

Step-III:

Approach of Nucleophile

184
When nucleophile (AlCl4 ) approaches phenonium ion it gives
a proton and form Aromatic ketone. While AlCl3 i.e. catalyst is
reproduced.

(B)

Oxidation Reactions:
The - bond system of benzene is very strong so
it is quite resistant to oxidizing agents. However at higher
temperatures it may oxidize.
(Page-11)
(i)

Combustion:

When benzene is burnt in air, it burns with smoky


flame producing carbon dioxide water vapours.
2C6H6 + 15O2

12CO2 + 6H2O
(ii)

Oxidation by Strong Oxidizing Agent:

Benzene cannot be oxidized by strong oxidizing agents


like KMnO4 or K2Cr2O7. However carbon of side can be
oxidized to carboxylic acid by these oxidizing agents.
Whatever is the length of alkyl group of alkyl benzene the
oxidation product will be benzoic acid.

185
Ethyl benzene
Catalytic Oxidation:

(iii)

Benzoic acid

When benzene is strongly heated with air in


presence of vanadium oxide catalyst it oxidizes to
maleic anhydride. In this reaction aromatic ring is
destroyed.

The maleic anhydride on reaction with water


produces maleic acid.
(C)

Addition Reactions:
Benzene shows only few addition reactions.
(i)

Hydrogenation:
When benzene is treated with hydrogen
addition of hydrogen takes place and
aromaticity is lost.
Pt
+

(ii)

3H2

o
Ni [200 C]

Cyclohexane
Halogenation:
When benzene is treated with Cl2 or Br2 in
presence of direct sunlight addition of these
halgens take place and aromaticity is lost.

186

+
(D)

3Cl2

Sunlight

Reduction:
When benzene is treated with hydrogen its
reduction occurs due to addition of hydrogen
and aromaticity is lost.
Pt
+

3H2

o
Ni [200 C]
Cyclohexane

Effect of a Substituent on further Substitution:


A substituent present on aromatic ring influences
further substitution in two ways
(1) Orienting effect
(2) Effect on reactivity of benzene ring
1.

Orienting Effect or Directive Influence:


If a substituent is already present on benzene ring,
then it directs the next coming group to a particular
position on the aromatic ring. It could be proved by an
experiment.
If we perform nitration of benzene first and then
chlorination we get m-Chloro Nitro Benzene.

187
On other hand if we perform chlorination of benzene first and
then nitration we get o-Chloro Nitro Benzene and p-Chloro
Nitro Benzene.

Nitro Benzene
This experiment shows Nitro group sends the next group to
meta position while Chloro group sends the next group to
ortho and para positions. Thus we can divide the substituent
of benzene into two categories meta orienting groups and
orto-para orienting groups
Ortho-Para Orienting Groups
Orienting Groups
1.
-OH (activating group)
(deactivating group)
2.
-R
(activating group)
(deactivating group)
3.
-OR (activating group)
(deactivating group)
4.
-NH2 (activating group)
(deactivating group)
5.
-C6H5 (activating group)
(deactivating group)

Meta1.

-NO2

2. -COOH
3.

-CHO

4. -CN
5.

-COR

188
6.

-NR2 (activating group)


(deactivating group)
-X
(deactivating group)*

7.

+
6. NH4
7.

+
HSO3 (deactivating group)
Usually in meta-orienting groups the key atom is either
multiple bonded to another atom or it is positively charged.
1.

Effect on Reactivity Of Benzene Ring:


The reactivity of benzene ring is affected by presence
of a substituent on the ring. Usually orto-para orienting
groups except halogens increase the reactivity of the
ring and are hence called activating groups. On other
hand meta orienting groups
decrease the reactivity of the ring so they are termed
as deactivating groups.
This can be proved by a simple experiment.
o
Nitration of benzene occurs at 50-60 C

Second nitro group can only be introduced on very strong


heating because the already present nitro group being
deactivating group decreases the reactivity of ring so
introduction of second nitro group become difficult.

189
To introduce third nitro group is very difficult.
o
On other hand nitration of Toluene occurs at 30-40 C, at
o
60-70 C two nitro groups get attached to the ring and at
o
100 C even three nitro groups get attached to the ring. So
nitration of toluene is easier than that of benzene.

These reactions show that nitration of toluene is even easier


than benzene. This is due to the reason that already present
methyl group being activating group increases the reactivity of
ring so nitration of toluene become easier.

190

Explanation:
Ortho-Para Orienting Groups:
Ortho-para orienting groups are electron sending groups, so
they send electrons to the aromatic ring due to which
negative charge appears on ortho and para positions as
shown below.

Due to appearance of negative charge on ortho and


para positions, the availability of electrons on these
position become more than that on meta position.
Definitely electrophile attacks where availability of
electrons is more thus it attacks on ortho and para
positions.
Furthermore ortho-para orienting groups increase the
reactivity of aromatic ring. The reactivity of the ring
increases due to two reasons.
(i)

(ii)

Ortho-para orienting groups being electron


sending groups send electrons to the ring and
increase the availability of electrons on the ring
so the approach of electrophile to ring
becomes easy and hence reactivity increases.
Presence of ortho-para orienting groups on the
ring increase the stability of intermediate
phenonium ion thus reactivity increases.

191

Meta Orienting Groups:


Meta orienting groups are electron puling groups, so
they pull electrons from the aromatic ring due to which
positive charge appears on ortho and para positions
as shown below.

Due to appearance of positive charge on ortho and


para positions, the availability of electrons on these
position become less than that on meta position.
Definitely electrophile attacks where availability of
electrons is more thus it attacks on meta position.
Furthermore meta orienting groups decrease the
reactivity of aromatic ring. The reactivity of the ring
decreases due to two reasons.
(i)

(ii)

Meta orienting groups being electron pulling


groups pull electrons from the ring and
decrease the availability of electrons on the
ring so the approach of electrophile to ring
becomes difficult and hence reactivity
decreases.
Presence of meta orienting groups on the ring
decreases the stability of intermediate
phenonium ion thus reactivity decreases.

192
Chapter 17: Alkyl Halides or Halo alkanes
The halo derivatives of alkanes are called alkyl halides
or halo-alkanes. The general formula of alkyl mono-halides or
mono-halo alkanes is
R X or CnH2n+1 X.
Where
R = alkyl radical
X = F, Cl, Br and I
They are divided into three groups on the basis of attachment
of halogen to the primary, secondary or tertiary carbon.

Alkyl halides are very reactive compounds and are thus used
for organic synthesis. They are used to introduce alkyl groups
into other organic molecules.
Structure of Alkyl Halides:
Lets follow the example of
methyl chloride, all the bonds in
methyl chloride are single
covalently attach to central
carbon. So the carbon is sp3
hybridized. During the process
of
bond formation the sp3 hybrid
orbital of carbon atom overlaps
with the half-filled p-orbital of halogen atom to from sigma
bond. Similarly all the bonds are formed which are sigma and
the bond angle formed is perfect 109.50, with tetrahedral
structure.

193
Preparation:
Following are few methods of preparation of alkyl
halides.
i)

By Halogenation of alkanes:
Alkanes on treating with halogens in presence of
o
sunlight or heating at 400 C gives a mixture of
haloalkanes. e.g.
4CH4 + 4Cl2
UV
CH 3Cl + CH2Cl2
+ CHCl3 + CCl4 + 4HCl
But this method is oftenly not used because it is
difficult to separate mixture of haloalkanes.

ii)

By Hydrohalogenation of Alkenes:
The addition of halogen acids is called
hydrohalogenation. Hydrohalogenation of alkenes
produce alkyl halides. The order of reactivity of
halogen acids towards this reaction is
HI > HBr > HCl
Addition of halogen acids to alkenes follows
Markawnikoffs rule.

Here addition took place according to Markownikoffs rule.

194
i)

From Alcohols:

(a) By Reaction of Alcohols with Halogen Acids:


The reaction of alcohols with halogen acids produces
corresponding alkyl halides.

The order of reactivity of halogen acids towards


this reaction is
HI > HBr > HCl
As reaction of HCl is difficult so it needs use of
ZnCl2 catalyst.
Primary, secondary and tertiary alcohols produce
primary, secondary and tertiary alkyl halides.
(b) By Reaction of Alcohols with Phosphorous Halides:
Phosphorous trihalide as well as phosphorous pentahalide
replaces OH from alcohol by halogen and produce
corresponding alkyl halides.

(c) By Reaction of Alcohols with Thionyl Chloride:

195
Alcohols on reaction with thionyl chloride, produce
corresponding alkyl chlorides.

Reactivity of Alkyl Halides:

Bond Energies: To understand the reactivity of alkyl halides


in terms of bond energies. Lets look at the table:
Bond
C-F
C-H
C-Cl

Bond energy
467 kj / mol
413 kj / mol
346 kj / mol

Bond
C-Br
C-I

Bond energy
290 kj / mol
228 kj / mol

The C F bond is highly polar so is stronger bond


and is difficult to break on other hand C I bond is
less polar and is less stronger so easily can be
broken. The electronegativity difference of halogens
with carbon decreases from fluorine to iodine thus
bond strength decreases as a result reactivity
increases. Therefore order of reactivity of alkyl
halides is
R I > R Br > R Cl > R F

The reactivity of alkyl halides also depend upon


nature of alkyl group such that

196
Most of reactions of alkyl halides are nucleophilic substitution
reactions but they also show elimination reactions.
(A)

Nucleophilic
reactions):

Substitution

Reactions

(SN

The alpha carbon is partially positively charged hence is


easily attacked by a nucleophile and as a result
nucleophilic substitution reactions occur.
The reaction in which an atom or group of atoms is
replaced by a nucleophile is called nucleophilic
substitution reaction.

Substrate:
The molecule on which action is
made is called substrate. In above case alkyl halide is
substrate.
Leaving Group: The group which detaches is called
leaving group. In above case X is leaving group and it is
a nucleophile.
Entering Group: Attacking group is called entering group.
In above case OH , SH , OR etc are entering groups.
Rate Determining Step: The slow step of a reaction is its
rate determining step.
Molecularity of a Reaction: Number of molecules or atoms
or ions appearing in the balanced equation of rate
determining step of a reaction is called its molecularity. If

197
one molecule is involved in rate determining step the
reaction is called unimolecular reaction, if two molecules
are involved then it is called bimolecular reaction, for
more than two molecules reaction is called polymolecular
reaction.
Rate of Nucleophilic Substitution Reactions: The rate of
these
reactions
depends-on:
1. Nature of the substrate (Alkyl halide)
2. Nature of the attacking nucleophile
3. Nature of the leaving nucleophile
4. Nature of the solvent
Mechanism of Nucleophilic Reactions:
Alkyl halides may undergo nucleophilic substitution
reactions in two different ways.
(i) Unimolecular Nucleophilic
1
(SN mechanism).

Substitution

Reactions

(ii) Bimolecular Nucleophilic Substitution Reactions (SN


mechanism).

(i) Unimolecular Nucleophilic Substitution Reactions


1
(SN mechanism):
This mechanism involves two steps.
Step-I
In this step formation of carbonium ion takes
place. The alkyl halide molecule dissociates to
produce carbonium ion. This is energy absorbing step
and is slow step.

198

Step-II
In this step nucleophile attacks carbonium ion
from either side i.e from side from which halide has
gone or from opposite side with equal ease. As
leaving group had already gone, also the carbonium
ion thus formed is planar so it allow the nucleophile to
attack on it from both sides with equal ease. We,
thereforeobserve 50% inversion of configuration and
50% retention of configuration.
This is bond formation step so energy is released and
is fast step.

As only one molecule is involved in rate determining step


(slow step) so molecularity of the reaction is one and thus
reaction is unimolecular nucleophilic substitution reaction.
The rate of reaction depends only upon concentration of alkyl
halide and not on that of nucleophile.
Rate [alkyl halide]
Tertiary alkyl halide shows this mechanism. e.g. consider
hydrolysis of tertiary butyl bromide.
Step-I
The tertiary butyl bromide molecule dissociates to produce
carbonium ion. This is energy absorbing step and is slow
step.

199
Step-II
In this step nucleophile i.e OH attacks
carbonium ion from same side from which bromide ion
has gone. In this step energy is released and is fast
step.

(ii)

Bimolecular Nucleophilic Substitution Reactions


2
(SN mechanism):

This is a single step mechanism. In this mechanism bond


breaking and bond formation take place simultaneously. As
soon as nucleophile starts attacking the electrophilic carbon
of the substrate (alkyl halide), leaving group starts breaking
its bond at the same moment.
Nucleophile attacks from the side opposite to the leaving
group. In order to give enough room to nucleophile for its
attack, the electrophilic carbon of substrate changes its
hybridization from tetrahedral sp3 to planar sp2.
During reaction inversion of configuration takes place.

200
Molecularity of the reaction is two as two
particles are taking part in the reaction. Thus it
is
bimolecular
nucleophilic
substitution
reaction.
The rate of reaction depends both upon
concentration of alkyl halide and that of
nucleophile.
Rate [alkyl halide] [nucleophile]
Primary alkyl halide shows this mechanism.
e.g. consider hydrolysis of methyl bromide.

Secondary alkyl halide may show SN1 or SN2 mechanism


depending upon nature of solvent. Polar solvents favour SN1
mechanism while non polar solvents favour SN2 mechanism.
Explanation:
In SN1 mechanism carbonium ion formation take place, so
alkyl halide whose carbonium ion is stable will follow this
mechanism.
Order of stability of carbonium ions is:

201
SN1
1. It is two step reaction.
2.
It
is
unimolecular
reaction.
3. Rate of reaction depends
only on concentration of
alkyl halide.
Rate [alkyl halide]
4. Rate depends on the
structure of alkyl halides in
the following order Ter RX >
Sec RX > Pri RX
5. Reaction is favoured by
polar solvents.
polar solvents.
6. Reaction usually occurs
with weak bases.
7. Carbonium ion formation
take place.
8. Nucleophile can attack
from any side.

SN2
1. It is one step reaction
2. It is bimolecular reaction.
3. Rate of reaction depends
both Upon concentration of
alkyl halide as well as
nucleophile Rate [alkyl
halide] [nucleophile]
4. Rate depends on the
structure
alkyl halides in
the following order
Pri
RX > Sec RX > Ter RX
5. Reaction is favoured by
non
6. Reaction usually occurs
with strong bases.

9. There are 50% chances


of inversion of
configuration.
Some of important nucleophilic substitution reactions of
alkyl halide:
1. Reaction with aqueous KOH:
Alkyl halide on treating with aqueous potassium hydroxide,
show substitution reaction and produce corresponding
alcohol

202

Mechanism:
Ethyl bromide is primary alkyl halide so it will follow SN 2
mechanism

Mechanism:
Ter-butyl bromide is tertiary alkyl halide so it will follow
SN1 mechanism
+
KOH
K
+
OH

203
Step-I
The tertiary butyl bromide molecule dissociates
to produce carbonium ion. This is energy absorbing
step and is slow step.

Step-II
In this step nucleophile i.e OH attacks
carbonium ion from same side from which bromide ion
has gone. In this step energy is released and is fast
step.

2. Franklands Reaction:
The reaction of Zinc with alkyl halide to produce
higher alkane is called Franklands reaction.

204

(B)

Elimination Reactions:

The reaction in which atoms or group of atoms are removed


from two adjacent carbon atoms in the substrate molecule to
form multiple bond is called elimination reaction.
In these reactions two sigma () bonds are lost and as a
result a pi () bond is formed and unsaturated compound is
obtained.
Alkyl halides show -elimination reactions. In these reactions
first a hydrogen atom is removed from -carbon, nucleophile
attacks electrophilic hydrogen attached to -carbon and
removes it so it is called -elimination reaction.

Mechanism of Elimination Reactions:


Elimination reactions of alkyl halides follow two mechanisms.
(i)
(ii)

Unimolecular elimination reactions (E1).


Bimolecular elimination reactions (E2).

1. Unimolecular elimination reactions (E1 Reactions):


This mechanism involves two steps.
Step-I

205
In this step formation of carbonium ion take
place. The alkyl halide molecule dissociates to
produce carbonium ion. This is energy absorbing step
and is slow step.

Step-II
In this step nucleophile attacks hydrogen of carbon (having least hydrogen) and remove it.
Hydrogen detaches as proton leaving electrons
behind, as a result pi () bond is formed.

As only one molecule is involved in rate determining


step (slow step) so molecularity of the reaction is one
and thus reaction is unimolecular elimination reaction.
The rate of reaction depends only upon concentration
of alkyl halide and not on that of nucleophile.
Rate [alkyl halide]
Tertiary alkyl halide shows this mechanism.
2.

Bimolecular elimination reactions (E2 Reactions):


This is a single step mechanism. In this mechanism
the nucleophile attacks and the leaving group leaves
at the same time with the formation of carbon carbon
double bond.

206

Molecularity of the reaction is two as two particles are taking


part in the reaction. Thus it is bimolecular elimination reaction.
The rate of reaction depends both upon concentration of alkyl
halide and that of nucleophile.
Rate [alkyl halide] [nucleophile]
Primary alkyl halide shows this mechanism.
Secondary alkyl halide may show E1 or E2 mechanism
depending upon nature of solvent. Polar solvents favour E 1
mechanism while non polar solvents favour E2 mechanism.
Some of important Elimination reactions of alkyl halides:

1. Reaction with alcoholic KOH:


Alkyl halide on heating with alcoholic potassium hydroxide,
show elimination reaction and produce corresponding alkene.

207
Mechanism:
Ethyl bromide is primary alkyl halide so it will follow E 2
mechanism.

Grignards Reagent (R Mg X):


These are organo metallic compounds. They are very
reactive and are important for synthesis of organic
compounds. They are called alkyl magnesium halides.
Preparation:
They are prepared by heating alkyl halide and
magnesium in presence of completely anhydrous ether.
Alkyl halide, magnesium metal and dry ether are taken in a
round bottom flask. The flask is fitted with a water condenser
carrying a guard tube. The guard tube contain CaCl 2 in it
which absorbs moisture. The flask is heated in a water bath.

208
The reaction at start is slow but then it becomes brisk. The
Grignards reagent is not isolated because it is very reactive
and is oxidized by air.
The reactivity of alkyl halides with magnesium depends both
upon halogen as well as alkyl radical. The order of reactivity
of alkyl halides with magnesium is as follows.
R I > R Br > R Cl
CH3 X > C2H5 X > C3H7 X
Physical State:
Grignards reagents are non volatile colorless solids.
Reactivity:
Grignards reagent are very reactive. Their reactivity is
due to higly polar C Mg bond. Magnesium being metal is
more electropositive so electrons are shifted towards
carbon and renders a partial negative charge on carbon. Thus
this carbon attacks polar molecules at point of low electron
density.

The reactions of Grignard reagents are divided into following


types.
(A)

Nucleophilic Substitution Reactions:

Grignard reagent undergoes nucleophilic substitution


reactions with polar saturated compounds. The nucleophilic
carbon of grignard reagent attacks electrophile centres of
polar molecules.

209

1.

Reaction with compounds containing active hydrogen:

The hydrogen that can be donated as proton is called


active hydrogen. Grignard reagents on reaction with
compounds containing active hydrogen, produce alkane.
(a)

Hydrolysis by water:
Grignard reagent on hydrolysis by water in
presence of ether, produces corresponding alkane.

(B)
Nucleophilic
Reactions:

Addition

Grignard reagent undergoes nucleophilic addition


reactions with carbonyl compounds.

The
addition product thus obtained then on acid hydrolysis gives
useful organic compounds.

1.

Reaction with Aldehydes:

210
Reaction of Grignards reagent with aldehydes
followed by acid hydrolysis produces primary or
secondary alcohol.
(a) Reaction with Formaldehyde:
Reaction
of
Grignards
reagent
with
formaldehyde followed by acid hydrolysis
produces primary alcohol having one more
carbon than that of grignards reagent.

(b)
Reaction
with
Aldehydes
other
than
Formaldehyde:
Reaction of Grignards reagent with aldehydes other
than formaldehyde followed by acid hydrolysis produces
secondary alcohol.

2.
Reaction
with
Ketones:

211
Reaction of Grignards reagent with ketones
followed by acid hydrolysis produces tertiary
alcohol.

3.

Reaction with esters:


Reaction of Grignards reagent with esters
followed by acid hydrolysis produces secondary or
tertiary alcohol.
(a) Reaction with Alkyl Formate:
Reaction of Grignards reagent with alkyl
formate followed by acid hydrolysis produces
secondary alcohol.

The addition product


is not stable thus it undergoes rearrangement and produce
aldehyde

212

The aldehyde thus produced further reacts with Grignards


reagent and gives an addition product which then on acid
hydrolysis produce secondary alchohol.

(b) Reaction with Esters other than Alkyl Formate:


Reaction of Grignards reagent with esters
other than alkyl formate followed by acid
hydrolysis produces tertiary alcohol.

The addition product is not stable thus it undergoes


rearrangement and produce ketone.

213
The Ketone thus produced further reacts with Grignards
reagent and gives an addition product which then on acid
hydrolysis produce tertiary alchohol.

4.

Reaction with Carbon dioxide:


Reaction of Grignards reagent with Carbon
dioxide followed by acid hydrolysis produces
carboxylic acid having one more carbon than
grignard reagent.

214
5.

Reaction with Epoxide:


Reaction of Grignards reagent with epoxide
followed by acid hydrolysis produces primary
alcohol having more carbon(s)..

Amines:
These are nitrogen containing organic compounds.
Amines are the derivatives of NH3 (ammonia) in which one or
more hydrogen atom is been replaced by the similar or
different alkyl group. The functional group may be
Physical Properties of Amines:

1. Low molecular wt amines are generally gases at room


temperature.
2. They have characteristics ammonia like smell
3. They have higher boiling points than alkanes of similar
weight due to presences of stronger hydrogen
bonding.
4. The molecules of primary and secondary amines have
high boiling points as they are capable to from
hydrogen bong among themselves.
5. Molecules of tertiary amines cannot form hydrogen
bonding. Thus have low boiling points than primary
and secondary amines.

215
6. Most importantly all the amines can form the hydrogen
bonding with water molecules due to presence of lone
pair of Nitrogen, thus soluble in water.
Structure of Amines:
As we know that amines are the derivatives of ammonia. So
it has similar structure to that of ammonia that is trigonal
pyramidal shape, with the bond angle of 107.50.
Basicity of Amines:
Amines are basic in nature, its basicity is due to the presence
of lone pair of electrons of Nitrogen atom, due to which it is
capable of accepting proton. According to Bronsted-Lowery
concept proton accepting specie is called base. Similarly
according to lewis concept electron pair donor is called base.
Amines reacts with acid to from salt.

Amines are weak bases and, therefore partially ionizes in


aqueous solution.

Aliphatic amines are stronger bases than ammonia, because


alkyl groups are electron donor and increases the density of
nitrogen. So they increase the power of accepting a proton
from acid. Higher the number of alkyl group greater will be

216
electronic density on nitrogen and higher the power of
accepting proton.
Preparation of Amines
Amines can be prepared by variety of methods. Some of
important are given below:
1. Ammonolysis or Hoffmann Reaction:
The reaction of alkyl halides with alcoholic solution of
ammonia to produce amines is called ammonolysis or
Hoffmann reaction. On heationg mixture of ammonia
and alkyl halide, alkylation of ammonia occurs and
mixture of amines is obtained.

Mechanism:
Formation of Primary amine

217

Formation of Tertiary amine

218
Formation of Quaternary ammonium salt

2. Reduction of Nitroalkane:
Primary amines can be prepared by the reduction of
nitroalkane with Hydrogen in the presence of suitable
catalyst like Pt / Pd or Ni.

3. Reduction of Nitriles:
When nitriles are reduced, they yield the
corresponding amines.

219

Reactivity of Amines:
Amines are reactive mainly due to the presence of lone pair
of nitrogen atom. This lone pair of electron is available to the
electrophile (electron pair deficient specie). On the basis of
this lone pair amines act as nucleophile in nature. These are
important organic compounds. Amines react with no of
different molecules to produce valuable compounds.
1. Reaction of Ammonia with Alkyl Halides:
The reaction of alkyl halides with alcoholic solution of
ammonia to produce amines is called ammonolysis or
Hoffmann reaction. On heationg mixture of ammonia and
alkyl halide, alkylation of ammonia occurs and mixture of
amines is obtained.

2. Reaction of amines with Aldehyde and Ketone:

220
Primary amines react with aldehyde and ketones, yield
condensation product called Imines. These imines are also
called as Schiffs Base.

Making amides from acyl chlorides


Acyl chlorides (also known as acid chlorides) have the
general formula RCOCl. The chlorine atom is very easily
replaced by other things. For example, it is easily replaced by
an -NH2 group to make an amide.
To make ethanamide from ethanoyl chloride, you normally
add the ethanoyl chloride to a concentrated solution of
ammonia in water. There is a very violent reaction producing
lots of white smoke - a mixture of solid ammonium chloride
and ethanamide. Some of the mixture remains dissolved in
water as a colourless solution.
You can think of the reaction as happening in two stages.

221
In the first stage, the ammonia reacts with the ethanoyl
chloride to give ethanamide and hydrogen chloride gas.

Then the hydrogen chloride produced reacts with excess


ammonia to give ammonium chloride.

. . . and you can combine all this together to give one overall
equation:

Making amides from acid anhydrides


An acid anhydride is what you get if you remove a molecule
of water from two carboxylic acid -COOH groups.
For example, if you took two ethanoic acid molecules and
removed a molecule of water between them you would get
the acid anhydride, ethanoic anhydride (old name: acetic
anhydride).

The reactions of acid anhydrides are rather like those of acyl


chlorides except that during their reactions, a molecule of
carboxylic acid is produced rather than the HCl formed when
an acyl chloride reacts.

222
If ethanoic anhydride is added to concentrated ammonia
solution, ethanamide is formed together with ammonium
ethanoate. Again, the reaction happens in two stages.
In the first stage, ethanamide is formed together with ethanoic
acid.

Then the ethanoic acid produced reacts with excess ammonia


to give ammonium ethanoate.

. . . and you can combine all this together to give one overall
equation:

Preparation of Di-azonium Salt:


When primary aliphatic amines are treated with nitrous acid,
they produce highly unstable salts called as diazonium salt.
The solution of phenylamine in hydrochloric acid
(phenylammonium chloride solution) is stood in a beaker of
ice. The sodium or potassium nitrite solution is also cooled in
the ice.
The solution of the nitrite is then added very slowly to the
phenylammonium chloride solution - so that the temperature
never goes above 5C.
You end up with a solution containing benzenediazonium
chloride:

223

The positive ion, containing the -N2+ group, is known as a


diazonium ion. The "azo" bit of the name refers to nitrogen.

224
Chapter 18:
ALCOHOL, PHENOL & ETHERS
Alcohol, Phenol and Ethers are quite similar with each other
in relations to their arrangement of atoms. They are assumed
to be derivatives of water.
Alcohols are hydroxy derivative of aliphatic hydrocarbons.
Classification of compounds having OH functional group:

225

There are two important members of alcohol family and they


are methyl alcohol and ethyl alcohol.
Industrial Preparation of Methyl Alcohol:
Names: Methyl alcohol,Methanol
,
Wood spirit
(Common system)
(IUPAC system)
Methanol can be prepared by following methods.
1.

By Destructive distillation of Wood:


o
When wood is heated at 400-450 C in absence of air
(destructive distillation), three fraction are obtained. These
fractions are gaseous fraction, liquid fraction (Pyroligneous acid) and tar. The liquid fraction contains 3-5%
methanol and 10% ethanoic acid. By fractional distillation
of liquid fraction methanol is obtained.
o
400-450 C

226
Wood
Methanol + Ethanoic acid +
Miscellaneous compounds In absence of air
Commercial or Industrial Preparation of Ethyl Alcohol:
Names: Ethyl alcohol , Ethanol,Spirit of Wine, Grain Alcohol
(Common system)
(IUPAC system)
It is also called simply Alcohol or Spirit.
Ethanol can be prepared by fermentation. of carbohydrates.
The carbohydrates have three classes.
(i)
Monosaccharides: The carbohydrates which do
not hydrolyse are called monosaccharides. They
consist of one sugar unit.
e.g. Glucose (C6H12O6) present in grapes.
Fructose (C6H12O6) present in fruits.
(ii)
Disaccharides: The carbohydrates which on
hydrolysis give two molecules of mono
saccharides are called disaccharides. They consist
of two sugar units.
e.g. Sucrose (C12H22O11) present in Cane sugar
juice and molasses.
Maltose (C12H22O11) present in sprouted grain.
(iii)
Polysaccharides: The carbohydrates which on
hydrolysis give many molecules of mono
saccharides are called polysaccharides. They
consist of many sugar units.
e.g. Starch (C600H1000O500) present in Barley,
Wheat, Rice, maize, Potatoes and many other
grains.
Cellulose (C600H1000O500) present in Saw dust.
Denaturing of Alcohol:
Mixing of methyl alcohol in ethyl alcohol to poison it
and unfit for drinking purpose is called denaturing of alcohol.
Pyridine is also added to develop bad taste. This alcohol is
also called methylated spirit.

227
Physical properties of Alcohols:
(i)
Lower alcohols are colourless toxic liquids having
sweet smell and burning taste.
(ii)
Higher alcohols having more than 12 carbon
atoms are solid.
(iii)
Boiling point of alcohols is higher than
corresponding alkyl halide and alkanes due to
hydrogen bonding in alcohols.
o
(iv)
The boiling point of methyl alcohol is 65 C and
o
that of ethyl alcohol is 78.5 C.
(v)
Their boiling points increases with increasing
molecular masses.
(vi)
Alcohols are readily soluble in water but solubility
decreases in higher alcohols. The solubility of
alcohols is due to hydrogen bonding which is
prominent in lower alcohols but diminishes in
higher alcohols.
(vii)
Lower alcohols are more soluble in water while
higher alcohols are more soluble in organic
solvent.
(viii) Dihydric and aromatic alcohols are less soluble in
water than monohydric alcohols.
(ix)
Lower alcohols dissolve many ionic and polar
solutes easily than higher alcohols.
(x)
Alcohols have no effect on litmus paper.
Structure of Alcohol:
Alcohols are the alkyl derivative of water molecules, as water
molecule has angular structure, same as for alcohol which
has similar geometry like water with bond angle of 1050.
Acidity of Alcohols:
Alcohols are acidic in nature, because the O-H bond is polar
in alcohol due to E.N difference of these two atoms. This
allows the release of proton. Due to acidic nature alcohols
reacts with metals like Na or K to form alkoxide with the
release of Hydrogen gas.

228
Reaction with Sodium metal (Alkoxide formation):
Alcohols are weak acids so they react with sodium metal
which act as base and produce ionic compound alkoxide and
hydrogen gas is liberated.

However alcohols are weak acids with Ka values of 10-16 to


10-18. The alkyl group in alcohols release electrons to oxygen
atom, which increases its partial negative charge hence it
becomes difficult to release proton. That is the reason
alcohols are less acidic than water.
Preparation of Alcohols:
Hydrolysis of Alkyl Halides
Alkyl halide on treating with aqueous potassium hydroxide,
show substitution reaction and produce corresponding
alcohol.

Mechanism:
Ethyl bromide is primary alkyl halide so it will follow
SN2 mechanism

229

By catalytic oxidation of Alkane:


Lower alkanes on heating in air in presence of copper catalyst
and applying pressure, oxidize to mixture of useful products.
Alkanes oxidize to corresponding alcohols.

Hydration of Alkenes:
When alkenes are treated with cold concentrated H2SO4
addition of acid take place.

In asymmetric alkenes addition takes place according to


Markownikoffs rule.
The alkyl hydrogen sulphates on dilution with water and
boiling give alcohols

230
As acid is replaced by water so actually addition of water has
taken place, therefore, the reaction is called Hydration of
alkenes.
Reaction of Grignards Regent with Aldehyde and
Ketone:
When aldehydes are treated with grignad reagents followed
by acid hydrolysis, primary or secondary alcohols are
produced.
(a)

Reaction of Formaldehyde:
Reaction of formaldehyde with Grignards reagents, followed
by acid hydrolysis produces primary alcohol having one more
carbon than that of grignards reagent.

(b) Reaction of Aldehydes other than Formaldehyde:


Reaction of aldehydes other than formaldehyde with
Grignards reagents, followed by acid hydrolysis produces
secondary alcohol.

231

When ketones are treated with grignad reagents followed by


acid hydrolysis, tertiary alcohols are produced.

Reduction of Aldehydes and Ketones:


When aldehydes are treated with hydrogen in presence of Pt
or Ni catalyst addition of hydrogen (hydrogenation) take place
and corresponding primary alcohols are produced.

232

When Ketones are treated with hydrogen in presence of Pt or


Ni catalyst addition of hydrogen (hydrogenation) take place
and corresponding secondary alcohols are produced.

Reaction of R-Mg-X
with Esters:
Reaction of Grignards reagent with alkyl formate followed by
acid hydrolysis produces secondary alcohol.

233

The addition product is not stable thus it undergoes


rearrangement and produce aldehyde.

The aldehyde thus produced further reacts with Grignards


reagent and gives an addition product which then on acid
hydrolysis produce secondary alchohol.

(b)

Reaction with Esters other than Alkyl Formate:


Reaction of Grignards reagent with esters other than alkyl
formate followed by acid hydrolysis produces tertiary
alcohol.

234
The addition product is not stable thus it undergoes
rearrangement and produce ketone.

The Ketone thus produced further reacts with Grignards


reagent and gives an addition product which then on acid
hydrolysis produce tertiary alchohol.

Chemical properties of Alcohols:


Reactivity:
Alcohols react with other reagents in two ways.
(i)
Reactions involving C O bond fission.
(ii)
Reactions involving O H bond fission.
When nucleophile attacks then C O bond fission take place
and when elctrophile attacks than O H bond fission take
place.
The order of reactivity of alcohols when C O bond fission
take place.

235
Tertiary alcohol > secondary alcohol > primary alcohol
The order of reactivity of alcohols when O H bond fission
take place.
Primary alcohol > secondary alcohol > tertiary alcohol
Reactions of alcohols are divided into following categories:
(A)

Reactions in which O H bond fission take place:


Reaction with carboxylic Acid (Esterification):

When alcohol is treated with Carboxylic acid in presence of


conc sulphuric acid, ester is produce. Sulphuric acid absorbs
water and stops reverse reaction.

236
(B)

Reactions in which C O bond fission take place:

1.

Reaction with Halogen acids;

Alcohols react with halogen acids to produce alkyl halide and


water.

Order of reactivity of this reaction depends both upon nature


of alcohol as well as halogen acids.
Tertiary alcohols > Secondary alcohols
> Primary alcohols
HI
>
HBr
>
HCl
This reaction can be used to distinguish between pri, sec and
ter- alcohols and is called Lucas reagent test.
Lucas Reagent Test:
A mixture of conc HCl and anhydrous Zinc chloride is
called Lucas Reagent. When an alcohol is treated with this
mixture corresponding alkyl halide is produced which is
insoluble so causes turbidity.
Tertiary alcohols react rapidly and produce alkyl halide so
they give turbidity immediately.
Secondary alcohols give turbidity within 5-10 minutes.

237
Primary alcohols being least reactive give turbidity only on
heating.

4. Reaction
with Thionyl Chloride:
Alcohols on reaction with thionyl chloride produce alkyl
chloride.

Dehydration of alcohols

When alcohols are heated with excess of conc H2SO4,


o
at 170-180 C they undergo dehydration and produce

corresponding alkenes.
Reaction takes place in two steps. First at room temperature
o
alkyl hydrogen sulphate is produced which then at 170 C

238
undergoes elimination and produce alkene. Hydrogen
sulphates eliminates from alpha () carbon and hydrogen
from beta () carbon.

When excess of alcohols are heated with conc H2SO4,


o
at 140 C they undergo dehydration and produce
ethers.

Alcohol also undergo dehydration when heated at


o
350 C, in presence of Al2O3 and alkenes are
produced.

2-Butanol

239
Alcohol also undergo dehydration when heated at
o
250 C, in presence of Al2O3 and ethers are produced.

Cleavage of 1,2-diols (Glycols):


Ethylene glycol when treated with KMnO4 (acidic) or
Potassium di chromate , results in the formation of methanoic
acid due to the cleavage of carbon-carbon bond.

The Sulpher Analogues (Thiols RSH):


Both Oxygen and Sulpher belongs to the same group of
periodic table (VI-A). There are sulpher analogue of alcohols
and ethers in which sulpher is present instead of oxygen
atom.
R-OH-----R-SH
R-O-R------ R-S-R
The sulpher analogue of alcohols are called Thiols or
Mercaptanes. The functional group of thiol is SH. This is
called suphydryl or marcapto. When they react with mercuric
salts they form insoluble salts known as mercaptanes.
Methane thiol is a gas
Ethan thiol and higher members of this group
are colorless, volatile liquids at STP.
Lower members have strong repulsive odors. It
is added in natural gas to detect the gas
leakages.
Thiols have lower boiling point than
corresponding alcohols due to lack of
hydrogen bonding, due to which they are
insoluble in water but soluble in organic
solvents.

240

Uses of Alcohols:
Methanol:
(i)
It is used as solvent for oils, fats, paints and
varnishes.
(ii)
It is used as antifreeze in automobile radiators.
(iii)
It is used for denaturing of ethyl alcohol.
Ethanol:
(i)
It is used in the manufacture of drugs, dyes and
perfumes.
(ii)
It is used as fuel in spirit lamps and stoves.
(iii)
It is used for preserving biological specimens.
(iv)
It is used as antiseptic.
(v)
It is used in alcoholic beverages.
Alcoholic beverage Alcohol %age (v/v) Source
Beer
3-6%
Barley
Cider
3-6%
Apple juice
Champagne
8-10%
Grape juice
Brandi
40-45%
Grape juice
Gin
40-45%
Maiz
Cognac
40-50%
Grape juice
Whisky
40-50%
Barley
Rum
40-55%
Molasses
Identification tests for Alcohols:
1.
Sodium metal test:
When sodium metal is added to alcohol, hydrogen gas is
liberated which burns with blue flame and popping sound.
2.
Esterification test:
Alcohols on reaction with carboxylic acid produce esters
which have fruity smell.

241

3.

Lucas reagent test:

Phenol:
Compounds having OH attached to aromatic carbons
are called phenols. Phenol is also called carbolic acid. This
was first obtained from coal tar by Runge in 1834

Preparation:
1.

Dow Process:

Chlorination of benzene is carried out to get chloro benzene.

o
Chloro benzene is hydrolysed by 10% NaOH at 350 C and
200atm. Sodium phenoxide is obtained which then further
reacts with HCl and produce phenol.

242
2.

Fusion of Sodium Benzene Sulphonate with


Alkali:

Benzene is treated with Sulphuric acid to obtain benzene


sulphonic acid.

Benzene Suphonic acid is made to react with aqueous NaOH


(neutralization) to produce Sodium Benzene Sulphonate.

Sodium Benzene Sulphonate


Sodium Benzene Sulphonate is then fused with solid NaOH,
as a result Sodium phenoxide is obtained.

243
Sodium phenoxide is then made to react with HCl to obtain
Phenol.

Structure of Phenols:
The hydroxyl group is
attached to benzene
ring. The molecule is
planer, the C-O-H bond
angle is 109, which is
almost the same as that
of tetrahedral structure.
In phenol all the six
carbon atoms are sp2 hybridized. In alcohol the C-O bond
length is 1.42A while in phenol this length is 1.36A the reason
is hybridization is SP2 in phenol and SP3 in alcohol.
Physical Properties of Phenol:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
(ix)

Phenol is a colourless crystalline solid.


It has a very characteristic odour.
It is deliquescent solid.
o
It is low melting solid. Its melting point is 41 C.
o
It boils at 182 C.
It is poisonous.
It is sparingly soluble in water at room temperature
o
but above 68.5 C it become completely soluble.
It is a weak acid.
It has corrosive action for skin.

244
Chemical Properties of Phenol:
The reaction of phenol can be divided into two categories.
(A)

Reactions due to functional group OH:

(i)

Acidic Behaviour:
Phenol is a weak acid than carboxylic acids but stronger acid
than water and alcohols.
Carboxylic acids > Phenol > Water > Alcohols
-10
Its acid dissociation constant (Ka) is 1.3 x 10 . Its pH is 5-6.
+
In aqueous solution it furnishes proton (H ion) and
phenoxide ion. Its acidic nature is due to stable phenoxide
ion. The stability of phenoxide ion is due to resonance. The
negative charge
spreads over the ring and become delocalized. Due to
delocalization of negative charge, the phenoxide ion becomes
stable. On the other hand negative charge of alkoxide ion of
alcohol is not delocalized so alkoxide ion is less stable and
thus alcohol is much less acidic than phenol.

Phenol being acid reacts with alkalis to produce salt and


water.

245
(ii)

Reaction with Na Metal:

Phenol on reaction with alkyl halides in presence of aqueous


NaOH produces ethers. The reaction takes place in two
steps.

(iii)
Reduction:
Phenol on heating with Zinc dust reduces to Benzene.

(B)

Reactions due to Aromatic Ring:

(i) Nitration:
Phenol on reaction with dil HNO3 at room temperature
produces ortho and para Nitro phenols.

246
o
Phenol on reaction with conc HNO3 at 100 C produces
Trinitro phenol.

(ii) Reaction with Bromine water:


Phenol reacts readily with an excess of bromine water and
produce white precipitate of 2,4,6- tribromo phenol.

(iii) Sulphonation:
Phenol on reaction with conc H 2SO4 at room temperature
produces ortho and para Hydroxy benzene sulphophonic
acids.

Difference
between Alcohols and Phenols:
In both Alcohols and Phenols functional group is
same.
In alcohol OH group is attach to non-aromatic carbon
atom while in phenol it is attach to the aromatic
carbon.

247

OH group attach to the aromatic ring in side chain or


you can say indirectly attach to the ring is not called
phenol its aromatic alcohols.

Uses of Phenol:
(i)
(ii)
(iii)
(iv)
(v)
(vi)

It is used as antiseptic in soaps lotions and


ointments.
It is used in manufacturing of pharmaceuticals like
aspirin, salicylic acid, salol, phenacetin etc.
It is used in manufacturing of picric acid.
It is used in manufacturing of bakelite which is a
plastic.
.
It is used as ink preservative.
It used for washing toilets.

Ethers:
Ethers are organic compounds having C O C
functional group. The most important member of ether family
is Di Ethyl Ether.
Preparation:
1.
Williamson synthesis:
In this process ethers are prepared by the reaction of
alcohols, alkyl halides and sodium metal.
Alcohols react with sodium to produce alkoxides.

The alkoxides are powerful nucliophiles, so react with alkyl


halides and produce ethers.

248
2.

By dehydration of Alcohols:

When excess of alcohols are heated with conc H2SO4, at


o
140 C they undergo dehydration and produce ethers.

o
Alcohol also undergo dehydration when heated at 250 C, in
presence of Al2O3 and ethers are produced.

3.

By reaction of Alkyl Halides with dry Silver Oxide:

Reaction of alkyl halides with dry silver oxide produce ethers.


2 C2H5Br +Ag2O
C2H5OC2H5+ 2AgBr
Physical Properties:
(i)
They are usually volatile liquids.
(ii)
They are highly flammable.
(iii)
They usually have lower boiling points than the
respective alcohols as they have no hydrogen
bonding between their molecules.
(iv)
Although they have no hydrogen bonding between
their molecules but the form weak hydrogen
bonding with water molecules so ethers are
slightly soluble in water.
(v)
They are freely soluble in organic solvents.
Physical properties of diethyl ether:
(i)
It is a colourless and volatile liquid.
o
(ii)
Its boiling point is 35 C.
(iii)
It is highly flammable.
(iv)
It is an excellent solvent for fats, oils, gums etc
due to its least reactivity.

249
Chemical Properties:
The C O C linkage is very strong and not easy to break so
they are inert. Therefore they do not react with oxidizing
agents , reducing agents, bases, sodium etc at ordinary
conditions. However they react with acids as they possess
lone pair of electrons which they can offer to acids.
(i)

Reaction with HCl and HBr (formation of


Oxonium Salt):

On reaction with these halogen acids they produce di alkyl


oxonium halides.

(ii)

Reaction with Sulphuric acid:

On reaction with sulphuric acids they produce alkyl oxonium


hydrogen sulphate.

(iii)

Reaction with HI:

250
On reaction with HI they produce oxonium ion and Iodide ion.
The iodide ion being strong nucleophile attacks an alkyl
radical and offers its electron to it. The alkyl radical breaks its
bond with oxygen leaving its electrons to the oxygen. Thus as
a result of this reaction alcohol and alkyl halide are produced.

(iv)

Reaction with

Acetyl Chloride:
Ethers react with acetyl chloride in presence of anhydrous
ZnCl2 and produce ester and alkyl chloride.

(v)

Reaction with Phosphorus pentachloride:

Ethers react with Phosphorus pentachloride to give alkyl


chloride.

Uses of Diethyl Ether:


(i)
(ii)
(iii)

It is used as general anesthetic because it causes


unconsciousness without effecting heart and
lungs.
It is used in preparation of artificial silk.
Its mixture with alcohol under the trade name
Natalite is used as substitute of petrol.

251
(iv)
(v)
(vi)
(vii)

It is used for the manufacture of smokeless


powder.
It is a good organic extractant used for extracting
organic compounds.
It provides an inert medium for organic reactions
so is used in Wurtz reaction, Frankland reaction,
preparation of Grignard reagents etc.
It is an excellent organic solvent and is used for
dissolving adhesives ( gums, glue), fats, oils,
waxes and resins.

252
Chapter 19: Carbonyl Compounds I:
Aldehydes and Ketones

Preparations
:
Aldehydes can be prepared by oxidation of primary
alcohols. They can also be prepared by ozonolysis of
alkenes.
Ketones can be prepared by oxidation of secondary
alcohols. They can also be prepared by ozonolysis of
alkenes.
Preparations of most important members of aldehydes and
ketones:
Preparation of Formaldehyde:
Formaldehyde is obtained in laboratory by dry distillation of
Calcium formate.

253

Commercially acetaldehyde is produced by the hydration of


acetylene.
When acetylene (ethyne) is treated with dilute (10%) H 2SO4 in
presence of mercuric sulphate hydration occurs. Addition of
water take place at about 80oC and vinyl alcohol is produced.

Vinyl alcohol is unstable so it undergoes rearrangement to


form aldehyde.

Preparation of Acetone:
(i)

Laboratory method:

Acetone is obtained in laboratory by dry distillation of Calcium


acetate.

254

(ii)

O
ther
methods:
(a) By oxidation of secondary alcohols:

Acetone and other ketones are produced by oxidation of


secondary alcohols with strong oxidizing agents like chromic
mixture.

(b)
(b)
(b)
By Hydration of Alkynes:
Alkynes other than Ethyne on hydration give ketones.

255
The unsaturated alcohol is unstable so it undergoes
rearrangement to form ketone..

The
unsaturated alcohol

is unstable so it undergoes
rearrangement to form ketone..

(c) By Friedel-Crafts Acylation:


Reaction of benzene with acid halide is called acylation.
Benzene on reaction with acid halide in presence of AlCl3
produces aromatic ketones.

Structure:
The carbon of carbonyl group is sp2 hybridized. Carbon
makes sigma () bond with oxygen atom as well as with other
two atoms so total three sigma bonds. The remaining

256
unhybridized p-orbital overlaps with p-orbital of oxygen and
forms pi () bond. The carbonyl group is planar having bond
o
angles of about 120 .

Bond between carbon and


oxygen are both polar and unsaturated so aldehydes and
ketones are reactive. Carbon can be attacked by nucleophiles
and oxygen can be attacked by electrophiles but nucleophilic
attacks are more prominent.
Aldehydes and ketones beside other reactions also show
nucleophilic addition reactions.
The carbon and oxygen atoms in the carbonyl group is
present in aldehyde and ketones, which consists of one
sigma and one pi bond. Both carbon and oxygen are SP2
hybridized. The three atoms attached to carbonyl carbon lie in
the plane with bond angle of 1200. There are still two
unshared electron pairs on oxygen atom. The C=O bond
distance is 1.23A, shorter than C-O bond distance in alcohols
which is 1.43 A.
Nucleophilic Addition Reaction:
Aldehydes and Ketones mainly undergoes Nu addition
reaction due to presence of unshared electron . These
reaction may be either acid catalyzed or base catalyzed
reactions.
(i)

Acid Catalyzed Addition Reaction:


Due to presence of unshared electron pair on
oxygen, carbonyl compounds are weak lewis bases and can
be protonated. Acid can catalyzed the addition of weak
nucleophiles to carbonyl compounds by protonating the

257
carbonyl oxygen atom. In acid catalyzed reaction the addition
process is initiated by proton of the acid to from oxonium ion.
This increases the electron density of carbonyl carbon and
thus enhances its ability for undergoing the attack of weak
nucleophile.
The carbonyl carbon, which is trigonal and sp2 hybridized in

the
starting
aldehyde and ketones becomes tetrahedral in the reaction
product.
(ii)

Base-Catalyzed Addition Reaction:


Such reactions will occur with the strong
nucleophile. The base reacts with reagent and generates the
nucleophile. That will attack on the carbonyl group because it
has partial positive charge on carbonyl carbon as pi electron
also moves to the oxygen atom of carbonyl group. The
reaction is complete by the addition of proton to the negative
oxygen atom.

Stearic Hindrance:
The carbonyl carbon is more crowded in ketone than
aldehydes. In nucleophilic addition reaction, the attacking
group come even closer because in the produce hybridization
changes from SP2 to SP3 and the angle decreases from 1200
to 1090.

258
Electronic Effect:
As alkyl group is electron donor compared to hydrogen. They
tend to neutralize the partial positive charge on carbonyl
carbon, and decreases its reactivity towards nucleophilic
attacks. Ketones have such alkyl groups while aldehyde have
only one.
Physical Properties:
Aldehydes:
(i)
Lower aldehydes are colourless liquids except
formaldehyde. Formaldehyde is a colourless gas.
(ii)
Lower aldehydes have unpleasant pungent smell.
Formaldehyde has suffocating odour.
(iii)
Aldehydes are polar compounds so they have high
boiling points than corresponding alkanes but lower than
corresponding alcohols as they have no hydrogen bond in
their molecules.
(iv)
Density of aldehydes is less than water.
(v)
Lower aldehydes are soluble in water due to
formation of hydrogen bond with water while higher members
containing more than five carbons are insoluble in water.
Ketones:
(i)
Lower ketones are colourless liquids. Aromatic
ketones are solids.
(ii)
Lower ketones have pleasant sweet smell.
(iii)
Ketones are polar compounds so they have high
boiling points than
corresponding alkanes but lower than
corresponding alcohols as they have no hydrogen bond in
their molecules.
(iv)
Density of ketones is less than water.
(v)
Lower ketones are soluble in water due to
formation of hydrogen bond with
water
while
higher

259
members containing more than five carbons are insoluble in
water.
Chemical Properties:
1.

Addition Reactions:
Aldehydes and ketones show nucleophilic addition
reaction on carbonyl group.

(i)

Clemmenson Reduction:
When aldehydes are treated with hydrogen in
presence of Zn-Hg called as zinc amalgam
catalyst addition of hydrogen (hydrogenation) take
place and corresponding alkanes are produced.

When Ketones are treated with hydrogen in


presence of Pt or Ni catalyst addition of hydrogen
(hydrogenation) take place and corresponding
secondary alcohols are produced.

(ii)
Wolf-Kishner Reduction:
when aldehyde or ketone is heated with hydrazine, a
corresponding hydrazone is obtained, which on heating with
KOH in boiling ethylene glycol give the corresponding
alkanes.

260
Reduction using Hydrides to give Alcohol:
Complex hydrides (NaBH4 or LiAlH4) also reduce aldehydes
to corresponding primary alcohol and ketones to
corresponding secondary alcohol.

Mechanism:
The complex ion gives hydride ( H ) ion which attacks
carbonyl carbon.

The alkoxide ion then get proton from water and produce
alcohol.

(iii)
Addition of Hydrogen Cyanide:
When aldehydes are treated with hydrogen cyanide in
presence of a base addition of hydrogen cyanide take place

261
and corresponding cyanohydrins are produced. This is a base
catalyzed addition reaction.

When Ketones
are treated with hydrogen cyanide in presence of base
addition of hydrogen cyanide take place and corresponding
cyanohydrins are produced. This is a base catalyzed addition
reaction.

(iv)

Addition of Grignard Reagents:

262
When aldehydes are treated with grignad reagents followed
by acid hydrolysis, primary or secondary alcohols are
produced.
(a) Reaction of Formaldehyde:
Reaction of formaldehyde with Grignards reagents, followed
by acid hydrolysis produces primary alcohol having one more
carbon than that of grignards reagent.

(b)
Reaction of Aldehydes other than Formaldehyde:
Reaction of aldehydes other than
formaldehyde with Grignards reagents,
followed by acid hydrolysis produces
secondary alcohol.

When
ketones are treated with grignad
reagents followed by acid hydrolysis, tertiary alcohols are
produced.

263

2.

Oxidation:

(a)

Oxidation by strong oxidizing agents:


When aldehydes are treated with strong oxidizing
agents like chromic mixture (Na2Cr2O7+H2SO4 or
K2Cr2O7+H2SO4)
they
are
oxidized
to
corresponding carboxylic acids.

When ketones are treated with strong oxidizing agents like


chromic mixture (Na2Cr2O7+H2SO4 or K2Cr2O7+H2SO4) they
are oxidized to two molecules of same or different carboxylic
acids. Carbon adjacent to carbonyl carbon having less
hydrogen is preferably oxidized.

264

(b)

xidation by mild oxidizing agents:


When aldehydes are treated with mild oxidizing agents like
Felings soln, Benedicts soln, Tollens reagent etc they are
oxidized to corresponding carboxylic acids which further react
to produce their salts.
Fehling Soln: It is a mixture of CuSO4, NaOH and Tartaric acid.
Benedicts Soln: It is a mixture of CuSO4, NaOH and Citric acid.
Tollens Reagent: It is a mixture of AgNO3, NH4OH.

Fehlings Soln and Benedicts Soln oxidizes aldehyde to


Sodium salt of carboxylic acid while its self reduces to reddish
precipitate of cuprous oxide. This reaction can be used for
identification of aldehydes as well as for sugars.

265
Tollens Reagent (ammoniacal silver nitrate soln) oxidizes
aldehyde to Ammonium salt of carboxylic acid while its self
reduces to metallic silver that deposits on the walls of the test
tube and makes mirror.

This

reaction

can
be
used for identification of aldehydes and is known as Silver
Mirror Test.

3.

Aldol Condensation Reactions:

Aldehydes and ketones possessing alpha () hydrogen on


reaction with cold dilute alkali produce additions product
known as aldols. -bond of carbonyl group of one molecule is
broken up while -hydrogen of other molecule detaches and
gets attached to the oxygen of first molecule while rest of the
part adds to the carbonyl carbon.
e.g. (i) Acetaldehyde (Ethanal) has -hydrogen so it
undergoes aldol condensation.

266
The aldol then loses water on heating with dilute acid to form
unsaturated carbonyl compound.

e.g. (ii) Propionaldehyde (Propanal) has -hydrogen so it


undergoes aldol condensation.

e.g. (iii) Acetone (Propanone) has -hydrogen so it


undergoes aldol condensation.

4.

Cannizzar
os Reaction:

Aldehydes that have no -Hydrogen undergoes cannizzaros


reaction when they are treated with alkali.
This is a self oxidation-reduction reaction. In it an alcohol and
a salt of carboxylic acid is produced.

267
e.g. (i) Formaldehyde (Methanal) has no -hydrogen so it
undergoes cannizzaros reaction when treated with alkali.

e.g. (ii)
Benzaldehyde has no -hydrogen
so it undergoes cannizzaros reaction when treated with
alkali.

Identification of Aldehydes and Ketones:


Following are few tests used for identifications of
aldehydes and ketones.
1. Benedicts Solution Test:
Benedicts Solution is a mixture of CuSO4, NaOH and Citric
acid. It is a blue colour solution. When an aldehyde solution is
added to benedicts solution and boiled a brick red coloured
precipitate of cuprous oxide is formed.
Ketones do not give this test.

268
Methanal

Sodium methanoate

(Reddish ppt)

This test is also used as clinical test for sugar. Glucose (a


sugar) is secreted in urine of diabetic patients. Urine of the
patient is added to benedicts solution and is boiled,
precipitate of cuprous oxide is produced. Colour of precipitate
determines quantity of sugar in urine. Darker is the colour of
precipitate greater is the amount of sugar in the urine.

2. Fe
h
lings Solution Test:
Fehling Solution is a mixture of CuSO 4, NaOH and Tartaric
acid. It is a blue colour solution. When an aldehyde solution is
added to fehlings solution and boiled a brick red coloured
precipitate of cuprous oxide is formed.
Ketones do not give this test.
(Reaction same as in above)
3. Silver Mirror Test or Tollens Reagent Test:
Tollens Reagent is a mixture of AgNO3, NH4OH. When
an aldehyde solution is added to tollens reagent in a test tube
and the tube is warmed gently, silver is produced. The silver
thus produced is deposited along the inner side of test tube
and forms mirror.

269
Ketones do not give this test.

4. Sodium Nitroprusside Test:


When alkaline sodium nitroprusside solution is added drop
wisely to a ketone, blood red or orange red colouration is
produced.
Aldehydes do not give this test.
Uses of Formaldehyde:
1.
2.
3.
4.
5.
6.
7.
8.
9.

It is used as a general antiseptic.


It is used for manufacturing plastic such as
bakelite.
It is used for preparing dyes such as indigo, pararosaniline etc.
Its 40% aqueous solution called Formalin is used
as an antiseptic, a disinfectant, a germicide, a
fungicide and for preserving biological specimens.
Formalin is also used for sterilizing surgical
instruments.
It is used for silvering of mirrors.
It is used for preparing anti-polio vaccine.
Formaldehyde and lactose are used in throat
lozenges.
It is used in making Urotropine urinary track
antiseptic.

270
10.

It is used to prepare cyclonite which is a powerful


explosive.

Uses of Acetaldehyde:
1.
2.
3.
4.
5.

It used for manufacturing of acetic acid,


acetic anhydride, ethanol etc.
It is used as an antiseptic inhalant in nasal
infection.
It is used in silvering of mirror.
It used for preparing 1,3-butadiene which is
used in rubber.
It is used in making drugs and dyes.

Uses of Acetone:
1.
2.
3.
4.
5.
6.
7.
8.

It is used as nail polish remover.


It is used for storing acetylene.
It is used for extraction of essential oils.
It is used as organic solvent.
It is used for preparing chloroform (an anesthetic)
and iodoform ( an antiseptic).
It is used in artificial scent.
It is used in making cordite (smokless gun powder)
and plexiglass (unbreakable glass).
It used for making mono, di and tri chloro acetones
which are chemical weapons which deactivate
eyes temporarily.

271
Chapter 20: Carbonyl Compounds II
Carboxylic Acids & Functional Derivatives
The compounds having COOH functional group are called
Carboxylic Acids. They are also called Fatty Acids.

The compounds in which OH of functional group is


replaced by another group are called Derivatives of
Carboxylic Acids e.g.

The carboxylic acids in which one or more H-atoms of alkyl


group is replaced by another group are called Substituted
Acids e.g.

Preparation:

(A) Laboratory Methods of Preparing Carboxylic


Acids:

272
1. From Primary Alcohols and Aldehydes:
When primary alcohols are treated with Chromic mixture
(K2Cr2O7+H2SO4) the oxidize to their corresponding
aldehydes which further oxidizes to corresponding
carboxylic acids.

2. By Hydrolysis of Esters:
a. Acid Hydrolysis:
When esters are treated with dilute acid, they are hydrolyzed
to give carboxylic acid and alcohol.

b. Alkali Hydrolysis:

273
When esters are boiled with concentrated alkali solution, they
produce salt of carboxylic acid which then on treating with
dilute acid (HCl) produce carboxylic acid

3. By the reaction of Grignard Reagents with CO2:


Reaction of Grignards reagent with Carbon dioxide followed
by acid hydrolysis produces carboxylic acid having one more
carbon than grignard reagent.

4. Hydrolysis of Nitriles:
Compounds having a cyanide group are called alkyl
nitriles or alkyl cyanides. The carbon-nitrogen triple bond of

274
alkyl nitriles can be hydrolyzed to a carboxylic acid in
aqueous acid medium.

Structure:
The structural feature of carboxylic group are most prominent
in formic acid. It is planer with C-O is shorter than other
carbon and oxygen bond. The bond length of carbonyl group
is 120pm while the bond length of other carbon and oxygen
atom is 134pm. Similarly the bond angles of H-C=O is 124 0,
while H-C-O is 1110, and O-C=O is 1250. This suggests SP2
hybridization of carbon and carbon-oxygen double bond
similar to that of aldehyde and Ketones. Similarly sp2
hybridization of hydroxyl oxygen allows one of its unshared
electron pair to be delocalized by orbital overlap with pi
system of carbonyl carbon.

Acidity:
The carboxylic acids are acidic in nature as they
donate proton and forms salts with bases. The
carboxylate ions formed after loss of proton, are sable
due to resonance.

275
If electron pulling groups (like Cl, Br, F, OH, CN etc)
are attached with the carboxylate ion it will increase the acid
strength and if electron donating groups (like R etc) are
attached with the carboxylate ion it will decrease the acid
strength.
Being acid, they on reaction with alkalis produce salt and
water

With bases having carbonates or bicarbonates, they beside


salt and water also produce carbon dioxide.

Propanoic acid (PKa = 4.87), Ethanoic acid (PKa= 4.76),


Methanoic acid (PKa = 3.68)
Chloroacetic acid (PKa= 1.29), Trichloroacetic acid (PKa=
0.65).
Physical Properties:

276
(i)
(ii)
(iii)
(iv)
(v)

The first ten carboxylic acids are colourless liquids


with disagreeable smell while higher members are
colourless odourless wax like solids.
Aromatic acids are crystalline solids e.g. benzoic
acid.
The first four members are soluble in water due to
hydrogen bonding. The solubility in water gradually
decreases with the increase in molecular mass.
The boiling points of carboxylic acids are higher than
corresponding alcohols due to hydrogen bonding.
The melting points of carboxylic acids increase
irregularly with increase in molecular mass. The
melting points of carboxylic acids having even
number of
carbon atoms are higher than the preceding
and following members having odd number of
carbon atoms.

(vi)
(vii)

Their boiling points increase regularly with


increase in molecular masses.
They are weak acids. Their acidic strength
decreases with increase in molecular mass.

Reactivity:

Freezing point of anhydrous acetic acid is


o
16 C. So at this temperature it is in solid
form. The ice like solid form of anhydrous
acetic acid is called glacial acetic acid.

277
The carboxylic group is so named because it contains
carboxyl group and hydroxyl group. These two groups
influences each other to such an extent that reactivity of
carboxylic acids resembles to both aldehyde & ketones and
on the other hand with alcohols. Carboxylic acid contains
carbonyl group but
like aldehyde and
ketones they do
not
undergoes
condensation
reactions, because the carbonyl carbon is less positive than
aldehyde and ketones.
The Polar carbonyl group attracts the electrons away from
OH bond and make it easier from the hydrogen atom to
ionizes than in the case of OH bond of alcohols. Hence
carboxylic acid shows different chemical reactivity than
alcohols. Similarly the flow of electron form OH to carbonyl
carbon is reduced and decreases is partial positive charge so
it also reduces the probability of attack of nucleophile.
Chemical Properties:
1. Formation of Acid Halides/ Acyl Halides[R-CO-X]:
When carboxylic acids are made to react with phosphorus
halides or thionyl chloride, corresponding acid halides are
produced. Acid Halides are derivatives of Carboxylic acids.

278

2.

Formation of Esters:
Carboxylic acids on reaction with alcohols in presence
of strong acids (H2SO4), produce esters. Esters are
derivatives of Carboxylic acids.

Mechanism of the reaction:


Step-I:
Protonation of carboxylic acid
In this step a proton from acid catalyst is added to carboxylic
acid.

Step-II:Attack of Alcohol
In this step alcohol molecule offers its lone pair of electrons to
positively charged carbon of protonated acid and get attached
with it.

Step-III:

Hydrogen ion transfer


In this step a hydrogen ion transfers.

279

Step-IV:
Elimination of water and proton
In this step a water molecule and a proton is
eliminated and thus ester is produced.

3.
Formation
of Acid
Anhydrides:
Carboxylic
acids
undergo
dehydration
with
phosphorus pentaoxide to form acid anhydride. Acid
Anhydrides are derivatives of Carboxylic acids.

Amides:
They are less reactive derivatives of carboxylic acids. Here
the OH is replaced by NH2 group. They are also known as
acid amides. They are named by replacing ic acid or oic
acid of corresponding acid by the word amide.

280

Acetamide

Formamide

Amides can be prepared by the reaction of ammonia with


carboxylic acid to from amides and ammonium salt.
Formation of Acid Amides:
Carboxylic acids are first converted to acid halides or
acid anhydrides which then on reaction with ammonia
produces acid amide. Acid Amides are derivatives of
Carboxylic acids.
(i)
Method-I

Reduction to Alcohols:

281
Carboxylic acids on reaction with lithium aluminum hydride
reduce to corresponding alcohol.

Decarboxylation Reactions:
The removal of Carbon dioxide from carboxylic acid is
known as decarboxylation. This reaction takes place when
salt of carboxylic acid is heated with soda lime ( dry mixture of
caustic soda, NaOH and quick lime CaO) to form alkanes.

Reactions of Carboxylic Acid Derivatives:


Friedel Crafts Acylation Reaction:
When benzene is treated with acyl halide in
presence of FeBr3 or AlCl3 it gives substitution product i.e.
aromatic ketone.

Acylation of benzene gives mono substituted product.


Hydrolysis of Acid Anhydride:

282
On hydrolysis anhydrides yield corresponding carboxylic
acids.
Hydrolysis of Ester (Saponification of Esters):
Esters are commonly hydrolyzed with bases. This is
called saponification reaction, because this type of reaction is
used to make soaps from fats. When Na is used we get bar
soap, when K (potassium) is used we get liquid soap.

Reduction of Esters:
Esters can be reduced to primary alcohols in the
presence of reducing agent (lithium aluminum hydride) in
ether which is used as solvent.

Reaction of Esters with Grignard Reagent:


Reaction of Grignards reagent with esters other than alkyl
formate followed by acid hydrolysis produces tertiary alcohol.

The addition product is not stable thus it undergoes


rearrangement and produce ketone.

283

The Ketone thus produced further reacts with Grignards


reagent and gives an addition product which then on acid
hydrolysis produce tertiary alchohol.

Reaction of Amides:
On hydrolysis amides form the corresponding carboxylic
acids. The reaction is slow and requires acid or base as
catalyst.

Reduction of Amides:

Amides can be reduced to primary amines in the presence of


suitable catalyst.
Reactions of Nitriles:
Nitriles are also considered as derivatives of carboxylic acids,
because they can be obtained from carboxylic acid.

284
Hydrolysis:
On boiling with dilute acids or alkali they produce
carboxylic acids.
Reduction:
When treated with a reducing agent such as LiAlH4,
nitriles are reduced to primary amines.

285
Chapter 21: BIOCHEMISTRY
The substances on which life depends are called life or bio
molecules. They are built from carbon skeleton. Many of them
are very large molecules and are called natural polymers or
biopolymers. They include carbohydrates, lipids, proteins,
enzymes and nucleic acids.
Carbohydrates:
They were given the name carbohydrates as they were
believed to be hydrates of carbon e.g. glucose C6H12O6 or
C6.6H2O,
sucrose
C12H22O11
or
C12.11H2O.
Thus
carbohydrates can be represented by general or empirical
formula Cx(H2O)y. The carbohydrates are also called sugars
or saccharides.
But later on investigations showed that there are compounds
which are hydrate of carbon but they are not carbohydrates
e.g. Formaldehyde CH2O, Lactic acid C3H6O3. Similarly there
are compounds which carbohydrates but they are not hydrate
of carbon e.g. Mannitol C6H14O6. So the word Carbohydrate
have lost its original meaning and now-a-days carbohydrates
are defined as poly-hydroxy aldehydes or poly-hydroxy
ketones.

286

Carbohydrates are mainly consists of carbon, hydrogen and


oxygen in ratio of 1:2:1, but some time ratio is different as in
Mannitol. Some hydrocarbons also contain nitrogen and
sulphur. Cabohydrates provide 4 kcal energy per gram.
They are mainly classified into three categories.
(i)

(d)

Mono saccharides:
The carbohydrates which cannot be hydrolyzed to further
simpler substances are called monosaccharides. They further
divided into:
(a)
Trioses: They consists of 3 carbon atoms e.g.
glyceraldehyde C3H6O3.
(b)
Tetroses: They consists of 4 carbon atoms e.g.
erythrulose C4H8O4.
(c)
Pentoses: They consists of 5 carbon atoms e.g.
ribose, arabinose
C5H10O5.
Hexoses: They consists of 6 carbon atoms e.g. glucose,
fructose, galactose and mannose C6H12O6. Hexoses are the
most important class of monosacchrides.
(e)
Heptoses: They consists of 7 carbon atoms e.g.
sedoheptulose C7H14O7.

287
Oligosaccharides:
The carbohydrates which on hydrolyses give 2-10
monosaccharides units are called oligosaccharides. The one
which consists of 2 monosaccharide units are called
disaccharides e.g. Maltose, Lactose, Sucrose etc C12H22O11
and the one which consist of 3 monosaccharide units are
called trisaccharides e.g. raffinose C18H32O16. Upon hydrolysis
they either give similar or different types of monosaccharides.
For example maltose yields the same kind of two glucose
units upon hydrolysis.

While sucrose yield two different types of


monosaccharides upon
hydrolysis.

Glycosides Linkage or Bond:


It is the linkage or bond between two rings in
an oligosaccharides or
polysaccharides
during the formation of new molecule. Two
monosaccharides units combines together via
oxygen atom and water
molecules
is
eliminated. Such kind of linkage is called glycoside linkage or

288
bond. For example maltose yields the same
kind of two glucose units
upon hydrolysis.

While sucrose yield two different types of


monosaccharides upon
hydrolysis.

(ii)
Polysaccharides:
The carbohydrates which on hydrolyses give many
monosaccharides units are called polysaccharides e.g.
starch, dextrin, glycogen, cellulose etc.
(C6H10O5)n + nH2O dil H2SO4n C6H12O6
Starch
Glucose
Starch:
It is the most important source in human diet. It is
present in wheat, rice maize, potatoes and barley. It is a
polymer of -D-glucose. Starch gives blue colouration with
iodine.

289

Cellulose:
It is the most abundant form of polysaccharides.
Plants produce 100 billion tons of cellulose per year. Cotton is
99% cellulose, woody parts of plants are more than 50%
cellulose. It is the building material of plants. It is polymer of
-D-glucose.
Glycogen:
Glucose changes to glycogen and is stored in liver. It
is also called animal starch.

Functions of Carbohydrates:
The basic and important function of carbohydrates is the chief
source of energy to perform vital daily activities of life. That is
why they are called as fuel of life. They oxidize to produce
energy.
Carbohydrates + Oxygen------------------ Carbon Dioxide +
water + energy (4.1K cal).
1. Glucose is used as an immediate source of energy for
sick and sportsmen. Used in the preparation of jam
and jellies.
2. Fructose is used as sweeting agent in confectionary
and medicinal products like syrup. It is also used to
prevent the formation of yellowish color in ice cream
(sandiness). Most importantly used as an alternative
of table sugar for obese and diabetic patients.
3. Sucrose is used as food and important ingredient in
jam , jellies and other sweet products. Used in the
preparation of sucrose octa octate for denaturing of
alcohol and for making anhydrous adhesives.

290
4. Starch is mainly used as food. Used for the production
of ethanol industrially. In paper industry starch is used
as stiffening agent, while in textile and laundry also
used for same purpose.
5. Cellulose has no food value but it provides bulkiness
to our diet for the normal peristaltic motion of our
intestine.
6. Oligosaccharides are involved in the formation of
secreted proteins like antibodies and blood clotting
factors.
7. The receptor on the cell membrane are complex
carbohydrates with certain proteins. These receptors
are responsible for molecular recognition.
8. Some derivatives of carbohydrates like glycol, heparin
sulphate are involved in the attachment of adhesion
of neurons to one another during the development of
nervous system. Heparin sulphate a linear
polysaccharides formed in all animal tissues, have an
important role in Alzheimers and Parkinsons
diseases.
Role of various Carbohydrates in Health and Diseases
Different kind of carbohydrates are involved in health and
disease of living beings. Some of important functions are
listed as follow:
1. Sucrose: it is disaccharides, used as sweetening
agent and as source of energy. But the use of sucrose
is primarily responsible in tooth decay and obesity. It
deposited the plaque which is sucrose on our teeth.
2. Lactose: it is also disaccharides of glucose and
galactose, also known as milk sugar, mainly found in
the milk of mammals. Human milk contains 6.8% while
cow milk contains 4.8% lactose. Lactose is digested
by lactase enzymes. Although milk is universal food
but some of human being cannot digest milk due to
deficiency of lactase enzyme this is called lactose
intolerance. General indications of this disease is
abdominal bloating, cramps, flatulences, colic pain,

291
nausea, watery diahoerrah. Symptom appears usually
within 30-90 minutes after the ingestion of milk. To
avoid such problem fermented milk products like
yogurt, cheese should be consumed.
3. Glucose:
the
most
common
and
popular
monosaccharides.
Found in sweet fruits like grapes which contains 2030% glucose.
Used for quick energy source.
Important part of human blood. Normally human blood
contains 65-110 mg of glucose per 100 ml
The excess glucose is stored in liver in the form of
polymer known as glycogen, which upon hydrolysis
give back glucose at time of need.
Human pancreas secretes a hormone known as
Insulin. Which helps in the metabolism of glucose to
produce energy.
Sometime defects in metabolism of glucose occurs
which leads to increase level of glucose in blood
causes a disease known as diabetes mellitus.
The consequences of unchecked diabetes causes
hardening of blood vessels, dysfunction of kidneys,
diabetic coma which causes premature death.
Nutritional Importance:
Carbohydrates are most important energy containing
nutrients for living organisms.
Plants contains stored carbohydrates called starch,
while animal carbohydrates are glycogen.
Both these polymers are broken down into the
simplest units known as glucose.
Upon oxidation reaction glucose molecules liberates
energy in the form of ATP which is 4.1 K cal per gram
of carbohydrates used for the normal function of
human body.

292
Proteins:
The term protein is derived from the Greek word Proteose
which means of Prime importance. This name was chosen by
Mulder in 1839 for a group of nitrogen containing compounds
that he believed were fundamental constituents of protoplasm.
In fact, proteins are the building block units of the cellular, subcellular and organic structures. Hence, they are the most
essential bio-molecules required for growth and maintenance of
life. In biochemical terms we can define them as follows:
Proteins are complex nitrogenous polymeric
substances, which being macro-molecular are
colloidal in nature, and built up of amino acids
joined together by amide (peptide) bonds.
The amino (NH2) group of one amino acid and the
carboxylic (COOH) group of an other amino acid form the ionic
linkage (-Co-NH-) with the elimination of water. This covalent
linkage is called the peptide linkage or bond. The resulting
compound called a peptide. The consists of 51%C, 7%H,
23%O, 16%N , 1-3% S and 1% P. Protein on hydrolysis
produce amino acids.
Protein is major structural component of animal tissue as
cellulose is that of plant cells. They have vital role in life as life
without protein is not possible.
Proteins, carbohydrates and fats are three major classes of
food stuff collectively known as Triumvirates, but function of
protein is more important as beside providing energy (4.14.8kcal per gram) it also furnish certain essential components
of living tissue of organism itself. They are carriers of
vitamins, O2 and CO2. Furthermore they also have catalytic
and signaling role.
Proteins are very complicated substances and very
changeable in composition.
CLASSIFICATION

293
The precise classification of proteins is not possible on
chemical basis as their structure is more complex. According
to a system recommended by American Society of Biological
Chemists, the proteins have been divided into three main
groups, which are further sub-classified into a number of subgroups. This classification is based on the chemical
composition and solubility of proteins. The three major groups
are:
i.
ii.
iii.

Simple Proteins
Conjugated Proteins and
Derived Proteins

i.

SIMPLE PROTEINS
These are the proteins which on hydrolysis yield only
amino acids or their derivatives. They are further sub-divided
into:
a.
Albumins: They are soluble in water, coagulated by
heat and deficient in glycine. They occur in both plant and
animal kingdoms. Examples are:
Serum albumin (in blood)
Ovalbumin (in eggs),
Lactalbumin (in milk), and
Legumelin (in plants).
b.
Globulin: These are insoluble in water, but soluble in
dilute salt solutions, and are heat coagulable to a variable
extent. Examples are:
Serum globulin (in blood),
Ovoglobulin (in eggs),
Lactoglobulin (in milk) and
Legumin (in legumes),
Vicilin (in legumes).

294
c.
Globins: These are rich in histidine. They combine with
heme (an iron containing pigment) to form hemoglobin (Hb).
They occur only in animal as their blood component.
d.
Glutelins: They are insoluble in water and other neutral
solvents, but soluble in dilute acids and alkalies. They occur
only in plants. Examples are:
Glutelin (of wheat) and
Oryzenin (of rice).
e.
Gliadins or Prolamins: They are also insoluble in
water, neutral solvents and absolute alcohol, etc, but soluble in
70 to 80% alcohol. As the name indicate, prolamines contain
much proline, but deficient in lysine. They are the plant proteins
generally found in seeds. For example:
Zein (in corn seeds)
Hordein (in barley seeds) and
Gliadin (in wheat seeds).
f.
Histones: They are soluble in water, but insoluble in
dilute ammonia. They are readily soluble in dilute acids and
alkalies, and coagulated by heat. Histones are strongly basic as
they are rich in arginine. In combination with deoxy-ribose
nucleic acid (DNA), they form nucleoproteins or more correctly
nucleohistones, which occur in cell nuclei forming chromatin
material. Examples are: thymus histone in animals and glutenin
in plants (i.e. wheat).
g.
Protamines: They resemble histones, but unlike them
are soluble in ammonium hydroxide. They are large polypeptide
and yield basic amino acid on hydrolysis (particularly arginine).
They are not coagulated by heat and can precipitate other
proteins from solutions.
Protamines are present in sperm cells. They are
relatively of small size. Examples are the salmine of salmon
(fish) sperm, and the protamines of other sperms.

295
h.
Scleroprotins or Albuminoids: These are the least
soluble proteins. They are insoluble in water, salt solutions,
dilute acid and alkalies, and in alcohol. They are of animal
origin and do not occur in plants. Examples are:
Elastins of elastic tissues (tendons, arteries),
collagen of bones and cartilage, keratins found
in nails, hairs, wool, hoofs and horns etc; and
fibroin of silk.
ii.
CONJUGATED PROTEINS
These are the proteins which are formed by the
combination or conjugation of simple proteins with non-protein
substances called prosthetic groups. The conjugated
proteins, sometimes also known as compound proteins, are of
great biological significance. They are part of the enzyme
systems in most biochemical reactions that are indispensable
for life. Some hormones are also conjugated proteins and
regulate the metabolic processes.
a.
Nucleoproteins: Nucleic acids conjugate or attached to
certain basic proteins (histones and protamines) and form
nucleoproteins.
b.
Glycoprotins: Carbohydrates unite with simple
proteins, the resulting compound is known as glycoproteins.
c.
Mucoprotins or Mucoids: These are the combination
of mucopolysaccharieds with simple proteins. They generally
contain more than 4% hexosamine. Examples are several
gonadotropic hormones, such as interstitial cell stimulating
hormone (ICSH) and follicle stimulating hormone (FSH).
d.
Liporoteins: Lipids such as lecithin, cephalin,
cholesterol and fatty acid combine with simple proteins and
yield lipoproteins. They occur in blood plasma, nervous tissue,
egg yolk, milk and cell membranes.
e.
Phosphoproteins: These are the phosphorous
containing proteins. Phosphoric acid or other substances
containing phosphorus (e.g. lecithin, cephalin, etc) combine

296
with simple proteins to form phosphoprotein. Examples are the
caseinogen found in milk and vitellin found in egg yolk.
f.
Chromoproteins: These are the compounds of
proteins with coloured substance, which serve as prosthetic
group. Pigment such as heme combine with globins to form the
red coloured hemoglobin (Hb).
g.
Metalloproteins: Some metals or metallic compounds
combine with simple proteins and yield metalloproteins.
Common metals in these proteins are iron, cobalt, zinc, ferric,
magnesium and manganese.
iii.

DERIVED PROTEINS

These are the derivatives of higher proteins produced


by the action of enzymes, chemical reagents, and various
physical forces. They may be (a) primary or (b) secondary
derived proteins.
(a) Primary derived proteins: They are formed by processes,
which cause only slight changes in the protein molecule. There
is no or little hydrolytic cleavage of the peptide bonds. These
include four kinds of proteins:
Proteans: These are the insoluble derivatives formed by the
action of water, dilute acids or alkalies and enzymes on simple
and conjugated proteins.
Metaproteins: These are produced by the action of acids and
alkalies. For example, the acid albuminates, and the alkali
albuminates.
Coagulated Proteins: These are formed by the action of heat,
UV-light, X-rays and alcohol. They are actually denatured
proteins. Examples of such proteins are cooked egg albumin,
cooked meat proteins, and alcohol precipitated proteins.

297
(b)
Secondary Derived Proteins: These are the products
of the progressive hydrolytic cleavage or breakage of the
peptide bonds of simple proteins. They are water soluble and
not coagulated by heat.
7.4

STRUCTURE OF PROTEINS

Protein functions are directly related to its structure.


The biological activity and all the properties of a specific
protein depend on the structure of the molecule as it exists in
its natural surroundings, that is, in the body tissues or fluids.
Proteins range in complexity from a small simple polypeptide
to a more complex globular protein. The various levels of
complexity or organization of proteins, which constitute their
complete functional structure are primary, secondary, tertiary,
and or quaternary.
(i).

Primary Structure:

It refers to the numbers and order of amino acids in a


polypeptide chain. As
stated earlier, amino
acids joined together
by covalent peptide
bonds, and constitute
a polypeptide. So the
structure of a specific
polypeptide will be
different from other
polypeptide by the number and sequence of amino acids. This
is known as the primary structure of proteins. It should also
indicate whether the peptide chain is open, cyclic or branched.
The number of amino acids in a peptide molecule varies
from a few to several hundred or more. The substitution of a
single amino acid by another in a peptide chain may result in a
drastic change in its properties and biological functions.

298
Bovine (beef) insulin was the first protein, whose
primary structure (amino acid sequence) was established in
1955. This was done at Cambridge University in England by
Frederick Sanger, who was awarded the Chemistry Noble Prize
in 1958 for the said work.
Insulin is a small protein hormone produced by the -cells of
pancreas which has a physiological influence on glucose
utilization by other tissues.

299
ii.

Secondary Structure:

The
regular
arrangement or coiling of
segments (amino acid
chains) of a polypeptide is
known as the secondary
structure.
One
such
arrangement, called the
-helix, occurs when the
amino acids form a coil or spiral. The coil consists of loops of
amino acids held together by hydrogen bonds (between the -H
of the -NH2 of one amino acid and the O of the C = O of the
acid part of another amino acid. Each turn of the helix contains
an average 3.6 amino acids Such a structure is both flexible
and elastic.
The -helix protein structure was discovered by Linus
Pauling of the California Institute of Technology, who is two time
winner of the Noble Prize for his work on protein structure.
iii.

Tertiary Structure:

It refers to the specific


folding and bending of the coils
into specific layers or fibers. The
compact and rigid structure thus
formed, called the tertiary
structure of the polypeptide, is
responsible for its biological
activity. The tertiary structure is
maintained and stabilized by four
different types of interactions or
bonds. These are:
a.

Hydrogen bonds formed between different


segments of the coil,

300
b.
c.
d.

Disulfide bonds formed by cysteine groups in


different parts of the coil,
Ionic bonds (salt bridges) formed between
positively and negatively charged groups within
the polypeptide molecule.
Hydrophobic bonds (Vander Waals forces)
between non-polar side-chains, which are inside
the folded structure, so that to be in close
contact with one another, and in minimal contact
with the aqueous solution surrounding the
polypeptide.

The polypeptide with a stable shape as its tertiary structure,


constitute the monomeric protein unit, called protomer.
iv.

Quaternary Structure:

When more than one


polypeptide units (protomers)
joined together by noncovalent bonds, the resulting
oligomeric protein structure is
called the quaternary structure.
In other words, the association
and fit of one protomer into an
other in an oligomeric protein
constitute
the
quaternary
structure. Each polypeptide
unit or protomer within an
oligomeric protein is already coiled and folded into its
secondary
and tertiary structures. These fully arranged and folded units
are then associated with one an other through attractive weak
interactions, which may be hydrogen bonding, salt bridges, and
especially hydrophobic interactions.
An example of a protein with a quaternary structure is
hemoglobin, the oxygen carrier within the red blood cells. It
consists of two identical alpha monomeric units, and two

301
identical beta monomeric units. Each unit enfolds a heme (iron
containing) group. The alpha and beta units fit together to yield
the quaternary structure of hemoglobin. It is maintained by noncovalent interactions, particularly by hydrophobic interaction
among the four sub-units. Common examples of globular
proteins are the native albumins, globulins, insulin, hemoglobin,
myoglobin, pepsin, trypsin and zein. An important example of
fibrous protein is collagen of connective tissue and myosin
fibrin. Perutz and Kendrew who established the tertiary
structure of myoglobin, a protein related to hemoglobin also
received Noble Prize in 1962.
IMPORTANCE:
Proteins are the basic life components. More than two
thousands different kinds of proteins are widely distributed in
nature. These proteins are vital cell constituents, which make
up its structure and regulate its functions. As part of the
chromosomal structure, proteins serve as the hereditary
materials.
Proteins in the form of enzymes catalyse all biochemical
reactions. In plants, enzyme proteins form complexes
with
chloroplast
pigments
(chlorophylls
and
carotenoids). The coloured protein or chromoprotien
complexes so formed are involved in the capture of
solar energy, and in the CO2 fixation during
photosynthesis

Proteins in the form of haemoglobin act as oxygen


carriers and thus transfer oxygen to the remote corners
of the body. As cytochromes, proteins are involved in
the electron transport system, which regulate the energy
production. Some hormones (e.g. insulin) are proteins..

Some proteins act as antibodies, which protect the body


against infectious diseases, while others are part of the
buffer system of the cell and extracellular body. The

302
proteins present in the blood plasma exert an osmotic
pressure of 25 to 30 mm Hg.

The presence of proteins in the muscles and tendons


facilitate the movement of the body. Some proteins as
constituent of skin and hairs provide an outer covering
of the body. Proteins in blood plasma take part in the
blood coagulation or clotting process, which is important
to prevent excessive bleeding of wounds and injuries.

For the above reasons, proteins are the essential part of


our daily diet and serve as a source of energy. Each
one gram of protein furnishes 4.1 kilocalories when
oxidized in the body.
Deficiency of protein in the diet results negative nitrogen
balance and a fall in plasma protein and hemoglobin
(Hb) levels. This adversely affects the growth and
development, and normal functions of the body. Hence,
protein malnutrition in infant caused marasmus
disease, and in children of 1 to 3 years result in disease
conditions, called kwashiorkor. These diseases are
characterized by diarrhea, infections, swollen belly
discoloration of skin and hairs, mental apathy, low
intake of food and stunted growth. In adults and elderly,
low intake of protein caused muscle degeneration and
body weakness.

In order to understand how proteins play so many vital


roles as mentioned above, we must study their
structures and properties, and relate them to their
biological functions. Let us first define and classify
proteins, and then touch their other biochemical
aspects.

Enzymes:
The word enzyme is Greek in origin. En means in and
zyme means yeast, so enzyme means in yeast.

303
Mode of enzyme action: In 1888 a Swedish chemist
Svante Arrhenius suggested that substrate combine with
enzyme catalyst and forms enzyme-catalyst complex of lower
energy, which then changes to products.
S + E E-S P + E
Actual mechanism is yet not completely understood. However
it can be better explained by lock & key model. The substrate
fits into active site of enzyme as key fits into lock. As a result
enzyme-substrate complex is formed, which then dissociates
and products are produced while enzyme is regenerated and
ready for next molecule of substrate.

The
functional
groups which are essential for the formation of enzymesubstrate complex are present on specific site of enzyme
molecule known as active site. While the site which is not
active is called allosteric site. Active site is usually a cleft and
is complementary to the structure of substrate.
It may be defined as soluble organic catalysts, which are
colloidal and protein in nature and are produced by the living
organisms. In other words, enzymes are protein catalysts,
which regulate and accelerate the rate of specific chemical
reaction both within and without the living cells that produced
them. All enzymes in their inactive state are called Proenzymes or zymogens. The substance on which an enzyme
act is called its substrate.
Enzymes may be simple or conjugated proteins. In conjugated
enzymes a non-protein segment (molecule/ion) is attached with
a specific protein. The protein part of the enzyme is called apoenzyme, while the non-protein component is often referred to
as co-factor. This co-factor if joined loosely to the protein is
usually known as co-enzyme. The term prosthetic group is

304
used for a co-factor bound very tightly by covalent linkages to
the apo-enzyme.
The complete enzyme with catalytic activity is known as holoenzyme. In case of conjugated protein, the holo-enzyme
consists of the apo-enzyme + co-factor (co-enzyme or
prosthetic group). An enzyme which has the same catalytic
activity but different molecular structure is called isozyme.
FACTORS AFFECTING ENZYME ACTIVITY
Variation in enzyme activity is important for the
regulation and control of metabolic processes. In healthy body
enzyme activity is turned `up' and `down' as needed. There are
ways in which enzyme activity can be increased or decreased
by external agents, such as drugs and poisons. Changes in
enzyme activity are also caused in diseased or pathological
conditions. The important factors which affect enzyme activity
or the rate of enzymatic reactions are briefly discussed as
follows:
a.

Enzyme-substrate contact

In order to proceed an enzymatic reaction, the formation


of enzyme-substrate complex is essential. For this purpose the
enzyme must be in good contact and well mixed with the
substrate. Such complex mixture will be more effective to
complete the reaction. If the substrate is soluble, the contact
can be established easily.
Enzyme-substrate contact also
depends on the number of active sites and the structure of both
the enzyme and substrate. For an effective contact, it is also
important that both the enzyme and substrate must be present
in proper concentrations.
b.

Concentration of Enzyme

All enzymatic reactions are of the first order which


indicate that the rate of reaction is directly proportional to the

305
concentration of enzyme. This is true when all other factors,
such as concentration of substrate, pH and temperature are
kept constant. In such cases when enzyme concentration is
plotted versus reaction rate, a straight line will be obtained.
C. Concentration of substrate
The rate of enzymatic reactions increases with an
increase in substrate concentration to certain limit. When this
limit is exceeded, no further increase in rate of reaction is
observed. This means that the reaction is of the first order to
certain extent of the substrate concentration, but it become the
zero order reaction with further increase in substrate
concentration.

Effect of enzyme concentration on reaction rate with constant


substrate concentration.

306

Relationship of substrate conc. with enzyme activity. (Vm


=maximum velocity, Km = Michaelis-Menten Constant) The
straight curve indicates the first order reaction and the flat
portion shows the zero order reaction.
The concentration of the substrate at which the velocity of the
reaction is half of maximum velocity is called MichaelisMenten Constant, denoted by Km. This relationship of the
substrate concentration with enzyme activity .
d.

Concentration of products

The concentration of the end product of an enzymecatalysed reaction often affects the rate of reaction. Since all
enzymatic reactions are reversible, the product must be
removed. Otherwise, it will rebind with the enzyme and the next
substrate molecule will have no access to the enzyme. This
condition, also known as negative feedback, reduces the
enzyme activity. Moreover, excess accumulation of end
products may affect pH of the reaction environment and thus
cause a drastic change in enzyme action.

307
e.

Effect of Temperature

The enzyme activity increases with a rise in temperature


upto to 50C. An increase in temperature increases the number
of effective collisions between enzyme and substrate to form
the activated complex, and thus accelerate the reaction velocity.
However, in contrast to an ordinary chemical reaction, the rate
of enzymatic reactions ceases at much higher temperature.
This is because enzymes being protein in nature are denatured
and become inactive at temperature above 50C. Most
enzymes are irreversibly destroyed between 70 and 80C.
Most enzymes are active in the temperature range
between 10 to 50C. The temperature at which an enzyme
activity is maximum, is known as its optimum temperature.
This temperature of enzymes working in the body of mammals
is about 37 to 40C. Some phyto-enzymes (e.g. plant urease)
act best at temperature around 60C. The effect of temperature
on enzyme activity is shown in Figure-10.4.

Enzyme activity as a function of temperature.

308
f.

Effect of pH

Enzymes are very sensitive to the reaction of their


environment. Changes in the hydrogen ion concentration will
greatly affect their activity. This is because all enzymes are
proteins or contain protein. A small change in pH may influence
the ionic character of the amino and carboxylic acid groups on
the protein, and thus affect the catalytic (active) site and
conformation (shape) of an enzyme. In addition to the purely
ionic effects, low or high pH can cause considerable
denaturation of protein, and thus inhibit enzyme activity.
As pH affects the apo-enzyme, co-enzyme and
substrate, it must influence the combination of enzyme and
substrate to form an effective complex and thus regulate
enzyme activity. Each enzyme has an optimum pH at which
its activity is maximum. This pH varies from about 2.0 for
pepsin to about 8.0 in case of trypsin. The optimum pH of the
same enzyme also varies depending on the nature of the
substrate. The effect of pH on the velocity of the enzymecatalysed reaction can best be shown by a bell-shaped curve.
The plateau indicates the optimal pH.
Enzyme
Optimum pH
Pepsin
1.4
Sucrase or Invertase
6.2
Pancreatic amylase
7.0
Trypsin
8.0
g.
Effect of light
Enzyme activity is also affected by light. Ultraviolet light
destroys or modifies the action of enzymes. The rate of
destruction is independent of the temperature, but affected by
pH etc. Purified enzymes are more easily destroyed by the
ultraviolet rays than impure enzymes. The ultraviolet light
probably affect the protein conformation of enzyme and thus
reduces their catalytic activity. Urease is inactivated by
ultraviolet rays irreversibly.

309
h.

Presence of Activators/Inhibitors

As stated earlier, many ions and molecules have the


ability to activate or inhibit certain enzymes, and thus enhance
or reduce their catalytic activity. Activators act as inducers or cofactor of the enzyme system. Metal ions (e.g. (Fe, Zn, Cu, Co,
Mg and Mn) are activators of a number of enzymes. The
enzyme either contains these ions in their molecular structure
or need them for activation. Some organic molecules act as
inducer of catalytic activity by modifying their structure.
Proteolytic zymogens are activated by splitting a peptide bond,
which is accomplished by activators. In certain instances an
enzyme act as an activator of other enzyme.
Industrial Application of Enzymes:
Enzymes are used in the chemical industry and other industries
where extremely specific catalyst are required. Useful enzymes
are obtained from plants, animals, microorganisms, fungi etc.
some of the useful applications of enzymes in industry:
1. Biological Detergents:
For washing most of the enzymes comes from bacteria adopted
to live in hot springs. The enzymes used for presoak condition
and direct liquid applications helping removal of protein and
starch stains. They are also able to digest fat, oil and grease
stains.
2. Fruit, Juice Production:
During manufacturing of fruit juices. Fruit cells have been
broken down before extraction of juice. Plant cell wall is built of
cellulose fibers, which are held together by pectins and
hemicellulose and are extremely tough. The fruit are crushed
and enzymes are added. This will break down the cell wall and
liquid (juice) is released.
3. Production of Ethanol:

310
In biofuel industry, cellulase are used to breakdown cellulose
into sugar which can be further fermented to produce ethanol
by the action of various enzymes.
Then another enzyme is secreted known as maltase or
invertase which further hydrolyze maltose into glucose.
Then a third enzyme is secreted known as zymase which
changes glucose into ethanol and carbon dioxide.
4. High Fructose Sugar:
A sweetener that is widely used in food and drinks is high
fructose corn syrup. It is prepared from starch in corn fruit.
Grains are milled to starch slurry and enzyme amylase is
added . finally the syrup is passed down to column of
immobilized glucose isomerase enzymes which converts
much of glucose into fructose.
5. Paper Industry:
In paper industry enzymes like amylase, xylanases, cellulase
and ligninase are used. Amylase used to break starch into
lower viscosity, sizing and coating of paper. Sylanases
produce bleach required for decolorizing. Cellulase smoothen
fibers , enhance water drainage soften the paper.
Lipids
Naturally occurring heterogeneous group of organic
compounds which are insoluble in water and soluble in
organic solvents like ether, chloroform, alcohol, benzene and
acetone, are called lipids. Chemically they are either esters of
fatty acids or substances which are capable of forming esters.
They are found in animals and plants.
They are simple or complex lipids. The simple lipids are
esters of fatty acids. Simple esters on hydrolysis produce fatty
acids and alcohols. They include fats, oil and waxes.

311
Fats are saturated esters while oils are unsaturated esters.

Iodine number is used to determine the extent of


unsaturation in a fat or oil. It is defined as the number of
grams of iodine which will add to 100 grams of fat or oil to
make it unsaturated. Higher is the iodine number more is the
unsaturation.
Complex esters or compound esters on hydrolysis produce
other substances in addition to fatty acids and alcohols. They
include phospholipids, glycolipids, sulfolipids, lipoproteins,
steroids including cholesterol.
Lipids beside providing energy they do other jobs also e.g.
they provide insulation for vital organs, protecting them from
electric shock and maintain optimum body temperature. They
contain fat soluble vitamins and essential fatty acids.
CLASSIFICATION
Lipids generally contain five elements: carbon,
hydrogen, oxygen, and (less frequently) nitrogen and
phosphorus. These elements form several types of lipids with
diverse structures. Since many lipids have ester linkages, which
are susceptible to saponification (formation of soap), a common
reaction of esters. Some complex lipids are non-ester and
hence non-saponifiable. Therefore, we can classify so many

312
lipid compounds into two major categories: (i) saponifiable lipids
(esters), and (ii) non-saponifiable lipids.
i.

Saponifiable Lipids:

They are those lipids, which react with strong alkalies


(e.g. NaOH, KOH) and yield salts of fatty acid (soap), alcohol,
and/or other components. They are further sub-divided into:
a. Simple Lipids: Which upon saponification yield only
alcohols and salts of carboxylic acids (soap). These
include fats/oils and waxes. On hydrolysis they yield
fatty acids and alcohols.
b. Compound Lipids: Which upon saponification yield
other compounds besides the above mentioned ones..
They may be:
Phospholipids: Which contain phosphoric acid and as
a chemical moiety. These include: lecithins, cephallins,
phosphoinositides, phosphatidic acids, plasmalogens,
and sphingomyelins.
Glycolipids: Which contain carbohydrate and a
nitrogen compound. They are also called cerebrosides
because they are found in the cerebrum of the brain.
Lipo-proteins: Which contain proteins. In order to
solubilize simple lipids, which are hydrophobic, they are
complexed with proteins that are hydrophilic. Some
lipid-protein complexes formed larger structures called
chylomicrons.

313
ii.

Un-saponifiable Lipids:

It is the lipid fraction, which remain after saponification


and can be separated by ether. The important un-saponifiable
lipids are (a) prostaglandins (hormone-like substances), (b)
steroids (sex hormones and other sterols and the fat soluble
vitamins (e.g. vitamin-D) and (c) carotenoids (carotenes and
xanthophylls , that are plant pigments).
It is note-worthy that lipids, such as fatty acids, glycerol
and other alcohols, etc are also called derived lipids, because
they are derivatives of simple and compound lipids. Fatty acids
are the most important derived lipids found in nature. Since they
are the basic essential components of most lipids, they deserve
our first attention in order to understand the structure and
properties of other lipids. We therefore, discuss fatty acids first,
and shall then deal with other important lipids.
WAXES - Simple Lipids
Waxes are the esters of the fatty acids with long chain
monohydric alcohols. Generally, the acids and alcohols
constituting waxes contain unbranched carbon chains with an
even number (12 to 36) of carbon atoms. For example,
Beeswax consists largely of palmitic acid (C15H31COOH) and
myricyl alcohol (C30H61OH). It is chemically known as myricyl
palmitate

(C15H31COOC30H61).

The

naturally

occurring

substances commonly called waxes contain not only true


waxes, but also mixture of other hydrophobic compounds such
as long-chain fatty alcohols.

314
Physical Properties:

iv.

Pure fats and oils are generally tasteless and adourless,


white or yellow solids or liquids at room temperature.
They are insoluble in water, but soluble in organic
solvents, like acetone, benzene and ether.
Both fats and oils are lighter than water and have a
greasy feeling.
They form temporary emulsion when shaken with water.
The emulsion may be made permanent by the addition
of an emulsifying agent, such as soap.
Fats and oils must be emulsified by bile in the body
before they can be digested.
Fats are also non-dialysable, that is they cannot pass
through a membrane.
Chemical Reactions

Fats and oils exhibit the usual reactions of ordinary


esters. Triglycerides containing unsaturated fatty acids also give
the addition and oxidation reactions characteristic of alkene
(Straight- chain compounds with double bonds). Some
important reactions, of fats and oils are:
(a)

Hydrolysis

Fats and oils are easily hydrolysed in the presence of


mineral acids, alkalies or enzymes, called lipases. The
hydrolytic products are fatty acids and glycerol. When tripalmitin
is hydrolysed, it forms three molecules of palmitic acid and
glycerol.

315
This reaction caused by lipases, takes place in the digestive
tracts of animals and human beings. The fatty acids so
produced play an important role in metabolic processes.
(b)

Saponification

Alkaline hydrolysis of fats and oils yields glycerol and


alkali-metal salts of fatty acids. The reaction is called
saponification because the alkali metal salts obtained are used
as soaps.

The sodium soap is the bar-soap. When the saponifying agent


is KOH, potassium soap is produced, which is soft and used as
liquid soap. Various substances may be added to soaps to give
them pleasant colour and odour.
*Iodine value: Number of G of Iodine observed by 100g of
Fat/oils
**Saponificatoin value: Number of mg of KOH required to
saponify 1g of fat/oils
(c)

Hydrogenation (Hardening of oils)

Fats and oils are similar compounds except that oils are
more unsaturated, that is, they contain double bonds. These
double bonds may be changed to single bonds upon the
addition of hydrogen. Vegetable oils may be converted to fat by
the addition of hydrogen in the presence of a catalyst (usually
nickel, Ni). This process is called hydrogenation or the
hardening of oils.

316

The hydrogenation of oils is used for the production of


vegetable ghee. In actual practice, vegetable oils are not
completely hydrogenated. Enough hydrogen is added to
produce a solid at room temperature. If the oils were completely
hydrogenated, the solid fat would be brittle and unsuitable for
cooking purposes. Finally, it is mixed with flavouring agent and
synthetic vitamins A and D. The product obtained resembles
ghee in appearance, and therefore, it is marketed as vegetable
ghee or Dalda ghee, also called Banaspati ghee.
d)

Hydrogenalysis: (Reduction to Alcohol)

When excess of hydrogen at high pressure and


temperature is passed through a fat or oil, in the presence of
copper chromite, glycerol and a higher alcohol is produced:

This
reaction which cleaves the fat by hydrogenation is termed
hydrogenolysis.
(e)

Halogenation

317
Fats and oils containing unsaturated fatty acids add
halogen to the unsaturated linkages (double bonds).
-CH = CH - + I2 ------------------------> - CHI - CHI The quantity of halogen added (or absorbed) indicates
the degree of unsaturation of fats and oils. This is usually
measured in terms of iodine value. It is defined as the number
of gram of iodine absorbed by 100 grams of oil to completely
saturate it. The greater the iodine value, the greater is the
degree of unsaturation. The iodine value of some important
commercial fats and oils .
(f)

Rancidity

Fats and oils develop an unpleasant odour and taste


when expose to air, light and heat. This is due to the hydrolysis
and/or oxidation of the triglycerides, which produce bad
smelling and off flavour volatile acids, aldehydes and ketones.
This process is known as rancidity or rancidification. The
product is usually referred to as the rancid fat/oil.

When butter is kept at room temperature, hydrolysis takes


place between the fats and the water present in the butter. The
products of this hydrolysis are fatty acids and glycerol. One of
the fatty acids produced, butyric acid, has the disagreeable
odour that causes one to say that the butter is rancid. This is
known as hydrolytic rancidity.
IMPORTANCE

318
Lipids serve as our food. They provide more energy
than carbohydrates and proteins. The oxidation of each gram of
fat supplies about 9.3 Kcal, whereas that of carbohydrate and
protein provides only 4.1 Kcal. We store lipids in our body as an
energy reserves in the farm of adipose tissues.
In addition to their function as a concentrated source of
energy, lipids are the structural units of membranes, Thus lipids
(i.e. phospholipids and sterols) create boundaries between
cells, and sub-cellular organelles, such as nucleolus,
mitochondria, chloroplasts, etc. Without such boundaries the
structure and function of the cell is not possible. Hence, lipids
are vital bio-molecules, which make-up the major part of the
membranes of each of the 10 trillion cells in our bodies.
Lipids also play an important role in the body transport,
metabolic and nervous systems. They are carriers of the nonpolar (hydrophobic = water repelling) compounds, such as the
fat-soluble vitamins (e.g. A, D.E and K). They serve as
lubricants in the alimentary canal and in other sites of the body.
Lipids degradation products are the starting material for the
biosynthesis of other compounds involve in the body building
and other processes. Some hormones are lipids in nature. They
serve as 'chemical messengers' and regulate the metabolic
processes of the body. Certain lipids (e.g. cerebrosides) are
constituents of brain, which regulate the nervous system.
Some simple lipids, such as fat is stored in the form of
adipose tissue and serve as a protector for the vital organs.
That is, fats surround the vital organs to keep them in place and
also act as shock absorbers. Fats in the outer layers of the
body act as heat insulators, helping to keep the body warm in
cold weather.

Nucleic acids:

319

In 1807, scientists found a substance Nuceinstoff in nucleus


of cell which was then named as nucleic acid. Nucleic acids
are

found

in

every

living

cell.

They

are

complex

macromolecules, as might be expected from the role they play


as the information and control centers of the cells.
A nucleic acid is a molecular tape that is coded with
directions for proper construction of enzymes and other
proteins - which, in turn, operate all the other structures and
functions of the organism. It is now known that each
chromosome is a single nucleic acid molecule with a protein
sheath. By means of chromosomes in the nucleus of a fertilized
ovum, parents donate to offsprings a complete set of
information for the individual's biological existence.
Nucleic acids are divided into two types DNA and RNA.
Nucleic acids are responsible for reproducing, storing and
transmitting genetic information.
DNA (deoxyribonucleic acid) is found in nucleus of cell in
association with chromosomal material. Genetic information
are coded along the length of polymeric molecule, DNA. Thus
it is chemical basis of heredity and is fundamental unit of
genetic information. DNA has double stranded structure which
was pointed by James Waston and Francis Crick in 1953.
Double stranded structure uses a process known as
replication. Replication is the process which provides a
mechanism for duplicating genetic information.
RNA (ribonucleic acid) is found in the cytoplasm of cell and
also smaller amounts are present in the nucleus. Genes
control the synthesis of various types of RNA, most of which
are involved in the synthesis of proteins.

320

TYPES OF NUCLEIC ACIDS


There are two main types of nucleic acids, deoxyribose
nucleic acid DNA, and ribose nucleic acid RNA. DNA is
primarily responsible for the transfer of genetic information,
whereas RNA is primarily concerned with the synthesis of
protein. The distinctive features of their covalent structures
(primary structure) are as follows:
i.

In RNA every pentose residue is ribose, and in DNA


every pentose is deoxy-ribose. The prefix deoxy means
without oxygen. Deoxy-ribose contains one less
oxygen than does ribose
ii. The nitrogen bases (heterocycles) attached to the
polymer skeleton of DNA are all selected from a set of
four possibilities: A, G, C or T. The set of four possible
bases used for the construction of RNA are A, G, C or U.
Note that three of the bases are the same in the DNA set
and the RNA set.
Difference between DNA and RNA
Parameter

DNA

RNA

i.

Location
in the cell

found mostly in
nucleolus

found in the
cytophosm

ii.

Structure

double stranded
(double helix)

single stranded
(Not double helix)

321
iii.

Chain
length

much longer than


RNA

much shorter than


DNA

iv.

Molecular
Wt.

much higher than


RNA (may be up 100
millions or more amu)

much smaller than


DNA (25,000 to
one million amu)

v.

Pentose
sugar

deoxy-ribose

Ribose

vi.

Nitrogen
bases
(heterocy
cles)

contains thymine
besides other three
bases

contains uracil
instead of thymine
alongwith other
three bases

vii.

Role

real genetic material


(carrier of heredity)

direct protein
synthesis in the
cell

viii

Types

only one type


duplicate or replicate
itself

three types: mRNA, t-RNA and rRNA.

STRUCTURE OF DNA
DNA has the kind of secondary structure as shown in
Figure. Two molecular chains of DNA are aligned antiparallel
(that is, side-by-side, but oriented in opposite direction) and are
held together by hydrogen - bonds between their bases.
Although the short segment of double stranded DNA
portrayed in (a) of appears to be Flat, Watson and Crick
proposed that the two DNA strands actually wound around
each other forming a double helix as pictured schematically in

322
(b) Figure 9.4. The molecular weight of the double helix DNA
molecule may be upto 100 millions or more amu.

Double helical structure of DNA.


STRUCTURE AND TYPES OF RNA
RNA differ from the DNA double helix in three respects:
(i) the sugar unit is ribose instead of deoxyribose, (ii) the
thiamine in DNA is replaced by uracil in RNA, and (iii) RNA
consists not of a double helix but a single strand or chain of
nucleic acid monomer, forming a chain considerably shorter
than DNA. RNA molecules have a molecular weight from
25,000 to about one million amu.

323
DNA AS STORAGE OF GENETIC MATERIAL
Of the two types of nucleic acids, in plants and animals
DNA is the true genetic material, the master file of information.
Each chromosome is actually one immense double-strand DNA
molecule with a protein coating. Humans have forty-six
chromosomes per cell, and other mammals have thirty to forty
four.
Each of the parents contributes half of the number of
chromosomes.

Less

complex

organisms

require

less

information storage; peas have fourteen chromosomes and


bacteria have one. Because of the incredible amount of
information that must be stored, these molecular tapes are
surely

the

polymer

chains

known.

Each

mammalian

chromosome (DNA) contains about 1.2 x longest 108 base


pairs and the double strand is about 4 cm long. This length
could easily be seen with the naked eye if the thread were
thicker. Inside the cell, it must be coiled very tightly.
There are three types of RNA that participate in the process of
protein synthesis in the cell. All are produced using information
from the DNA in the cell by a process called transcription ).
i.

Messenger RNA (m RNA): Carries the genetic code,


which specifies the sequence of amino acids in a
protein.

324
ii.

Transfer RNA (t RNA): is a small molecule that serve


as a 'shuttle' to bring amino acids to the m-RNA in a
process called translation .

iii.

Ribosomal RNA (r-RNA) provides the site for protein


synthesis by combining with protein to make the
ribosome surface that can accept the m-RNA molecule.

Minerals of Biological Significance:


Bio-minerals or minerals essential for life are the inorganic
nutrients that are needed by living organisms for vital
functions, but cannot be synthesized by them. They are
naturally present in the soil and river water. Plants take-up
minerals from the soil. Animals get their minerals in drinking
water and by eating plants as food. We receive these
inorganic substances from both animal and plants in our diet.
Sometimes, drinking water also supply appreciable quantity of
minerals. Purified salts, such as sodium chloride (NaCl) used
in food preparation, are also good sources of mineral for
human consumption.
Minerals in food and food products are present in both organic
and inorganic combinations. Inorganic salts, such as the
phosphates, carbonates, chlorides, sulphates and nitrates of
sodium and potassium are common. Salts of organic acids,
such as maleic, oxalic, acetic, pectic, etc. are also found in
most food/feed and their products.
When a food/feed sample is ignited at high temperature (500600C), it is completely oxidised and the inorganic carbon free
residue so left is called ash. It constitutes the mineral matter
and contains element such as sodium, potassium, calcium,
phosphorus, sulphur, etc.

325
MICRONUTRIENT- IRON
Iron is found in combination with a number of complex
biomolecules. It is an essential constituent of hemoglobin,
which transports oxygen from lungs to other tissues of the body.
It is also an integral part of myoglobin, cytochromes and several
oxidative enzymes.
Dietary iron is mostly in the form of ferric ions (Fe +++). In
the digestive system these ions are reduced to ferrous ions (Fe +
+

), which are then absorbed into the bloodstream from the

stomach and duodenum. In the blood plasma, ferrous ions are


oxidised to ferric ions, which then become part of a specific
protein - transferrin, a -globulin. The liver, spleen and bone
narrow are able to extract the iron from transferrin and to store
that iron in the form of two proteins - ferritin and hemosiderin.
The major portion of iron extracted by bone marrow from
transferrin is used in the synthesis of hemoglobin - the vital
protein of blood. The iron content of blood is 40-mg/100 ml.
As a constituent of hemoglobin, iron is involved in
cellular respiration and blood cleaning process. Hemoglobin
transports CO2 from the tissues to the lungs, and carries
oxygen from the lungs to various tissues. As a co-factor in
several enzymes iron play an important role in the biological
oxidation-reduction and energy production. The iron containing
enzymes, catalases decompose H2O2 formed as a result of

326
oxidation of many metabolites. Note that hydrogen peroxide
(H2O2) is a toxic radical. So iron in the form of catalases perform
a protective function in our body.
Iron deficiency adversely affect the hemoglobin (Hb)
level of blood. This reduces oxygen supply to the body tissues,
and causes anemia, a general weakening of the body, and pale
facial expression. Iron deficiency anemia may be due to a low
intake of iron because of a diet high in cereal and low in meat,
because of poor absorption of iron due to gastrointestinal
disturbances or diarrhea, or because of excessive loss of blood.
This type of anemia may be treated with a daily dose of ferrous
sulphate in the diet, if absorption is normal. The loss of blood,
which occurs with menstruation, results in a small loss in the
body's reserves of iron. Thus, for women between puberty and
menopause, higher dietary intake in necessary.
The daily iron requirement of a normal human adult is
10 to 15 mg/day. Infants and children also require the same
amount of iron for their growing bodies. During pregnancy and
mensuration an additional 5 mg of iron is required daily. Food
especially rich in iron compounds include red meat and liver.
Other good sources of iron are egg yolk, fish, beans and
spinach. Milk contains only small amount of iron.

327
MICRONUTRIENT-ZINC
Zinc occurs in the body in several enzymes, such as
DNA

polymerase,

alkaline

phosphatase

and

alcohol

dehydrogenase. Zinc complexes with insulin are present in the


beta cells of the pancreas. The absorption of zinc by the small
intestine involves pyridoxine of B-series.
Zinc is essential for normal growth and reproduction. It
has a beneficial effect on wound healing and tissue repair. This
suggests that zinc may be involved in protein synthesis. As a
co-factor for many enzymes zinc directly affect the metabolic
processes of the body.
Zinc deficiency symptoms include a diminished taste
sensation, growth retardation, sexual immaturity, and poor
wound healing.
The recommended daily allowance of zinc is 15 mg/day
for adults with an additional 15 mg/day during pregnancy and
10 mg/day during lactation. For children, the recommended
allowance is 6 to 10 mg/day. Food sources of zinc include:
seafood, red meat, liver, eggs, milk and whole grain cereals.

328
CALCIUM AS MACRONUTRIENT
Calcium is one of the major structural components of
the body. It is mainly found in bone and teeth as calcium
hydroxyapatite. It has been estimated that about 1.2 kg calcium
is present in a normal human adult of 70 kg body weight. In the
body Calcium is absorbed from the small intestine in the
presence of acids, particularly bile acids. The blood calcium
level of our bodies varies from 9.0 to 11.0 mg/100 ml. About
more than half of the total blood calcium exists in the ionic
state, which is diffusible. The rest is bound to blood protein and
thus in a combined state. It is non-diffusible. The calcium level
of the blood is affected by vitamin D, parathyroid hormone, sexhormones, proteins and amino acids. The parathyroid
hormones regulate the ionic calcium level of the blood. Usually
the ionized and protein bound calcium are in equilibrium.
The important physiological functions of serum calcium
include:
i.

normal formation of bones and teeth,

ii.

muscle contraction,

iii.

blood clothing or coagulation,

iv.

enzyme-activation,

v.

transmission of nerve impulses,

vi.

regulation of membrane permeability and

329
Deficiency of calcium in infant and children may be a
cause of rickets (abnormal formation of bones). Likewise, in
elderly

persons

dietary

deficiency

may

produces

osteoporosis, a condition in which bones decrease in size and


become increasingly fragile. Recent research indicates that low
intake of calcium may be correlated with a higher incidence of
hypertension. Calcium deficiency can be corrected by taking
such readily available sources of calcium as calcium gluconate,
calcium lactate, and calcium carbonate.
The daily calcium requirement of infant range from 360
to 540 mg and of children 600 to 800 mg. Teenagers need 1200
mg/day and adults 800 mg/day. During pregnancy and lactation
the requirements increased upto 1200 mg/day.
Milk and milk products are the best natural sources of
calcium. Milk contains 1.4 g of calcium per litre and cheese
from 5 to 10 g per kg. Whole wheat is the routine source of
calcium in Pakistan since wheat is our staple diet. It contains
about 40 mg calcium/100g. Green vegetables also contain
some calcium in the form of calcium oxalate, citrate, phytate,
etc.

330
PHOSPHORUS AS MACRONUTRIENT
Like calcium, phosphorus is also one of the structural
components of the body. It is also mainly found in bones as
calcium phosphate, but phosphate is also present in every cell
of the body. It has been estimated that upto 700g of
phosphorus is present in a normal human adult weighing 70 kg.
In blood phosphorus exists in the form of acid phosphates,
H2PO4, and HPO4. The normal level of inorganic phosphate in
the serum is 3.0 to 4.5 mg/100ml. Phosphorus absorption of the
body is greatly affected by calcium : phosphorus ratio. The
optimal ratio for maximum absorption of both is 1:1 and may
vary from 1.5 to 2.0. An excessively high ratio results in the
decreased absorption of phosphorus, and thus lower down the
blood phosphate level. The presence of Fe +++ reduced the
absorption of phosphate due to the formation of insoluble iron
phosphate. Serum phosphate levels are also greatly influenced
by parathyroid hormones. Low in hyperparathyroidism (more
parathyroid activity) and high in hypoparathyroidism (low
parathyroid activity).
Physiological functions of phosphate include:
i.

development of bones and teeth,

ii.

maintenance of the structure and function of biomembranes in the form of phospholipids,

331
iii.

formation of active enzyme systems (e.g.


oxidoreductases) as phospho-proteins,

iv.

formation of RNA, DNA and ATP (adenosine


triphosphate, the energy rich compound).

v.

constitution of buffer system in the cell, extracellular fluids (e.g. blood),

vi.

synthesis of phospholipids, such as lecithins,


cephalins and plasmalogens, etc., and

vii.

participation in carbohydrate metabolism by


forming esters of sugars. For example, glucose6-phosphate, fructose-6-phosphate etc.

Deficiency symptoms of phosphorus may be similar to


calcium since both are involved in maintaining the structural
integrity of bones. Dietary deficiencies of phosphorus are not
well known. However, as with calcium, there are sometimes
absorption problems, which may reflect vitamin D deficiency.
The daily requirement of phosphorus varies from 1.0 to
1.5 g depending upon the age, and stage of pregnancy and
lactation.
Rich sources of phosphorus include; milk and milk
products, legumes, cereals, meat, fish and poultry.

332
Chapter22:
INDUSTRIAL CHEMISTRY
Industrial chemistry is that branch of chemistry which deals
with the chemical processing of raw material into useful and
profitable products. Chemical processing may be defined as
The industrial processing of raw material leading to the
products of enhanced industrial value.
Safety Considerations necessary in the process of
industry:
1. Proper material of construction should be selected by
designing and chemical engineers in order to prevent
any loss.
2. To avoid harmful impurities present in raw materials ,
carefully process control by periodic analysis is
required as well as modern instruments should be
installed.
3. Suitable containers must be provided for supply.
4. To ensure safety of workers and the plant, all
procedures must be carried out in non-hazardous
manners.
5. To guarantee progress to continue profits and to
replace old processes and equipments. Money should
be spent on research and development.
6. To prevent contamination of water and air, factories
must be warned to avoid discharge of toxic material
into the air and water.

333
Chemical Composition of Dyes:
A colored substance which adds value to products of their
costs is called dye. In most of cases, color of product is
reason of its sale. A dye is a coloured substance that has
an affinity to the substrate to which it is being applied. The
dye is generally applied in an aqueous solution, and requires
a mordant to improve the fastness of the dye on the fibre.
Both dyes and pigments appear to be coloured because they
absorb some wavelengths of light more than others. In
contrast with a dye, a pigment generally is insoluble, and has
no

affinity

for

the

substrate.

Some

dyes

can

be

precipitated with an inert salt to produce a lake pigment, and


based on the salt used they could be aluminium lake, calcium
lake or barium lake pigments.
A dye consists of colour producing structure called

the

chromogen or chromopore [ electron acceptor]. The solubility


and dying properties called the auxochrome [ electron donor],
without these two parts material is simply colourless body.
The chromogen is aromatic containing a color giving group,
commonly called the Chromopore. They act as follow:
1) absorb light in the visible spectrum (400700 nm),
2) have at least one chromophore (colour-bearing group),
3) have a conjugated system, i.e. a structure with alternating
double and single bonds.
4) exhibit resonance of electrons, which is a stabilizing force
in organic compounds (Abrahart, 1977). When any one of

334
these features is lacking from the molecular structure the
colour is lost.
5) In addition to chromophores, most dyes also contain
groups known as auxochromes (colour helpers), examples of
which are carboxylic acid, sulfonic acid, amino, and hydroxyl
groups. While these are not responsible for colour, their
presence can shift the colour of a colourant and they are most
often used to influence dye solubility

Some of common chromophores are given as:


Nitroso group NO [-N=OH]
Nitro group
NO2
Azo group
-N=NCarbonyl group
CO
Carbon-nitrogen
CN
Carbon-sulpher
CH3-SH
Ethylene group
-C=C-

335

Dyes are of many types. Dye may be classified as follow:


1. Acid Dyes:
Such kind of dyes are used for dying protein fibers such as
wool, silk, nylon, leather and paper. They contains one or
more sulphuric acid substituent or other acidic group.
Example is acid yellow 36 ( metanil yellow).
2. Basic Dyes:
Used to dye wool or cotton as duplicator inks, carbon paper,
typewriter ribbons. In solvents other than water, they form
writing and printing inks. Basic dyes are mostly amino
compounds dissolved in acids and made insoluble by the

336
solution being made basic. Examples are basic brown
(Brismark Brown) , basic violet (crystal violet).
3. Azo dyes:
These are brilliant and long lasting dyes. They are used to
dye the goods made up of both cotton and wool or silk. Azo
dye solubility is generally reduced by adding salt. Examples
are direct orange 26 and direct black 22 are typical azo dyes.
4. Direct Dye:
Such dyes are used to dye the cotton directly, without adding
any mordant. They are also used to dye union good. These
are usually azo dyes and their solubility in the dye bath is
reduced by adding salt. Direct orange 26 and direct black 22.
5. Disperse Dye:
Some fibers such as plastic, cellulose acetate, polyesters,
Nylon fibers are difficult to dye. Disperse dyes are very fine
particles which are absorbed on these materials, and they
form solid solution with them. Examples are disperse red 4,
disperse red 77, disperse orange 25, and disperse blue 27.
6. Fiber-Reactive Dyes:
These dyes react with substrate, usually cellulose to form
covalent bond between dye and fiber like cotton, rayon and
some nylons are dyed with this dye. Vinyl sulfone are typical
example.
7. Mordant Dyes and Lakes:
Some dyes combines with metallic salts to form highly
insoluble coloured materials, called lakes. They are usually
pigments. If a cloth made of cotton, wool or other portentous
fiber is impregnated with lake forming dye, the metallic
precipitate form in the fiber and color becomes far more
resistant to light and washing. The azo and anthraquinone
nucli, having attached the groups like OH and COOH can act
as mordant dye.
8. Sulphur dyes:
These dyes have been used
since long time. They are
large low cost group of dyes
which produce dull shades
on cotton. The chromophore is complex and not well defined.

337
Sulphur dyes are usually colorless
when inthe reduced form in sodium
sulphide bath but gain color on
oxidation.
9. Solvent dyes:
The spirit soluble dyes are usually azo-triaryl methane are or
anthraquinones which is organic compound. These are used
to color oils, waxes, varnishes, shoe polish etc.
10. Vat-Dyes:
Vat dyeing is a process that refers to dyeing that takes place
in a bucket or vat. These are water
insoluble organic pigments, and
becomes water soluble when mixed
with powerful reducing agents. The
reducing operation formerly was
carried out in wooden vats. They
have highly complex structures and
mostly
are
derivatives
of
indanthrone. Vat dyes are expensive and are used on cotton
cloths that are subjected to often washing and bleaching.
Some vats are applied as pastes for printing. The best known
dyes of this class is Indigo, which is one of most popular color
in the world.
Pesticides:
Pests amdparaser such as insect, fungi, weeds, nematodes
and bacteria which adversely affect the crop plants and
reduce yield and quality of the product. When other
preventive measures such as cultural, are inadequate to
suppress these pests, then chemicals are used as an
effective weapon against the pests and parasites. Such
compounds, which are injurious to the pests and protect the
crops from their harmful effects, are called pesticides. They
also include compounds for the control of rodents, mites,
household and stored products pests.

338
Pesticides are essential tolls of modern agriculture.
They form an integral part of the overall strategy because
production has hardly any meaning without protection. They
have changed the prospects of crop production worldwide.
Pesticides have played a significant role in green revolution
and in increasing crop yield per unit area. They brought
revolutionary change in farm practice. Pesticide use in
developing countries is indispensable in the struggle against
hunger and disease. Emphasis should be given to judicious
and safe use rather than the banning and restriction of
pesticides.
According to the plant protection Department of
Pakistan, the estimated loss in yield due to pest damage
ranges from 15 to 20% and occasionally it is as high as 60 to
70% Pesticide use in Pakistan is based on minimum curative
applications and on controlling epidemic infections. In
Pakistan over 70% pesticides are used on cotton and the rest
mainly on rice, sugarcane, fruits and vegetables. At present
400 products comprising over 200 active ingredients are
registered.
CLASSIFICATION
Pesticides may be classified on the basis of their
action against a certain group of organism. They may be:
i.

Insecticides: which kill harmful insects, e.g.


aphids, grass hoppers and stem-boreres, etc.

ii.

Fungicides,

which

are

used

to

combat

pathologenic fungi (fungal diseases), such as rusts


ad smuts on cereals.

339
iii.

Herbicides/weedicides: which control undesired


herbs, shrubs and weeds, like wild oats i.e
JangliJai (Avena fatua L) and wild onion i.e Piazi
(Asphodelus tenuifolius, Cor).

iv.

Nematicidies: which kill nematodes that are


parasitic for crop plants, e.g root-knot nematode
(Macrophomina javania) in tobacco nursery.

v.

Bactericides: which are used against bacterial


diseases, e.g leaf blight of rice and mungbean.

vi.

Acaricides: to check phytoparasitic mites, such as


spider mites.

vii.

Rodenticides, which are toxic to field rodents that


feed on crop plants. They are usually stomach
poison baits.

Another classification of pesticides is based on


physiological response of the organisms (pests and
parasites). Thus they may be

i.

Contact pesticides; which kill the pest by contact


action, presumably by absorption through the
cuticle. These pesticides are also called protectant
or surface pesticides because they are applied on
the plant surface and protect the crop from
damage by the pests..

340
ii.

Stomach poisons: which are ingested and


become toxic after digestion

iii.

Fumigants: are those compounds, which exhibit


toxicity in volatile or gaseous state. In closed
compartment or rooms the toxic gas penetrate into
the pests respiratory system.

iv.

Systematic Pesticides: These are compounds,


which are absorbed and translocated within the
plants through sap. Such insecticides are mostly
effective

against

sucking

insects.

These

compounds used for plant disease control are also


called plant chemotherapeutants.

v.

Eradicants: Those pesticides which eliminate the


pest after invasion are called

eradicants.. An

established infection in the field can be vanished


by the application of such compounds. Both
protectants

and

systemic

compounds

have

eradicant properties.
On the basis of their chemical nature, pesticides
are also categorized as inorganic and organic.
The earlier compounds used for insect and
disease control in crop plants were inorganic,
followed by the introduction of organic compounds
in 1950s. Further pesticides may be categorized or

341
(i) organochloines: which include
chlorinated

eyclodiene

and

(a) DDT, (b)

(c)

kexachloro

eyclohexanos (HCH) (ii) organephosphates: which


are organic esters of phosphoric acid. World used
more than 100 such cmpounds are use as fast
acting

systemic

pesticides.

(iii)

Carbonates:

These are the derivative of carbonic acid, acting


as nerve poison. The were discovered in early
1950, the first chemical product was carbarye,
marheted by union carnide carparation. They are
used as in sectdes. (iv) Pyrethsorids:

these are

orlyliqvid insoluble in water and soluble inorganic


solven to pike alcouol and acetone . These
neusotoxins were first obtained from the flower of
chrysanthemum species. (C) Because of the high
cost of matural pyrothseen, synthetic compounds
have been introduced in 1976, which are used as
effective insecticides.
Mirex:
It is chlorinated hydrocarbons that was commercialized as an
insecticides and later on banned because of its harmful
impact on environment. This was derivative of white
crystalline cyclopentadiene.
Chlordane:
It is an organic chlorine compound used as pesticide. Till
1983 it was being used in citrus crops, legumes and as
garden.

342

Heptachlor:
Used as organochlorine as insecticides. Available as white
tan powder.
Aldrin:
Widely used until 1970 as insecticides.
Dieldrin:
It was produced in 1948 by J Hyman as insecticides. Both
dieldrin and aldrin are named after the Dielder reaction with is
used to form Aldrin.
Petrochemicals:
These
are chemical
products derived
from petroleum.
Some chemical compounds made from petroleum are also
obtained from other fossil fuels, such as coal or natural gas,
or renewable sources such as corn or sugar cane.
The
two
most
common
petrochemical
classes
are olefins (including ethylene and propylene)and aromatics(i
ncluding benzene, toluene and xylene isomers). Oil
refineries produce olefins and aromatics by fluid catalytic
cracking of petroleum fractions. Chemical plants produce
olefins
by steam
cracking of natural
gas
liquids like
ethane and propane. Aromatics are produced by catalytic
reforming of naphtha. Olefins and aromatics are the buildingblocks
for
a
wide
range
of
materials
such
as solvents, detergents, and adhesives. Olefins are the basis
for polymers and oligomers used
in plastics, resins, fibers, elastomers, lubricants, and gels.
Global ethylene and propylene production are about 115
million tonnes and 70 million tonnes per annum, respectively.
Aromatics production is approximately 70 million tonnes. The
largest
petrochemical
industries
are
located
in
the USA and Western Europe; however, major growth in new

343
production capacity is in the Middle East and Asia. There is
substantial inter-regional petrochemical trade.
Primary petrochemicals are divided into three groups
depending on their chemical structure:

Olefins
includes ethylene, propylene,
and butadiene. Ethylene and propylene are
important
sources of industrial chemicals and plastics products.
Butadiene is used in making synthetic rubber.
Aromatics includes benzene, toluene, and xylenes.
Benzene is a raw material for dyes and synthetic
detergents,
and
benzene
and
toluene
for
isocyanates MDIand TDI used
in
making polyurethanes. Manufacturers use xylenes to
produce plastics and synthetic fibers.
Synthesis
gas is
a mixture of carbon
monoxide and hydrogen used
to
make ammonia and methanol. Ammonia is used to make
the fertilizer urea and methanol is used as a solvent
and chemical intermediate.
Primary precursor petroleum- Petrochemicals

Raw
Precursor
material by
Distillation
Refinery
Gases
Acetylene
Isobutene
Ethane
Ethylene
Propane
Propylene
N-butane
N-butanes
Hexane
Heptanes
Refinery
Napthas

Intermediates

Final products

Acetic acid
Acetic
anhydride
Isoprene
Ethylene oxide
Butadiene
Adipic acid
Ethyl benzene
styrene

Acetates
Fibers
Rubbers
Fibers
Styrene
Rubbers

344

345

346

The lower members of olefin and parafine series have been


the preferred and most economical sources of organic raw
materials for conversion.
Petrochemicals from Methane
Basic
Ammonia
Carbon Black
Methanol

Uses, (Percent)
Fertilizers (80%) plastics and fibers
(10%) explosive (5%)
Tyrese (65%) other rubber (25%)
colorant and fillers (10%)
Polymers (50%) solvents (10%),
derivatives (HCHO, CH3COOH, 40%)

Chloromethane
Methyl
Chloride Silicons (57%), Tetramethyl lead
(CH2Cl2)
(19%)
Chloroform (CHCl3)
Paint
remover
(30%),
Aerosol
Propellant (20%) dgreaser (10%)

347
Carbon tetrachloride Fluorocarbons (95%), fumigant etc
(CCl4)
(5%)
Acetylene
VCM(37%) 14, butanedial (25%) Vinyl
acetate (14%) Vinyl flouride and
acetylene black (5%)
Hydrogen Cyanide
MMA (58%) cyanuric chloride (17%)
chelating agents (13%) NaCN (9%)
Petrochemicals from Ethylene
Basic Derivatives
Ethyl Benzene
Ethyl Chloride
Ethylene Dichloride
Ethylene glycol
Ethylene oxide
Perchloro ethylene
Polyethylene
Low
High Density
Styrene
1,1,1 trichloroethane

Uses, (Percent)
Styrene (99%), solvent (1%)
TEL (90%) pharmaceuticals (5%)
VCM (84%) solvent (7%)
Antifreez (38%) polyester fibers and
films (49%)
Glycol (60%) Rthoxylates (10%) Glycol
ethers (10%)
Textile cleaning (40%) metal cleaning
(21%)
Film, sheet, molding and extrusion
plastics
Film, sheet, molding and extrusion
plastics
Polyestyrene (52%) ABS (9%) SBR
(7%) polyester resign(6%) SB Latex
(6%)
Cold
Cleaning
(40%
capour
degreasing 22%)

Fractional Distillation of Petroleum


Suspended solids and gases are first removed from crude oil
and it is then subjected to fractional distillation. Various
fractions of hydrocarbons are obtained at different boiling
ranges.

348

S,No

Fraction

Refinery
Gas

Petroleum
ether

Petrol
or
Gasoline

Benzine

6
7
(i)
(ii)

(iii)

Boiling
range
Below
o
20 C

Composition

Uses

C1-C4

30-70
o
C
70-120
o
C
120-150
o
C

C5-C6

Fuel,
making
other organic
compounds
Solvent for fats,
oil for varnish

Kerosene oil
or Paraffin
oil or jet oil

150-250
o
C

C11-C12

Diesel oil or
Gas oil or
Heavy oil
Residue

250-400
o
C

C13-C18

Above
o
400 C

C17
higher

C6-C8

Fuel
for
automobiles

C9-C10

Dry cleaning,
solvent
for
varnish
and
fats
Fuel
in
oil
stoves,
illuminant
in
lamps
and
lantern, jet fuel
Fuel in Diesel
engines

Lubricating
oil
Paraffin wax

C17-C20

Pitch
Asphalt

C30-C40

or

C20-C30

and

Its
vacuum
distillation
Gives following
Lubrications
Candles, boot
polish,
wax
paper,
Ointments,
Vaseline
Road surfacing

349
In internal combustion engines, fuel is compressed and is
then ignited to burn by electric spark. Some fuels especially
that consisting of straight chain hydrocarbons does not give
proper compression ratio and without the spark being passed.
It gives violent jerk to piston. This violent jerk causes a
metallic noise known as knocking. It lowers the efficiency of
engine and results in loss of energy.
The order of knocking problem caused by various fuels is
Straight chain alkanes > Branched chain alkanes > alkenes >
Cycloalkanes > Aromatic hydrocarbons
Quality of fuel is determined by its Octane Number.
Octane Number is defined as the percentage of iso octane
(by volume) in a mixture of iso octane and n-heptane, which
has same knocking as the fuel being tested.

The concept of octane number was given by Edgar in 1927.


He pointed that n-hexane gives maximum knocking while iso
octane gives minimum knocking. He arbitrarily gave Zero
octane number to n-heptane and 100 octane number to iso
octane.
The octane number of fuel is found by comparing its
performance with a mixture of n-Heptane and iso octane in a
standard test engine. If it shows performance like a mixture
of 25% n-Heptane and 75% Iso Octane, its octane number is
considered to be 75.
Fuel having high octane number gives low knocking. e.g.
octane number of regular petrol is 74 while that of super
petrol is 85, therefore, super petrol gives low knocking then
regular petrol.

350
Straight chain alkanes give more knocking so there
octane number is low. There are two methods of removing
this problem.
(i)
Addition of anti knocks: Anti knocks like TEL i.e. tetra
ethyl lead (C2H5)4Pb, TML i.e. tetra methyl lead (CH 3)4Pb are
added to remove knocking problem. 1 ml of anti knock is
added per litre of petrol. Anti knocks dissociate to give free
alkyl radicals which
convert straight chain hydrocarbons in to branch chain
hydrocarbons. Thus antiknocks increase the octane number
of the fuel but they give a serious problem i.e. their
combustion produce lead which goes in to air along with
exhaust gases and causes air pollution.
Scavenger (e.g. ethylene dibromide Br-CH2-CH2-Br) is added
to remove lead.
Addition Polymers:
The polymerization in which the monomer molecules are
added as a whole with no elimination is called addition
polymerization and the polymer is called addition polymer.
Unsaturated monomers polymerize to give addition
polymers.
Their molecular masses are some whole number multiples
of the molecular mass of their monomers.
They are of three types
(i). Homopolymers: The polymers which are produced by
polymerization of only one monomer are called
homopolymers e.g. Polyethylene, PVC, PVA, polystyrene etc.
1.

Poly Ethylene:

When ethylene is subjected to a pressure of 100 psi and a


o
temperature of 400 C it polymerizes to give polyethylene

351
which is a tough flexi plastic used to make shopping bags,
table cloths, plastic bottles etc.

2. Poly Vinyl Chloride (PVC):


o
When acetylene is heated with HCl at 150 C in presence of
catalyst, vinyl chloride is produced.

o
Vinyl chloride is when subjected to 52 C and 9 atm pressure
it polymerizes to poly vinyl chloride (PVC).

Commercially this polymerization is carried out in suspension


o
or emulsion. In emulsion low heating is required (20 C)
whereas is suspension higher temperature is required (50o
80 C).
If a plasticizer is added to it, its flexibility increases. It is a
cheapest plastic used globally. It is used to make pipes,
tubing, garden hoses, garbage bags, cable insulations, fiber
manufacturing and gramophone recorders.
Condensation polymers:
The polymerization in which the monomer molecules are
added after elimination of a small molecule like H2O, HCl,

352
NH3, CH3OH etc, is called condensation polymerization and
the polymer is called condensation polymer.
Saturated monomers polymerize to give condensation
polymers.
Their molecular masses are not whole number multiples of
the molecular mass of their monomers.
1.

Polyester:
Polyesters are condensation polymers, which are produced
by condensation polymerization of dicarboxylic acid and diol.
But this polymer has low melting point. But if an aromatic di
ester like dimethyl terephthalate (DMT) is polymerized with a
diol like ethan-1,2-diol, polyethylene terephthalate (PETP) is
obtain. PETP is a polyester, its trade name is Terylene. Its
o
melting point is 265 C.
o
Polymerization is carried out at 200-300 C under a high
vacuum. Many other polyesters can also be produced. They
are unattacked by chemicals.
Uses: They are used to make textile fibres. The garments
made from theses fibres, resist the formation of wrinkles.
They are used to make carpets.
They are used to make magnetic recording tapes.
Plastic soft drinks bottles are made from them.
Artificial blood vessels and valves are made from them.

2.

Polyamides:
These
are
condensation
polymers
produced
by
polymerization of dicaboxylic acids with diamines. The
synthetic polyamides are called Nylons. Their names are
indicated by numbering system e.g. Nylon produced by
hexamethylene diamine and adipic acid (hexanedioic acid) is
called Nylon-6,6.

353
Nylon-6,6 has good tensile strength, abrasion resistance and
toughness. It is resistant to many chemicals.
Uses: It is used as textile fibre.
It is for production of tyre cords and ropes.
It is a good substitute of metals thus is used in gears and
bearings.
COSMETICS
Lipstick:
Lipstick were introduced after world I. lipstick is the cosmetic
which is generally formulated to provide both protection ( for
the delicate tissues of lips) and color. They are made to be
neutral in taste, stable under normal conditions like
temperature, moisture, air flow and able to prevent toxicity
and irritation to lip tissues.
Chemical Composition:
Lipstick chemical composition varies greatly. It may include
mixture of oils, waxes, pigments, antioxidants and
preservatives, sometime perfumes are also added in small
quantity to eradicate the unpleasant smell of oils.
Most of the bulk of lipstick is usually a solid waxy material
mixed with a nonvolatile oil, so it can be spread easily but
remains stiff in the tube. Common compositions use beeswax
and castor oil, or carnuba wax. A recently patented
composition uses a solid silicone material with polyethylene
solidifier, and silicone oil.
Many different pigments are used. The dyes have to be
insoluble in water, so the color will last. Soluble dyes are first
'laked', that is, converted to insoluble particles by treatment
with metal oxides. Eosin is a commonly used red dye in
lipsticks:

354

Eosin, the red pigment in lipsticks.


Gray=Carbon, Red=Oxygen,
Brown=Bromine.
Click the image for a 3D Chime
model.

It becomes an intense red when it reacts with NH 2 groups in


proteins on the surface of the skin. The pigment is masked in
the tube by a laked green or blue dye, and the color change
when the lipstick is applied to the skin is sharp.
Many other ingredients insure that the lipstick has the proper
texture and melting point. For example, esters of fatty acids
(myristates) are sometimes added to give the lipstick
'stickiness'.
Characteristics:

it should be nonirritating and nontoxic

it should be stable both physically and chemically.

it should not dry on storage.

it should be free from gritty particles.

it should maintain lip colour for longer period after its


application.

it should give shiny and smooth appearance free from


sweating.

355
Nail Varnish :
Nail polish is a lacquer that can be applied to the
human fingers or toe nails to decorate and protect the nail
plate. The formulation has been revised repeatedly to
enhance its decorative effects and to suppress cracking or
flaking. Nail polish consists of an organic polymer with various
additives. Nail polish originated in China, and its use dates
back to 3000 BC. Around 600 BC, during the Zhou dynasty,
the royal house preferred the colors gold and silver. However,
red and black eventually replaced these metallic colors as
royal favorites. During the Ming dynasty, nail polish was often
made from a mixture that included beeswax, egg
whites, gelatin, vegetable dyes, and gum Arabic.
In Egypt, the lower classes wore pale colours, whereas high
society painted their nails red.
By the turn of the 9th century, nails were tinted with scented
red oils, and polished or buffed. In the 19th and early 20th
centuries, people pursued a polished rather than a painted
look by massaging tinted powders and creams into their nails,
then buffing them shiny. One such polishing product sold
around this time was Graf's Hyglo nail polish paste.
Traditionally, nail polish started in clear, red, pink, purple, and
black. Since that time, many new colors and techniques have
developed, resulting in nail polish that can be found in an
extremely diverse variety of colors. Beyond solid colors, nail
polish has also developed an array of other designs, such as
crackled, speckled, iridescent, and holographic; rhinestones
or stickers are also often applied. Some types of polish are
advertised to cause nail growth, make nails stronger, prevent
nails from breaking, cracking and splitting, and to stop nail
biting. Nail polish may be applied as one of several
components in a manicure.

356
Composition and Preparation:
There is no single formula for nail polish. There are, however,
a number of ingredient types that are used. These basic
components

include:

film

forming agents,

resins

and

plasticizers, solvents, and coloring agents. The exact


formulation of a nail polish, apart from being a corporate
secret, greatly depends upon choices made by chemists and
chemical engineers in the research and development phase
of manufacturing. Additionally, as chemicals and other
ingredients become accepted or discredited for some uses,
adjustments are made. For example, formaldehyde was once
frequently used in polish production, but now it is rarely used.
The primary ingredient in nail polish is nitrocellulose (cellulose
nitrate) cotton, a flammable and explosive ingredient also
used in making dynamite. Nitrocellulose is a liquid mixed with
tiny, near-microscopic cotton fibers. In the manufacturing
process, the cotton fibers are ground even smaller and do not
need to be removed. The nitrocellulose can be purchased in
various viscosities to match the desired viscosity of the final
product.
Nitrocellulose acts as a film forming agent. For nail polish to
work properly, a hard film must form on the exposed surface

357
of the nail, but it cannot form so quickly that it prevents the
material underneath from drying. (Consider commercial
puddings or gelatin products that dry or film on an exposed
surface and protect the moist product underneath.) By itself or
used with other functional ingredients, the nitrocellulose film is
brittle and adheres poorly to nails.

Nail polish is made


by

combining

nitrocellulose

and

plasticizers

with

color pigments. The


mixing is done in a
"two-roll" differential
speed mill, which grinds the pigment between a pair of rollers
that are able to work with increasing speed as the pigment is
ground down. The goal is to produce fine dispersion of the
color.
plasticizer. Butyl stearate and acetate compounds are
perhaps the most common.
Finally, the polish must have a color. Early polishes used
soluble dyes, but today's product contains pigments of one
type or another. Choice of pigment and its ability to mix well

358
with

the solvent and

other

ingredients

is

essential

to

producing a good quality product.


Nail Polish Remover:
A nail polish remover is an organic solvent that is used to
remove previously applied nail polish from nails. There are
many different types of removers on the market and different
brands may have different chemical compositions. The
principle ingredients in most, however, are acetone,
ethyl acetate or butyl acetate, and alcohol.
These chemicals are known to dehydrate the skin, cause
irritation to eyes, and make nails dry and brittle. They also
have a distinct chemical smell and are highly flammable. To
counter the dehydration and brittleness effects, many
removers also contain conditioning ingredients like castor oil,
cetyl palmitate, or lanolin.
Some removers are acetone-free, but this does not
necessarily mean that the product is without side effects, so
shoppers should screen the ingredients list carefully. Instead
of acetone, the nail polish remover may contain the more
toxic methanol. Consumers looking for safer and less-toxic
options can opt for water-based products.
Working
To understand how nail polish remover works, it is necessary
to know that fingernail polish and the remover both contain
similar organic solvents; the nail polish also contains drying
agents, thickeners, hardening agents, and coloring agents.
The organic solvent in a nail polish is what keeps it in a liquid
state. A solvent in the remover is what dissolves the hardened
polish and returns it back into its liquid form. When the

359
remover is applied to the nail polish, the molecules interrupt,
loosen, and break the polymer chains of the polish. This
dissolves the hardened polish and transforms it back into its
original liquid form so that it can then be wiped off the nail.
Hair Dyes
It is the practice of changing the color of hair. The main
reasons for this practice are cosmetic (e.g., to cover gray hair,
to change to a color regarded as more fashionable or
desirable, or to restore the original hair color after it has been
discolored by hairdressing processes or sun bleaching). Hair
dyeing, which is an ancient art, [1]involves treatment of the hair
with various chemical compounds. Hair color was traditionally
applied to the hair as one overall color. The modern trend is
to use several colors to produce streaks or gradations, not all
work on top of a single base color. These are referred to as:
Types of hair coloring
The four most common classifications are permanent, demipermanent (sometimes called deposit only), semi-permanent,
and temporary.
1. Permanent hair color
A very popular way to achieve permanent hair coloring is
through the use of oxidation dyes. The ingredients of these
products

include 1,4-diaminobenzene (historically)

or 2,5-

diaminotoluene (currently), a coupling agent, and an oxidant.


The process is typically performed under basic conditions.

360
The preparation (dye precursors) is in the leuco (which
means colorless) form. Oxidizing agents are usually hydrogen
peroxide, and the alkaline environment is usually provided by
ammonia. The combination of hydrogen peroxide and the
primary intermediate causes the natural hair to be lightened,
providing a "blank canvas" for the dye. Ammonia opens the
hair shaft pores so that the dye can actually bond with the
hair and speeds up the reaction of the dye with the hair. Now
people can dye their hair without bleaching it.
Various combinations of primary intermediates and couplers
provide a spectrum of shades of hair colors. The primary
intermediates are aromatic para compounds, such as 1,4diaminobenzene or 4-aminophenol. The couplers are metasubstituted derivatives of aniline. They come in three major
classes based on the color that they produce when they react
with the primary intermediate.

361
Couplers are chemical compounds that define the color of the
hair dye. Shown here are three red couplers (A,B,C), two
yellow-green couplers (D,E) and a blue coupler (F).

Blue couplers include 1,3-diaminobenzene and its


derivatives.

Red couplers include phenols and naphthols, such as


3-aminophenol

(CAS#591-27-5),

(CAS#2835-95-2)

and

5-amino-2-methylphenol

1-naphthol

(CAS#90-15-3).

The

combination of 2,5-diaminotoluene with the coupler 3aminophenol

gives

magenta-brown

dye,

while

the

combination of 2,5-diaminotoluene with the coupler 1

naphthol gives a purple dye.


Yellow-green couplers

include

resorcinol,

4-

chlororesorcinol, and benzodioxoles. These compounds


produce broad-band absorption when they react to form dyes,
allowing for more natural-looking hair colors. The combination
of 2,5-diaminotoluene with the coupler resorcinol gives a
greenish brown dye.
The first step shows the oxidation of p-phenylenediamine to
the quinonediimine (C6H4(NH)2):

362
This species exists in equilibrium with the monoprotonated
form (C6H4(NH)(NH2)+) (not shown). The second step involves
the attack of this quinonediimine on the coupler. In organic
chemistry,

this

reaction

is

calledelectrophilic

aromatic

substitution:

In

the

third

and

final

step,

the

product

from

the

quinonediimine-coupler reaction oxidizes to the final hair dye.

The resulting hair dye is also much larger than the precursor
molecules, which causes the dye to bond to the hair.
2. Demi-permanent hair color
Demi-permanent hair color is hair color that contains an
alkaline

agent

other

than

ammonia

(e.g. ethanolamine, sodium carbonate) and, while always


employed with a developer, the concentration of hydrogen
peroxide in that developer may be lower than used with a
permanent hair color. Since the alkaline agents employed in
demi-permanent colors are less effective in removing the
natural pigment of hair than ammonia these products provide
no lightening of hair's color during dyeing. As the result, they
cannot color hair to a lighter shade than it was before dyeing

363
and are less damaging to hair than their permanent
counterpart.
Demi-permanents have several advantages as compared
with permanent color. Because there is essentially no lifting
(i.e., removal) of natural hair color, the final color is less
uniform/homogeneous than a permanent and therefore more
natural looking; they are gentler on hair and therefore safer,
especially for damaged hair; and they wash out over time
(typically 20 to 28 shampoos), so root regrowth is less
noticeable and if a change of color is desired, it is easier to
achieve. Demi-permanent hair colors are not permanent but
the darker shades in particular may persist longer than
indicated on the packet.
3. Semi-permanent hair dye
Semi-permanent hair color has smaller molecules than
temporary dyes. These dyes only partially penetrate the hair
shaft. For this reason, the color will survive repeated washing,
typically 45 shampoos or a few weeks. Semi-permanents
contain no, or very low levels of developer, peroxide or
ammonia, and are therefore safer for damaged or fragile hair.
However, semi-permanents may still contain the possibly
carcinogenic compound p-phenylenediamine or other such
ingredients. The U.S. Environmental Protection Agency
reported that in rats and mice chronically exposed to PPD in
their diet, it simply depressed body weights, and no other
clinical signs of toxicity were observed in several studies.

364
The final color of each strand of hair will depend on its original
color and porosity, so there will be subtle variations in shade
across the whole head. This gives a more natural result than
the solid, all over color of a permanent color. However, it also
means that gray or white hairs will not appear as the same
shade as the rest of the hair. If there are only a few grey/white
hairs, the effect will usually be enough for them to blend in,
but as the gray spreads, there will come a point where it will
not be disguised as well. In this case, the move to permanent
color can sometimes be delayed by using the semipermanent as a base and adding highlights.
Semi-permanent color cannot lighten the hair.
4. Temporary hair color
Temporary hair color is available in various forms including
rinses, shampoos, gels, sprays, and foams. Temporary hair
color is typically brighter and more vibrant than semipermanent and permanent hair color. It is most often used to
color hair for special occasions such as costume parties .
The pigment molecules in temporary hair color are large and
cannot penetrate the cuticle layer. The color particles
remain adsorbed (closely adherent) to the hair shaft and are
easily removed with a single shampooing. Temporary hair
color can persist on hair that is excessively dry or damaged in
a way that allows for migration of the pigment to the interior of
the hair shaft.

365
Chapter 23: Environmental Chemistry
The branch of chemistry which deals with pollutants, their
toxic effects and solution to pollution problems is called
environmental chemistry. .
Earth when formed about 4.5 billion year ago, was very hot
and there was no life on it. But then it started cooling. Steam
condensed to water, atmospheric gas formed, ozone layer
formed in stratosphere. With this, earth became suitable for
life. Life was peaceful but when industries and machines were
developed pollution problems started, which are becoming
worse day by day.
Components of Environment:
(i)

Lithosphere:

The upper rocky crust of earth which extends to the depth of


100km, is called lithosphere. It includes soil, minerals and
organic matter present in the earth crust.
Total land above sea level is 36.6 billion acres, out of which
11 billion acres are directly useable by man. About 6 billion
acres are used for agriculture. But agricultural land is
decreasing due to erosion and urbanization by increasing
population.
Composition of lithosphere is
O
46.6%
Si
27.72%
Al
8.13%
Fe
5%
Ca
3.63%
Na
2.83%
K
2.59%
Mg
2.09%
Ti,H&P
1%
C& trace elements
0.02-0.1%

366
(ii)

Hydrosphere:

Various forms of water on earth, make hydrosphere.


These include oceans, lakes, rivers, streams, snow, glaciers,
polar ice caps and ground water reservoirs i.e. water below
earth surface.
71% of earths surface is covered with oceans and 3.5%
by polar ice. 97% of earths water is contained in oceans, 2%
by polar ice and glaciers while only 1% is fresh water (ground
water, lake, river, stream etc). We use fresh water for
agriculture, industry, transport and domestic purposes.
(iii)

Biosphere:

The region of the earth which supports life is called


biosphere. It includes lower atmosphere, oceans, rivers,
lacks, soil and solid sediments that interchange materials with
all type of living organisms.
Biosphere can also be defined as the place where living
organisms interact with other earth system.
Ecosystem is smaller unit of biosphere, which consists of
community of living organisms and their interaction with
environment.
(iv)
Atmosphere:
Envelop of gases that surrounds the earth surface
is called atmosphere. It is extended to 1000 km
above earths surface. Half of its mass is
concentrated in lower 5.6 km. It contain
N2
78%
O2
21%
Ar
0.9%
CO2
0.03%
Trace gases 0.07%
Trace gases includes H2, O3, CH4, He, Ne, Kr, Xe, water
vapours etc

367
Atmosphere maintained life on earth. O2 is required for
breathing, N2 is used by nitrogen fixing bacteria, CO 2 is used
by plants for photosynthesis, water vapours for sustaining life.
Atmosphere saves life from hostile environment of outer
space. It absorbs cosmic rays, U.V rays coming from outer
space.
It maintains heat balance of the earth. It is responsible for
hydrological cycle (water from oceans to land and back to
oceans).
The atmosphere is divided into four spheres:
(a)
Troposphere: It extend from 0-11km. The
o
temperature ranges from 15 to -56 C.
It decreases with altitude.
It constitutes 70% of the atmosphere.
It contains N2, O2, CO2, water vapours.
Its temperature falls with increase in
altitude.
(b)

Stratosphere: It extends from 11-50 km.


o
Its temperature vary from -56 to -2 C.
Its temperature increases with altitude.
Its important constituent is ozone O3. Its
temperature increase with increase in altitude
Ozone layer is a shield against U.V rays
coming from sun.
(c)

Mesosphere:

(d)

Thermosphere:

It

extends

50-85 km. Its


o
temperature varies from -2 to
-92 C. It contains
NO+ and O2+. Its temperature decreases with increase
in altitude.
It

extends

from

up

to

500 km. Its


o
temperature varies from -92 to +1200 C. Its major
chemical species are NO+ and O2+. Its temperature

368
increases
with
increase
in
altitude.
Here
electromagnetic radiations change the gases to
plasma state.
Human interaction with environment:
Human is in continuous interaction with environment.
Man needs oxygen, food, space, shelter, cloths and energy.
In beginning humans life was very simple but with passage of
time he developed industries, transport means which have
made environment unfriendly due to pollution caused by
them. One should seriously think about it.
Air Pollution:
The air is polluted when harmful substances which
damage the environment, human health and quality of life are
mixed in it. The pollutants (solid, liquid, gases) travel through
air due to circulation of air and reach to oceans other places
and man. Gases gradually accumulate in the air and
eventually reach to the level beyond TLVs (threshold limit
values) and thus become pollutants.
Gases and other substances that accumulate in air and
reach beyond threshold limit values are called pollutants.
Presence of pollutants or contaminants in air is called air
pollution.
The pollutants of air are dust, grits (tiny pieces of stones),
fumes, gas effervescence, mist fog, smog, soot, smoke,
cloud, poly aromatic hydrocarbons (PAH), poly acylnitrates
(PAN) and vapours etc.
Types of Pollutants:
Pollutants are divided into two categories:
Primary pollutants:
The substances that are directly
emitted from sources are called primary pollutants e.g. H2S,
SO2, NO, NH3, HF, HCl, CO, CO2 etc.

369
Secondary pollutants: The substances that are formed in the
atmosphere by chemical interactions amongst primary
pollutants are called secondary pollutants e.g. NO 2, SO3,
H2SO4, ketones and ozone.
Sources of Pollutants:
Sources of pollutants are divided into two categories:
(1) Natural source:
It includes all wind blown or wind
assisted pollutants like sea salt, smoke gases, forest fires and
volcanic gases.
(2) Anthropogenic source:
It includes pollutants given by
man made industrial activities, power plants, fuel burning in
automobiles.
Some main air pollutants:
1. Carbon Monoxide:
It is colourless, odourless gas. It is three times lighter
than air. It is slightly soluble in water.
It is highly toxic and is asphyxiant gas. (The gas which makes
some one unable to breath and can cause death is called
asphyxiant gas). CO get bonded to haemoglobin more
strongly than O2 so oxygen thus excludes from respiration.
Exposure
to
CO
results
in
headache,
fatigue,
unconsciousness and eventually to death if exposure is for
longer time. CO poisoning can be reversed by giving high
pressure oxygen.
Sources:
Natural sources: Its natural sources are volcanic eruption,
natural gas emission and oxidation of methane in air.
Methane is also formed during decay of organic matter and it
then on oxidation in air produces CO.

370
Anthropogenic source: It is mainly produced by incomplete
combustion of carbonaceous materials. Its chief sources are
exhaust from automobile, railway, aircrafts and burning of
coal. Beside these other sources are industries e.g. iron (blast
furnace operation), petroleum, cement etc.
2. Sulpher dioxide:
It is colourless gas. It has pungent smell so is irritating
and suffocating. In air it produces sulphate aerosols which
causes respiratory troubles particularly in older people. It is
cause of acid rain also.
Sources:
Natural sources: It is produced by volcanoes, also by
oxidation of organic matter.
Anthropogenic source: It is produced by burning coal, crude
coal oil and other fossil fuel.
3. Oxides of Nitrogen (NxOy):
The oxides are Nitric oxide(NO), Nitrous oxide(N 2O)
and Nitrogen dioxide(NO2).
Oxides of nitrogen are second most abundant atmospheric
contaminants.
Sources:
Natural sources: Decay of dead organisms.
Anthropogenic source: It is produced by burning fossil fuel
(nitrogenous compounds are present in these fuels), bacterial
action on fertilizers.
4. Combustion of hydrocarbon based fuels:
The hydrocarbon based fuels are solids, liquids and
gases. e.g. coal is solid fuel, Kerosene oil, gasoline, diesel,

371
furnace oil etc are liquid fuels, Natural gas, coal gas etc are
gaseous fuels.
These fuels beside CO, SOx, NOx also produce following
pollutants
(a) Particulate matter
Aerosols: Microscopic size solid or liquid particles dispersed
in gaseous media are called aerosols e.g. mist, fog, dust etc.
Aerosols varies in size from 0.01m to 100 m.It is produced
Dust: It is produced by crushing and grinding coal. Fly ash
from chimney also produce dust.
Smoke: It is produced by incomplete combustion. It is mainly
consists of carbon particles. Size of smoke particles is less
than 1 m. TML and TEL used as antiknocks on burning of
fuel produce lead (a particulate matter) in the smoke.
(b) Carbon Dioxide:
It is produced by combustion of fossil fuel, decay of organic
matter etc.CO2 causes green house effect and thus global
warming.
(c) Hydrocarbons: Vehicles emit hydrocarbons including polyaromatic hydrocarbons (PAHs) in air.
The Green House Effect
The greenhouse effect is a process by which thermal
radiation

from

planetary

surface

is

absorbed

by

atmospheric greenhouse gases, and is re-radiated in all


directions. Since part of this re-radiation is back towards the
surface and the lower atmosphere, it results in an elevation of
the average surface temperature above what it would be in
the absence of the gases.

372

Solar radiation at
the

frequencies

of visible
light largely
passes

through

the atmosphere
to

warm

the

planetary surface, which then emits this energy at the lower


frequencies of infrared thermal radiation. Infrared radiation is
absorbed by greenhouse gases, which in turn re-radiate
much of the energy to the surface and lower atmosphere. The
mechanism is named after the effect of solar radiation
passing through glass and warming a greenhouse, but the
way it retains heat is fundamentally different as a greenhouse
works by reducing airflow, isolating the warm air inside the
structure so that heat is not lost by convection. If an ideal
thermally conductive blackbody were the same distance from
the Sun as the Earth is, it would have a temperature of about
5.3 C. However, since the Earth reflects about 30% of the
incoming

sunlight,

this

idealized

planet's effective

temperature (the temperature of a blackbody that would emit


the same amount of radiation) would be about 18 C. The
surface temperature of this hypothetical planet is 33 C below
Earth's actual surface temperature of approximately 14
C. The mechanism that produces this difference between the
actual surface temperature and the effective temperature is

373
due to the atmosphere and is known as the greenhouse
effect.
Earths natural greenhouse effect makes life as we know it
possible. However, human activities, primarily the burning of
fossil fuels and clearing of forests, have intensified the natural
greenhouse effect, causing global warming.
By their percentage contribution to the greenhouse effect on
Earth the four major gases are:

water vapor, 3670%

carbon dioxide, 926%

methane, 49%

ozone, 37%

The major non-gas contributor to the Earth's greenhouse


effect, clouds, also absorb and emit infrared radiation and
thus have an effect on radiative properties of the atmosphere
Effect of Polluted air on Environment:
1.

Acid Rain:
pH of clean rain (unpolluted rain) is 5.6 as it
contain CO2 of atmosphere, But acid rain is the
one whose pH is below 5.6 upto 2.
All precipitations i.e. rain, snow, dew etc that have
pH below 5.6 are called acid rain.
In unpolluted rain CO2 is dissolved producing
H2CO3 thus its pH is 5.6.
CO2 + H2O H2CO3
The acid rain on other hand has pH less than 5.6.
large quantities of sulphur and nitrogen oxides are
emitted into atmosphere from the chimneys of

374
various industries. The oxides of sulphur and that
of nitrogen produce H2SO4 and HNO3 respectively.
SO2 + O2 + H2O H2SO4
NO2 + H2O HNO3
Due to acid rains water of streams, lakes etc
become acidic and it then harms aquatic life. It kills
fishes, reduces their growth and reproductivity. It
also prevent hatching of fish eggs. Green algae
and other beneficial bacteria, which are essential
for aquatic life are killed.
It is threat to human health also as drinking water
becomes contaminated.
It effects plant growth also.
It corrodes buildings, monuments, statues and
metals.
2.

Smog:
Smog is combination of smoke and fog.
Appearance
of
brownish
colouration
in
atmosphere is due to smog. Worse disaster
occurred in London in 1952, When on Thursday, 4
December 1952 a cold- air mass enter valley of
River
Themes. Then on Saturday smog completely
covered London, that was a dark day. On Monday
about 100 people were died. Later on 4000 to
5000 death occurred due to smog. Minor disasters
also reported in Los Angles (in forties), Mouse
valley (Belgium) 1930.
There are two types of smog.
(i)
Photochemical smog:
The smog which is caused by oxides of
nitrogen
and
hydrocarbons
is
called
photochemical smog or Los Angeles smog.
The cities where there is heavy traffic
(Automobiles), during combustion of fuel at

375
high temperature, beside fuel N2 of air also
reacts with O2 and produces NO. The NO
emits to air in exhaust.
N2 + O2 2NO
In air NO reacts with O2 to produce NO2, which
is of brown colour. It irritates eye and damages
the respiratory tract.
2NO + O2 2NO2
When NO2 exposed to sunlight, it is converted
into NO and atomic oxygen
NO2 NO + O
The atomic oxygen reacts with molecular
oxygen and produces ozone. It irritates eyes
and respiratory tract. It cause coughing and
fatigue. It also causes deterioration of fabrics.
It cracks rubber and damages plants and
crops.
(ii)
Industrial smog:
Some time it is also called reducing smog
or London smog. It is caused by SO2. It is
produced in areas where coal is burnt in large
scale. On combustion, the sulphur contents
produce SO2.
S + O2 SO2
It irritates eyes, causes lungs and respiratory
diseases. It suppresses plant growth and is
corrosive to metals.
It further reacts with O2 of air produces SO3
which dissolve in water and produces H2SO4
and thus causes acid rain.
2SO2 + O2 2SO3
SO3 + H2O H2SO4
3.

Ozone:
It is a gas present in stratosphere (15 to 50 km
above earth surface). It filters U.V rays and
protects us. But if present in lower atmosphere it

376
has adverse effects. When NO2 exposed to
sunlight, it is converted into NO and atomic oxygen
NO2 NO + O
The atomic oxygen reacts with molecular oxygen
and produces ozone. It is produced in tropical
regions and transported to Polar Regions.
It causes irritation of eyes, asthma, coughing,
chest discomfort etc. It is harmful to plants and
other materials also.
Depletion (reduction or decrease in overhead
amount) of ozone is occurring world wide but
especially over Antarctica. Here by the mid 1980s,
50% depletion of zone occurred. It is called ozone
hole.
The pollution of air by Freon or chlorofluorocarbon
compounds (CFCs) is the main cause of ozone
depletion. CFCs are used as refrigerants, they are
inert in troposphere but they diffuse into
stratosphere where they are exposed to UV rays
and produce Cl free radical which reacts with
ozone.
.
CFCl3 CFCl2 + Cl
.
.
Cl + O3 ClO + O2
.
.
ClO + O Cl + O2
Water Pollution:
Water is essential for life. Water gets contaminated due to
Physical, Biological and
Chemical pollution. A few of them
are following:
Agricultural Waste:
These include pesticides, fertilizers and heavy metals. Now a
days farmers are using large quantities of pesticides and
fertilizers to get good crops. They make their way to ground
water by leaching with rain water and to rivers and streams by

377
runoff water. Thus they pollute water and are threat to human
health as well as other animals.
Industrial Effluents:
Industrial effluent (liquid waste material) contains many
pollutants. Industrial waste water mainly contains:
1. Occluded gases like CO, CO2, H2S, HCN, COS etc.
2. Dissolved gases like NH3
3. Inorganic salts like carbonates, bicarbonates,
sulphates, sulphides etc.
4. Organic compounds like benzene, toluene, phenol,
xylene etc.
5. Pathogens
Paper Industries, metal Industries and petrochemical
Industries add degradable organic pollutants to water.
Tanneries (leather industries) give effluents with dark colour
and very bad smell, high BOD and high salinity. K 2Cr2O7 used
in tanning is highly toxic and is cancer causing. Arsenic is
also used for hair removal from hide. Both arsenic and
chromium are not suitable for drinking water. The other
serious problem that tanneries give is smell nuisance.
Slaughterhouses, textile industries also give water pollution.
Domestic or Municipal Waste:
It is important source of water pollution. Domestic water
mainly contains soap and detergents. Domestic water causes
following effects on fresh water pollution
1. It causes turbidity and effect aquatic life.
2. It is a source for growth of pathogens.
3. It gives bad smell to fresh water due to having
nitrogenous matter in it.
4. Detergents in it have phosphates witch stimulate
algae growth. Algae covers the water surface and cut
sunlight which is threat to aquatic life.
5. It contains suspended matter which also blocks
sunlight to aquatic life.

378
Petroleum Spills:
Petroleum leaked from ships spread on water. It affects
photosynthesis and dissolved oxygen, also birds when dive in
search of fishes, their feathers clogged with oil and then they
cannot fly and ultimately many of them may die.
Many petroleum products are poisonous and cause health
problems to humans, animals and aquatic life. Hydrocarbons
particularly polycyclic aromatic compounds are carcinogenic.
Livestock Waste:
Mostly livestock waste is either dumped on open land or
discharged to canals, rivers etc. It causes infectious diseases
like dysentery, typhoid and hepatitis.
Pesticides:
They are insecticides, herbicides and fungicides used to kill
insects, herbs and fungus. Beside it they also helped in the
eradication of malaria, yellow fever, sleeping fever etc.
But when, they get to fresh water, cause serious problems to
human and animals.
Water quality:
Drinking water should possess following qualities:
1. It should be colourless and tasteless.
2. It should be free from turbidity i.e. turbidity should not
exceed 10 ppm. Turbidity of water is caused by
suspended solids, dissolved solid, chlorides,
sulphates, phosphates etc.
3. Its pH should be in range of 7.0 8.5.
4. It should be free from disease causing bacteria and
germs.

379
Some of parameters used to check the quality of water are:
1. Dissolved oxygen (DO):
Its
concentration
in
water is 4 8 ppm. It oxidizes organic matter
dissolved in water. If its concentration is less than 4
ppm then water is polluted.
2. Biological/Biochemical Oxygen Demand (BOD):
It
is the capacity of organic matter in natural water to
consume oxygen within a five days period. A sealed
o
water sample is maintained in dark at 20 25 C. The
reaction is catalyzed by bacteria. Amount of oxygen
consumed is measured after five days.
3. Chemical Oxygen Demand (COD): The
organic
content of water which consumes oxygen during
chemical oxidation is evaluated by COD. It is
measured by treating with K2Cr2O7 (strong oxidizing
agent). The organic mater is oxidized and remaining
dichromate is determined by titration. COD is a
measure of chemically oxidizable matter in water. High
COD valu indicates more pollution.
4. Total Organic Carbon (TOC)
5. Total Dissolved Solid (TDS)
6. Total Suspended Solid (TSS)
7. pH
8. Colour
9. Odour
10. Bacteriological measurement etc
Preparation of Potable Water:
Ground water is comparatively clean than surface
water. So, surface water needs treatment to make it fit for
drinking purpose (potable). Following methods are used for
water treatment to make it potable (safe and fit for drinking):
1.

Screening and filtration:


Floating and visible solids present in water are
removed by screening/filtration. Cross linked iron bars may

380
serve as screen. Floating solids are held by screen and water
pass through.
2.

Aeration:
Air is passed through water to remove dissolved
gases like H2S, organosulphur compounds and volatile
organic compounds. Aeration also oxidizes soluble Fe+2 to
Fe+3 which then forms Fe(OH)3 and is removed as precipitate.
Aeration also increase dissolved oxygen in water.
3.

Coagulation:
Colloidal substances are removed by coagulation,
flocculation* and sedimentation processes. Alum or
Aluminium sulphate (coagulants) is added for this purpose. If
natural alkalinity is not present in the water, then lime
[Ca(OH)2] or sodium carbonate must be added. In alkaline
medium following reactions occur>
K2SO4.Al2(SO4)3.24H2O + 3Ca(OH)2 3CaSO4 + 2Al(OH)3
+ K2SO4 + 24H2O
Al2(SO4)3 + CaHCO3 3CaSO4 + 2Al(OH)3 + 6CO2
The colloidal substances adsorbs on the surface of gelatinous
precipitate of aluminium hydroxide.
4.

Disinfection of Water by Chlorine:


Chlorination of water is carried out to kill disease
causing bacteria and other pathogens. Other candid (fair)
techniques to kill pathogens are ozonation and UV
irradiation. But chlorination is widely used technique. Chlorine
reacts with water producing hypochlorus acid
Cl2 + H2O HOCl + H+ + Cl
Hypochlorous acid the decomposes and gives nascent
oxygen which kills pathogens.
HOCl HCl + O
Addition of excess of chlorine is called Breakthrough
Chlorine, it is carried out for satisfactory disinfection of water.

381
However chlorination cannot kill viruses, also it cannot
remove taste and odour neither it can oxidize organic
compounds in water.

Waste Management:
In past when no industries were developed, waste
material was only domestic wastes and agricultural wastes
which were easily disposed in country sides.
But now waste material are diverse materials and their
disposal is a problem.
Dumping wastes in sea and rivers: Dumping wastes in sea
and rivers is a common practice. Waste contain toxic
chemicals which is threat to aquatic life. The waste also
contain radio active material, metals, debris, explosives,
garbage and many more. All these are harmful to aquatic life
as well as human (indirectly). Many disasters such as deaths

382
occurred at Port of Manimata (Japan) due to Minimata
disease caused by eating of mercury contaminated fishes.
Plastic, Paper and Metal as solid waste:
Plastic use is very spread now-a-days. Plastic became
larger part of municipal solid waste (MSW) and is a problem.
Paper is also very extensively used for various
purposes and its disposal is a problem.
Metals are used for packing e.g. Aluminium
and tin cans are used for packing foods, vegetable ghee, dry
milk etc. Disposal of which, affected landfills capacity and
created visual pollution.
*Flocculation is related to destruction of colloidal sol. The
aggregation of particles is called coagulation and resulting
sedimentation is called flocculation.
So aggregation of destruction of colloidal sol is called
coagulation and resulting sedimentation part is called
flocculation.

Green chemistry,
It is also called sustainable chemistry, is a philosophy of
chemical research and engineering that encourages the
design of products and processes that minimize the use and
generation
[1]

of

hazardous

substances.

Whereas environmental chemistry is the chemistry of the

natural environment, and of pollutant chemicals in nature,


green chemistry seeks to reduce the impact of chemistry on
the environment by preventing pollution at its source and
using fewer natural resources.

383
As a chemical philosophy, green chemistry applies to organic
chemistry, inorganic

chemistry, biochemistry, analytical

chemistry, physical chemistry and even chemical engineering.


While green chemistry seems to focus on industrial
applications, it does apply to any chemistry choice. .
Goals of Green Chemistry:
1. To reduce adverse impacts on environment by
appropriate and innovative choice of materials.
2. Develop processes based on renewable rather nonrenewable raw materials
3. To develop processes that are less prone to release
toxic chemicals, fires and other harmful substances.
4. To minimize byproducts in chemical transformations
through redesign of reactions sequences. To achieve
better Atom Economy
% Atom Economy= formula wt of the product / Sum of
the formula wt of all the reactants * 100.
5. To develop products that are less toxic or require less
toxic raw material.
6. To develop products that degrade more easily.
7. To improve energy efficiency by developing low
temperature and low pressure also by adopting
improved catalysts.
8. To develop efficient and reliable methods to monitor
processes.

384
Chapter 24:
ANALYTICAL CHEMISTRY
It is that branch of chemistry which deals with the
determination of qualitative and quantitative composition of
substances.
Bio chemical analysis; is thus the offshoot of analytical
chemistry in which the quality and quantity of biochemical
compounds/substances are studied.
TYPES OF ANALYSIS
Biochemical analysis are of two kinds ie, qualitative and
quantitative.
QUALITATIVE ANALYSIS;
is the identification of a chemical specie in a given substance.
QUANTITATIVE ANALYSIS;
is the determination of that specie in a given substance.
TYPES OF ANALYSIS;
QUALITATIVE
Qualitative inorganic analysis seeks to establish the
presence of a given element or inorganic compound in a
sample.
Qualitative organic analysis seeks to establish the presence
of a given functional group or organic compound in a sample.

385
QUANTITATIVE
Quantitative analysis seeks to establish the amount of a
given element or compound in a sample.
Example; The qualitative and quantitative analysis can
understand from example of pollutant which the killing the
fish in a river
In such a case analyst have to determine first the chemical
identity of a said pollutant. So by means of qualitative
analysis He can explore whether the pollutant is a heavy
metal ( Pb. Cd, Hg and Ni etc) or some other substance.
Once the chemical identity of the concentration (quantity) of
that pollutant in the sample (river) by quantitative analysis
i.e if it is observed that the river pollutant is mercury (Hg) then
its concentration can easily be estimated
B) INSTRUMENTAL METHODS;
Instrumental Analysis depends on instrument of some sort,
either to make a critical measurement during as analysis to
be performing the entire analysis.
Example; if the endpoint of the titration of HCL with NaOH is
located with an instrument Analysis

386

387
Combustion Analysis:
It is one of the estimation techniques. A weighed amount of
sample is placed in combustion tube. The tube is connected
to cylinder of oxygen gas and the gas is passed for some time
to remove air from the combustion tube.

The two u-shaped tubes, one containing water absorber and


other containing CO2 absorber are weighed and connected to
the combustion tube as shown in fig. The compound in the
combustion tube is strongly heated to burning. Carbon and
hydrogen (if any) of the compound will be converted to CO 2
and H2O respectively. The increase in the weight of absorbers
will give the mass of CO2 and H2O produced. From the mass
of CO2 percentage of Carbon is calculated while from the
mass of H2O percentage of Hydrogen is calculated.
I.Calculations of Emperical Formula:

These calculations involve following steps


Step-1 Amounts of elements present in the compound are
determined.
Step-2 Moles of elements are calculated.
Step-3 Simple molar ratio is calculated by dividing moles of
each by lowest number of moles.
Step-4 If simple molar ratio is not in whole numbers, it is
either rounded or multiplied with some suitable number to get
whole number ratio.

388
Step-5 Symbols of the elements are written while their
corresponding numbers are written in subscripts. Resulting
formula is empirical formula.
II.
Determination of Molecular Mass:
Molecular mass is determined experimentally. Various
techniques are available for this purpose, which include
elevation of boiling point, depression of freezing point,
lowering of vapour pressure, Victor Meyer method etc.
III.
Calculations of Molecular Formula:
These calculations involve following steps
Step-1 Emperical formula mass is calculated.
Step-2 Ratio between molecular mass and empirical formula
mass is calculated.

Step-3 Molecular formula is calculated as


Molecular formula = n x empirical formula
Molecular Absorption Spectroscopy:
Molecular absorption spectroscopy, particularly in the
visible region (400-750 nm) of EMR, is based on Bear-lamberts
law, which states that absorption of light by coloured solution is
proportional to (a) the number of molecules (concentration) of
the absorbing compound, and (b) the length of the light path
(i.e. the area through which light passes). Mathematically this
statement can be written as:
AC
A= k.C.l
Where A = absorbency
k = is a constant, which varies with the nature of
compound.

389
C = concentration of compound in mol/liter.
l = length of the light path, which is usually l cm.
Thus if l and k are the same, that is
compound is tested in the same light-path, then:
This shows that keeping other factor
absorbency is equal to the concentration of the
compound in solution.

the same
A= C
constant,
absorbing

As different compounds have different absorption


maxima, hence Bear-Lamberts law holds strictly for
monochromatic radiation (that is for radiation with a narrow
band of wavelengths).
Many system in dilute solution follow Bear-Lamberts
Law, however, absorbance varies in a non-linear manner with
respect to concentration. Such behaviour is called a deviation
from Bear-Lamberts Law. True deviations occur only when the
concentration of absorbing species is so high that the index of
refraction for the absorbed radiation is changed. Consequently,
solutions with concentration below 10-2 M should be used in
molecular absorption spectroscopy.
Infrared IR
Infrared spectroscopy (IR Spectroscopy) is the subset
of spectroscopy that deals with the IR region of the EM
spectrum. It covers a range of techniques, with the most
common type by far being a form of absorption spectroscopy.
As with all spectroscopic techniques, it can be used to identify
a compound and to investigate the composition of a sample.
The infrared portion of the electromagnetic spectrum
is divided into three regions; the near-, mid- and far- infrared,
named for their relation to the visible spectrum. The farinfrared, (approx. 400-10 cm-1) lying adjacent to the
microwave region, has low energy and may be used for
rotational spectroscopy. The mid- infrared (approx. 4000400 cm-1) may be used to study the fundamental vibrations

390
and associated rotational-vibrational structure, whilst the
higher energy near-IR (14000-4000 cm-1) can excite overtone
or harmonic vibrations.
Infrared spectroscopy works because chemical bonds
have specific frequencies at which they vibrate corresponding
to energy levels. The resonant frequencies or vibrational
frequencies are determined by the shape of the molecular
potential energy surfaces, the masses of the atoms and,
eventually by the associated vibronic coupling. In order for a
vibrational mode in a molecule to be IR active, it must be
associated with changes in the permanent dipole. In
particular, in the Born-Oppenheimer and harmonic
approximations, i.e. when the molecular Hamiltonian
corresponding to the electronic ground state can be
approximated by a harmonic oscillator in the neighborhood of
the equilibrium molecular geometry, the resonant frequencies
are determined by the normal modes corresponding to the
molecular electronic ground state potential energy surface.
Nevertheless, the resonant frequencies can be in a first
approach related to the strength of the bond, and the mass of
the atoms at either end of it. Thus, the frequency of the
vibrations can be associated with a particular bond type.
Simple diatomic molecules have only one bond, which
may stretch. More complex molecules may have many bonds,
and vibrations can be conjugated, leading to infrared
absorptions at characteristic frequencies that may be related
to chemical groups. The atoms in a CH2 group, commonly
found in organic compounds can vibrate in six different ways,
symmetrical and asymmetrical stretching, scissoring,
rocking, wagging and twisting.

391

INSTRUMENTATION
A beam of infra-red light is produced and split into two
separate beams. One is passed through the sample, the
other passed through a reference which is often the
substance the sample is dissolved in. The beams are both
reflected back towards a detector (Fig. 10.2), however first
they pass through a splitter which quickly alternates which of
the two beams enters the detector. The two signals are then
compared and a printout is obtained.
A reference is used for two reasons:

This prevents fluctuations in the output of the source


affecting the data
This allows the effects of the solvent to be cancelled
out (the reference is usually a pure form of the solvent
the sample is in)

392
Infrared Spectrophotometer

Atomic Emission and Absorption spectroscopy:


Atomic spectroscopy includes both Flame Emission and Atomic
Absorption spectroscopy. Flame Emission or Fame photometry
refers to the measurement of the radiations emitted by certain
elements when exposed to high temperature of a flame. Atoms
of such elements absorb energy from heat and thus become
excited, i.e. an outer electron shift to a high energy level. Atoms
in their excited state are unstable. Therefore on cooling the
electron falls back to the lower energy level, and atoms
returned to their original stable form, known as the ground
state. During this process the atoms emit the absorbed energy
in the form of radiations. This is known as atomic emission. The
type of radiation emitted or the wavelength of the emitted
radiation is referred to as emission spectra. Each element has
characteristic emission spectra, which aids in the identification
of elements. Since the intensity of the emitted radiation is
proportional to the number of atoms of the element in a given
sample, this technique is also useful for quantitative analysis.
The instrument used for this purpose is known as flame
photometer.
In atomic absorption spectroscopy, the wavelength and
intensity of the radiation absorbed by the atoms are measured
rather than the emission. So AAS is an improved technique,

393
used for routine analysis of different mineral elements. Like
emission spectra, each element has a characteristic absorption
spectra, which can be used for both qualitative and quantitative
analysis. In both atomic emission and absorption spectroscopy
the sample solution is aspirated into a flame, where it is
vaporized and atomized (broken into atoms). The atoms then
absorbed or emit the energy.
INSTRUMENTATION
Atomic
Absorption
spectrophotometer
essentially of the following parts

consists

Radiation source (Hollow cathode Lamp)


Cell (Burner & Nebulizer)
Chopper (Rotatory sector Wheel)
Detector (Photomultifier tube)
Meter read-out system

Part of Atomic Absorption spectrophotometer

394
Nuclear magnetic resonance (NMR) spectroscopy
Nuclear magnetic resonance (NMR) spectroscopy deals with
the behavior of atomic nucleons in magnetic fields. Most
nuclei, including the proton and the electron, possess
inherent magnetic fields. In the presence of another (external)
intense magnetic field, the nuclei absorb energy
(electromagnetic radiation) and can assume specific
orientations with corresponding potential energy levels.
Techniques have been invented to detect the minute amount
of energy absorbed or emitted as the nuclei jump from one
energy level to another. This is the basis of nuclear magnetic
resonance (NMR). It has been used for the last 50 years as a
reliable and sensitive method for determining the structure of
biomolecules.
The high resolution NMR of homogenous solutions
provides information about:

Functional group analysis (chemical shifts)


Bonding connectivity and orientation (J coupling)
Through space connectivity.
Molecular conformations, DNA, peptide and
enzyme sequence and
Chemical dynamics (Line shapes, relaxation
phenomena).

PRINCIPLE
The nuclei of all elements carry a charge. When the
spins of the protons and neutrons comprising these nuclei are
not paired (i.e. the nuclei possess an odd number of protons,
an odd number of neutrons, or both) the overall spin of the
charged nucleus generates a magnetic dipole along the spin
axis, and the intrinsic magnitude of this dipole is a
fundamental nuclear property called, the nuclear magnetic
moment. It varies with each element. The symmetry of the

395
charge distribution in the nucleons is a function of its internal
structure and if this is spherical (i.e. analogous to the
symmetry of a IS hydrogen orbital), it is said to have a
corresponding spin momentum number of 1 = . Examples of
such nuclei are 1H, 13C, 15N, 19F and 31P, etc.

Two Orientation of the Nucleus


a. against the magnetic field ( high energy)
b. parallel to the magnetic field ( low energy)
If the oriented nuclei are now irradiated with
electromagnetic radiation of the proper frequency, the lower
energy state will absorb a quantum of energy and spin-flip to
the high energy state. When this spin transition occurs, the
nuclei are said to be in resonance with the applied radiation,
hence named nuclear magnetic resonance.
The NMR signal for a given nuclei is referred to as the
chemicalshift, and, in general, protons or carbons adjacent
to electronegative atoms will be deshielded and moved to a
higher chemical shift (undergo transition at a lower applied
field). The scale utilized for measuring chemical shifts is
defined by the equation shown below:

396
Chemical shift () = (shift observed/oscillator frequency) x 10 6
ppm.
The factor of 106 is introduced into the equation to give a
simple whole number scale for convenience.
Experimentally, for both 1H and 13CX NMR, the Scale
is anchored at zero by the NMR absorption of the molecule
tetramethyl silane ((CH3)4Si) in which the carbons and protons
are more highly shielded than those observed in most
common organic molecules, For 1H NMR, the scale
generally extend from 0-12 ppm; the scale for 13C nuclei,
however, is much larger and covers the range 0-220 ppm.
On the scale for 1H for NMR simple hydrocarbon
protons tend to absorb in the region 0.5-1.5, protons on a
carbon adjacent to a carbonyl are shifted to 2,
electronegative atoms (oxygen or halogens) move -protons
to 3-4, alkene protons are shifted to 5-6, aromatic
protons to 7-8, aldehydic protons to 10, and the most
highly shifted protons are generally those of carboxylic acids,
with values of 12.
For 13C NMR, simple methyl carbons tend to absorb in
the region 20-65, electronegative atoms (oxygen or
halogens) move attached to 40-80, alkyne carbons are
shifted to 70-90, alkene carbons to 100-150, aromatic
carbons to 120-170, and most highly shifted carbons are
generally those of carbonyls, with values of 180-220.
For
a
molecule
such
as
diethyl
ether,
CH3CH2OCH2CH3, two types of protons would be predicted to
appear in the NMR spectrum; a simple CH 3 in the area of =
1, and a CH2 shifted down to about = 4 by the
electronegative oxygen. The NMR spectrum of diethyl ether,
however, displays seven peaks.

397

Fig 12.2 NMR spectrum of diethyl ether


This multiplicity is due to the phenomena known as
spin coupling and arises because of interaction of the proton
magnetic field with bonding electrons. In essence, each
proton can have one of two possible spin orientations in the
applied field, so that the magnetic field sensed by adjacent
protons can have one of two possible values. The result is
that n protons will split adjacent protons into (n + 1) peaks.
The intensities of these peaks are simply a result of the
possible spin orientations, thus, the protons of a CH2 group
can have the following possible spins:

The middle pair is degenerated therefore a proton


adjacent to a CH2 group will be spited into three separate
peaks in the ratio 1:2:1.
The separation between these peaks is referred to as
the coupling constant J, which is measured in Hz; typical
values for J seldom exceed 20 Hz and it is important to note
that sets of coupled protons will display exactly the same
coupling constant.

398

NMR spectrum methyl Isopropyl ether


10.6

INSTRUMENTATION

An N.M.R. spectrometer contains a massive and


intricate collection of electronics of which we can consider
only the basic elements. We must remember that we are
dealing with intense magnetic fields requiring enormous,
precisely controlled power supplies, and precisely controlled
frequencies. Unfortunately, most of the kilowatts required by
the instruments are dissipated as heat and the few microwatts
of signals that we obtained from the sample must be amplified
by another intricate electronic system. The complexity of
operation of the instrument represent a barrier to its wide
spread use, but even so it is rapidly becoming nearly
available as an infrared spectrometer. The basic components
of a typical NMR spectrometer are given as under in (Figure
12.4):

Magnet: with a strong, stable, homogeneous field.


The field must be constant over the area of the
sample and over the period of time of the experiment.
A sweep generator: which supplies a variable D-C
current to a secondary magnet so that the total
applied magnetic field can be varied (swept) over a
limited range.

399

Radio frequency: a radio-frequency oscillator


(transmitter) connected to a coil which transmits
energy to the sample in direction perpendicular to the
magnetic field.
A readout system: consisting of an amplifier,
recorder, and possible additional components for
increased sensitivity, accuracy, or convenience.
A sample container: usually a glass tube spun by an
air-driven turbine to average the magnetic field over
the sample dimensions.

Schematic diagram of N.M.R. Spectrometer


MASS SPECTROSCOPY (MS)
The mass spectroscopy (MS) sort out charged gas
molecules (ions) according to their masses. It is the most
useful technique to determine structures of complex organic
molecules. It is very sensitive analytical tool that can detect
0.1 g or less of material. It is also unique in that for the great
majority of compounds it directly determines the molecular
weight of the sample. In addition, it also detects functional
groups, hetero-atoms and their arrangement in the molecule.

400
The sensitivity of the instrument plus the usefulness of data
make it an ideal unit for coupling with a gas chromatograph or
a high performance liquid chromatograph (GC-MS and LCMS). This coupling results in a powerful tool for the
quantitative and qualitative analysis of complex compounds.
Material separated by thin layer chromatography (TLC), paper
or column chromatography, etc. may also be analyzed by the
mass spectrometer.
PRINCIPLE
The mass spectroscopy (MS) is based upon the
principle that the sample is first ionized by bombardment with
stream of electrons from a hot filament, a process known as
electron impact (EI) ionization. The positively charged ions so
formed are then separated according to their mass to charge
ratio. Dispersion of ions occurs through deflection by electric
and magnetic fields. After separation, the ions enter a
detector and then on to an amplifier to boost signal. The ions
are identified from their masses and their intensity is
measured from their corresponding electrical signal.
Computing integrating unit records all the data and converts
the electrical impulses into visual display, a hard copy of
which can also be prepared. The computer also drives the
mass spectrometer.
Since each compound has a unique fragmentation
pattern, so compounds can be easily identified from their
known ion fragments. Many compounds, e.g. fatty acids,
sterols and pesticides have been accurately identified by GCMS.

401
INSTRUMENT: (MASS SPECTROMETER)

A typical mass spectrometer consists of five basic units


(i)

An inlet system: To introduce the sample, which


in first heated to vaporize it; the vapor is then
allowed to diffuse into the electron source unit.

(ii)
An electron source unit/chamber: To produce a
beam of electrons to ionize the sample. Usually a 70-V
electron beam is applied. This is
energetic enough to
break any bonds likely to be present within the
sample.
(iii)
An analyzer region: To separate ions according to
their mass to charge ratio by electric and magnetic fields.
The quadruple mass analyzer (or
filter) is
commonly
used. It
consists of four parallel rods, on which are
impressed a specific radio frequency and variable DC
voltage.
(iv)
A collector and recording system: To detect the
ions and measures their
intensity
(v)
A vacuum system: To maintain high vacuum in the
instrument for normal functioning.

402
11.4

MASS SPECTRUM (FRAGMENTATION PATTERN)

When an organic compound having low ionization


potential is bombarded with an electron beam, the initial result
is formation of a molecular ion carrying a positive charge. It is
formed by the removal of one electron from the sample
molecule leaving a positive charge on it. Hence it is called
molecular ion or parent ion. This ion denoted by M + is a
radical ion which is usually formed with sufficient excess
energy so that some or many fragment ions are also formed
due to the breakage of bonds within the molecule. Each
compound yield characteristic molecular ion (M+) and
fragment ions, which are useful to identify the compound and
elucidate its structure. The series of fragment ions of a
compound is called its fragmentation pattern or cracking
pattern/mass spectrum.
The mass spectrum consist of a series of peaks of
various amplitude, each peak is recorded as value of mass
divided by charge (M/Z). Since we deal with singly charged
ions (i.e. Z=1) such a value is the mass (m) of the ion
corresponding that peak. Peak heights are proportional to the
number of ions of each mass. The galvanometer records a
slight ion current at each mass unit.
The first step in making use of the data is to assign
M/Z values to the various peaks. This is generally done by
referring the spectra to that of calibration compounds of
known M/Z values. After assigning of mass numbers, the
intensities of various peaks are tabulated. The intensities are
generally expressed as percentage of the most intense peak
in the spectrum, called the basepeak. In most cases the base
peak will not be the molecular ion, i.e. ion due to the ionized
but undissociated molecular species.
The mass spectrum/fragmentation pattern is commonly
presented as a bar graph as shown in (Fig 11.2), the MS of nbutane. Note that the molecular ion (M/Z= 58) gives a relative
small peak while the peak at 43 is the most intense (the
largest peak) called the base peak. This indicates that a

403
fragment peak of mass number 43 is more resistant to further
cleavage than was the parent molecule itself. In this case it
must have been formed by the loss of a fragment of mass 5843=15, clearly a methyl (CH3) group, so the base peak is due
to C3H7 ion.

Mass spectrum of n-butane


Mass spectra, even with a moderate resolution, can
provide a wealth of information related to the composition and
structure of a sample. IN addition to the molecular weight ,
important fragment can often be identified, including such
groups as phenyl (mass 77) or benzyl (M=91). A series of
peaks such as 15, 29, 43, 57, 71 85, etc. separated by units
of 14 (CH2) suggest a long aliphatic chain. Primary alcohols
and amines are often identified by the presence of the CH2OH peak at 31 or the CH2NH2 peak at 30 amu.