Chemistry 2nd Year Complete File
Chemistry 2nd Year Complete File
Chemistry 2nd Year Complete File
Blocks:
(b)
(c)
(d)
2
(ii)
(iii)
(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
3
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.
4
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)
elements: sodium,
phosphorus, sulfur,
two, sodium and
the s-block of the
5
periodic table, while the others are members of the pblock
Chemical element
11
Na
Sodium
Chemical
Electron
series
configuration
Alkali
[Ne] 3s1
metal
12 Mg Magnesium
Alkaline
[Ne] 3s2
earth
metal
13 Al
Aluminium
Post-
transition
metal
14 Si
Silicon
Metalloid
15 P
Phosphorus Polyatomi
c
nonmetal
16 S
Sulfur
Polyatomi
c
nonmetal
17 Cl
Chlorine
Diatomic
nonmetal
18 Ar
(1)
Argon
Noble gas
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
6
distance between nuclei of two identical atoms
bonded together through single covalent bond.
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
8
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
(4)
(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:
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
10
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)2 = +844 kJ/mol
(2,7)
(2,8)
11
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.
12
Name of Element
Symbol
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
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
14
Trends across Period 3 of the Periodic Table
15
16
Properties of Oxides and Chlorides of Period 3 Elements
Element
Chlorine
NaCl
Na2O
MgCl2
MgO
AlCl3*
Al2O3
SiCl4
SiO2
PCl3
P4O6
SCl2
SO2
Cl2
Cl2O7
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
Good
Good
Good
Good
Poor
Good
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
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.
17
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.
18
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.
Argon
There is no reaction between argon and water.
19
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:
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.
20
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:
Sulphur
Sulphur burns in air or oxygen on gentle heating with a pale
blue flame. It produces colourless sulphur dioxide gas.
21
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.
22
Sulphur
If a stream of chlorine is passed over some heated sulphur, it
reacts to form an orange, evil-smelling liquid, disulphur
dichloride, S2Cl2.
23
MgO
Al2O3
SiO2
P4O10
SO3
Cl2O7
P4O6
SO2
Cl2O
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.
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.
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.
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.
26
27
The pure un-ionised acid has the structure:
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
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:
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(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.
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.
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.
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.
35
exist in solution. Any attempt to get them out of solution
causes them to decompose to give the carbonate, carbon
dioxide and water.
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.
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
lilac (pink)
Rb
red (red-violet)
38
Cs
Ca
orange-red
Sr
red
Ba
pale green
Cu
Pb
gray-white
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:
Calcium:
Strontium:
Barium:
Radium:
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
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.
(3)
Li2O
MgO
+
+
H2O
H2O
NaCl +
H2O
Ca(OH )2 + 2HCl
CaCl2 +
2H2O
Carbonates:
43
alkaline earth metals as well as that of lithium are
insoluble.
Li2O +
CO2
CaCO3
CaO +
CO2
44
CaO (Quick lime).Quick lime is used for cement and
glass industries.
(4)
Bicarbonates:
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
2NaOH
Na2BeO2
H2
(Page-4)
(vii)
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:
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.
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:
50
51
Fajans' Rules
In inorganic
chemistry, Fajans'
Rules,
formulated
Covalent
Large cation
Small cation
Small anion
Large anion
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.
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.
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)
(vi)
(vii)
Si
O
Si
O
Si
O
Si
O
Si
O
O
O
Si
O
O
O
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:
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.
59
These oxides all react with acids to form salts.
For example, they all react with concentrated hydrochloric
acid. This can be summarised as:
are
talking
about
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:
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
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:
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.
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.
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)
69
3.
4.
5.
6.
7.
8.
General Characteristics:
1.
Radii
Sc
Ti
V
Zn
Cu
Cr Mn Fe Co
Ni
Atomic Number
1.
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:
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)
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
(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
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
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
.. ..
..
.. .. ..
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)
79
(III) chloride
K3[Fe(CN)6]
[Ag(NH3)2]Cl
Diammine silver (I) chloride
Na3[Ag(S2O3)2]Sodium dithiosulphato argentate (I)
[Ni(CO)4]
Tetracabonyl nickel (0)
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.
82
If you add hydroxide ions, these react with the
hydrogen ions. The equilibrium tips to the left to
replace them.
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.
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:
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.
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.
88
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.
90
The overall equation for the reaction is:
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:
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.
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.
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.
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.
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
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
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
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.
ii.
104
iii.
iv.
v.
vi.
vii.
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
(truncated
icosahedron)
which
Sean
O'Brien, Robert
Curl,
and Richard
to Buckminster
Fuller,
as
C60 resembles
his
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
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.
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)
112
(3)
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)
113
Procedure:(1)
(2)
(3)
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)
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.
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)
116
Carbon, Nitrogen and Sulphur from organic compound
react with the sodium to form sodium thiocyanide.
Na + C + N + S
NaCNS
NaS
NaX
(A)
Detection of Nitrogen:
(i)
(ii)
(iii)
(iv)
(v)
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)
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
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
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)
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
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.
123
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.
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
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.
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
137
Uses of Alkanes:
(i)
(ii)
(iii)
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.
Ter-alcohols
are most reactive among alcohols so they need
139
still lower concentration of acid and also least
heating.
2.
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.
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.
145
The elecrophile (Bromonium) makes permanent bond with
one of the carbon and leaving +ve charge on other carbon.
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
146
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.
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.
149
5.
In
asymmetric
alkenes addition takes place according to
Markownikoffs rule.
The alkyl hydrogen sulphates on dilution with
water and boiling give alcohols
B.
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.
Epoxide Formation:
151
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.
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
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:
Chain Isomerism:
155
(ii)
Position Isomerism:
(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:
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.
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.
159
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:
162
a result reagent molecule breaks up and its +ve ion
(electrophile) forms a temporary bond with two multiple
bonded carbons.
163
Addition of hydrogen is called hydrogenation.
Molecular hydrogen cannot break -bond however
atomic hydrogen can break it. Therefore to
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.
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.
166
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
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
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)
169
(White precipitate)
Unlike sodium and potassium acetylides silver
acetylide is a covalent compound.
(iv)
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
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
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
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-III:
Approach of Nucleophile
When nucleophile approaches phenonium ion then
there are two possibilities of giving final product.
(a)
(b)
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.
179
Step-III:
(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.
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
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.
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:
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
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.
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:
12CO2 + 6H2O
(ii)
185
Ethyl benzene
Catalytic Oxidation:
(iii)
Benzoic acid
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
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.
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.
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.
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.
(ii)
191
(ii)
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.
194
i)
From Alcohols:
195
Alcohols on reaction with thionyl chloride, produce
corresponding alkyl chlorides.
Bond energy
467 kj / mol
413 kj / mol
346 kj / mol
Bond
C-Br
C-I
Bond energy
290 kj / mol
228 kj / mol
196
Most of reactions of alkyl halides are nucleophilic substitution
reactions but they also show elimination reactions.
(A)
Nucleophilic
reactions):
Substitution
Reactions
(SN
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
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.
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)
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.
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.
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:
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.
206
207
Mechanism:
Ethyl bromide is primary alkyl halide so it will follow E 2
mechanism.
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.
209
1.
Hydrolysis by water:
Grignard reagent on hydrolysis by water in
presence of ether, produces corresponding alkane.
(B)
Nucleophilic
Reactions:
Addition
The
addition product thus obtained then on acid hydrolysis gives
useful organic compounds.
1.
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.
212
213
The Ketone thus produced further reacts with Grignards
reagent and gives an addition product which then on acid
hydrolysis produce tertiary alchohol.
4.
214
5.
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:
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.
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
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.
220
Primary amines react with aldehyde and ketones, yield
condensation product called Imines. These imines are also
called as Schiffs Base.
221
In the first stage, the ammonia reacts with the ethanoyl
chloride to give ethanamide and hydrogen chloride gas.
. . . and you can combine all this together to give one overall
equation:
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.
. . . and you can combine all this together to give one overall
equation:
223
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
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.
Mechanism:
Ethyl bromide is primary alkyl halide so it will follow
SN2 mechanism
229
Hydration of Alkenes:
When alkenes are treated with cold concentrated H2SO4
addition of acid take place.
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.
231
232
Reaction of R-Mg-X
with Esters:
Reaction of Grignards reagent with alkyl formate followed by
acid hydrolysis produces secondary alcohol.
233
(b)
234
The addition product is not stable thus it undergoes
rearrangement and produce ketone.
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)
236
(B)
1.
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
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.
2-Butanol
239
Alcohol also undergo dehydration when heated at
o
250 C, in presence of Al2O3 and ethers are produced.
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.
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:
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.
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)
244
Chemical Properties of Phenol:
The reaction of phenol can be divided into two categories.
(A)
(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.
245
(ii)
(iii)
Reduction:
Phenol on heating with Zinc dust reduces to Benzene.
(B)
(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.
(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
Uses of Phenol:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
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.
248
2.
By dehydration of Alcohols:
o
Alcohol also undergo dehydration when heated at 250 C, in
presence of Al2O3 and ethers are produced.
3.
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)
(ii)
(iii)
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)
251
(iv)
(v)
(vi)
(vii)
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
Preparation of Acetone:
(i)
Laboratory method:
254
(ii)
O
ther
methods:
(a) By oxidation of secondary alcohols:
(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..
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 .
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)
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.
(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)
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)
264
(b)
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.
266
The aldol then loses water on heating with dilute acid to form
unsaturated carbonyl compound.
4.
Cannizzar
os Reaction:
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.
268
Methanal
Sodium methanoate
(Reddish ppt)
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.
270
10.
Uses of Acetaldehyde:
1.
2.
3.
4.
5.
Uses of Acetone:
1.
2.
3.
4.
5.
6.
7.
8.
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.
Preparation:
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
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
276
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
Reactivity:
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.
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:
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
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.
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.
283
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:
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
(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.
288
bond. For example maltose yields the same
kind of two glucose units
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
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
Primary Structure:
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:
300
b.
c.
d.
Quaternary Structure:
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
302
proteins present in the blood plasma exert an osmotic
pressure of 25 to 30 mm Hg.
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
Concentration of Enzyme
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.
306
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
308
f.
Effect of pH
309
h.
Presence of Activators/Inhibitors
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.
312
lipid compounds into two major categories: (i) saponifiable lipids
(esters), and (ii) non-saponifiable lipids.
i.
Saponifiable Lipids:
313
ii.
Un-saponifiable Lipids:
(C15H31COOC30H61).
The
naturally
occurring
314
Physical Properties:
iv.
Hydrolysis
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
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
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
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
found
in
every
living
cell.
They
are
complex
320
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
iv.
Molecular
Wt.
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
direct protein
synthesis in the
cell
viii
Types
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.
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
the
polymer
chains
known.
Each
mammalian
324
ii.
iii.
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 +
+
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
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.
ii.
muscle contraction,
iii.
iv.
enzyme-activation,
v.
vi.
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
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.
ii.
331
iii.
iv.
v.
vi.
vii.
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
the
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
335
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.
ii.
Fungicides,
which
are
used
to
combat
339
iii.
iv.
v.
vi.
vii.
i.
340
ii.
iii.
iv.
against
sucking
insects.
These
v.
eradicants.. An
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
(c)
kexachloro
systemic
pesticides.
(iii)
Carbonates:
these are
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
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%)
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.
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:
351
which is a tough flexi plastic used to make shopping bags,
table cloths, plastic bottles etc.
o
Vinyl chloride is when subjected to 52 C and 9 atm pressure
it polymerizes to poly vinyl chloride (PVC).
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
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
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.
combining
nitrocellulose
and
plasticizers
with
358
with
other
ingredients
is
essential
to
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
or 2,5-
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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).
(CAS#591-27-5),
(CAS#2835-95-2)
and
5-amino-2-methylphenol
1-naphthol
(CAS#90-15-3).
The
gives
magenta-brown
dye,
while
the
include
resorcinol,
4-
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
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
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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:
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(ii)
Hydrosphere:
Biosphere:
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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)
Mesosphere:
(d)
Thermosphere:
It
extends
extends
from
up
to
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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.
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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.
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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,
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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
372
Solar radiation at
the
frequencies
of visible
light largely
passes
through
the atmosphere
to
warm
the
sunlight,
this
idealized
planet's effective
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:
methane, 49%
ozone, 37%
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
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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.
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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.
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.
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.
383
As a chemical philosophy, green chemistry applies to organic
chemistry, inorganic
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
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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.
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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.
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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
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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.
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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:
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Infrared Spectrophotometer
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
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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:
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
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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.
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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.
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398
INSTRUMENTATION
399
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.
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INSTRUMENT: (MASS SPECTROMETER)
(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.
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11.4
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.